Qc Sponsoring Etor: Peer Rene Project Eto: Naney ight Manuseript Eto: Rath Ves Designers: Gary A. Head and Shaten I, Sith Production Coonsinatr: Frank Mint ‘Mlastaton Coordinator: Batyoh Fanos Arts: Flin Coopee Syntax leterntionl DAA SS OK S2 ADSo c oPy 4 Library of Congress Cataloging in Puiston Data ae wien ad Compary bosk maybe reproduced by any raphe, petmisson fromthe publics Printed inthe United Stat of Ameen “Twenty fest pr 13,2000 1 Kroemer, About the Authors Charles Kittel has tought sol ty of California at Berkeley since 1951, having previously been at the Bell Laboratories, 1 undergraduate work in physics was done at M.LT. and at the Laboratory of Cambridge University. His Ph.D. research was in nuclear physics with Professor Gregory Br He has been awarded three Gugge te Physics, and, fr contrib of the American Assocation of Physics Teachers. He is a member o National Academy of Science and of the Ametican Academy of Arts ad SSlences His research has been in magnetism, magnetic resonance, semi: ‘ductors, and the statistical mechanics of solids id technofogy of semiconductors igh-requency transistors, negative- lasers, the Gunn effect, electron-holePreface This book gives an elementary account of then simple, the methods ars powerful, and Ro other physical theory is used more widely throughout seience and engineering. and for electrical engineering students generally orposes have strong common bonds, mast notably a conce ses, whether in semiconductors, metals, stats, oF ied by the clarity of the we were taught when we were stude We have not emphasized several t are no loge and tome because 1 eal mechanics would make the course more diffe nour Gel Wheeter, Help was given by 1 kos, Margaret Geller,treface Verhoogen, John Wheatley, and Carol Tung for the typed manuscript and Sari the index, K of the greenhouse effect in the 1994 on page 115, added t0 page 223 in 2000. instructors who have adopted the course for classroom use, a solutions manual is available via the freeman web site (hitpsshfrecman, ‘comu/hermalphysics). Berkeley and Santa Barbara Charles Kitel Herbert Kroemer Note to the Student um coverage of the concepts presented in each chapter, the the following exercises. Chaps Chapter 4: 1,24, 14,15; Chapter 7:2, 3.5.6 ‘Chapter 10: 1,2, 3; Chapter 3.7.8, 10; Chapter 14: 1,3, 4, 5; Chaptor 15: 2, 3,4, 6 2: 1,2, 3; Chapter 3:1, 2.3.4.8, 8; Chapter 5: 1, 3, 4,6, 8 Chapter 6: 1,2, 3,6,12, 3, 5,6, 7; Chapter 9:Contents Guide to Fundamental Defi General References xv Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter Chapter 12 Chapter 13 hapter 14 Chapter 1 Appendix. Appendix B Boltzmann Distribution and Free Energy 55 ‘Thermal Radi \n and Planck Distrib remical Potential and Gibbs Dis Weal Gas 151 Fermi and Bose Gases ‘SHeatahd Work 225 Gibbs Free Energy and Chemical Reactions 261 Phase Transformations 275 Binary Mixtures 309 Cryogenics 333 Semiconductor Kinetic Theory 389 ies 353 Propagation 423 Some Integrals Containing Expone 445 439 ‘Temperature Sc xAppendix © Appe Appendix Inder 465 Db Guide to Fundamental Definitions 19 Boson 183, Chemical potential Classical regime, n < Ensemble of systems Enthalpy, HH = Ut p¥ 246 Entropy,e 40 Fermion 183, bs factor, expf(Nu— ele] 138 Gibbs fee energy, G=U—10 + pV 262 Gibts or gfand sum, 3138 Heat capacity, C63 Heat,Q 68,227 Helmholtz free energy, F = U~ 10 68 Landau free energy function, F, 298 1 ‘aiGuide to FundamentetDefaitons Quantum concentration, ng & (Mr/2xh)? 73 Reve le process 64 Temperature, 41 ‘Thermal average 62 Thermal equilibrium — 39 Work, WW 227 General References Thermodsnay A.D. Pippard, Elements of es 196 MW. Zemanshy and RH ‘thermodynamics, Combridge Univesity Press, tan, Hew book, 6th cay MEGraw-Hil, 198) Wiley, 1988, is 2and 3 reat applications nas been expanded iota the HB. Dvigh, Tables of integrals and o 1961, A widely useful small Applications Asteophysiss RJ. Toyion, The sar ready sate and Springer, 1985General References Coyopenies end low tinperatire OK Wi Pres, 1987 Irreversible thermodynas 2A. McLennan, nn 1539, 1. Prgosine and 1. Stenges, Onder out of chaos: Random House, 1984, : , 1986, 1976, HL Jensen, Transport phenamena, Oxford University Press, 1989, Phase transitions P. Peay and G. Toulouse, ‘Metals 2nd atlogs P.Hiasea, Piysical m lurgy, 2nd ef, Cambeidge Univesity Pr Bousdary value problems HS. Cardaw and J.C. Jaeger, Conduction of heat in solids, 2nd ed, Oxford Univer: sity Pres, 1986, ©1989, Semiconductor devices ‘0 applied sold state physics, Plenum, 1990, K Seeger, Semiconductor physics: an inroduction, Sth ed, Springer, 1991 SUM. Sze, Physics of semiconductor devices, 208 td, Wiley, (981. Solid state physics C Kittel, Intracuction solid state physics, 6th ed, Wiley, 1986, Reeredtoas ISSP.Thermal PhysicsIntroduction pearance, the leading charac the Boltzmann factor, the chemi sion fonctions ‘The enteopy mee A close system: 25 the number af quantum states aceeseible toa esto ‘be in any ofthese quantum states and (we assume) than exp( 10), and of gis ‘When wo system they may transfer number of accessible states: more is better, and moce likly. T the kernel ofthe law of increase of entropy, whict isthe generat express energy. What isthe most probable outcome of the encounter? One system will, ‘gain energy at the expense of the other, and meanwhile the total entropy ofthe two systems the num for ‘the given total energy. Is not dificult to show (Chapter 2) that the maximum,Invocton 0 €9f@U}xy for one sysiem ig equal tothe value of forthe second st n. Thisequality property for two oir has energy Up and wi ' When the smalls)stem sin the state of energy othe have energy Ug — cand fo ~ 8} states access it. By the fundames he probs small syste of fin 20) _ Ws ~ 9 Fo) 0 7 The reser encopy @ may be expanded io» Taylor serie olWa)~ Hot = ot, o temperature. Higher ord energy (4) ofthe v0 st: perature ¢ Plt.) = O-P(O) + ePie) me FSP =U) nd > T Te ey, Iuadecton suum of the prob 0 he average energy of ‘Chapter 4 as the frst, tor at temperature z and we do this step in the derivation of the Planck radiation law. ‘The most important extension of the theory is to systems reservoir, For two systen Ibe a maxima ray. Not For two systems in thermal and difusive contact, ry = ry and ly = py. The sign in (7) evosen to ensure that the direction of particle {s approached js from high chemical poten he Gibbs factor of Chapter 5 is an extens one with 1 particle th reservoie at temperature + and ‘extend (3) forthe reseevoie entropy: a{Ue ~ ENy = 1) = olUaiN) = eesti = a(UaiNe) ~ ut + af. PO) = expfe ~ eve] « PU) = 0) ele=Chapter 1 s fs own a the FermiDirac dissibution funtion and is wed pa the theory of tetas fo deserib temperature nceneation (Chapter 7h. “The classic ditibition function used is jot te limit of) when the ose ‘This pac leciron gas at low jon ofthe ideal gas law ancy PAs) s much less than L Stat Pla) = expll ~ ae es of a Model System is of the idea! gas ave developed fr fre enetgy F = U i result in Chapter 6 — te appears as an import ion (2F they = —o offers BINARY MODEL SYSTEMS » computa ty Funeton 4 he easiest method 7 6 18 2 2 2 SUMMARY. 26 scopie and the macroscopic.Cheptee 1 Stes of a Motel Stem land Becouse i yields depar 1 Gibbs pressive the greater she si tore different kinds of things it relares, pide aloud ad applicability. Therefore A. nstcin tes ofa Mode Sytem ‘Thermal physic isthe fei Mechanics tells us the mea heat. Thete are ordinary mechani their definitions is theceater ur point of departure for the d of the stationary quantum states of a ssstem of paticles. When sve ean cou the quantum states accessible to @ system, we know the entiopy af the sy for the entropy is defined as the logirithm of the numberof states (Chapter 2) dependence of the entropy on the energy ofthe system defines ture. From the entropy, the temperatue, andthe fieenerpy we ind the pressure, and all other thermodynamic properties ofthe system, ry quantum state, al observable physical properties such as the energy and the nutnber of panicles are independent ofthe tine For brevity we usually omit the word stationary; the quantum states that we ars stationary except when we discuss transport processes in Chapters ‘The systems we discuss may he composed ofa si ‘of many particles. The theory is developed to handle general systems of inten, pauticles, but powerful simplifications eam be made in speciat problems for which the interactions may be neglected Each quantum state has a defini istic and mechanical of work; ermal physics ferinal physics that do n0t appe: entropy, temperature, and fee energy. We shal w frst three chapters and deduce their conse le particle or, more oft ial energies ace ty or degeneracy of an ith very nearly the same| a fined to a cube of side L are shoven in Figure 1.2. We shal find in Chapter 3wo Chapter 1: States ofa Met of a free particle ean be eh quantum numbers n ‘The energy is the figuee. The three orbitals rl to (4, alla the corresponding energy level & To describe i Properties ofa system of & ofthe: ‘is esential CRY C(N), where isthe energy ofthe quantum ies uch as smay be assigned to the quantum ‘ary way, but two diflereat states should net be {2 good ides to start our progr model systems for 35 a model a 3 by studying the properties of simple .AN)ean be calculated exa binary system Because the ger system are experiment. What general st 2S we goalong. BINARY MODEL SYSTEMS ‘The binary model system is rated in Figure 1. We assume there are NV fixed in space, shown for convenience on a line. tY magnet that ean point only up a venctic moments bm. To understand the system is This requites no knowledge of magnetism: an element atthe system can be any 9 states, labeled as ys ono, ced 0 b Binary Model Systems 120304 5 6 7 8 5 Number of the site 3. Model system composed of 10 elementary Imagiets at fte sites ona in, exch ‘moment +m. The aumbers shown ae attached io the sitess teractions anong the rues and thet eno external sete Ret. Each magnetic moment may te ovfented in {70 a8, up or down 9 that there ace rangement of he 10 magoetic momseats shown inthe rsleced ina random pees, articular arangenent shown Fire 1 State ofa parking fot spaces The @'s denote spaces. ssenote vacant epase, This pr shown in Figure 13, tnunitt @ autes themselves are assumed to be arranged snumbersthe eft 10 right, as we to this conv state 2) also can be Written 28 definite order. We may Figute 13. According Ifalalalstetatatotso @ system, the state moment on site fis + 2, the moment is 3,the marnent is ~mj and so forth, not hard to convince yourself 1 every distinct state of the system is ined in a symbolic product of N factors: (a Lolth +b haba + bah ” (ht With # = tht hl tit + hb 6 ion generates @ sum of 2* terms, one foreach of ‘the2" possible states. Fach term isa product of individual magnetic moment uy magnet on the line. Each term denotes an independent state ofthe system arid is @ simple product of the farm Dy (ts + Aa) es of Figure 1.5 Gey Ie} b= tat tele + bite + bale © ‘The sumisnotastaiebut isa way offi product on the left-hand sie oft it generates the states of the system, Binary Mode 53 sof a system of three magnets is Tat Leia + La ‘This expression on mul ‘Three magnets up ‘Two magn ‘One magnet up: None up: joment of ovr dodel system of NV magnets each of n will be denoted by AM, which we will relate to the energy ina magneticfield. The value of M vases from Nm to ~ Nn. TE values is given by Me 0 ‘The set of possible values of Mis obtained if we start wi magaetsare up(M = to obiain the ulin he state for which all ind reverse one ata time. Wemay reverse N magnets states. When N’2> 1, we values ofthe total moment, IFN = 10, there are 2"° = Among 11 different values ofthe total magnetic moment. For lerge N’ many different states of the system may have the same valve of the to We will eleulate in the next Only one state of a syste ttt tit 6 with one Mites ttt © titan (10) a“ agnet down are formed from (8) by reversing total moment M = N, Enumera = AN 4 5 magnets up and Ny = {N ~ s magnets ‘where isan integer. When we turn one magnet fiom he up to the dow * IN + 5 goes to N+ 8— Land IN —s goes to LV oa 1 ‘ber up ~ number down) changes feom 2s to 2s ~ 2. The down, dierence Ny-M,= 2s a iscalled the spinexcess. The spin exeess ofthe 4 states in from lef to right, The factor of 2 but twill prove to be convenie ‘The product in (4) may be wri 1anets up or down. It we drop the he order in which the arrows appear in a given product, then (5) bee eosin es tits se att + Uy AN NSIT & AN — Doty? goog ye (2) Enumeration of Sates and he Biutipity Function ‘We may write the exponents of x and y ina form by replacing ¢ with 4 — 3 yi gE 03) the symbolic expression (F + 1)* becomes Pee nt ses pave = Ser arcgel ro) ‘The coefficient of the term in [2¥** Ny = IN + 5 magnets up and N, 8 spin excess Ny ~ note the number of states int = 4N ~ 5 magnets down, This class of = 2s and net magnetic moment 29m. Let us this class by g(Ws), fora system of V magnets nr WITH a5) tothe spin system: in a magn shave different values ofthe ‘model system have the same energy, ‘may be taken as zero, the total number of es is given by Ja ba aADBBAB AH BgDyhs cA Aas -ay(Chapter: State of « Made System ny oy system on N sites is contained int (Qc # BIA + BAL + BY y 4B), (9) 1 Ay By, wh wumber of A atoms is Ny = (1 —xJNV and the number of B toms is Nq = aN. Here x les between O and | ‘The symbolic expression analogous to the result (12) The coefficient ofthe term in AY“! BY gives tl ber g(N,1) of possi We know from common experience that systems have major predi exceedingly a at constant temper ‘defined properties; this stability of physical properties is a ‘of thermal physics. ly that for a very n gL.) defined by (15) is peaked very sharply about ook for an approsi 0k atthe togar stake the logarithm of both sides of (15) obtain Jogg{N3) = loa Wt ~ log + 9) — tog = 9h, (23) by virtue ofthe characteristi property ofthe logarithm of product logay = logs + logy; togtw/y) = togx ~ logy. Hy the notation NesiNes; Maes ey for the number of nels up and down, (22) appears as logetNs) = tog = tog, ~ fog ‘We evaluate the logarithm of 11 in (25) by wse of according to which NM cpl 9) is result is derived in Appendix A. For sufficiently large NY, the ++ im the argument may be neglocted in comparison with N. thm of bot sides of 26) to obtain log! log2e 4 (N+ SplogN ~ N, en log Nyt & Hoga + (Ny 4 log — logit & Hog2 + + Hoa ~ mm, for (25) ogg & Hog(l/2xN) ~ (Ny + MNUN) = 0M, on »0 Copter): States ofa Model System y be simplified because logiN/N) = log {tl + 29N) = —log? + togtt + 2s:N) (espn (2) by virtue of the expansion logll + x) ex fst valid for x & 1 Si ~ 25)8) = lop? ~ RYN) = Bs "Gy fon in (31) we obtain ogg & {log(/xN) + Ntog2 - 224)v, 04) [ ss a6,eap 20) 09 where (0.0) = (fey, with = 0; (0) = on Daerah a. fe ay et ioe ‘splint eere Forexample he ait Bsetoram to fled int 4 (UBD, which apprches a8 appease (100, 4) 1078 om (37). The approximate ted in Figure 1.9 is centered ina maximum at s = 0. When s* = N, the value of gis reduced toe"! of the ‘maximum value. That is, when ai = (RN)? , 89) ly defined, in a relative sense. Its this sharp peak anc th 3 the multiplicity function far from the peak that 1 physical properties of systems in thermal eq ‘mean value of 2 sare drain fom thea (Chapter I: States ofa Model System AVERAGE VALUES ‘The average value, o mean valu tion function Ps) is , of @ function fis) taken over a proba ned as SP) =F So Pts) BI) rovided hat the distribution function is aormatized to unity LPO) = 1 0) «an Wa thea Pls} = S32", and we have YP) = 1. The average of over this dividing wil be 6D = TAs) PIN), 2) 29 (3) = 3. fn the epproximat that led to (35) and (89), we replace in (42 the sum J" overs by an inte: between — co (peng 2 ds st exp —252/0) G> = oe = RA (AYP a2 NPP? ini)? , CP =E Cy x 3) 1 quant 2319) isthe mean square spin excess. The root spin excess is 4s) te IN, (64) tht Energy of he Binary Magnctic Sytem and the fractional fu inction becomes relatively more sharply defined as the size of the system increases, the size being measured by Dumber of sites W. For 10° particles, # = 10, which is very smal ‘Bnergy of the Binary Magnetic System ‘The thermal properties of the ney U is D> Sure -0 $m, Caen) aw “n In this exampl see later sinuous or qus the spacing between adjacent energy | Figuee 1 2Chapter 1a States ofa Blake Systems : 5) toa as) “St o A ae “a tsa tty $———— 2535 o——— 9 om 553 th ——— ob 535 9 was st Ht ao Ht ° tay level ofthe model syste of 10 iva magnetic ld. The levee be not entirely is desivation, The modern ay 19 = she, (8) frequency of ofeach one Now find the c= Sho = oho (0) Enrgy ofthe Binary Megnatis Sp Fy Y= Somme, NUN IKE 2) “That for the system of ssilators, ath, 1 of N osctatrs, the generating fonction is 3) 6 69) =26 (Chapter 1: States of « Model Syne ith spin excess 25 = 0 = eames * we th No> 1, we have the Gaussian approximation exp 232/09, 3 of the model spin system are equal >= f° 3: The fractional fluctuation of s is defined as Gey yaw 4. Thee N and is eq Fay of the model spin system ina state of spin excess 2sis isthe magnetic moment of one spin and B i the may Chapter 2 Entropy and Temperature FUNDAMENTAL ASSUMPTION PROBABILITY Example: Construction of an Ensemble Most Probable Configuration ‘THERMAL EQUILIBRIUM ‘TEMPERATURE ENTROPY Example: Entropy Increase on Heat Flow Law of Increase of Enttopy LAWS OF THERMODYNAMICS, Entropy as a Loga Example: Perpet SUMMARY PROBLEMS Entropy and Temperature I Motion of the Second KindPs Chapter 2: Entropy and Temperature The general conect by proba increase the probabil. M, Planck Fundamental aasumgtion define the average value systems in thermal femperature. The second law of yermodynamics appear as the bsteact in the book. The constant volume, and constant values off influence the system, including Aguas specification ofthe system: the exergy of thes which the enecpy ofthe system is specified, inthe range within whieh the numberof pa ‘we can never know either of these exactly, but it and BN/N 1 ausal properties of a system may sometimes cxtiin states to be accessible ducing For example, the states of the erystaline form of SiO, are inaccessible at low peratures in any observation that starts with the glassy or amtorphous (orm: fused silica ina low-temperature is type by common sease. the system is under observation, iat are not accessible ate suid to have zero probability. is possible to specify the configuration of a closed system to a point that properties as such ae ofno interest. Ifwe specify thatthe »2 (Chapter 2s Entropy and Temperate system i exactly ina stationary quantum the problem, aspect i eft in ly to be in any For a closed system, the average value of X is oa » Probubity woys equal to u state is unity aa Chapter 2s Eatcapy on ot tt at att tt tot t Pe rrp ety att tp toy tote is represented inthe ensemble by one system in a Figure 22. We ass Figure 23 an ensemble 10 sin ences 2 1. The eneay of ‘se of sin spin eicess with Gur cpISEUS One ofthe multiples of \ quent use of a6 a state index o label} Each sytem a Mose Probable Cofguration ‘quant states thin netg. The « 2s 3; 10 systems have 2e = 1s 1D sens fave 26 “3; and Lyeona has 2s 3 Most Probable Canfigu Let two systems 5, and 43 be brought into contact so t Aransferted frealy from ane is called thermal contact Figare 2) The two systems in contact form a larger closed system $= 3, + 3 with constant energy U = U, + Uy. What determines whether there will bea ‘net flow ofencray from onesystem to another? The answer leads to the concept of temperature. The direction of energy fo is not simply a matter of whether the energy of one system is greater than the enerey of the 2, because the aas Chaper 23 Entropy and Temperaare Two closed ny Iy : 4s 7 ductor energy Figue 25. Fstablshmeat oft * benen to sstems 8, and Sy. systems can be diferent in size and const shared in many ways between two systems, The most probable division of the system has the for the two systems, ‘The actusl exchange of energy might take place bean combined system will bed wheres = sy 4 5,7 energy of ned system is dicey prop \ UU) = Oslo) + Uso) = ~2nBls, + 53) = Sms 6 spin exeess: ‘The total number of pacicles is N= Ny 4 Ny ‘Most Probable Configuration rer system is always pos total energy is const two systems are brought contact a redisteib permitted in the separate values of s,s, and thus i t = Laas Nas — NS Bia 9a are given by expressions of the fest system spin excess 255. config, tnay occur together with any of the gy(N gy) accessible states of the second sslem, Ths total number of states in one configuration of the combined system iven by the product y funetions of 8, and S,. Because s, = § wetten as feof 5, 54 n for which 9,95 46 a wax configu number of sates init is al = RAS Ke hoene a1 Chapter 2: Entropy and Mort Probeble Confsueaion BC, UD »U~ Uy X ge i Te pi: the shacpnes ofthe pod es the numberof ates accessible othe combined system whea the spin sombited system is 2s al the spin exces ofthe fs sytem 2 alo of{1}asa function of, when the tla spin evens 2s iced nergy ofthe combined systems is consent. eb coovenisnt ‘ovcurs at he same sale of x25 the epresntaton of the dependence ofthe pity onthe diison of he total energy becssen two systems 8, aad th respect 10 changes in s, will be Figure 26. A relatively small number of config al propertis of the combined sy I se tr when the ist deiatite with respect tos 26. An ex Vremam may be # mavimurt, a maim, oF 3 gost of inflection, The enti te eae bend ina sense that we wil fine ay, Me 5 at result follows thatthe values ofthe average physical properties silgalWas ~ 5} =~ FE + oy =o, (1 “Be system in thermal contact with another large system ate accurat ly : > ‘scribed bythe propetes ofthe most probate configuration, the configu, eda ion for which the number of accessible states is a maximum. Such average mr ged £8 bet constant 382, wai. The second deste 2244 of "alice use in either ofthese tia senses) are elled thermal ies "ey rite meng of Yoel avaniy oe a acobiecniguion (by snateanee ih pbeconfevon)itheanpe bow eectannem ee Insuchavencenen sn hadticcne eon Because of the shatp maximurn, * The pode nan fue Gatsin fanaios iatay 2 Gata” (Chapter 2: Entropy and Temperature Thorton potable conguation ‘nich (12) i sutistied: : 3) Thetwossstemsarcineuilibriam wihrespe oiterchange ofenersy when the fection nensest after isequal vo the fractional spin excess of stern 2 accesible sates of the comb and fy denote the vals of y abd 5, oaks ~ 5) = alO)a,O)exp(—26 e My, 3 _ To investigate the sharpness of the ma a e me tum of 05 31a given wale of roc 5 Hehe beans, ag om thie wales 3 the manne of ga. as aH BES, whi ve subitittein umber of states 45,5 2a) = fo.9dano( Cab + Dads = = edaner = FE). rium is very sm = 10", Then 25/8, = 200, and the : Thermal Euilibium of is maximum value, This i an exten be 10°" or farger i fond 10! outtoa value ofthe onde of sor of probability Integrated probabil is given by Wx 10 ternal contac. te Yas: or which the pd items with valans of. What does team {have resonable chance ofsucessiasuh ane\petin oo dt iam ation of small atic in suspension fn eantet witha atone tine on Large system over fog period of THERMAL EQUILIBRIUM ‘The result for the number of accessible stales of two model spin systems in summed over all valuesof U, < U, Here g states of system 1 at energy Uy. A conti by thevalueof i, toge »” (Chapter 2 Entropy ond Feupevenre governs the properties ofthe tot (eas a ; ao = (So) avs + ofS s) ts <9) dy ed =o 9) '9 obtain the thermal (203) which we may write 25 Wedefine he 2) For example ig sy ben fds, = 12s and yh = Bo Temperature ly to the concept of temperature. We um the temperatures of the to Snow the everyday rules in systems are equal They ey We defer the di to Appendix B because we ‘This temperature difers fcom the Kelvin temperature by the scale facto, ky | rohr | en Beeausea isa pu fonda of energy. We can use as a temperature sca Hemperature thas the dimensions ‘energy scale, in whatever unita (Chapter 2: Entropy ant Temperatore ‘may be employed for point of Historical twas possible n of temperature 10 inderstood, Even at presen, itis stil posible to ith thermometers calibrated to a higher eciproal of +a the ps lo ake the reciprocal of oth sso write 28) Xt meaing. ta 26). the entepy 6 U and Naso = o(UM) Hence + ‘constant implies U = ln both case, but iti expressed a6 “The question “What are the indepe Evtropy (0) the definition fence of the entropy on the neyelopacs of entropy «is modyosenics in the ty of the concep a“ Chapter 2: Enron and Fenperatare “The total entropy AU ~ G9IK The temperature aes conto Ty = $090 + 290)K = 320K. AU, = BSDEK™Y(—30K) = 173, and AU, = AU, = 171. fer as calculated above. Besse the energy we may suppose he specimens are approximately 2 the tures of 0 and 290K. Theeneopy of the fist Rody s decreased by 0.13 oye FO 086 x 10-4 AS. S50K Ty — 290K) = G8IK™G50K ~ 7), Law of rere of Eneapy i099 of ke second Body is increased by on AS, = Bad oe 345 LOK, Sy BAe = BAS 10K py inceaees by AS, + AS: = (~286 4 345) x WYK! 059. 10K“ 1 Intense of entropy is O59 x IOS 059 x WK iy By Ea DTT OA HO, Gry ais that the mnber of acesible states tases by he ator explo) = expiO3 m0) Law of focreass of Entropy We ean sh ‘opy always increases when two systems ate brought We have just demonstrate this in a special ease Hf te sotal energy Um Uy + U, is constant, the total im systems are in thermal contact is oW) ~ Patou - 04) , ) by (18). This expression contains the term gy(Uye)g3(U — Us, iy before contact and many other te nergy ofsystem 1 and U — Uso isthe teria in 33) are positive numbers the mi ‘establishment of thermal contact between two syst nergy ofsystem 2 Because icity is always increases by tems. This is a proof of the \ law of increase of entropy for a well-defined operation, { ‘The significant erect of contac the eect that stands out even afer taking the isnot just is large, but thatthe lrgest single he summation may be very, very multiplicity, Tha i, Gi) # 04(0,)9,(U — B,) oHws {haper 2: Entropy and Temperate wooo = $ & Time 7 Lis pean at may be very very fic larger than t gilUsolasU ~ Used. 05) Hse 0, denotes the value of U, for which the product 9,9) is @ maximum, om inthis opera probable, Lav of ncease of Entropy ” se the Woys to Add AWM enccey Leta linear polymer eudl up increase the entropy ofa syste, 10 increase the entropy ofa system are shown i arguments in suppart of each process will be developed in the chapters low.a Chapter 9: Bamepy and Fora large system* fe actual entropy and the ion of the macroscopie system very 6 of the contact bi prepared the system een E60 Sst iy in some special way. none system parallel Such extreme Special prepa to one another oF cal leule I the gas by removal of par same average energy, come very quickly les in both halves of the ing else will ever be observed to system to leave the most probable configura prepared cont of physics ate reversib reappear late even though theequat LAWS OF THERMODYNAMICS Whea thesmodynamics is studied at a n subj fae introduced. These postulates ate called the laws of four postulates two systems are in thermal equi rium witha thid system, they must be in thermal equi ith each other. This law isa cons of Thema (ie), - In other words, rs ¢y and ty = ry imply x, 7 process 19 ‘of heat from a reservoir und the per- formance of an equivalent amount of work An engin the second lave by extracting the energy of one heat reservar is said to be performing ofthe second Kiad, We atthe Kel py of a sysiem approaches a consiant ‘emperature approaches zero, The eatliest statement of at the absolute zero the entropy dilerence disappears configura w ground stare corresponding entropy i o(0) = logg(0) as t ~ 0. of view, the law does not appear to say mivch that is he definition of entropy, provided, however, that the system is Towest se of quantum ‘of the order ofthe number of atom N. Wt in reat lifes that curves of many reasonable physical quantities plotted against: ‘must come in fat as «approaches 0. ”so he 2: Eps ed Tope / (ropy asa Logarithm the entropy of two inde} separate entropies, Second, the entropy is es the precision 6U with whi aceessible states depend err such at principte 5) of acces (U) = fox 0 on he system of order of 2°. Ifthe total enerey is of partite eng imber of states will be of the order of N times some average one- ay Athen OU) ~ 2A, Thus ab) = 82 log. NA + log SU, Let N = 10"; A = 10" ergsand SU = 10° ere. 9(U) = 0.69 x 10° — 1382 ~ 23. 09) Net @ ~ NIOgU + logdU. Aga term in Nis do fependent of even the system of units used for more enrsy Summary sn ered to another part of the being used to power the energy meses t9 from the fw tempe 6) = Exar, 3. An ensemble of systems is composed of very many systems, all constructed alike, 7 TLL 7 : Nemambercfacceile sates othe combined ystems Land zis) es 90) = Satsians ~ 5), Ss , os wheres #5, = e 5. The ion Ss kyo connects the al entropy a. perature a the entropy of a system is moved,2 (Chapter 2: Entropy ond Tewperatce um values of the physical propertss of a system are 5 overall sates accessible when the systr i properties are given acu 1st probable configuration alone, PROBLEMS (5) = log g6X.0) ~ 27/N , 49) for [p< N. Hint: Show that io this approximation OU} = 65 ~ Ua BEN ay Ye= ~UpaP BN, where U des 3. offequency as af fonction (1.55) and make the Replace N'~ 1 by W.() Let U denote he ttal eee Express the entropy 4s o(U,N). Show that the total energy id the entropy ofa set of N 0s bern. Use them mn logN} = Nog. temperature 16 “ in in Chapier 4 by a powerful method funetion. jon’ of the earth, We suppose that a monkey « heys por second. A typewriter may have 44 keys: we the original statement less library, ferary production of the monkeys, iy of entropy for two spin systems, Given two systems of Ny = iplicty fon 1288 function ofs sel ply peakedat sy = §.Fors) = 's reduced by 10°" Irom its peak value, Use the ty function; the form {17} may be Gaussian approx sel {a) Compute 9193/09,9shun for 5, = §, + 10" and s = 0. mag 1 Jeans yer waves, Cole Univesity Pres, 198,p.4 The sateen atte ss(6) How large is the frac factor? 6. Integrated deviation. For the example that gave the res pproximatcly the probability that the lractignal deviation feom ecqlbriven S/N, is 10° or larger. Take N, = Ny = 10, You will find it convenient to le an asymptotic expansion for the complementary ertor function. When xr, mal error in t centcopy when you ignore (1D, cael 2eexp(at) [exp(—e?)de = 1+ small terms, Chapter 3 Boltzmann Distribution and Helmholtz Free Energ BOLTZMANN FACTOR Partition Function Example: Energy and Heat Capacity of a Two S t Syste Definition: Reversible Process PRESSURE nodynamie Wenig HELMHOLTZ FREE ENERGY Property of the Free Energy of a ie System GAS: A FIRST LOOK (One Atom in a Box Example: 4’ Atoms in a Box Energy Examj + Equipartition of Energy Exany Entropy of Mixing SUMMARY PROBLEMS Free Energy of a Two State Sy Magne 38 st 2 6 ” oe n n 6 %6 n 8 80 a si 3 st st 8 8 ss56 —— Chapter 3: Rotemann Distribution and Hetbolte Free Energy ” he thermal action of ‘another from tha to specify cases of ther8 co) of a system as a finction of the temperature. We oY) -a™ Assume tht the system Sof inerest tous i in thermal equ large system Gt, called the reservoir. The system aret common temperature + because they are i ‘The total system & +S is a closed st influences, as in Figure 31.7 I external total enerey Uy = Ua + Uy is constant. In : of energy. Eniropy of the reser energy of Energy ofthe reservoir——— spiem accessible oR +8 is Constant energy ta® Lm Ga suse for our present purposes we have specified the state of $ Jf the system energy is, the reservoir enetgy is Uy ~ Gy. The number of states acessbleto the reser ianisoa(Us — ; i ‘The ratio ofthe probability is in quantom slate 1 at energy 7 10 the peobai in quanta state 2 at energy 6 ratio ofthe tw Figure 34 Representa eerie tin ths ofa closed tata: ‘contact with stem 8 ray Ue = _ gale ~ 8) BOLTZMANN FACTOR jesare vory, very lage = expfaaltis — &) = sala — esd}. GP Pee esploaiVo ~ ext] s oeChaps 4: Bottomann Diuribtion and Heats Free Erg a Eneegy Uy~ re ola ~ #5) states 15 © du(Uy~ ) ~ alo ~ Ea)» 6 the probability ratio forthe two states ,2 of the system is simply Pla) = expla) 0 Pa) [Let us expand the entcopies in (8) in a Taylor series ex ‘The Taylor series expansion of f(x) about f(x) is sion about aa(Vab (FA) + © ‘Thus 6 (Up ~ 0) = alls) ~ ellaglOU yn +* sm oalUg) = eft to o where Ift & (@oq/EUh gives the temperature. The partial derivative is taken Portis Function at energy Us. The higher order terms in the expansion vanish in the Himit of a infinitely large reservoig fore Aa. defined by (4) becomes, Aas - @ “The final cesult of (8) and (8) i is over the Boltzmann factor jon function is the pro- and the Boltamann factor Peay = SEH! ‘The resul ie) pase!) ay ne z (3) immeinteya (Chapter 3: Bolenoen Bi 0s ot We] 0 | — Se al | ~~ ° 1 2 vee or called the thermal average or ensemble average for <¢> in conform See) uy slates as —fe and and co = ~feteni(eno, ‘The heat capacity Cy ofa system at constant volume is deine as 4 Weneld ¥ com sole. Prom iz)Process, A process i reve! ‘0 the equilibrium entropy slage ofa rever ‘A voluine change that leaves the system ‘example of an isentropic seversible process. the system always remai same state the e be zero between, an ensemble (p. PRESSURE Consider a system in the quantum states of energy’ e, We ass fy 16 Of the syste. The volume is decreased slowly from ¥ to V ~ AV by application of an external force. Let the place suficiently slowly thatthe system theo lume change take may be characterized by its umber of 210s i the wavefunction ler the reversible volume change is EF = AV) = (0) — (dea JAY + Consider a pressure p, applied normal t work done on the system by the pressu ‘cube volume from V mechanical re 3.6) of the to V ~ AY appears asthe change of energy ofthe systems UW — AY) = UY) = AU = —(dedY)AY. 22) T Energy, solatve sale Presse66 (Chapter 4: Bolrmann Distribution amd elaoles Fee Energy Hare U denotes ths et cube; then 1 of the system, Let A be the area of one face of the Ala + Ay + 2) = AP, @ ifall inceements AV and Ax = Ay = Az are taken as positive in the compres: sion. The work done in the compression is AU = pAlOx 4 Ay + A2) = AV, ey £0 that, on comparison with (22 ro) Pressure on a system in Weaverage (9) over . The ent number of states in we have deseribed. We the pressure on a systern mai ‘Welook for other expressions for the pressure cutrapy depend only om U and on ¥, for a fixed number of particles, 30 t only the two variables U and V describe the system. The eiffeensial of UU) = (3) we en i difforential change of the entropy for arbitrary independent chats WU and dV, Assume no Thermodynamle enity «cancel. The overall entropy change do will be zero. If we denote these \ependent values of JU and d¥ by (SU), and (SV), the entropy change w be ze: o= (2) un. « (S)n. es Air division by (GV), °=(a)ent * GB), ” But the ratio GU, /BV), i constant a: respect to Guy, l= (2U/av),. 69) With this and the defi ion Ife = (2o/2U)., Ea, (29) becomes (9-0) ” and side of 31) =p. whence Pp» (), 02) donlav stay, 63) or oros Chapter Bottonann Dis ‘This useful reation wil be called the thetmody nan variable will oppear in (5.38) A simple AU = cdo ~ pl¥, of dU = Tas ~ pa. (G4) the actual process of change of stat of the system is reversible, we can identify edo asthe heat added to the system and ~ pV as the system, The increase of energy is caused in part by mec Part by the transfer of heat, Heat i defined as the transfe tio systems brought work done on work and of energy betwoen, HELMHOLTZ FREE ENERGY The function 6s) 8 the part in thermal ses at constant temperature that the energy U plays in ordinary mechanical hare always understood to be at constant entropy, because no 3 of state are allowed, Fy = dU, ~ tag 69 at constant temperature. But 1/r = (2ey/2Us)y, $0 that dUy = ede at com stant volume. Therefore (36) becomes aF,=0, ey Which is the condition for F to be an extremum with respect to ‘¢constant volumeand temperature. We lke F Because we cen calculate from ‘the energy eigenvalues ¢, ofthe system (se p. 72) Conmem, We can show Cyd Uy Thea th © oy + oy = eal ~ Uy) + o4lUs) & ot) ~ Usleag/ Ulin + aU Wekuow tat (ani?Uady = a soy) ~ Felts neigy ofthe syste Now oa( sayy ina get etd it~ Don whe “Thee energy fonction (tbe eed 1 ~ teh ov ),f racat~ aan (04am f(r tthe minimum of F632) withsexpect Goce energy eh Thats, Filed) ) = FB beens) ina ‘minima of F with espect othe pla eacrscscrs whet N+25 (Leahy = O= ~InB + clog ES Sy es)u($ +3) —(G= ol funetonbecomes equal is Pres Eseray 1 The tal ences fs U 08) 09) isconsants and we am sa maim wit respeet 10 Ue falls orn hemos probable energy af paramagnetic stent. Conse the 69(Chapter 3: Fotcmana Disnibation and Helmbols Free Energy ‘Thos in the magnetic field B ermal valu ofthe spin ences 2 ten by N+ Qo co = aaa ), a) Wo ea = PNB: ert &% on dividing numerator sn denominator by expln8th 25) = Neon 5) ++ exp(— mye) = 2eosh(n Bye, ro) Now ese the relation F = clog a derived below. Mull by to obtain the reul oC N magnets (The magnetiaation is derived more simply by the method of Prabion 2) (34a), dP = -odr ~ pdVs (48) (S--2 (B=. en Lo eee rewind ge of volume; contrast TT Caleaation of F from Z may be written a5, (0) by use of Fa U ~ ta, hand side of (50) represent ‘what wo may call the energy pressure and the entropy pressure, The energy pressure ~(6U/2V}, 1s dominant in most solies a (Opy pressure 20/2V), is dominant in gases and in elastic polymers such as rubber (Problem 10), The entropy contr the importance of the entrory’ the naive feeling from it AU JAY must tell everything bout the pressure is seriously incomplete fora process atc erature, because the entropy can change in response to the valume change cv ‘nergy is independent of votume, as far an i (ole), = pee obvious, Other Maxwell ations by similar arguments. The methodology of of namie relations is discussed by R. Gila, 3. Chem, Phys. 5,596 where 2 ”85) satislies the 6 lfeeatia equation 32), would appear possible for Fx to contain an additive constant « such F = =rlogZ + at, How entropy must reduce to loggy when temperature isso lowe Z = expl— Fn 69 1) for the occupancy probit of a quantum sales = expl(F - 23/4). sn, IDEAL GAS: A FIRST LOOK One a ina box. We calevlate he partion fonction Z, of one atom of ‘mass M ffee to move ina cubical box of volume ¥ = £2. The orbitals ofthe fee particle wave equation ~(iPM1)6%9 = bare Wyre) = A sin(agns L)siniylL)sin(n.nz/L) 658) where M, not give tegrs, as in Chapter 1. Negative integers do jon, The enecey ne) 69) ler structure of the atom, so that a state of the he valves Of Malan: A Fst bagk By Provided the spacing of adjacent eneesy values is small ws may replace the summations by integrations: 20 fam, Ma, [da enel a n comparison w Thenotation a? = may be ‘i'x*/2ML3zis introduced for convenionce, The exponential asthe product of three factors expla? hexpl— 2% Vexpl= 2, 4 = cr fraconine) ae, By ry = mgY = @ + yar = Nav = Malm» terms ofthe concentration n = 1/¥. Here No = (Mspaany | (63) om ina cubs of side equal to 1 . ‘which i @fength roughly equal to W/ALCe) ~ HA", Here Ce) isa therm miconductor theory, and For helium at atmospheric pressure at room temperature, m= 25 x 10"em™? and i = O8 x 108*em™, Thus, wig = 3 x 10°% which is veryhae fatemen Dito ed Het Fe Engg td Ga Fo Lk = ‘all cmpar io unity, so shat sum is vey ite unde noc ondtons : 7 > Whenever ng Vve say that the ge inte hea ree, Wea : : Sedofied ana go of nniterating soa lathe dea hk ‘ae then aseage energy of the atom inthe bon ! Foret? Aa. pace stn fe ties nh oe pen enh Yeveipl—eie) ofS boxes Toecrtapng forone pale ance vn» aang zea, co because 2,~" expt ey 1 probability the system isin the state n.From(62), Figue38 Atoms ctaifecent species ia Jog Z, = —flog(l/e) + terms independent of « , single box, ‘so that for an idea! gas of one atom [p=] ea He = byT, whece ky is the Boltemann constant, ‘known result for the energy per atom of an ideal ges. ‘The thermal stom ineachof di he patton fasctionis the separate one atom pact Zena Zt) Zi) ZN) , (65) ‘cause the product om the right id side includes every independent state of the N boxes such 2 the ste of energy. equality FADE oI wn whore x Bs it of 4 x 10°* for the occupancy of an lard 60 ‘occupancy must he «1, We note that ey as de fora feee stom, 21) 2,1) 2,06) 24) , ‘ental, ofthe16 (Chapter: Roltomann Disebuton and Hetil Fee Energy in the casa regime, Here ng = (Me2aK° “Thete isa sep inthe si se stways rot introduced by this Energy. The energy of the ideal gas function by use of 12} U = H(elogZ,/02) = Ne , 6) '5)for one purticle, The fre energy is F = ~1logZy = ~rlog 2," + clog 70) With thea V = (Mfe?2eh4)>2V and the w approxima Fo ~eNlog{Me/2sh!}32¥)] 4 eWog a ~ en, a From the free energy we ean calculate the entropy and the pressure ofthe ideal ‘8 of N atoms. The pressure follows from (9) P= ~(CF/OV), = NYY, ~ or pene, | 7 eal Gass Firs Look scaled the eal gos fay my “The entzopy follows fromm {49} ° NaN, (13 o = Nilosiraie) + i] ro) with the concentration n = N/V. This result is known as the Sackur-Tetrode equation for the entcopy ofa monatomic esl gas Teagrees ‘The result involves fr through lg, 80 even for the cassical ideal the entcopy involves quantum concept. We shall decive tl ‘Chapter 6 by a direct method that doesnot expl argument. The energy (9) also follows fom Um F + x0; with use of th experima (7) and (76) we have U = Ne 7 of entry. ‘Theenerey U = 4Nefsom! ‘ution $s rom each “degree of feedom of each freedom ithe numberof eimensions ofthe space in whic Se In the class fom of ic ener ofthe particles ina For one fee particle 21 fffesvt= (ot + 0,8 + PVM doedeydp, 7) on are 00 for enh component, The thera average energy may be ealeuated by wr of 12) sn is equal o fe ‘Tae result generalize inthe lassical theory. Whenever the haritonian of thesystece {shomopeneousof degre 2in 3 canonical momentum componente sass lini et. thermal average kinetic energy associated with that enmmentn wil be fe Frthey ithe ‘amitonan s homogeneous of degre 2a postion eordiatecomporent the heal ‘sverige potential energy asocated with that eoardiate wil als be fe The cet thuss Chapter 32 Wend Hells Foce Enory Neal Gass A Fst took Vibe Rotation Mixing entropy 253015103250 Seo" 1000” 2500 So0g ‘Temperate, K Figure 39° Heat capciy a constant volume of one molesee of H. ‘he os pase. The veri ele ia fname in convemional units ruliply by hy. The cor Srarslations dee enemies eae ya fem thetno coaional epes ininom when Aad Bae presenta ext popatns (2 09, sind the entropy is Zev oe pure A ot pote ON) = NlogN ~ N —(N ~ log —4.N =e ~rloge +1 = Nlog. ~ (N ~ 1)logtv = 0 = togr = UN = logit ~ x) — Hoga) , In Chapter we calculated the number of posible arrange Bina solidimadeupot ¥ ~ ratoms A sad ¢stom B, We ound ia U2), ananen ot) = = = 9 4) + vlogs 180) aN = a oy = ‘This result gives the entropy of, “Thee hese arrangements {8,4 = logg(Nu) = log! ~ log — a! tose, 79) dis la n Figure 310 for ~ 28. This contribution ote total1 ” Pootens Foe Fo cols) = Fo + Nell ~ s)loglt ~9) + slosx] , : Ye must compa wih Fa(t~ fe tty Fe presuce piven by P= CURRY), = Hef 4 The Helmholtz fice energy is defined as F =x U — stant, V. oe» ~sNlogs (8 tec eoery is Zu = (QV PINE, Fl) = MOU + slo ee = NV «x mg. The quantum conc 5 (M/26h"P, Further, whic nasa mini when PY = Ne; Cr = aN. GFldx = NU + loge + x) =O, @) 8 is reve infinitesimatty close to the 7 ium state at X= expl—Hexpl= Ufa, (6 PROBLEMS aa 1, Fiee energy of a teo state system (a) Find an expression for the free \rBy a8 2 function oft of a system w SUMMARY Plo) = expe) temperature and magnetic field for the iS in @ magnetic field. The result for the magnetization is Af 3), a8 derived in (46) by another method. Her is the probability of finding a system in a state sofencegy e, when the system.a 10) as a tam sea fonction 05 18 is ‘Note that at high temperatures such ‘of the logarithm to obtain F = rlog(4u/r).(b) From (87) sow that The entropy is shown in Figure 3.13 and the heat capa 4. Energy flcteations. Pron " F z| 2 x t z 3 thom Figwe3.13 Entropy sero temperate fr harmon eater of fgucocy enuy or the ree energy & Fe tox{t ~ enh) sn hat «> hea we may expand thearguncat entropy 6 ay ~ Hoult ~ exot—). ro) Con: jut the term {by defnition docsim Chaper Prablems here to a rigorous definition of temperature, wx give the result a> = FIC, 0) but this shou!d be viewed as just another form of (89) with Ae set equ AUIC,, We kaow that AU & Cy As, whence (90) becomes {(AU}'> = 1 which he average number of open links, The n ‘of tworsteanded DNA molecsles—sce sts 37,817 (1969). mechanical or heat reservo mm of energy & Hece is some numerical factor, tamane factor for this abnormal we can add 4 to the eneray of 1 ‘eservoir passes tothe system the qua increase of enery of ned toa cube of side ergy ofthe particle ‘occupancy of lowest oxbital always has higher occupancy ip thus defined is equal to defined by (63), within factor of 9. Partition funtion for ZU oft Pls) 2c exp[—U0 ~ oer} ves the statistical Dass ofthe Overhauser effect wheschy 1 4 magnetic field ean bee: systems, Show that the part systems I and 2 to the system ftom an external source, said to be in a steady state, Cl. A. W. Overt 6, Rotation of diatomic molceules. I our frst Wook atthe ideal gas we con. ional energy of the particles. But mozeules ean rotate, systems: Zi + y= 20z0, 04% ter 3 Botersann Distibution and Helmots Free Energy of polymers. The dimensions tls = du ~ ar 9 ine and dis the extension of the ‘eto find (96) ‘The direction of the force is opposite to the con. pressure 2Nt 5) = 7 Yo) NT a) (61 For sl << N show that 3 = 10) ~ Fane. 03) Ww thatthe force at extension Lis = kN Chapter 4 Thermal Radiation and Planck Distribution Hem amen atta sore maT PLANCK DISTRIBUTION FUNCTION » PLANCK LAW AND STEFAN-ROLTZMANN LAW ” Enision and Absorption: Ktchholf Law 56 Estimation of Suctace Temperature 7 Example: Cosme Black Body Background Radiation 58 ELECTRICAL NOISE 8 PHONONS IN SOLIDS: DEBYE THEORY wor Number of Phonon Modes ts SUMMARY 109 PROBLEMS 10 1, Number of Thermal Photons 2. Surface Temperature of the Sun 5. Average Temperature ofthe Interior of the Sua 4 Age of the Sun 5. Surface Temperature of 6 Pressure of Thermat Ri 1 8 9 Free Energy of a Photon Heat Shields of Solids in High Temperature Limit of Photons and Phono ions in a Solid at Low Temperatures of Liguid “He at Low T Isentropic Expansion of Photon Gas Rellective Heat Shield and Kivehhof’s Law ‘SUPPLEMENT: GREENHOUSE EFFECT arn Chapter 4: Therma Ra ton and Planck PLANCK DISTRIBUTION FUNCTION spectrum of the ina cavtty. Approximately, it describe heated by a welding torch. “mode” characterizes a particula ox the eavty orn the solid. We shall always refer to. = 2af a6 the radiation. The characteristic feature of the rad of osc fon problem is that a mode of frequency w may be excited only in units of the qua energy fia, The energy &, of the state with s quante is the mode is where sis 2er0 oF any p energy Hi. “These energies are the same asthe energies ofa quantum harm of Frequency o, but 4 maa fe States ofa osilatr that % reprerent mode of requency w ofan 22 Ghctomagneti | the orbit of energy » tos photons inthe mode 1 eat -l »ic energy of Intotior of th earal thermal physics of language used to describe an excitation is different: sfor or is called the quantum number, and s for the quantized electro- magnetic mode is called We fist calculate the mode, ‘when these photons ae in thermal equilibrium witha reservoirata temperature «The pation function (3.10) fs the sum over the sta 2 = ¥ erst e 1 2 eap(shaliy 0 Planch Law and Sicfon man Lave ‘The probability thatthe system is inthe state 2 sof encray shao is given by d Boltzmann factor: “The thermal anerage ale of sis 6) = E srt = 2 Ssexpl—stoyey. With y = for, the summation on the : ay. Ysewi-9) = - LY From (3) and (5) we find a asingle mode of frequency ev. Equs ner of phonons in the mode. The result applies to any energy in the orm of (1), PLANCK LAI AND STEFA BOLTZMANN LAW average rey se ho 6» ho = 0 an(Chapter 4: Thermal Ration and anck Diaributon ay 0 Pia The high temperature limit + hus ie often called the class exp(ti/t) may be approximated as 1 + hule + average energy is in. Mere 1 whence the classical ae 6 ‘There isan infinite number of electromagnetic modes within any cavity, Each rode n has its own frequency o,. Far radiation confined within a perfectly conducting cavity in the form ofa cube of edge L, there isa st of modes ofthe form Jsin(n,ny/L)cos(neafL) (9) Here EE, and E, are clectrie field components, and E, E,p ate the corresponding amplitudes. The three components are dont, because the field must be divergence-free: Planch and Stefan Botznonn When weinser (9) into (10) and drop al common factors, we find the condition ay ilet of integers nest ‘hen the frequencies are of he form The ceneigy of the photoas inthe cavity is, 6 X66) = Epil) = T ad “The sum is over the triplet of integers Positive integers alone wil dsseribe all independent modes ofthe for (We replace the Hom O¥ET My ‘nym by an integral over the volume clement dh espace ofthe mode Indices. That i, we set xe A flomeant-9 a o* ‘octant of the space is Standard practice ist over a dimensionless variable, We set x = The defn © value Such as Dwight (cited in the gene ' the fourth powe of radiation. is defined as the eneray per us ange, and is denoted as u,, We can (2) “Theconstan Se Planch Law and Stfen-otts on as acy fe Taps ue %Chapter 4: Thermal Raiation end Planck a hole is said to radiate asa black body-—which ic of a thermal equilibrium dis rate of energy emission pet u Jo = [UY] (sors fst) en “The geometrical factor is equal to J; the der energy Bx is ation i the subject of Probh es by use of 20) forthe energy density U/V. The result is often writen a¢ Jy ants e, te Stefan-Boltzmano consta oa ay 60 (2a) has the value $670 x 10°* W m"® K~* or $670 x 10° exg em™? st K~* (Here 69 is not the entropy) A bods sa black body. A mia radiates at this rat is said to radiate jole ina cavity whose walls are in thermal equilibrium xe T will radiate as a black body atthe cate given in (26). The rate ion ofthe walls ofthe cavity and de- Emission and Absorpt ‘The ability of 2 surface to emit radiation is proportional to the ability of the surface to absorb radiation. We demonstrate this relation, frst ora black body or black surface and, second, for a surlace with arbitrary properties. An object ugh times front the cavity joss back though the hole. “The radiant ens energy flux from the Black object to the he thermal average energy fut from ‘We prove the following: If x non-black object at tem fraction 4 ofthe radiation incident upon it, the radi fed y a black body at the same ity, where the object ise times object must em a Mus emitted by U Fs to be we special ease of a parfect refisctor, ait ) = el) for any sueface ion of Surface Temperature One way to estimate the sutt temperature of a hot body suck as a star i from the fequency at which the maximum emission of radiant energy takes place (ste Figure 44), What this frequency is depends on whether we look atthe ‘energy Aux per unit frequency range or per ut energy density pr unt frequency cange, the maximum is given from th law, Ea. 22) a5, 3 - 3expl-x} = ”8 Chapter 2 Thermal Rai mand Planch Dsibuion eal Noi ‘This equation may be solved numerically. The root is T scone Permalhal Se 3282 | tester CN Cie measrements en asin Figure 44, ws oH eth radulion evolved inp cold by expaus eatops to atenperatute of? 9K T asin eatropy if the feguanc each mode the numberof photons each mode Lept con ithe nuncberof photons in ech Spocteal ox (Wen? seradian ca“) ton 29K Black bouy—~ whieh ate called noise, were dis HL Nyquist? The the peak, and were measured balloon bore infared spectrometer at fequenies above the peak ason and explained by esy of PE. Riches, of Jobason noise 8:2 dep 1B3, Seesons 27°90 ”loo (Cheptcr 4 Threat Radiation and Planch sx toy 4 2 5) é 2 ZL. *Carbon filament $ 7 +Adva | v C050, ia HO Se ore intuing eecticlstes Alter Apparatus. In the original form the Ny square voltage across a resistor of resi temperature # given by raat. | eo where Af is the frequency* bandwidth within which the voltage @uetuations are measured; all frequency components outside the given range are ignored Weshow below that the thermal noise power per unit feequency range delivered toa matched load i he factor 4 enters where it docs because fa 47, the power delivered tan achilzarytesitve lod is ayy oe DR OR ER ad which at match (R’ = Ris CV*Y/AR. nhs scion the woe guy to es pet wi ine and nat to rine pretties Blecrca Noise resistance) Figwe 4 Equivalent ccut ora resistance & with rl non thal divers power toa load Rt Thecurent squat vllage fctuation applic. Consider as in Figure 48 losses ran teristic of feequency 2af, = 2na/L fom (15), 30 ‘quency range Frei, 60) where propagation velocity on the tne. E hwo Bplay) 1 wor10 Chapter 4: Thermal Rasiation and Planck Diss De AN) = WL Ale ‘The rate at which energy eames off the line in one dies + af 6) the line at one end is all absorbed in the terminal re reno reflections when the terminal impedance brim the load must emit energy to the temperature would rise, Thus the powee iaput The power coming of impedance R at matched to at the same rate, or else tothe lead is P= CPR= af, 69 = 2RI, so that (28) is obtained. The result has been used in low tempera- lure thermometry, in temperature regions (Figure 49) where itis more cot venient t0 measure <¥) than +. Jolinson noise is the noise accass a resistor here) appears nade current flows. PHONONS IN SOLIDS: DEBYE THEORY Phowons in Sods: Debye Theory 103 03-— B oa Figure 49 Meon square avis stage a gy} — 7 Aemperatue indicated thesmomict. Aller RR Gillan kA. We and J.C. Wheatley, J. Low Tern Physie 6 533,973 6 : 010 3050 P. Debye id is quantized just as the energy of an ic wave in a eavity is quantized, T) of eneray of annot account foe the ‘minimum of computation. ‘There are two important features ofthe experi ofa nant eed of the observed results in Chapter 7 er of possible electromagnetic modes in a cav ie modes ina finite solid is bounded. I'the solid consists three dogrees of freedom, the total number of modes is two transverse and ns ofan electron contrast tothe two possible pol ‘wave. Ina transverse inal wave the displace= {0 the propagation direction, The sum of a qué refactor 3, ment is pa ns. We want 10 fi to aN: 1 ffram re was no corcespor ‘austamary 10 write np, alter Debye, fr as Suet that the total number of elastic modes is equi = 3N, on In the umber of becomes Joton problens nodes, feng? = BN; ny = (62/0) 63) ‘The thermal energy of the phonons i, from (1 fo Ua LG = Desde Dee, 09) of Phonon Soues 69) a ay the volume V. Here, with (38), the uppee nofLe = (GRAN, EY, ra) usually weitten as Xo = UIT = bye. oy hots 0s called the Debye temperature: 0 = (hefner? Spon the integral is much ‘may be replaced by infinity. We note from Figure 44 bution to the BetNet _anthgT Sige = ap «6, Proportional to 7%. The heat capac «-(), fore « byl orT «6, (47a)eases Chapter 2 Thermal Ra | [Number of Phonon Moder wo nu panne + ra w lo & a i 1 o [a Fn 2 B sx Z 3 g ia [28 ae 3 a8lo 3 aus a A 66 98 =Talel | 00 | ed against ih he Debye 7" aw. The value of 8 fom hese dais 92K. Courtesy of. Fineold aad N.E Phlige Sm i Pa Na] Pm Pr Pe UY 12M ky (TY? W) ey eng is known as the Debye 7? lay.* Exp co ic 18. results for argon are ed in Figure 4.10. Representative experimenial values of the Debye tern. perature are given in Table 4.1, The calculated variation of Cy versus 1)0 is Ih temperature Debye temperature Oy in K T > 0 is the subject of v 2 ore: The subseript zero onthe ddenole bs lw tampa lini the nperimeal vals, Tebte tt108 Chapter 4: Thermal Radiation ond Planch Simery 3 40 x 20 i nop} | | 5 4 Figure 41 tetera Cy otassia, a 19 the Debye approximation, The ° z "| suse ind Re Tae a ¥ col ial tt tperive a £ oo 7 normalize tothe Debye temporatre 0,The 310 —| 2 fegoatthe eistelow Oils The, | Aol EE SyopisthentghuneetTits 2 é Z : =o} ~ ; =30) —— ot os 06 08 101 : ~%F OF ie is o f—~ Tatle2 Vater of Cy $V and Fa he Daye try. nes ol"! —~—E—ES—e—eOOOO OO 11 Eesty U ands snes F 2 U — ro ofa ow & fia ing othe Daye they The Deby enpestre ~ See ‘sind 3 mon iss oe a ue cas ; cS tes SUMMARY ite oy ae Planck disttbtion function i oye 1. The Plack dstibution 3 hae ib oR \ is his © = Saiany =i * 2 3033 ; i633 ; 169 forthe theomal average aumber of photons ina cavity mode of fequeacy 5 o00 2. TheStefin-Boltanana law 5 a StefanBoltzmann law is i a6 8 345 Ul, 9 253 vse > % isn 3 oats for the radiant energy den: jn. cavity at temperature,sand Plenck Distribation ck radiation law is of radiant energy is Jy = opT*, where ay is the Stefan- 5. The Debye low tempera tof the heat capacity of a dielectric solid here the Debye temperature er of thermal photons. Sho easily of volume Vis er of photons <5) in WN = 2408" (/he)* fons in the Universe is 10° larger thas rons). Because both entropies are of X= O.136J5"Fem™®, Problems (@) Show thatthe total rate of energy generation ofthe Sun is 4 x 10°° J5t, ) From this result and the Stefan-Bol 10°17 $5"* cm? KS, show that theeff Sun treated asa black body is: the Sunas 15 x 103 3. Average temper ofthe interior of the Sen. (a) Estimate by a dimen sional argument or otherwise the order of magnitude ofthe gravitational self energy of the Sun, with Mo = 2x 10) gand Ro = 7 x 10cm, The grav. {stional constant Gis66 10° *dynecm? g-2, The self-energy willbe neps separation. (b) Assume Sun is qual to ~f times the grav theorem of mechanics. Fstimat temperature for diferent stars, excl ‘matter for which the law of perfect gases 86 which have excessively st between 1.5 and 30 x I WH. Pillans, Eten 4. Age ofthe Sun. Supposed x 10**35~ raulites energy atthe present tim. (a) Find for radiation, on the rough a of hydrogen (atomic weight 1.0078) the reaction stops when 10 percer to helium. Use the Eins! lite expectancy of 1 10 x 10° years. (A good discus Weinberg, cited 5. Pressure of thermal vadiation. 1 for a photon gas (a) P= (CULV), ~ ~Ssp (50(2) pressure of i of the The average bbe nese 2% 10° ighly nonuniform and rises to nese 100molecm”? at the ce kinetic pressure is considerably higher tl 7. Free encrgy of photon gas. (s} Show that the partition function of a photon gas is given by 2 = [IL ~ expl-toy : (53) where the product is over the modes directly rom (33) as b) The Helmbolta free energy is found logft ~ exp(—hon el} (4) “Transform the sum to an integral; integrate by parts to ind Fe nv fsiee, 63) 8, Heat shields. A black (nonrelleative) plane at temperature T, is parallel to a black plane at temperature 7), The net energy Mux d ‘oveen the two planes is Jy = ay constant used; Ta. Find T in terms of 7, nt energy flux density is cut in hall because of principle of the heat shield and is wi transfer. Co “The result for N independent ng in temparature between the planes T, and T; is that the lu = o9lTat — +1) Consider a transmission line of length £ 08 ify the one-dimensional wave equation OEIC me GE(E0, where E is an electic eld component. Find the heat capacity ofthe photons onthe lin, when in thermal ea 9.. Photon gas in one di which clectromage librium at temperature Peebles 10, Heat capacity of intergalactic space. Intergalactic space i believed to he occupied by hydrogen atoms also oveupied by of lide © heat capacity of a solid goes towards al larger than ve form nonvanishing erm nthe su, Chek your esultby inset T = O.and comparing with Table 4,2. : 7 : heat reservoir. Use the results on energy fy ler 3 10 show that the ro > i given by Pa dem correo = BAY 6 Suppose that T = 10-?K;0 = 200K and N ~ 103 for particle0.01 em on a side; then © = 002. AC LOK the fractional fuctuatio order of unity for a dicletric particle of volume Lem" cenergy is of nsnt Chapter 4: Th nal Radiation and Planck bistbston value sugpests th below 06K 15. Angular distribution of radiant energy luxe tray Mtoe that arrives the an 16, Image of a radiant object. Let a tens Ay on a black object of atea A, Product 4p Qy t0 46% where lens as viewed from the Property of is also true when I rays are nearly pac I. En ‘cosmic black body radi ‘of photons in each mode has de © = (54 Ilog’s +1) = Gy lowes». (59) to start from n function. < Consider the gas of ina cube of volume V work during the expan- ‘drop. From the result for the 1 expansion, (a) Assume was decoupled from the wore at 3000 K. What was the radius of the radius bas Prottems 19. Reflective hea shield and Kiveth Hal of absorp id helium ‘many, perhaps 100, layers of an aluminized Absent such a layer, the te determined primarily by the of solar radiation incident on between the lax ie Earth and the flux of reradiation fiom the Farthithe reradition flux is proportional tothe fourth power ofthe tempera, {ate of the Earth, as ia (4.26), This energy balance is the subject of Provlecg 43 and leads lo the result Ts = (Ry/2Dsq)"@T, where T, is the emperating ind Tis that ofthe Sun; here Ry isthe eadius of the Sua and D.- arth distance, The tesult ofthat problem is Tz 280 K, assuming T= Son is much totter than he geometry (the small solid angle ie Sun) reduces the solae lux density ineide ‘an absorbent layer that transmits falls onit from the Sun, but absorbs and re-emits all the ta rared), from the surface of the Earth. We ‘the absorption by the layer of the i incident solar the upward flux will balance the so ALS ds, The net downward flux will be the sum of the sola Mux 1. a flux J, down from the layer, The latter increases the net thermnal us atthe surface of the Earth, Thus lg Ip hy = Uy (59) wwhece dry isthe thermal flux from the Earth ia the presence of the perfect nssiecuhiouse effect. Because the thermal ux varies a8 7%, the new temperature Othe surface of the Earth is Ty WT q (1.19) 280 K = 333 K, (60) so that the greenhouse warming of the Earth is 333 K ~ 280 K = 53 K for this entreme example.” * For detailed dacuions ce Climate change a Climate change 192, Cabs UP. 1990 04 1992 J.T, Houghton etal, or. Chapter 5 Chemical Potential and Gibbs Distribution DEFINITION OF CHEMICAL. POTENTIAL Example: Chemical Potentia! of Mot ina Mage Field Example: Bauteries GIBBS FACTOR AND GIBBS SI Number of Pa y id Negative Tonizat and Entropy aSa Atmosphere a Gravitational 1 System Energy Example: Occupancy Zero or One Example: Impurity Aton SUMMARY PROBLEMS L. Centrifuge 2. Molecules in the Es 3. Potential Energy of Gas 4 ansport 5 Concentration 6. Gibbs Sum for a Two Level 7. States of Positive 8. Carbon Monoxide Poisoning 9. Adsorption of O in a Maz 10. jon Fluct 11. Equivalent Defi 12. Ascent of Sap in Trees 15, Isentropic Expansion 14, Multiple Binding of 0, 15, External Chemical Potential eld ng. 20 In ns ie bs 10us Chopter : Chemical Potential and Gibbs Ditbution Pefiton of Chemist Petentiat a9 System §, [222 temperatures of wo systems ate diferent, enerey with the higher temperature to the systern wi Now consider systems that can exchange pa ms are said to be in diffusive (ant from one sys systems are flow from the system the lower temperature ey Resenoie & Eneray exchange“ MESA Example af wo at ea large reserva ough a permeable interface, Two ‘equilibrium with respect to particle exchange when the net pote the systems, just two systems with a single ne femperature and have the same value of the will be no net particle flow and no net energy flow Hf the chemical potentials of the two ssstems are di Pasticles will low from the system at system at the lower cheinicsl pofeatal of electors at one termi: terminal. When: ve chemical po of a storage battery is higher than at the other inals ate connected by a wie, electrons will ow in the vemical potential Consider the esta hat are in Q system & in thermal equ a ergy of 8 wi ature © and 0 dy wy Because N is constant, the eva () 7 is 2 miimom Nyro Chapter 8: Chemie Ps ish end Gidbs Diseburon whoce Ine Creel rw. Theo snd Nis posit Now from 8, 10 8, ral potential to the system of low chemical a deriva 25 important as the temperature, wh sat can exchange both energy and pat iv when their temperatures and i of enerty, several chemical species are present, each has its own chemical potential. For species, , wherein the eiferes forthe species j _Exampte: Chemlal potential ofthe ideal gar. In (370) we showed that the fee eneray of ideal gs is F = —x{NlogZ, ~ log ¥1] , ® where o approaches es ~HlosZ, ~ Wwe N) = or, by ), ‘pendence on concentration of an ial 9 fortwo temperatures the boiling temperature aPie x 10000 atm a = +— iy 1 1 > v0 Te oe Internal and Total Ct The best way equilib in the presence of a poter ots of idea gs al potential ie to discuss li step that acts on the particles. This Internat and Total Chemical Poteriat ns a] problem has wide application and includes the se discussed in Chapter 13, We again consider FigereS.3 A potent step between two sjstems of charged partises can bs established and we al difference by Ayu rium chemical pote fe pautcles carry a el way toe ep isto apply betwee AV su aAV = alls ~ Y= 0 he polarity shown in Figure 5.3, A difference in alsocan serve asa potential of mass AI by he gravitatiPotential and Gibbs Distbation ‘The chemie potential is equiva) energy: difference in chemical potential between two systems is equal to potential barrier that wil bring the to systems into diffusive equilibrium, ofthe chemical poten- potential dilfeences of the chemical potential depenits on the zero of the pote scale. The ideal gos result (12) depends on the choice ofthe zer0 of energy of a fe as equal to the zero ofthe kinetic energy nal potential steps are present, we can express the total chemticat enerpy pa © my can be expressed a5 we, ion between external and internal chemical potential ature Some wiles, p ry and of semicondu x use the words cher ‘Sometimes is not made charged particles often mean, ithout a further chemical potent the potentiat barriers of interest are electiostatic. 5 Gitta he pote sures erences ng the Ineruat and Tate C system fegen ae = clogtnyng) + Mah an tg] + Migh = ttogfn and the concentration ah at height satisfies = m(OJexpl—Atahis) sy26 (Chapter 5: Chemical Potential ad Gitbs Dissbaton Uhcerat and Total Chemical Potent by 19) ‘hetmal behavior, Thest the datapoints of Figue 8S spansa pressure 1 th) = ite range from hy = 2a 0 hy = 48hmn. Ne rH rom (ing * og? en 02 og. en 04} sothattheslope of tele i Af ofthe observed eu T = thy = DIK. Thenom intersection AO) = Liscauted by the higher tempera: urea lower ttiudes, os 116 tha one specs of gus. Ia atomic percent fenton of ey ale at sa level 38 pot N21 pot Oy aed 00 ps ae SScOUME for ese thea pt each The ne on T= 300K (TC) a raative hum 1 ine has astope ‘cotrespoading toa temperature P= 227 K. Pressure, relative to ground 130 The ston send consetatin vats soot mal ee ea i titer A would be i exulitvom wih ua The cre “ AlvithaseprsteBltemannfacorothelormerrt- ty a te mole ise essa of th ‘. 7 0.003) Esauple: Chemical potcatial of mobite magnetic. partictes ii asin of dete peer nent. Fer spy spose oni Sich ements dete {oan applied magnet ° | Then po ee : snd Wena : ard one lena The pastes fad | ae asdisnpustabe een feieo siete and | as distinct species in equilibria with cach ster, concentration; hereto te pessure The inter ofthe patil viewed asic gases with concent yandn ate chemical potest, Plt) = plO)exp(~Atghjs) = plOexp(— hy) fc prssrecptaton Ties the dependence ofthe press ‘of singe chemical species. At the pressure decreases by consider an ofr 8 Tis 40 x fy is 85k, approxiotelyns CChemioal posential species in bemical potentiate Hall) = const 3 “The deste lations of{2) and (28) ate easly een by aus H(B] = Anexplmsfe}s (8) = Jw(O)expl—mBye} (24) where nO) ny at a poi whore the feld B = 0, The totat mag Be = 5B) & (8) = dn NB) = n(O}cost to fine feromagneic pa are used inthe laboratory in the study ofthe mag 2d he domain strectare of ferromagnet tet fore structural eracks in ih: landing gear. Whentheseareconted with ferromagnetic Positive electra: "The reatons given arent rations. The actual et so. Ingraatand Total Chemical Pot ops are more complet. nn30 Chapter 5: Chemist Potential and Gibb Dishibucon al Potential and Entropy (>) etecxose (ode During he hay take place, because now an ye sole fons eae) te ~2 AV. = 4(S0,">). (282) top when 7 FGAV, Ault’) (286) als oF alfa! EME'S SV = —Davol; ayy = 4 16vole rence develoyed acoss an fll cell ofthe fy 135 required to stop the dision reaction, : AV = AV, ~ AY. = 20voIt, 29) From the nega shea the we We have ignored fee electrons in the cle econ (Chemical Potential and Entropy In G) we defined free po) way 1 a 1Gis Di «-(8),, 6 vives! changes dU, d¥, and Further, select the temperawure olde, dU, trary, independent difer 1V = 0 for the processes under consideration. 5 of da, dU, and dN in such a way that the overall ar) OU), , (2 . (Stem * Ge), “ at constant Gi), G+ Gi. % 69 we (y= Gila and on comparison wi (63) we obtain : eo | os ‘The two expressions (5) and (35) represent two different ways to express the same quantity jt The difference between them is the following. In (5), Fis a atant Exuopy a Tablet Summary the presuce py ae nial derivnves of ‘nexgy F,with 0, U, and F given 35 fn same variables. In (31) we assumed ¢ = o (35) yields jas a function of U, ¥, N. The quantity u isthe same in both (3) 4nd (15), but expressed in terms of different variables. The obiect of Problem Lt isto ind a third relation for HOVN) = (GUL a + 6a and N.Table$.1 compiles expressions for r, p, and seas derivatives of 6, U, and F. All forms have their uses, Thermodynamic identity. We can genet identity given in (3.34a) jawed to change. AS ize the statement of the thermo- da = dUje + pas ~ pdNje 63)ne Chapter $: Chemical Potenta nd Gis Distribution ed to give [# we pV aN, o nent of the thermodynamic identity than we were able to develop in Chapter 3, GIBBS FACTOR AND GIBBS SUM Boltzmann factor, derived in Chapter 3, Probability that a system will bein a state of energy ¢, tothe probat syst be in state of energy efor a system in thermal contact reservoir at temperature t: prrreke blot Pre” epi eya) is thegencitt ‘contact with a reservoir at temperature + ment retraces much of thet presented in Chapter 3 ‘We consider a very large body with constant energy Up end constant particle ibet No. The body is composed of two parts, the very large reservaie R and the system 3, in thermal and diffusive contact (Figure 58}. They may eacha and chemical poten those ofthe reservoir. Whe! N pastictes, the reservoie has Ng ~ N particles; when the reservoir has energy Us - e To obiain the statistical peaperties of the system, we make observations as before on idenicl copies of the system + Feservoir, one copy for Jn. Whaat to con- obsectt having some specified number of partic The energy Cy isthe enerey of the sates of the N-pacticls syst only fu if the meaning i i 1 Gis Factor and Gils Sune Reservoir £58 A syst 8 large eservoir ofenerey an of A + Sis insulated (oom the externa world, so thatthe “The temperature ‘ofthe reserviz and the chemical pot ‘equal ta the chemical pote snay be as small as one atom of it may be mactoseopi,b she reservoir i always to be ehought ofa mu the system. Let P(g) denote the probability that the system has N particles and is lar state s. This probability is proportional to the number of accessible states of the reservoir when the state, ofthe system is exactly specified. That of 8, the number of accessible states of G+ $ is just the number of accessible states of @: HO 8) = gia) x A wdsus State, The g(t) states ofthe ceseevoi ise the system probsns Chaper $2 Chemical tee ond Gibbs Di ere g refers to the reservoir alone and depends on the in the reservoie and on the e intber of particles 8, one that the system isin PN ue) _ 9(Me — NuUa ~ 6 FiWlaea)~ ale = Nay 62) ° co) where g refers to By definition of 1 state ofthe reservoir. The: entropy jown in Figure 59. StMoU) = explo(NoUa)] . ay so that the probability ratio in (43) may be w PUue) _ expla — Null ~ eM 3) PON) expla(No = Naso ~ e2)}" PU) ~ S*PLOIND ~ NaWo ~ 6x) ~ o(No ~ Nao — 03)} = expla), eo) (Gibbs Factor and Gibbs Sum Here, Acs entropy diference 89 oly = Nyy ~ G1) = 6g ~ Ne ~ 6) a the system, and Ag may be er terms ina series expansion i ehat relate tothe system. The enteopy ofthe reservoir becomes A= WU. 0 = amv ~ a8) = (22) go on For Ac defined by (47) we have, to the frst ord (6508) on Poe) _ expl(Nun — eV] PUNat) expliNan = t/t] 9) aya8 ‘of two expone ‘exp{lvn ~ ot]. A term of this form that the system is ina state 5 of of particles N. The result was fist give referred t0 it as the grand canonical distribution, ‘Thesum of Gibbs factors, Ry 1.W. Gibbs, whe Hla) = F Peron ~ syalel Yelp ~ ‘This called the Gibbs sum, or the grand sum, o the grand pa ‘The sum isto be carried out over all states of the system for al ASN, We have written &, a8 egy) 10 emphasize the dependence of the stae on the number of ps 49) 18 the energy of the state s(N) af the enact W- ferm N = 0 must be included; if we assign term in J willbe ‘The absolute probability that the system will be found in a st siven by the Gibbs factar divided by the Gibbs sum: 8 energy as zer0, then the fist PUN ye) = SN ss aie) (54) ratio of any two P'S is consistent with 0 factors. T Gibbs Factor and Gibbs Sn Avenigs values over the systems in diffusive and sescrvoie are easily found. IT X(N.) fs particles and isin the quantum states, 2X XiNshenp[iNye — «aa be obtained ffom the definition of FL y weutin— a whence Quy 2 Ee, , oloeg. Fa 2 (99) fu a les is easly found from the Gibbs son fusion arises, we ie N for al average (N). When we speak later of the occupancy of an orbi Lor (fw iy for W or CN). We often em LeNo ‘The Gibbs sum sw Br LE Mowing = EP ev-ai (61) and the ensemble average number of particles (5 «wy = 28 togg. 2) | because in many actual problems we deter ke (ND come out eq ne A by to the given number of Energy. The thermal average enerey ofthe systern is Esexol an ~ e)] Y= to Be : (on) here we have temporae write U for (¢), Observe f= If. We sh On S= yo FS = Fogg , (6) so that (59) and (63) may be combined to gi u-(¢2 @ 6) Example: Occupancy sro erens. A rotMooded example af @ system that may te ‘occupied by zeromolecales or by one molecules the heme Broup which may be vacant oF ‘be occupied by one 0, molecule~and never by more than one Oy enolecae (Figure 5.10) A sogle heme group occurs inthe protein myoglobin, which ie responsible forthe fed color of meat fe she energy ofan advarted molecule of O, relative to Oy at AIS Nb inn stance, then the Gibbs sun is Gala Rexpl—elh (66 Wehive Mb + 0, or BO, pr ‘myoglobin, a protein of mleeslr weight 17020 Twhete Mls denotes ‘occupancy rersus the concentration of oxsesn are show in Figure S11, Wecompare the observed oxygen saturation curves oF tyolebin jin in Figute $12. Hemoglobin the oxygen ca rand ech tran ned en ‘and each capable of bindinga single exygen molecule, Hi ion ofoxygen by hemoglobin x34 daneby Christan Bo [Niels Bohs. The eayeeasutoraton curve for hemoglobin (Hb) has wslwct deat Tow pressures, boas te binding enerey sins 0, toa molecule of Wh i lwer tsa for Mb. At higher pressures of oxygen the HD cure hs 4 teion that is concave upeads, because the biasing energy per O,iateases fe he fst ‘The ©, molecules oa hemes sein egitim with the O, in the surrounding iui, so ‘hat the chemical potentials of O, ae equal onthe ryoglobin and in soltion: HOMO2) = lO); H{MbO3) = 2103) wn whese 4 expla/s From Chapter 3 we find the value of ns of the gs pressure i= Wltg = lt (ss) ‘We assum: the ideal gas sult applits to 0, in so ion, AX constant empers = tome) dt 9 SATE dexp—ei) PRATT * _ Mt1 Gite Factor and Gib Som iw se fame 2 the Fe Dine discbuin finan died in Chapter 7. We ct neyo on — rey beviontas : sfamelcalecfOvatasie — [ eee EEE 00 myogloba molecule 58 4° pine et (0) ge ore 0; mite Thaseancsanow = {205 = rete the (action of myoglobia with adsorbed = 38a fiction ofthe partial pressere of Oy. The curves acer human sn amy z + $ ® Concentration of Oy relative scale ‘onication energy of the inp ‘on can be bound to an impurity stom either tiematon for 1 ol i is accesible Therefore the systert fas thse allowed sates--one one with an electron ateched tached with spi | hezeroefeseesyof & (5 M0, 0° Hb0,) ross of O,, in i Tre Gitbssum given by Bel 2explin e Nid 0Pestle PROBLEMS. om the dependence of teers of n(0) on Pincuusal) = & . 74) whic jos SUMMARY =WlofPN}cy. Two systems are in difusive ‘wm concentration, | 3. The Gibbs fetor ergy. Take the zero of the gra ceneeny at te bs we column, Integrate from PUN) = expL (Nn transport. "The concen ssium K* fons inthe internal sap ofa plant eel (or example, a fesh water alga) may exceed bya factor of LO" concentration of K.* ions in the pond water in wi of the K* ions is higher in the: ives the probability that a system at chemical pote will have N particles and 4, The Gibbs sum, wand temperature ¢ ina quantum state s of energy 6, BF enplle ~ ewe) inthe pondare nt i difasive eq 7 ly impermeable to the passive leak fe these: How isthe higl ip within thee metabolicenergy applied to energize the active ion tanspor is taken over + forall aumbers of particles, 2is defined by 2 = expluf) : (6. The thermal average number of pactiles is S. The absolute activ 5. Bagnetic concentration, Deter ft for which Figure 5.6 is 7 Grawn. If T = 300K, how many Bohr magnetons jig = eh? would the any = ab ong. : Particles contain to give a magnetic concentration eft of the magnitude ustuon rote 6, Gils wm frame level stem, 3) Consider a tem ha ay bo Peele lalallala eee ee occupied with energy tvo of Gtuped by one pale eer of to ley Oj) = 1% 10°F and {CO} = 1x 10° all a body temperature STC nereyetaitoncoferergy show tae Gsbrsumiorissytom & Neglect any spin mul factors. Fist conser the oystem tthe soos of CO, Evatante ey such tat 90 percent ofthe Hi tes ave occupied yO, BRERA hepa 76) Express the answer ineV pet Ox (0) Now CO wndse the spied ns Findey soc ha ony iOpecentol the Hbstesareaccupe ty Oy 9. Adtorpton of 0; ina magnetic eld. Suppose Bound to. me groupe Problem 8a 90 parent ofthe hemes occupied by O,, Consider Oy a5 having a spin of 1 andamogretiemomentf I How sttogamagneti fils neatetochanse = 300K The Gibbs sum inte init ofr hat of Problem & because thee the Spin 3 bound state ws neglected) ‘Our assumption excludes the possibilty of one particle in each state atthe same icude in thesumaterm for N = Oasaparticularstate ofa m of a variable number of partite, (@) Show that the thermal average accupaney ofthe system is 1 O, cam be that when Z(0,) = 10~* we have 24 Jexp(—e) cu = 4! 7 m & Show that the thermal average occupancy of the s at energy eis ENO> = dexpl—20/3- 9) Find an expression forthe thesenal average energy ofthe system, we $( 2) . eo wl at Oand at emay be occupied each by AH iy shaw that from (59). {a) Show that STA Reape) + Peapl-eeym 4 ALL + hexpl—aitlh (9) 2 . | coy = 20H ey Bie Jenbohausinomweheneteaeingedsstes | Bar 7. States of posites and ne drogen atoms, suppose that ea ve ionization, Consider a lattice of fixed hy- ‘The mean-square deviation ((AN)*) of N from GV) is defined by dal AAR) = CW = CSP = GHP = 2 yy of any if at END t CNY? = CAPD = CHD" 38) CANT) = e2END/E (6) Show that this may be w enetey ey by oF NrMe such as DNA of MIV 10" — and G. Feher, Proc. Nat, Acad. Sei. 73, 3) ich was used by Gibbs 10 define j,i equivalent to hat we have adopted, It wi process in which a particle ie added to a #)stem \emperature of the system is kept constant is a more natural proces ian one in which the enteopy is kept constant. Ad Ietoa system. temperature tends to increase its entiopy keep each system rough new, gua There is ao nacural bbe done. Hence the daintion (5) or (6), Js enpressed as the change in free energy pet ns of constant temapra , We point out that (85} will not give U = yon ¥)is a function of N; compare with five humidity isthe actual concentra ‘ion of water vapor in the tie atthe uppermost leaves in the saturated ai that stands immediately above 13, Isentvopic expansion. (a) Show that the entropy of ‘expressed as a fume of the orbital occupancies, show that x2” is constant in an isentropic expansion of as, Ii, Multiple binding of O;. A hemoglobin molecule. can ‘molecules, Assume that cis theenergy ofeach bound O>, 1 inte distance. Let 4 denote the absolute activity exp(j) of the free O. (in solution), Wi probability that one and only one O; isadsorbed on a Probleas cole? Sketch the result qualitatively as sal four and only four O, are adsor al porentiat. Consider a system at temperature 1, w 1 atoms of mass Af in volume ¥. Li 1G) = (0) 4 AMgh wyChapter 6 a Ideal Gas FERMI-DIRAC DISTRIBUTION FUNCTION 153 \ DISTRIBUTION FUNCTION 137 CLASSICAL LIMIT Chemical Potential Free Energy Pressure Energy Entropy Heat Capacity Example: Experimental Test ofthe Sackur-Tetrode Equation ‘Chemical Potential of Ideal Gas with Internal Degrees ot Freedom Example: Spin Entropy in Zero Magnetic Field Reversible Isothermal Expansion Reversible Expansion at Constant Ent Sudden Expansion into a Vacuum Py SUMMARY PROBLEMS 1 2 3 4 s 6. 7 Relation of Pressure and Enesey Density 8, Time for a Largs 9 10. 1 1 8 14, Ideal Gas Cateut 15, Diesel Engine Co1s Chapter b: Idec! Gat atom of low concent §s defined below in terms of the thetmal average value of icles that occupy an o The thermal average occupancy is calied the by chemists ows us to approx! ion ofa system of re are no int 1s a fundamental resul of quantum mechanies ld lead us astray fete) that all species af pai lases, fermions and bosons. Any particle with halFintegral 2010 oF integral spin is a boson, There are no diate classes. Composite purticies follow the same rule; an atom of He is composed of an odd number of particles? electrons, 2 each of spin §, so that *He a spi An aiom of “He has one more neutron, so there are an even numberof particles cf spa}, and “He must bea boson The fermion of boson nature of the particle species that make up a manj- body system has a profound and important effect on the slates of the system ‘The results of quantum theory as applied tothe orbital mode! of noninteracting particles sppear as occupancy rules 1. An orbital can be occupied by any integral number of bosons o ztmion ofthe same species, xchision principle, Thermal averages ital occupancies system must conform to one of the other rule. of occupancies need not be integral or hl of any indivie bbs sums lead to diffe mal average occupa {and we go on the properties system is placed ia igures 6.1 and 62. A re system may co 10 focus on one ot fealsystemare thought of as the reservois. Our prablem nd the thermal average occupancy of the orb to be 2er0 iT the orbit by one fer ‘The Gibbs sum now is simple: from the det 1 in Chapter 5 we have Go t+ texpl~eeh ‘The term 1 comes from the configuration = O.The term Lexpl-—tfs) comes when the orb , energy ise. The thermal average valu ofthe occupancy {erm in the Gibbs sum with Va: 1o the entire ‘occupancy NV = 0 ond energy is oceupied by one erm expla) 1 MOD Ty expla)” Paap eT 1ast hair: cbe 7 | Reserve fos Cee (Joss Ny fee U, enerey (My — 1 enions y be occupied at most by one the eservoir at temperature, The ofa free dleuron of a deh quantun sate may be icontain Ny fermions if ‘unoccupied and Np ~ 1 fermions ifthe system is occupied by one eion, Slo) = «NU. Recall from Chapter 5 We may wri here 41s the chemical poten 1 elle ary eT Sle) = ‘This result is known a3 ives the average number of fermions ina single or Bs Reservar System Reservoir ‘obvious method of viewing system of no ey fovea ringer equation, The ond equally system, The sytem inthis scheme may be the ‘te viewed asthe reece The Bal + temper al occupancy N= O,and the seni erm ass He = 0) = (= ey. 8Chapter 6s Meal Gas o—- of higher energy are unoccupied. At nonzero temperatut cal pot departs from the Fermi energy, 88 We If there is an orbital of energy equal to the chemical potent consequences of the FermiDirac distribution in Chapter 7, Right now we go on to discuss the distribution function af not ib Function interacting bosons, a fat ‘and bosons i la for both fermions BOSE-EINSTEIN DISTRIBUTION FUNCTION AA boson is a particle with a ropentes of a boson gas. There is @ sudden increase in the the heat conductivity of liquid *He below this temperate In of “He below 217K. was found to be less than 10°? ofthe viscosity ofthe Photons (the quanta ofthe electro of elastic waves i tor, we did in Chap We consider the distribution allofthe same species. Lete denote the energy of single orbital when occupied by one partite; when there are W particles in the oxbi as In Figure 6.5, We teat one exbital asthe system and1st pte Bs Heal Cae ‘The lowest level, the nen highest level contibutes i ‘eapl~ife; aad the subsequent cont * mee expen expl el Net and soo, The Gibbs a= Siton-neye Fren-uoy 8 N should be the total mumber of pa System and reservoir. However, the teservoir may be ati N may run from 2er0 to infin Let x a Lexp(—efs); then lesin Sot \ 3°) ra ima Provided that Zeap(—o/) <1 tn all poi eaualiotherwise he number sitane The thermal average o the Gibbs sum by we of 5.9), large, so that The setes 7} may be summed in closed form, Bose Basten Distribution Fe fe {T Fevmi bina fin units of + ig 6.6 Compacison of Rosen Listibaion fore ‘This defines the Rose-Einstef fom the Fermi-Dirae di 6.6. The ideal gas represents the: bution functions are approximately equs energy ¢ ie alas ‘of the discussed below. Thee! rary. The will affect the orbital is much less than one. T ‘emperature and atmospherie pressu lassi 13,reo Chapter: Hel Gor Fermion Boson Boson 1s order of. so ass sare identical, The quantum regime is the of the classical regime, These chavact aed CLASSICAL LMT classical forces in the box. We develop the propertics of an ideal gas with the use ‘of the powerful method ofthe Gibbs sum. In Chapter 3 we treated the ideal gas by uso al particle pe there was resolved by a method whose validity was not perfect The Fermi jon funetions in the classical al result forthe average number of atoms ia an orbital average occupancy of an orbital at energy e. Here ¢ is the energy ofa system of ata ay SO Satie RT ET n is forthe ED distribution and fl2) be meh smaller than unity forall orbitals, we ‘must have in this classical cegime. ecole ~ om Fed > espn ~ ae] zexpl~et) | wy i= expla. function, 1 is the functions when in comparison Equation (13), a result for particles lseribed by quantum mechanics: we ‘expression for 4 0F always involves the quantum eons be a classical theor ‘We use the classesl distribution function fte) = Zexp(—/s) to study the therml properties of the ideat gus. There ate entropy, chemical potential, heat capacity, the pressure-volume-temperature relation, and the distribution of atomie velocities. Ta from the classical disteibution terms of any topics of importance: the tion, we need Fist to fad the chemical pot of atoms Chemical Pott modes of motion. The total number of atoms ‘of atoms in each orbital, We use the sum ofthe average number 3) in (14) co obtain \n function Z, for a single fee atom in volume ¥, whence1 Chapter 6: Meat Gar In Chapter 3 it quantum concent ‘shown that Z, = g¥, where ng #4 (Me/2nh)?? is the ton. Thus = 1Z, = inh; = Ning = lng , 8) in terms of the number density = NYY. Finally, wan J = expluis) = at classical regime gasis -——— 1 = slogtoyn) (8) in agreement with (5.123) obtained in another way. The result may be written out to give = s[]OBN — logy ~ flog + Hogl2nh*/A4)} a) ‘he chemical potential increases 28 the concentration increases an eoreases asthe temperature increases, ean be subject to several ‘he 2er0 ofthe kinetic associated ad ree Energy have an added term ~tlogZ.. pet (48) below, where Zs the patti function of internal deprers of Geedom of one molecule (8) the ass {or u may be considerably more complicated; see ‘ely simple van der Waals approximation to. gis of incr: Free Energy ‘The chemical potentials related to the fee energy by CFL y = 1 en according to Chapter 5, From this, Feta) = [avanevy=s[Mavposw 64, 2) ‘here the integrand i found in brackets in (19). Now [dx logx = xlogx ~ x, so that Fa NeflogN 1 BV Hoge + Hog2nntan}, — @3) F = Neflostnjng) = 1 on ‘The free energy increases with concentration and decreases with temperature, ts The integral ia (22) should om 7 es) whieh integedonty inthe Sig stat eta NX) = logwt, 26) 163us Chapter 6 Moat Gas whote the intepal pave may be vse od nov Prossure ‘The pressure is related i free energy by (49) p= rer es With 23 for Fe have e) ich isthe ideal gas fa 35 rv in Che ptr 3, Eneeey ‘Tho thermal energy Us found fom Fs U ~ seo Ue Pewee FH uehittyy = -«(2 5) (0) With (23) for F we have so that for an idesl gas 62 ‘The factor J arises from the exponent oft in ny Because the gas is in thees dimensions; if mg were in one oF two dimensions, the factor would be $ or 1, energy of translational motioa inthe classical ‘aT per transational degece of freedom of an atom. ion ofencrgyamong degrees of freedom was discussed ‘The principle ofequipar fn Chapter 3 Heat Cpacity ay dillerenees between mal energy is Kinetic. A degrees of rotational freedom which ean be exci 1 degrees of rotational freedom, ‘The entropy is related to the fee energy by 0 = ~@F0r ey From (23) for F we have tl lie result (3.76) positive. The eesul (34) isknos entropy of a monatomic ideal in the thermodynamics of and many un sful attempts to do so were made in the eatly yesrs of this century, We ‘The enteopy of the ideal gas is directly proportional tothe numberof pa if their concentration m is constant, 28 we soe from (34). When two ide ‘Bases at identical conditions are placed side by side, each system having. the size ofthe system: the entropy’ concentration, Ifthe gases are not ide valve is opened (Problem 6) he entropy increases when the Heat Capacity, ‘The heat capacity at constant volume is defined in Chapter 3 as Cy = Calta. o9 1s106 Claprr 6: Hest Gas ‘shen the expression for (= EG +) 8 From this, for an ideal gos ean, 66) stant pressure wal must be added to perform, en ‘The energy of an ideal gus depends nperature, so that (2Uj2e), rave the same value as (BU cy, sshich sjust C by the argument of 1704 Brahe Seal 885 law V = Nef, 0 that the tem plOV{O0), = N. becomes Geen 68) famental CeO tay (338) ice agai he Wo systems of un 35 called the gas constant. The results (383, are written for an ideal eas without spin or other internal degrees of freedom of molecule. Foran atom Cy = 3N- a0 that dimensions For one mole, Niky is usualy beat (389) yp = Nig (38d) The ratio Cy/Cy is written as , the Greck letter gamma, Exurole: Experinestl ets ofthe Sackir-Tetrode equation. Expetimestal values of the ten found fam experimen rressure values of C, by nusnei tgtation of 37) 440) a0) = [Seca ©) lated compared w 's found by Ialloning contsiutions 1. Eat 2 Enteopy x 5 We give dete ofthe sony ‘entropy igven n tens ofthe soa 1 The heat capacity of under one atmos PY at the Lowest (lof thermodynamics sugges value ofthe entropy of (0) maybe set equal to ret unese tome ideal gas by we of the Sschur-Teirode 8 selxtd temp Py ietess On heating sl rom absolute zero to the melting point, (iscwsed in Chapter 10, of Clusus The ing point 455K. below 12.3K was 167Chapter 6 teat Gas tess as, BSSK = 164) molt K-! ‘opacity of the Tiquid was measred fom pein: of27.2K under oneatmosphere ofpressute The ea io pint to the boing eases founttobe AS = 3.855 mol K-2 inp sequied to vaporize the bid at 272K was observed t9 be 1761) ‘molt, The associated entropy of vapo 1761 Jot" AS, 9 RE 64623 mol" K-, Serene = SST = GEL Ol""K “The experimental val sphere adds upto ofthe entropy of neon gas at 272K ata presse of one atmo + MSwerion + ASiqas + ASvapriaon * 96403 mal” K-} ‘py of eon under the same condition is = 96455 mol" K-' Som the Sackue“Tetcode equation. The excelent a sives vs cntidence inthe bai of Tetode sition TI a Chemical Potent of bee of ldcal Gas beat bas @) where Gq fefes to the rotational and vibrational degrees of freetlom and , tothe translational motion ofthe center of mises ofthe molecule. The vibrational ‘cnerey problem is the harmonic oscil ie. The rota tional energy wes the subject of Problem’36 's classical regime the Gibbs sum forthe of Bm lt dewl-nids a where terms in higher powers of 2 are omitted because the average occupat ofthe orbital mis assumed to be <1, That i, we neglect the terms in 3h correspond to occupancies greater than unity, In the presence of intern energy states the Gibbs sum associsied with the orbital n becomes B= 14 AD eapl—le, + sali). (2) Bal empl—e/0F exp(—sade co) The sumamat nis just the pas function of the internat Lins = YOK —Cialt) » (4) Which is related to the internal fiee energy of the one molecule by Fay = ~ #108 Zq. From (43) the Gibbs sum is Bol 4 uexpl-alh @) 139Chapter 6: Heal Gas ‘The proba the state | motion ofthe Jin Ato the Gibbs sum J: lice as fle) <1, The result cise, but ZZ. now plays the role of 2 ‘monatomic ideal gas are diferent for “ny always use ng as defined for the fo spin} Because i = exp(y/s) we 1 | = tllostiing) ~ log Zi) 8) (8) The fee energy is Fay ~Ne103 Zi @) we {o)_ Theentrapy is increased by ecersile ot with the spin stone is this Bing the number independent tution tothe fee energy is (52) and the spin enropy is mperature is equal the final pressute is OtV) = Nlog ¥ + constant , 63) 82 ~ 91 = Nlog(Ve/h,) = Ntog? = (1x PY is Targer a in the larger volume tha some temperature, vrChapter 6: Beat Gas not Heat ow Figure 6. Workis done by ‘expansion, Here the Unde isomer so that the presute ‘expand. The presse How much work fs done by the ga Whea the gas expand: expan does work against piston, a8 in Figute 67. The work done on the piston when the volume is doubled is [fear [Pevunnar « weg) = 092. Weevaluate Ne directly as 414 x 10%erg = 41.43.71 Piston is, from (57 Nelog? = (41.45)(0693) = 2873 69 ‘The assumption that the process is reversible enters in (57) when we as tata knowledge of Vat every stage determines pat every stageoftheexpal We define W as the work done on the gas by external agencies. Thi etative ofthe work done by the gas on the piston, From (S We = [pu -2075 ResrsibleExponson at Constant Extops 05 he energy of an ideal mons ‘an exparsion at const eereases by Nelog 2, change in free encegy connection is discussed in (othe 90s from energy ofthe ideal gas remained constant wh ion of energy ‘as oceur from Q of heat added to the gas must be ‘ual, bet be opposite in sign, to the work done by the piston, because QW = 0. Thus Qa, | (60) fom the result (59) Reversible Expansion at Constant Enteopy We considered above an expansion at constant temperature, Suppose instead wat the gas eipands revessibly from 1 x 10%em? to 2 % 1Ohem? in a Process is carved out reversibly (slowly). A process without a 's called an Isentropic process or an adiabatic process. The tesm “adn has the specific meaning that there is no heat transfer in the process. For enttopie: isthe temperature ofthe gas ater expansion? The entropy of an ideal monatomic gas depends on the volume and the temperature as lV) = Nloge? + logY + constant), the entropy remains constant if loge#Y = constant; Y= constant (2) mn an expansion at constant entropy from V, to Vy we have 22, = 58H, (63 for an ideal monatomic gat mmwe oe $$. ms Chapter 6 Heat Gas ‘We use the ideal ges law pY = Ne to obtain two alternate forms, We ins ¥ = Nejp into (63) and cancel N on both sides to obtain ot cy Bb larly, We insert = pVIN in (63) to obtain AYSP o ppryssi, og P= pyr (65) (69, wn (6 Here 7 = Gy/Cy is the ratio of the heat capacities at constant pressure and constant volume, With Ty = 300K and 1%; Tz = (PQ00K) = 189K, ©) the final temperature after the expansion at constant entropy. The gas is cooted in the expansion process by Ty = Ty = 300K ~ 199K = 1K, 0) hod of ratigecation, we change (70), For an Us~ U = Glas) = iM 2), ‘Sudden Exparsion ita a Vacuums fin conventional uni Or ~ 0 = IWkT, ~ 7) HC 100.38 4 10> ere K-41 K) 7-23 x 108erg = —294, 1” ‘The energy decreases in an expansion a stant entropy. The wor the gas is equal the decrease in energy ofthe gas, ‘Sudden Expansion lato @ Vacuum versible energy Now between seurtally esualize conditions throughout the gas. We sume te ‘Hole process occurs rapidly enough so that no heat flow ie at is added in the ex % 0. Because the energy 825 is unchanged. The energy of a real yo the atoms are moved f the change of ‘The increase of entcopy ' given by (56) 49 = 0, ~ 0, = Nlog? = 0.069 x 10% a) For the expansion into a vacuum Q = 0, Expansion into a vacuum i ‘most probabie(eq rium) 2 a every stage ofthe ex usChapter 6: Hest Gar Table 63. Summary of ies! monatomic gu expansion experiments Fereversite ‘expansion into 6 1¢ two regions into which the system is divided does not correspond to an, ium distrib ‘central results of these calculations are sum- marized i Table 6.3, SUMMARY: STEPS LEADING TO THE IDEAL GAS LAW FOR SPINLESS MONATOMIC GAS, {a} flo = Aexpl—afs) N 0 t= as 6 a= 2 (gay Yoana mts [dl Zin the classical Energy ofa free pai gguantum umber volume ¥. (© 1 = Ningv (0) ng = (Mah)? Definition ofthe quantum concentration, {a} 4 = tlogta ng) 2. Symmeuy of filled and vacant orbitals. pears as flye + 8b Show that Set Sat ‘Thus the probal probability an orbital 5 below the Fer nes known as a hole, function for double occupancy starstcs. Let us imagine a new is in which the allowed occupancies of an orbital are 0,1, and 2. The values of the energy associated with these occupancies are assumed 10 be D, and 2g, respect Derive am expression for the ensemble average occupancy (IN), when the mi composed of this orbital is cconnaet with a resecvoir at temperature t and che ind derive an expression which is doubly de- ensemble average occupancy of an energy i; that is, two orbitals hav: ‘occupied the total energy is 2e 4. Energy of gas of extreme relativistic partic ‘the mean energy pet P: contrast to Je for ths ie problems are diseu ud Statistics, University of C cd by E. Fen 10 Press, 1966, paper 3. Integration of the thermodynamic identity for smodynamic identity at constant number of part (a)e* ideal gas. From the ther- raa Chapter 6 Hest Gas Show by integration that for an ideal gas the entropy is 7 = Cylogs + Mog + oy, 79 Suppose that a system of ¥ atoms of type A is placed ti sysiem of N atoms of type Bat the same temperature at after diffsive equilibrium is reached the total entcopy Srna fest lo82. The entropy increase 2N logis known asthe entropy of mixing. If the atoms are id fOpy When diffusive con been cal 7. Relation of pressure sure in a ys PV wen ee) pa 7 Sum is overall states of the system, (b) Show fora gas of fee particles (45. m 5 a result of the boundary condi wh 28 ofthe problem. The ces ther efers toa state of N noninteracting particlesor toan ot; for a'pas of fee nonrelativistic particles p= 2Upy , (79) Average energy of the system, This e {o the classical regime; it holds equal long as they are nonrelativis 8. Tine for a large fluctuation, We quoted Boltzmann to the ef Probtens 0.2 volume of 005 liter. How many Container, estimate the value of the ratio ppumber of states for which a umber of states for which i he collision rate of an atom is = 10!°5"!, what iions of all atoms in the system in a year? We use frequency with whi ith eternal degree of feetom, Consider tone for whi 10. Iscntropie relations of ideal gas. (a) Show that lel gas in an isentropic process satisfy ions apply even dlegrees of fretfom.(b) Theisentropicand i Boo -VieDiV is By = Vi /¥), 8) 28 B. = 5p; B, = p. The velocity of sound bye = Bato)" there is very bitte heat transfer in & $0 ‘eal gas of molecules of mass M we have p = pe/M, so that ¢ = Here pis the mass density tbrium ina wniform era where 2 is mosphere Pe pw 1180 Chapter 6: Mest Gos is greater that respect to convek ic gos in wo A = 12, The spin is zero. (b) Find an expression for the enorgy U of the gas, sal gas. (a) With the help of Zs = (ug S/N! from ‘the Gibbs sum for at (6) Find an expression for 13, Gibbs sum for is 3 = explingvL(b) SI ino PPO = 1 and EAL) = vy processes? (b) What isthe temperature atthe end of second process? Suppose the first process is replaced by an irteversible expansion into a vacuurn, tox total volume twice the initial voluine. is the increase of entropy in the iereversible ex 15, Diesel engine compression, A diesel engine is an internal con is sprayed into the eylinders after the air c s© highly comprested that it has attained a temperature sufi inders is compressed isentropic perature of 27°C (200 K.). Ifthe compression ra temperature in °C to the air is heated by the compression? Takey = ba Chapter 7 Fermi and Bose Gases FERMI GAS, Ground State of Fermi Gas in Three Dimensions Density of Stes BOSON GAS AND EINSTEIN CONDENSATION ial Neat Absolute Zero Example: Spacing of Lowest and Second Lowest O11 of Free Atoms Orbital Occupancy Versus Temperature Einstein Conden ions of Hetiura es and Super ui Supettuid Phases of *He SUMMARY PROBLEMS Dersi 1 2 3, Pressure and Entropy of Degenerate Fesmi Gas 4, Chemical Potentiat Versus Temperature 5. Liquid *He asa Fermi Gas 6, Mass-Radius Relationship for White Dwarfs 7. Photon Condens 8, Energy, Heat Capaci 9. 0. 1 2. 3. 4 Entropy of Degenerate Boson Gas Dwarf Stars Fermi Gas Fluctuations in a Bose Gas Chemical Potential Versus Concentration ‘Two Orbital Boson System 199 199 201 202 205 207 27 7 218 28 218, 20 219 219 21 2a 22 22 2m 2 m 23 stental esult of quantum theory that all particles, including a 'r fermions or bosons. They behave a in which the concentration is small in comparison 1 my 5 (ATA), ( 1 quantum regime and is called a physical properties between a quantum gas of 1 1d both ae unlike a gas in the classical Yow heat eapacity, fow ion rate, and exerts high even at absolute zero, A Bose gas or el Q tified by the condition n = ng. A gas in the quant is often suid to bea degenerate gust as realized by Nernst as 0. Qi he ro that the entropy of a ck gas diverges as log ory removes the dif fermion and boson he entropy goes to py is squeezed out on cooling a quantum pas (see In the classical regime (Chapter 6) hermal average number of particles inn orbital of energy cis given by Sl) = explty ~ aye @ gneraie tt more tan one mm is cegime, Sle) = twinghexpl—e) , ‘The form (4) assures us that the average occupancy af any or ly to bosons, so there Fermi Gas he usual choice of the origin of eat zero for the energy ofthe lowest orbital is fon the occupancy of any orbital, At absolute zero the ground I-the orbital of lowest energy—is occupied by all Asie temperature is increased the Contain a relatively small number of particles. We Abote += ry the around or ‘occupancy becomes FERMI Gas, A Pecmi gas i called degenet bealmost entirely vacant, An orb ly when it contains one fermion. A Fermi gas is said to be jienergy, as newes (Chapter 7: Ferm and tose Gases to ot —— 2 ef = £0 i é aol i= wet ont system at absolute zero. Suppose that it is necessary eracting electrons icons, then in the ground state the orbitals with oe <4 are filled, and the orbitals of empty. Any other arrangement gives «higher energy. To construct the ground ® = 1 atthe bottom, and we continue Is with electors until all V electrons are accommodated. ‘The orbitals that are filed in the ground state of @ system of 16 electrons are shown in Groua State of Foon Gas ix Thee Dimensions Ground State of Fermi Gas in Three Dimensions Let the system be a cube of side I and volume V = 1. The orbitals have form of (338) and their ener ‘nergy of the highest that the 6 empty orbitals. For the system to hold WV electsons the orbitals must be filled up 10, determined by $e Bats ~ mp = ON Nab x Be = ies ~ np = GNA! ) The factor 2 arises because an electzon has two posible pin orientations. The factor arses because only triplets, it the positive octant ofthe sphece in n spuce ace to be counted. The volume ofthe sphere is 4n4,/3. We may then write (3) as This relates the Fermi energy to the electron concentration N/V =n. The so-called "Fe ature” ty is defined as ty = ¢y total energy of the system in the grour 2 (yy 7 isan integer and isnot N/¥. Consistent Up =PE ware bx anf dante, = 18) 206+) 24a) fan? 0 in the conversion of the sum into an integral. Integration of (8 gives the round state kinetic energy: we Eee? ao) 18s195 Chapter 7: Fermt and Bose Gases Uy in units of 10% ergs tt] 010 2030" 403080908080 00 Volume, in em? 12 Tots le is Uy/N and is 2 of Density of States hermal averages for independent partite prablemms have OD = Y Hara form 7 al average occupancy, cl i in, We often express (¥) asan integral overt energy e, Thea (11) becomes 0 = fae Meena 3 Density of Stater Led fae Ore-4 (3) of energy between ¢ and e+ de. The nearly always called the density of states, i the density of orbitals because it refers tothe sol Problem and not to the states ofthe N particle system Cnser an example ofthe ealeulation of O(c) We sae rom (7) thatthe number W of fee electron orbitals of energy less than or equal to some es ity Di M0 = (VBA \QAYIAPRLIA ay, for volume V. Take the togarithm of both sides: log = Ploge + constant, ay) and take differentials of log N and tog, aN = GN/2ehde is the number of orbitals of energy between ¢ ide + de, so that DU) SANs = INe\2 a ls The two spin orieatations of an el is derivation because they were counted ‘B(e} as function of e alone because ron have boen n (6). We can counted throughout Neve = (ype from (14). Then (17) becomes a18s Chapter 7: Fermi end Bose Gores fe aca represents tal t absolute zen 0), x where f(t) s the Fermi-Dirae problems where requiring that uv rahe above inthe ground and the energy is Density of orbitals Energy, + ion function (Figure 6.3), the density of he density of occupied orbitals nay now be written as = fPemofers) , (20) poy lated from (20) be equal tothe = [Peemeaners. en all ovbitas age Mlled up electrons is equ he energy op, We fe en Uy = [deedia, 03 Presi sea hes cinensions. The elation is pehare ene Heal monscontlishment ofthe theory of the degenerate Feral ae eos wea nant es the heat capaci i but for lesvone nae ory Rush lower values found, The calculation that follows ones or ene HPeinenta results, The incase in the taal ery oh Shcgeleons wes heated fiom 0 to «is denoted by AU Um ~ 80 [Pectin ~ [sce 29 Here fle) Dirae fun ‘unit energy range, We m (0 isthe number of orbitals por es) (e 6) A= [Eble canoe + [ae ath rato en ight-hand side of 27) gives the energy needed to take “lection fos tothe orbitals of energy & > ey, and theo integral gives the enesgy needed to bring the electrons to a trem 01 low ep. Both Contributions to the energy are pos he product flsD(ele im the frst ed 10 orbi Of the clectron ges is found on liferent ‘Tespect to r. The only temporature-d 18 AU wi lent teem in (2) i fle, whence wo 19190 Figure 7.4 Temperature dependence of the energy of > ‘whese Vs the aur of eecrons, The te is poted 38. Chapter 7: Feri an Bose Cases theee dimensions. The S 9,5 }-—— sdformas AU/Nep, vee 19 i Ci a a Pky i its of 10° K Figere7.S. Fetmi-Dirac distribution fonction a various temporatutes for Ty = trky~ 50000 K. The rests apply to gs in tvee dimensions, Tae independent of trperatre. The chemical pt ep of Eg (20) and may be eed ol seaph as the energy at which f = §, Courtesy of B, Feldman, Heat Capacity of Electron Gar ~ Region of degenerate quantum gas assical gas —| can group terms to obtain au = gt, Gan = pacts ~ ep Loe es ‘Authe temperatures of interest in metals 1/e, < 001, nd we see from Figure 7.5 that the decivative fd i large omly at energies near e Its a good appx mation to evaluate the density of orbitals O(e) at ep negra Ca De) [Fdote ~ on 9) Examination of the graphs ia Figures 7.6 and 7.7 of the variation of g with « Suggests that when « «ep We ignore the temperature dependence ofthe chemical potential y in the Fermi-Dirac distribution function and replace ¢ by the constant ey. We have then: ete exnlle— ave) de SP Fexplle = aie] + I “ wnmn potential for tee electon Fee ‘ote and thee i ns eloely eq «slculted fom seve expansions ofthe foc the numb of prt (Chapter 7: Fermi amt Bose Cares on with temperature ofthe ions ta commen ‘oom temperature, so ep These curves were srl inthe system, One dimension. Weset x (e~ sales co) nd follows fom (29) and (30) that ee Ca = eDlep) [de wear G2, replace the lower fi temperatures such that e7/e ~ 100 or more. The it by ~a0 because the factor ef in the X= ~e//t if we are concerned wi tgral® becomes @ Heat Copaity of Electon Gut whence we ave forthe heat eapacty ofan electton gus, when ¢ « tp, wr. | 89 Ca = $e? Oe phy T. 69) In conventional units, density of orbitals atthe Fermi energy is Dey) = 3N/2ep = SNP 69 [ Cas bese | 6 there is an extra factor ky, so that Cae beNRSTIT, , ro) where kgT'p = ey. Again, T poi We can give a physical explanation of the form of the result (37). Whe specimen is heated from absolute zero, fan energy range + of the Fes ted by Figures 73and 75, Th of Nefer, and electro electronic contribution to the he capacity is given by = dU glide = Nojoy = Nelte 6s diseetly propor the experimental results, to tin agreement exact result (34) and(Chaptee 7: Ferm and Bose Gasce TatteTA Cateuated Fes ay pacanetess for Tee eles Conocion slestron Fermi tempeaturs energy Ts = eh eine Perini Gas in Metals “Tho alkali metals and copper, the conduetion electcons act a¢ a free fermion gos, energy ef may be calculated from (7) Aaa Sen ues of w and of ep are gi Table 7A and in Figure 78. The el velocity vy at the Fermi surfice is also given in the table; ic dened so the kinetic energy is equal to: yey? mer ay “where mis the mass of the electon. The values ofthe Fermi temperature Ty = xlky for ordinary metals are of the order of 5% 10° K, so thatthe assumption T « Tr, used in the derivation of (35) isan excellent approximation at room temperature and below. ‘The heat capacity of many metals at consta ie sum of an electronic contribution a Jow temperatures the sum has the form volume may be 1 latice vibration contribution, AL wart de, (02) Femi Gas in Metts Ro Cs. rep = 3833 12 cr) San nan . Hattobeladatel = Potassiam i § Beceee eee © a0! ink? Figure 7.9. Expedimenta heat capacity values for TE afte W.Ht Lien and NE, Philips Phys Rew hapter 4. The low temper is helpful to display the experimental values ofthe heat capacity for a ‘material as a plot of Cy/t versus 1?: Cyt pt At, 3) for then the points should lie on a straight line. The intercept at x = O gives the value of. Such a plot is shown for potassium in Figure 79, Observed values of yare given in Tables 72 and 73.: $e, 196 Chapter 7: Fermi and Bose Cases Waite Dwarf Stars wr Table7.2_Expeiment beat ea ree eleron etronie frder of 10° t0 10? gem", A ies of monovalent metals icely ionized ea gas, as (ep, Maat mses “The companion of Sirius was the fst white dwaf to be discovered, In 1844 estriol Re Bessel observed that the path of the sar Si us B was determined The radius of Sirius B is ‘cm by a comparison of the surface temperature and the nt eneray Mux, use the properties of thermal radiant enerny developed as as appraised by Ed 1926 in the N "Apart from the ineredi there was no. pacticular reason to view the caleuation with suspic st Ta higher denies: what named Van Maanen No. 2 as a mean detsity co] Ni [oa [ze [Ga | Ge 423 | 702 | 0695] 044 | 0596 Rh [Pa tag [ca in | Se 49 | 942 |a6ss|osse| 169 | 178 of 10% gem have a volume per atom equal to Y= (OF mot ema F6 x TSM atonismar ay 2 x 1m *em* peratom a a {os m1 | be [ai 0 tar | 258 | oos 0F2 x 10° peratam, The avers the order of 001A, as compared wi ighbor separation is thea of lear separation of 0.74 Ain a ity the omic tof the Sun, The mass and fo = 20x 10% 8; Ro = 10x 10 em, ow te dwarfs are very sin density ofthe Su, wi pechaps O02 that of the Sun. is a nocmal sar, is of the order of t gem e densities of white dwarfs ate exceedingly18 (Chapter 7: Femi and Wose Gases Ps about 10° higher than in a typical metal ‘The Fermi tempera clectrons is =3 x 10° K, as in Table 7.4. The actual of a white dwarfs be fly of the perature in the interior ved to bs of the order of 10° K. The electton ges in the (rior ofa white dwarfis highly degenerate because the thermal energy is much lower than the Fermi enerey. clectron energies in the rela ie regime? This question arises because our theory of the Fermi gas has used the nonrelativstie expresso p?/2m for the kinetic energy of an elzeteon of momentum p, The every equi valence of the rest mass of an electron is lear Matter Which nuclear matter is composed form a degenerate fermion gts, at least rly. We estimate here the Fermi energy ofthe nveleon gas: The radivs ofa nucleus that contains A nucleons is given by the empirical relation Ra (13 x 10" yx A 8) 1 per particle is consta volume goes as R?, which is proportional to 4, The concent in nuclear matte is forthe ion of nucleons 28 Ege weapa TOU = Mews G3 x 1 cmpP A ~ 7 o neanns © 005 x 10% cru"? as obtained from (49) on dividing by 2, The Fermi energy is ep (BAT x 1079)” = OAS x 1O*ere = 27Mew, (52) he average kinetic energy of a particle in a degen Fermi energy, so that in nuclear master the average per nucleon, BOSON GAS AND EINSTEIN CONDENSATION He effect occurs in a gas of noninteracting bosons at a esttain temperature, below which a substantial fraction ofthe total number sin the system single oxbital of loxtest energy, ied by a rel rhumber of particles. The total occupancy of ll orbitals will always be equal to ‘he specified number of particles in the system, The ground-orbital effect is called the Einstein condensation. here would be nothing suepe ‘occupancy ifit were val 10 us in this result for the ground stal ‘only below 10" K. This temperature is comparable the energy spacing between the lowest and next lowest orbitals in syste ‘of volume 1em?,as we show below, But the Finstein condensation temperature for @ gas of fictitious noninteracting helium atoms at the observed density of liquid helium is very much higher, about 3K, Helium is the most familiar ‘example of Einstein condensation in ation, ‘Chetnieal Potential Near Absolute Zero ‘The key to the Einstein condensation isthe behavior ofthe chemical pote ‘of 8 boson system at low temperatures. The chemical potent weChapter: Fernand Bose Caner zation ofa large population of particles orbital, We considera system composed ots ben the system energy. We can sho ato we put the: lemperatures, By of the ground orbital at zero on our energy scale, then in distribution funetion 1 (09 * Soe RTA i ‘6 obtain the occupancy ofthe ground orbital ate = as 1 a) = 54) $09 = aI (34) ‘When © 0 the occupancy of the ground orbital becomes equal to the total umber of pa 1 x SSE isi 7 Oe ise use of the series expansion exp(—a) = 1 — x 4 ++. We u(t, EUS desma in comparison wi 1 or otherwise F of particles WV could not be large. From this result we find Nm pe aul “| “5 ForN = Wat T= 1K, wehave wo —14 = 107 erg. We 6) Chemical Potential New Absolute Zero See ial office soma, “The ‘orbital ofan atom fee to move in aeubs of lume Pe Eo cE (Jiat by (5 Whee te 2 seg The eneiy {11 ofthe lowest obi is ay = (ay, a= (AJarren, (sa) sod the esiy <1] of one he eta et lowe bili mV G4 59) (Jaren ” The love exctaton cng the toms ‘Ae = (21 3x (ay (60) es — (1h) = ime, (60) TEAM 655 10-% gaol 1am Ae = BNB4 x 10° Y9.86) = 248 x 10° erg, (et) ittoconcivethatitcaa play an important te lowest reasonably ascenble tres fovever at the 1 mK temperature (58), t 1 MO * Sie RTS * ap a (63) (uefa 1°(Chapter 1: Ferland Hose Gator because 16 Orbital Occupancy Versus Temperature We saw in (19 the number of free particle orbitals per unit enerey range is v peaey v0 = a(R)" 6) for parti of spin eo. The total number of atoms oh he round and exited orbital is given bythe sum ofthe oseapanes eal nit N= The Nd + Nd = Neo + fF deepen. — (69) We have separated the sum over he number of atoms in the ground orbital at temperature t. The (66) gives the number of atoms Ne) in all excited orbitals, with Orbit Occuponey Vera Temperature pas Ken r condensed ito the ground pt. ‘Slex) as the Bose-Einstein distribution fanetion. The integral gives only the umber of aioms in excited orbitals and excludes th in the ground orbital, because the function D(e)is zero ate = 0, Toc we must count separately the occupancy Np ofthe orbital with e = 0. Although only a single orbital is involved, the value of Ng may be very large ia a gas of bosons. We shall cll Ng the number of a condensed phase a he number of atoms in the normal phase, The whole secret ofthe res followsis that at low temperatures the chemical potential pis very much closer in energy to the ground state orbital than the first excited orbital is to the ‘round state orbital. This tloseness of p to the ground orbital loads most of the population of the system into the ground orbital (Figure 7.10). an204 (Chapter 7: Ferm and Bose Gases ion function when written for the orbital at 1 Nd =a, (6 at eget 4 will pend on the temperature. The numberof patses in all excited orbitas increases as ¥ fay v0 = (2 or, with x 5 af, 149 = EP Notes the facor <1" which give the temperature dependence of N, low temperatures the number of pa Be number. Equation (67) ells us that unity whenever My is > 1. Then dis very accurately ton Saale of No frees tobe cose to unity. The condition forthe validity mis that Nq> 1, and it is not required that NY, «N. When integrand, the ¥ tions of from 1, so (9) "To caste the mies we write dy ytitgre betramsormed with Einstein Contemation Tenperaiure ‘Thus the number of atoms in excited states is ¥ ases\s ne SEE (ae) =25 a Ga Pe ea is again the quantum concenuation, We divide N, by inthe faction of stoms in excited orbitals: MIN & 2612nQ¥)N = 26 0 irte tale d= 1 OF 1 — 1/6 which fed to (7) i valid os long as a re ‘number of atoms are in the gr les have to be in some in the ground orbital. The number in "to small changes in 2, but the rest of ind orbital. To assure this we must take ‘urnber. Even TO? isa large nurnbee for in Atitg = 10°F of y ofthe ground orbital i > 10"? atoms fe. Thus our argument is highly accurate perature for the total number of W occupancy of the ground orbital is below rg the occupancy is macroscopic. From (70) W for the condensation temperature Homs. That is, Nez) = N. Above ot a miacroscopic number; with 1 for Ny, we 20s6 (Chapter 7: Farmland Bose Gi 19 Be Met'Ne ) ‘We subtract (79) from (77) 10 ot 1 Ive hyn ae Me 7 (0) ‘There isa lowest value of the magnitude of the velocity V for which this ‘equation can be satisfied, The lowest value will occur when the direction of k is parallel to that of V. This critical velocity is given by 2My ¥, = minimum of —28 eh) le simpler to express if we become very large, for then the masé Ma of the body a = minimum of &, 82 % 1 (2) -Abody moving with a loner velo in the Tguid, so that the motio to be zero, A body moving because of the generation of “There isa simple geometric ‘energy of a elementary exc excitation, We construct the st than ¥, will not beable to createexcitations be resistanceless. The vikcosity will appear struction for (82). We make a plot of the 8 function of the momentum hk of the from the origin which just touches the curve from below. The slope of BS ERIM, as for slope and the evtial Free atoms: frequency The locity ¥, wanevectors, which i ine the critica velocity is Kom Aitky = 5 x 10? 7 69 where A and t, are identified on the figure. Charged ions of helium in solution in experi- ‘equal to the calculated value of (85). Under other experimental condi- tions the motion of the ions is limited at a lower velacty by the creation of Vortex rings. Such vortex rings are transverse modes of motion and do not appear in the Longitudinal modes covered by Figure 7.17, It (84) for a necessary condition for the am the calculation we have given, O move without resistance through the velocity V of the body is less than the uid Tie If at absolute zero if ical velocity ¥,. However, at LoMeperand Re Pigs, Ree 13, (961.6. Raye Phy. Rev Ls 16, 9340566) 2s16 Chapter 7: Fer femperatures above absolute zero, but below t of the body. The superfto uid component may component lesks out ose Cares x Energy. in units of 1.38 X¢ 107% exp 1 20 30 Wavevector, in units of 108 emt 12K. The pacabote eur isin represents the theoreti m8 at absolute zero say and momentum of the mea vey fasboen drawn through the ng inary f temperature, of elementary excitations that are the id Component isthe source of existance to " appeacs fr ents in whic uid compos flows out throw the ee Summary critical velocity also holds for Aid relative to the walls of t ‘Superfluid Phases of "He Three superfuid phases of Ole ace known* (Figure 7.156), but~i te known us a Cooper ly like a diatom motecule, but the rai the average ieterelec molecu of the average ‘wo electrons that form a Cooper pair are spin state Inthe supeefuid states of a pair are in the t three maznetic supertluids are possible, tions ty = 1, 0, and —1, or mixtures of the supenluids have been explored en Supotluid properties have been confirmed, sales of the two He nucle corresponding to spin orienta se thtee slates. The magnetic and both the magnetic ent SUMMARY ermi gaeat low i Tow heat capacity. Th State. The energy of the (© of a Tree particle gos of f HE (atm “omy energy le ground state is Uy = Ne. 207Isa ep Bley) = 3N/2ep eal capscily of an election gas at + « Cay InP Oleple = 5. Fora Bose gas at r < tg the fraction of atoms in excited ork NIN = 261 = (ies he Einstein condensation tensperature of gs of no (san) ig boron ie PROBLEMS 1. Density of orbitals in one and two of rk i () Show that the den tals of a free electron in one dimension is : Duo =U : 66) where Lis the length of the 1. (b} Show that in Wo dimensions for a square ofacea A, fe) = Amjsn? , 6 Independent of Fermi ges. For electrons with an energy « > anc, here m isthe rest mass ofthe electron, the energy is given by ¢ = pc, where pis the momentum. For electrons in a cube of volume V = L? the momentum 's of the for (ni/L), multiplied by (n+ 1,2 + (a) Show that in this extreme gla ‘energy of a gas of N electcons i given by pm hne(Snfn)" 89) Problems where m= NYY. (b) Show th the total energy of the ground st gasis Uy = Nes (89) nt if fe Physi 47,542(1928), Pressure and entcopy of degenerate Fermi gas. (9) Show cloctron gas inthe ground state exerte a pressure sel 9 = OEE?.E (HY v0 Notice fate ~» O36 e+ 0, 4. Chemical potential versus temperature. Explain graphically wh ‘curvature of 1 versus + is upwatd for a fermion gas in one dimension and sovnward in three dimensions (Figure 77) Hint: The D,(e) and Dale} curves are diferent, where ®, is given in Problem 1.1 wil be found usefol to set up the integral Tor N, the puntber of particles, and to consider from the eraphs the behavior ofthe integrand between 2210 temperature and a finite temperature S. Liquid He as a Fermi gas, Thestom Hehas spin I = {and isa fermion. (@) Calculate as in Table 71 the Fermi sphere parameters op, er. and Ty for foe T EOL by A.C. Andecon, WR (1963); see also Figuce 718, Ex fe are given by J. Wilks, Properties of liquid id by J.C Wheatley, “Dilute solutions of "He in *He 1967, peratutes,” An of reftigerators based on *He-“He miatures are reviewed in Chapter 12 09 cryogenics; such reffigerstors produce steady temperatures down to 001 K ‘in continuously acting operation, Tow tem inciples 6, Mass-radive relationship for white dvarfe Mand radius R Let the electrons be degen are nondegenerate, (a) Show that the order of magnitude of the gravit self-energy is —GM/R, where G is the gravitational constant. (If the mass density is constant within the sphere of radius R, the exact potential energy is 29no so fae ttt Pure He otf z fA anne = [preted 5, Hein tte mS | er 30 ee 505 Temperature, in K Figute7.18. Heat capacity of igi “Hein guid thehorizontal lead of a5 percent sluton of (on the vertical ass C/T, and iis. Thus fora Fe ie are horizontal, id “He indicates acts a a Fermi gis; the degenerate region at low nondegenerate egion at higher temperate, ne experimental points for the solation is drawn Tr = 0331 K, which agrees with the ealeultion fr fee atoms ithe token 35238 times the mass ofan atom of "He, Cor Aine 5. Physic 36 (1968), ind My is the mass of a proton. ( energies ace ofthe same order of Protems Heat cupaeity, in units of W ‘mass is equal to that of the Sun (2 x 102g), what isthe de ‘dwart? (¢ I is believed that pulsars are staes composed of a as of neutrons. Show that for a neuteo " the value of henumbve fons we assume is given by the result of Problem 4 which i Nw 2404V0%/n203, Find the ton mode of lowest 3 described as photon condensate it Whi caleulated heat capac! ee tal curve was below te is 1own in Figure 7.12. Th a leat Roseand Bose Geses "wvcen the two curves is matked: It is ascribed to the effect toveea the ators none dimension Caloulite bosons, 2 for N42) for @ one: show that the integral does not converge. This result suggests that a boson grovnd state condensate docs not form ion. Take = 1 for the calevation. (The problem sh be treated by means of @ sum aver orbitals ona fini be great lergies & = pe, where p is, 2 Bnhjp. Problem 2 fon the assumption that ¢ = pe for a ‘of equal volume. (a) Use the standard vi fof N, Assume that the ‘encegy of the pro the value of N. A care value of N, but to a B.D Caayton, Pr 1968, pt theorem argument to predict the ole star is ionized hydrogen, but neglect the compared to that of the elecirons. (8) Estim Astrophysical concepts, Wiley, 1973, 11, Fluctuations én a Fermi gas. that CONF) = eNO = ND), oo if CN) fs the average number of fermi Ductuat energy s0 as in that orbital. Notice that the ‘energies deep enough below the Fermi ion, AN = N —~ CN), END as in (1 average occupancy system, ten from (5.83) show that CAN?) = QNDE + GND) 02) ‘Thus if the occupancy is large, with (IN) > 1, the factional fluctuations are Of the order of unity: ((AN)?)/QN)? = 1, so that the actual fluctuations can be enormous. It has been said that “bosons travel in flocks.” The frst edition of this text has an elementary discussion of the uctuations of photons, 13. Chemical potential versus concentration. (a) Sketch care versus the number of part lly the chemical es for a boson gas in volume V at yperature Include fot a system of fermions. classical and qui 44. Two orbital boson system. Consider a system of N bosons with of twice the popul and make what appro Ifthe atoms in a gas ) early successful Boulder, MIT, and elsewhere, Such expe extraordinarily comples, mark the exciting forefront of the ‘on BEC experiments and theory is on the Web, One set of experiments (MIT) ied with a beam of sodium atoms n oven at 60K at a cone em”. mis to be tapped reduced the release, using is in good agreement with th th this technique the signature of Bose-Einstein condensation is the sudden appearance of a sharp peak of atoms 28 the temperstore is Aecreased through rp, The peak comes from light scatered by atoms in the condensate; the wings of the Tine from light scattered by atoms in encitedChapter 8 Bs Heat and Work ENERGY AND ENTROPY TRANSFER: DEFINITION OF HEAT AND Work 2 HEAT ENGINES: CONVERSION OF HEAT INTO Work Carnot Inegu Sources of Irrevesi Refrigerators Air Conditioners and Heat Pumps Carnot Cycle Example: Carnot Cycle for an Ideal Gas Energy Convers ‘Second Law of Thermodynamics Path De 10d Work Ircever Exan HEAT AND WORK AT CONSTANT TEMPERATURE OR CONSTANT PRESSURE Isothermal Work ie Heat and Work Example: Electrolysis and Fuel Cel ‘Work Chemical Work for an teal Gas ‘Magnetic Work and Superconductors26 Captor 82 Heat and Work Refrigerator Energy end Entropy Transfer: Definition of Heat and ork ENERGY AND ENTROPY TRANSFE! DEFINITION OF HEAT AND WORK feat and work are two diferent forms of energy transfer, Heat is of energy to a system by thermal contact with a reservoir. Work isthe transfer of energy to a system by a change inthe external parameters that deseribe the system, The parameters may include volume, magnetic field, fi sravitational potential. The eason we di when we discuss energy conver transfer feom work will be clear work. The Industrial Revolution was made fh converts heat to work. The int nal com serves him, is a to convert heat to work. The problem of understanding the sleain engine gave sse 10 much of the development of thermo Enetgy conversion remains one of the centr because most electrical energy is generated from heat. ‘The fundamental difference between heat and work is the difference in the entropy transfer. Consider the energy transfer dU from a reservoir (o a system wth which the reservojy fj, thermal contact at temperature x} an enteopy transfer de = dUjr accompaties the energy transfer, according to the argue ‘of Chapter 2 This energy transfer is what we defined above as heat, and we see is accompanied by entropy transfer, Work, being energy transfer by a change as the postion ofa piston-~does not transfer any entropy tothe system. There ie no place for entropy te come from when only work is petformed or transferred, However, we must be carcful: the total energy ef two systems brought into ‘contact is conserved, but their total entropy is not necessarily conserved and ‘may increase. The entropy transfer between two systems in thermal contact is ‘welldefined only ifthe entropy of one system ineceases by asmuch as theentropy fof the other decreases. Let us restrict ourselves for the present to reversible processes such that the combined es ‘constant Later we will generalize the discussion to irreversible processes which are processes in which the total entropy ofthe two systems increases, as in the heat flow example in Chapter 2.28 Chapter 82 Hest We can give work, Let dU by ive expression to the di energy change of a system during a the entropy change, and ¢ is the temperature. We define 0 = we As theheat received by the syst Process. By the principle ofeonservat of encesy, dU = 4W + aQ, ey ch sys thatthe energy change is caused partly by work done on the system by heat added to the system from the cservoin, Then AW = WU ~ AQ = aU ~ we 6 system in the reversible process, Our reasons for work by dQ and AW a below. Forda = 0, we have pure work; for HEAT ENGINES: CONVERSION OF HEAT into WORK Cano nee. Hea and work hve difeen role proceses tecause ofthe difeence sence of the dtfecence 6) All ypes of cach othe, because energy conversion entropy transfer. Consider two con rk are freely convertible into mechanical work ans (8) Work can be completely conve feat cannot be completely conv st necessarily stip the entropy from converted to work. The entropy removed front bbe permitted to pile up inside the d ely be removed from the device, The on es? Conerson of Heat ino Wek " Rea thin the atiount converted to work, and to eet the excess iapat provided that it is ‘al energy-conversion devices operate in cycles, and thea0 Chet 8: Heat nd Work ; Naw sue INH gn ncopy contained inthe device vares periodically with tie, Such @ yeic device is called a heat engine, The colthiltion engine is an example “The entropy contained in each cylinder is at a minimum near the beginning ning of the exhan h the device returns ey ure Gan be converted into Work? The input entropy asso ‘he input heat iso, » Oy/y. To avoid confusing signs, we define in nergy, heat, and entropy Rows as po entropy is equal to the input enteopy: eae or Ole sothat = (6/00 o ‘The work generated during one cycle of a reversible process isthe difference between the heat added and the waste heat extracted: We QO = [1 (alma ~ 2 @ “The ratio of the work generated to the heat added in the reversible process is called the Carnot efficiency o “his quantity i named in honor of Sai Carnot, who derived it in 1824. Ke was 2 remariable feat: the concept of entropy had not yet been invented, and ‘Carnor's decvation precedt by some 15 yeas the recogition tha heat 2 form of ene. “The Carnot eficieny isthe highest possible valu ofthe energy comersion effcleney = W/Q4the output work per unit of input heat, any cyclic heat” eos Engiet: Conrerion of Heat ina Work 231 Ootput Figure 82 Eniopy and enerry ow in el bet en PY ow a the lower tp inflow atthe higher teniperatre engine that operates between the temperat id ty. Actual be cf ures 74 and ¢, Actual heat engines have lower efficiencies because the processes taking place within the device are Rot perfectly reversible, Entropy will be generated inside the device by irevers- ible processes. The energy-entropy flow disgram is modified as in Figure & 2 We now have three inequ: 7 a ese es © Qe = Oulu); W=Q-Os" Ft = ns (10)a Chapter 86 Hest and Work The at nergy 6 version efficiency y obeys the Carnot inequality TLL 1 = IQ, StH tes) He. | ay ScaSnAnennan = ne only in the and ejects heat at of reversible opers efficiency is obtained under reversible operation, Thi creases with increasing ty/z, but w 100 per The low-temperature waste hes engine must ultimately be ot be below the environmental iency requires n input tempera tures in practice are power plant stearn tuebines, nly for years, the upper temperature ed by various materials c which are expected to operate cont limited to about 600 K by pi io) @ @ Reiigerstore Irreversible expansion without work oe Net work Refrigerators are heat engines perature 10 fi Eniropy flow diagram of a reversible irony is 3 oma lowae Clapier 8: Heat end The eneray cy (7), But a of ns ‘consumed is Wa Q-q=% ‘The Carnot coeficient of refrigerator in place of (8). Further, and W = - O12 [ovied ~ 10 = 2", = Ore so that = QW 1). Two of them are iereopic, om 2920 Chapter 83 Hest and Wook Path Dependence of Hoot Work ut oop inte ais tothe area fine rectangle gue 85. We have = +044 atin Wes Mt iy = Whee Was = Ma We =H + Oa + Wouy SEMA On + Mow = Moy = apoattyi¥). en 9 = hi) Teun “The eat absorbed fom, was ges (20, s0 that HQ, = (0. ~ aD which jus the Comet relation (1). Energy Conversion and the Second Law of Thermodynamics ‘The Carnot (0 work and on the performance of refrigerators ace direst consequences ofthe law of increase of eniropy. The second law of thermodynaraict usually is fo it mention of entiony. We stated the classical Kelvin-Planck formulation in Chapter 2 “Its impossible for any cyclic process 10 occur whose sole elfect is the extraction from a reservoir and the pesformance af an equivalent amount of work." All eversible energy conversion devices that operate between the same tem peratures have the same energy conversion efficiency m = WW/Qy. Were this not 50, We could combine two reversible devices £m Woon — Qsner < Quer + 63) in agreement with (28) and (29) 2aMe area A, ea Ay Pty = Pedy Figure 89° systems fer the process o be rexeribie, ishichonfynotk but no beat is iransterred need not be atthe sane stare ‘stems. This is not the only soutee of irrevers ‘eat transfer, not involving any work, ‘wo systems having different tempera Chapter 2 In this process heat is tanstrted from a system at at the lower temp Ke Tp, We haves Uy = 40 & aA, The newly created entropy is irceversibe iit takes place between rs, We worked out an example in 10.9 syslem, Wy = We= tyes MQ, +40, = 0. (38) ‘eet and Work ut Consent Temperature or Constant Pressere BRAT AND WORK AT CONSTANT TEMPERATURE OR CONSTANT PRESSURE Chetty F = U~ se of the system, For a reversible process because de =0, so that AW dU ~ dQ = dl = dco) = dF. Thus in such processes the Helmho! on, more appropriate than the rocess in terms of the Helml Additional work that is oq system to the reservoir. Ofte for the ideal the work de fee energy ie the ange in an isot insystems open to pr ‘a isobaric process. A simple ex qui fray U. When we treat an isoth the major ie Helmholtz tree AQ = re = dtro}, cy ssatural energetic att of the work: mal process, and at take place essure is Said to be idas in Figure 8.10, the vapor he atmosphere pressure, asChapter: Heat and where the pressure on te piston is the external atmospheric pressure. Ifthe system changes its volume by dV, the work — pul” = —u(pW) is part of the total work done on the system. I positive ment and is fe to subteact ‘ork performed on the system, defined as AW we ANY § dlp) = aU + dlp) ~ AQ er where we have defined a new function He (38) pressure thi 38) is the see the Surroun the space to be occupied by the system. l there are other kinds of work besides t en. such a process, because no effective work is done, The heat of vaporization enthalpy difference between the vapor phase and the liquid phase ) Processes at constant temperature and constant pressure. Then dQ = ula = dca) and the eltective werk performed on the system is, from (36) and en, AW’ = dF 4 dlp) = a6, @) where we have defined another new function G=F4pV=Ut pow, (4) the Gibbs free energy, ‘The elfective work performed in al consta reversible process temperature and pressure is equal to the change in the Gibbs fire energy of the system. This is particulrly useful in chemical reactions where the vo nges as the reaction proceeds at a constant pressure The Gibbs free energy is used extensively in Chapter 9, and the enthalpy is used in Chapter 10, cellthehyéeoge ons nd fom matesular Bydogen gas: 2H* $e Hy (wy electrodes ‘lease of molecular oxygen at and election they decompose water with the S0.> + H,0- sss theough an eletrolye, uh of water into gaseous 1g done at constant ‘emperature and constant pressure ww8 Chapter 8: Heat and Work ing of thee ‘The efestve work ceguited 10 decompose L moe of the molar Gibbs fee energies ofthe eactan 17 = AG = G{H1,0} ~ G(tis) - 46(04) (4s) ‘the Gills fee every diference AG es —2371Ipermote at room narra a betoraedty a cucen I hat ows under an external vokage het Q = -2N,¢ = ~193 x 105 coulomb. a Weeqeate (4610 45}:0obiin the contin fo um voltage \olysis to take place This rites Ven ~AG2Ne (48) ster on the > Vouencess power (V — Va) ve 1 cape. and fr ¥< Vy nothing slestrodes as porous sponges igureB 121 Sucha device produces external cueent will were used as power produced drinking voltage Vf betwesn theelecteae flow. This trang four ets ued Nand Ni isan lectolysis call operate in rogen and oxygen shacatertisofanleteoytie ing the to oper 720 (Chapter €: Meat and Work Chemical Work Work performed by 1 transfer of particles to a system is called chemical ied with the chemical potential ransfered, the number of particles in the system is one bles on which the energy U depends. FU = Ulo,¥.N), 1a reversible process aU = do ~ pd + pl, (9) by the thermodynamic identity of Chapter 5. Here we have ceplaced the pi derivatives by thee familia equivalents (Table 5.1). By our definition of he the tds ferm represents the transfr of heat and the —plV and judN terms of work, all understood to be reversible: A = ~pl¥ + pil 0) The ~ pa¥ term is mechanical work iV, = wd, 6) Iethere is no volume change, dV = 0 particle tener there are usually two systems involved, both in contact ‘witha heat reservoir, and the total chemical work isthe sum ofthe contributions from both systems Inthe arrangement of Figure 8.142 pump transfers particles from system 8, to system 35. The chemical potentials are yi and py. If dN = dN, = AN, is the number of particles transfered, the total chemical ‘work pesformed is work is chemical AW, = dey + dWey = dy + Had te — (ay, dy = D)and it ‘The result (52) summarize the pro @ 7 1 potential of a system is the work required to transfer one particle into the system, fem 2 reservoir at zero chemical potential. (©). The difference in chemical potential between two systems is equal to the ‘et work required to move a partite from one system to the other. Figure 8.14 Chemial wook ithe work perforce when yom one sy (9 Ithewwo systems are in diftesive equi potential; no work is required to move a partide from one sy (G) The difference in (Chapter 5) between two barrier that maintains the ence the mechaneal work pet ident the result (53) The 251a2 Cheprer 8: Hest and Work Magnetic Work and Supercondactors B41) in gauss fonk and Supercondaciors 23 )8 af a Bas Ni fey g 203 . ae a 6 ge g aad 5 eee ¢ Wee = ° et a hs cy inthe supercon Tin KE Cy} city af gaia in the normal ad supereo TB event Her Cy ofthe het igure 88. (a) The heat cx fst f(b) the electronic cxponential sh T0U fu L/D) 286 050 ol pendence 0 Cnn = rans ion it isthe electconie system rather than the erystel structure ofthe metal ‘undergoes a phase transi © superconducting tates The! ‘ pronowneed discontinuity at the onset of superconduct ty is destroyed by a A be the phase of the supercondu ‘energy of the superconduct 1c magnetic field as we show free energy of the normal phase is approximately independent of the field, Eventually, as the field is increased, the free energy of the super- ‘conducting phase wil exceed that of the normal phase. The normal phase is je phase, and superconductivity is increase of the fiee energy of a superconductor i led asthe work requiced to reduce the magnetic field tozero inthe interior of the superconductor; the zero value fs required to account for the Meissner effect. Consider @ superconductor in the form ofa long rod of uniform cross section inside a long solenoid that produces a unifore field B, as in Figore 819, ‘The work required to reduce the field to zero inside the superconductor is equal to the work req in the superconductor a counteracting od tocreate w field ~ B that exactly cancels the solenoid field, We know from electromagnetic theory that the work per unit volume required to create a field B is given by s) Waal = BPs (55a) (cas) (590) 2s286 Figure 8.20. The fe energy density Fy ofa Chapter 8: Heat ont Work ‘enorgy density by which the free energy density inthe bulk superconductor of an external magn ‘experiment at cone hho comparable free energy increase for the normal conductor, is no seroening ofthe applied field. Thus () [Fate ~ Fst = B26V2 ne (56a) or (cas) [rte ~ Belly = B20. (S6b) In a plot of the free energy density of both phases versus the magnetic field (Figure 820), the fece energy of the superconducting phase sy rise bove that of the normal phase, so that in high fields the specimen will bein the normal phase, a8e is no longer the stable “This ts the exp! n of supeece field &, With increasi femperature the fee enceey Wierence Prodtens SUMMARY 1, Heat is the transfer of energy by thermal ¢ le process dQ» edo. Work is the transfer of energy by a change in the external parameters that describe the system. The entropy transfer in reve ly work is performed and no heat is trensferred, act with a reservoir, In a 3. The Carnot energy conversion effciens imit to the ratio 1/Q, of the work gen The Carnot caethic to the he = dito the srator perfor io QV of tl work performed on rooess is equal to the change ia the fel of the system, 6. The effective work performed on a system at consta Pressure in a reversible process is equal to the energy G5 Ure + pv ee eneigy Fz U ‘The chemical work performed on a system in the 1eversi les tothe system is pul. le transfer of hangs in the free energy density ofa superconductor (of Deaused by am external magnetic field B is 84/2) in SI and B82 in CCS, PROBLEMS at for a reversible heat pum ered inside the bu ergy required ing is given by the Carnot efficiency (6): tween the temperatu heat consumed at tu, t0 the 257a8 Chaprr 8: Heat and Werk 2. Absouption ceftigevator. Yn absorption retigerators the energy driving the process is supplied not us work, but as heat from a gas ia > ty. Mobile home and cabin etigers uel. (a) Give an energy-enteopy flow diy such tor, involving no work at hree temperatures ty, > ry > (6) Cel heat extracted at ¢ ~ ry, where Qyis the lea engine. Consider a Carnot et work substance @ photon gas. (a) Given ty and 1 Y, and Vp, det Vand ¥.(0) WI at Qy taken up and the work dane by the gas during isentropic stages cance ea wark done by taken up at x, and show te—reftigerator cascade. The ef improved by lowering the t valuet,, bel heat engine isto be ature of its Low-temperature reservoir to a ty by means ofa reigerator. The is part of the work produced by the heat engine. Assume and the rtrigerator operate reversibly, Calculate the of the net (available) work to the heat Q, supplied to the heat perature ty 15 possible to of ner net energy conversi S. Thermal pollation. A a water temperature T, = 20°C is to be used as the low temperature ceservoir of a large power ph ature of T, = 00°C. If ecological cor at can be dumped into the river to 1500 MW, output that the hhot-steam technology is have on the plant 6. Room air conditioner. A room aie condi ator between an outside tempe ‘The coom gains heat fro wed by the air condi dy stale er operates as a Carnot cycle iuperature of the room is Tr = (Ty + PRA) ~ [(T, + PAP - Te) {8) Ifthe outdoors is at 37°C and the room is maintained at 17°C by a cooling ower of 2KW, find the heat loss coeficint 4 of the room in WK". A good oe Frablome ing inside a 19f cool below room temperature? 8. Geothermal energy. A very large mass M of porous hot rock © ized fo generate electricity by resulting hot ie temperature of the rock drops, according to dQ, = —MCuT,, where C is the specifi heat of the rock, assumed tobe temperatore independent. ITthe plant operates at the Carnot calculate the 1 W of electrical energy extractable from the sock, if the temperature of the rock was Tye plant i 0 1 down when the emperatur 80 Ty = Ty. Assume lower reservoir temperature T, stays 30k), C= and explai aT. Assume it were possible to enol & ‘of reversible refrigerator perature reservoir, and for which the i ‘energy Fequired, Inreversibte expansion of a Ferm! gas. Consider a gas of N noi spin fermions of mass M 2s expand irreversibly v.81 {or the clasical limit to apply? Estimate the factor by which the gas should be ‘expanded for its temperature to seitle to @ constant final value. Give numer ues fo a9Chapter 9 Gibbs Free Energy and Chemical Reactions Saas Smo ree ee ARE GIBBS FREE ENERGY Example: Comparison of G with F EQUILIBRIUM IN REACTIONS jum for 1deal Gates Example: Equi of Atomic and Molecular Hydrogen Example: pH and he fonization of Water Example: Kinetic Model of Mass Action SUMMARY. PROBLEMS, 202 265 26 261 209 269 210 m m 21 273 2 m a 2611a Chopter 9: Gibbs Pree Energy and Chemisal Reactions free energy F constant volume roduced jn Chapter 3 describes a syste 1ny experiments, a GeU nt + pW 0 Chemists often call 0 ‘thermodynamic potent ‘The most important property ofthe: for a system Sia equilibrium a reservoir O, The dilferentisl of Gis the free energy, and physicists often call bbs free energy AG = dU ~ xo ~ oie + pa¥ + Vip. Consider a system (Figure 9.1) in thermal contact with a heat reservoir at temperature « and in mechanical contact with a pressure reservoir Ot, th ‘maintains the pressure p, but cannot exchange heat, Now de = and dp = 0, sothat the differential dG ofthe system in thees um eonfigueation becomes Gy = dU, ~ doy + ply ® ‘The thermodynamic identity (5.39) s doy = dU ~ py + pl @ so that (2} becomes dGy = dN, But dNy ~ 0, whence d0g=0, | “ Gis Free Exergy sysem Meat reseroie [27 | Heat esencie a 7 ay \ aro equalize presiore Pressure reseevaie 8. isd condition for G, (0 be an ext tions at constant pressure, temperature, and past fore, the natural variables for ther than a maximo follows di the entropy in (1): Any iereversible increase © and thus decrease Gy With 2, 6) ‘The diferent a (Q.a+(2) @ Comparison of (5) and (6 ives the relations OG /0N)., = w a OG/eIn5 = 0% @ 28264 ing bbs Fece Energy and Chemical Recctions Cafe, = ¥. Three Maxwell rea see Problem 1 Inthe Gibbs ree energy G = quantities: theydo not change valu But U, 0, Vand G ate linear in when two ident 's may be obtained from those by cross diferet ion; ~ t+ pV the variables cand pace intensive ie when two identical systems are put together, of of particles their value doubles where @ is independent of WV because al pressure and tempera ibs foe eneray = Wein) + WNo(n.9) = Nips) oes not in the process, tt lows from this ar CGEM. = gra. ay We saw in (7) that oy 03) ‘component system ie equal to the al yas, soe 21) below. GIN. Lor ‘species is prese all species: «) Ts Free Eneray The rmodynamic identiy becomes tds = dU + pV = S walng as and (5) becomes AG = SyydN, ~ ode + Vip. We shall develop the theory of cheascal equilibria by exploiting the property that G = SN isa minimum with respect to changes im the distribution of smolecules at constant, p. No new atoms come foto the sys on; the atoms that ace present redistribute themselves fom one molecalor (CELONIy = pl.¥) ro) and GION), , = we) i) found in (618) hat fora ideal gos HIN) = tlos(N)Vng) ©) wile F = Np system is kep!ateonstant volumeas: 81 increased, Instead, fom (624), Fe, ~ Haflog(W/tig) — 1 eo) bbs fe nee forthe ideal gs is O(c.) = F + pl m Neflogipfing) ~ + Ne = Nelogipfing) , @ ies gos wi Ni = ple. Wer ) he chemise Hop) = clostpfeng) , @26 (Chapte 9: Gibbs Free Energy and Chemical Reactions isle Ofcoutse, veare ee ovsitey as cther EQUILIBRIUM IN REACTI We may write the equation of a chemical reaction as wap b ake bod A=, 03) Ends, ey where the 4 denote the chemical species, and the ware the coefcients of the species inthe reaetion equation, Here vs the Greek letier nu, For there Hy + Ch, = 2HCIse have AveH Ape Ck; AySHCh y= “The discussion of chemical equilibria is us conditions of constant pressure and temperat 4G = ¥ wylN, — oe + Vip 9) Here pis the chemical potential of species jas defined by ny = (B60 constant pressure dp = Oand at constant temperature dx = O;then (26) reduces to = Eos, on ‘The change in the Gibbs free energy in a rea poteatiats of depends on the chemical 1 reactants In equilibrium G is an exteemum and dG roust be Ei iam for leat Gases ge AN, in the number of molecules of species is propo vinthed WA; = 0 Wemay write din the fore = yd, 3) ere di indicates how many times the reaction (24) takes place, Th 27) becomes sed a8. (3) In equilibrium dG » 0,20 that 60) jum in a transformation of matter at constant y= alogny — loge), on ‘where ny is the concentration of species j and = mest), 02) which depends on the temperature but not onthe concentration. Here Z(t) ernat pattion funetion, (6.48). Then (30) can be rearranged as Teylozn, = Lrylosey, 7 (3a) 7 7 nc equa esce the reaction doesnot proced fr Mealy aed earespected 26768 Chapter 9: Gibbs Free Energy and Chemicol Reactions loony? = Stage (33) ‘The left-hand side can be rewritten as logy = tog : (336) side can be exprested as tog Fes = log K(0 (Gx) wm constant, is fa perature, KG) & [Ing expl—y,6 ey 4 because the internal fice enerty is F, C4 weave N) = ~tlog Z,int). From (33ed) and = Kin), 69, Krownas theta of mas ction, The result saysthat the indicated product ef the sis. function ofthe temperacure atone. A change will force a change ia the equilibeium other reactants, ant K(t) in (34), to choose in| 4 consistent way the zero of the internal energy of each reactant. We need lecy here because the value of each part depends choice ofthe zero o different eras for the the energy oF free energy © this, but it does not 'out& conscious effort on our past, For a dissociation reaction si as H, 5 2H. the simplest procedures to choose the 26f0 oft of eat molecule) t0 coincide ) at rest. Accordingly, we plac le at Ey, where , To calculate the equitibri um for Ideal Gases ‘action to dissociate the composite pat and is taken to be positive, of the he reaction Hy = 2H or Hy = 2H = Oo he dimen at hyseogen into atomie tydeogen is in terms othe internal fee enerty of, perm eee te zzo of energy is taken for an fT atone more negatives FH} and the ion of Hi the i absote zero, fopy associated wi icles compeneser she los i r_ Tn igul water the ioniation proces HOH 4 Ne 0 coon temper product [HO YfOH) = 10 1s desctibat mol? I> , ey 26920 (Chapre 9 Gis Fre Emery and Chm Reatians liens for He a \whegetheiopisconcentatons are giben tent tnpurewater(H*] = (OHA] = atthe end ofthe tseond step ~ the rection proceeds, A reaction A+ B= C may ev ‘efor the Eeaction an occur A ar B may ba to negatlate a potential taeiee, ain a Figure 92. The bree height scaled aya flt = ty ~ Dian Alivasod energy where the rte donstant C describes thefomation of AB in a 3 eanslantD describes the overt proces tetera decay of AB ions ofall constiutens are constant tain = DIC 5 @) (athe aw of mast action that we jon of A and B, but it ‘Schematic coordinate AECAE, AE} BOABEE Figure 9.2. The quantity Ad measures the enery evolved in there z anid determines thee io (Altay (C)-T tion energy ithe eight ofthe pont arse to bs nepoited ‘before the eatin can proceed aod it determines the ate at which the reaction takes ple. + The domiast pecs pete t mow ety H* 41,0, acomple of water mleclsurrouné= lnyonegeoon Avonew iu pven by. igen sna 'Be Marj, Pr Roy. Soe (Lowden) AE. stag(Cheper 9: Gibbs Free Energy and Chemical Reactions SUMMARY ‘The Gibbs frve energy 2 (Gli = ~ 2 Glo.) = Nuts) 4 8 function ofthe temperature alone, PROBLEMS, 1, Thermal expansion near absotute zero. anal (wo subscripts ‘omit those subscr approaches zero as ¢ 0. GaU~wsny temperature and pressure, ¥ law of mass action for a chemical reaction is that (@) Prove the theee Maxwell rela (eV (00), & —(ealap, , larly in (45b) and (45e). 1s common to sc equalities. (6) Show Problems proton H*. (a) si sly the relation (ICH Y/0H] s ngeap(—ye), concentration of protons is equal to that of concentration i given by (2) = (AP ng!" exp{— 1720, (48) Semiconductor physics in connection with the ‘toms that are donors of electrons, (1) The exponent involves f and not fy ‘Boltzmann factor" problem, Here The electron concent wydrogen atom concentr (©) Mvwe add excess electrons tothe system, then the concentrat will decrease ergy. square root of the (6) Let [Hlesel] denote the equilibrium concenteation of H atom: first excited te, which is UI above the ground state. Compare ns atthe surface of the Sun, with (M] = 10" cm=? ation of donor impurities in semiconductors, ‘da donot) introduced in place of a tetravalont silicon acts tike a hydrogen atom in ree space, but and an elective mass» ee playing the role of playing the role of the electron mass m in the energy and radius of the ground state of atom, and alsa for the 4, Biopolymer growth, Consider the Of tinear polymees made up o Hic basic reaction step is ‘monomer + Nmer ~ (N+ Ipmer. Let Ky denote the equilibrium constam forChapter 9: Gibbs Free Energy and Chemical Reactions reaction, (a) Show from the law of mass action that weconcentt sy ON = CYR Ke ) (8) Show fom the theory of reactions that for ideal exe condo solution} Herons ~ Pe ~ Fad 9) Here tN) = Oat}? , cy where My is the mass of the Nmer motecul mer molecule, (@) Assume N 3 1, $0 reaction to goin ules we need AF < ~O-4eV, approni fed in Nature, but an ingenious pathway is ion. An elementary discussion is given by C.K Partite-antipavtcte equilibrium, (8) Find & mal equi reaction A* + rant in the pa may be electrons and po and antiprotons; or electrons and holes in a semiconductor Let the mass of either particle be MY neglect the spins of the partes. The minimum energy lease when A cotibines with A” i. Take the ro ofthe energy scale asthe les presen. (b) Estimate in em”* for an electron (or & hole) in a semiconductor T = 300K with a A such that A/c = 20. The hoe is viewed asthe antiparicle to theeletron. Assume that the cletron concent is equal to the hole concentration; assume also that the pails are in the tlassieal regime. (¢) Corcect the result of a) to let each particle have a spin of Partstes that have autipatiles are usually fermions with spins of Chapter 10 Phase Transformations VAPOR PRESSURE EQUATION 6 Derivation of the Coexistence Curve, p Versus ¢ 78 Triple Point 28 Latent Heat and Enthalpy 24 Example: Model System for Gas: ras VAN DER WAALS EQUATION OF STATE. 27 Method 38 al Points forthe van der Waals Gas 289 Gibbs Free Energy of the van der Waals Gas 21 Nucleation a Fecromagnetismn 25 LANDAU THEORY OF PHASE TRANSITIONS 298 Example: Ferromagnets 302 First Order Transitions 302 SUMMARY, 04 PROBLEMS. 305 1, Entropy, Energy, and Enthalpy of van der Waals Gas 305 40s 3 305 4 305 5 305 \ 6. "Thermodynamics of the Superconducting Transition, 306 17. Simplified Model of the Superconducting Transit 307 8, First Order Crystal Transformation 307 the ensopy pr ata. the section on Frtomagaesm,Chapter 10: Phase Transformations VAPOR PRESSURE EQUATION The curve of pressure versus volume for a quan er at constant perature is determined by the fee energy of the substance. The curve is called an isotherm. We consider the isothstmis ofa real gas in whi ‘molecules interact indet appropriate conditions c ‘stociate together in aliquid of solid phase, A phase is a portion of a system Uhat is uniform in composition, ‘Two phases may coexist, with a definite bounday between them. An isotherm }OW a region inthe p-¥ plane in which ‘each other, Asin holds also for the solid ges eq Liquid and vapor may coexist on a section of an isotherm only if the femperatuce of the isotherm lies below a critical temperature s,. Above the srtical temperature only a single phase—the Rid phase—exists, no matter how grea re is no more reason to call this phase a gas than pressure, ‘liquid, so we avoid the issue and call ita fluid. Values ofthe critica temperature for several gases ere given in Table 101 Liquid and gas entire extent of an isotherm to infinite pressure; they enexist at most only along he isotherm, Far a fixed t and fixed number of at bbe a volume above which all atoms present ate in the gas pl F the coexistence of two phates are the 10 systems that are in thermal, ditfusive, sigur wd orm, Vapor Pressure Equation | |cmanscne Tigeid Liquid + gas Figare 10.1 Prestucevolume isoterm of ret ga84 temperate suc ‘worphase region bu the volume mi and ts vapor Piston down, resureChapter 10: Phase Tramformations and mechanical contact. These condi sare that ty = tatty = fat Py for liquid and gas, =P BEG NAM Me Pye « where the subscripts f and g denote the liguid and gas phases. Note that chemical potentials of the same chemical species in the two phases must ‘equal ifthe phases coexist The chemical potent Dressure ard common temperature of reevaluated a and’ gas,s0 that @ Ata general point in the por plan the liquid phase alone is sta Metastable phases may occu two phases do not coes! and if jg Pog) (2 op)” (op) ich isthe dle equation ofthe coexistence euve or vapor pressure The derivatives ofthe chemical poten in terms of qu : o which oceur in (7) may be expressed ies accesible to measurement. Inthe treatment of the Gibbs20 Chapter 10: Phare Transformations five energy in Chapter 9 we found the retations Gm Netra (BE) = vs @. “ne. ° the definitions DEVIN, seg/N ® forthe volume and entropy per motecul x2) NP Jw in each phase, we have ‘Thea (7 for dps becomes to ys Gait ay om Here 5, molecule from 1 cof the system ease of eniropy of the system when we transfer one iguid to the gas, and v, ~ 0, is the increase of volume len we transfer one. ial 10 understand ly 08, The derivative refers to the very which the gas and liquid eon vary as the volume is @ constant. Here Ny and N, are the quid and gas phases, espe 5, ~ § 18 elated diccctly to the Qua system to transfer one molecule reversibly fiom the liquid ‘585, while Keeping the temperature of the system constant (If heat is ot added to the temperature eas) The quantity of heat a = a5, ~ 5), uy wection between heat and the chenge of entropy in a reversible prowess, The quanti (13) Derivation ofthe Corsistence Curcep Verne ¢ ines the latent heat of vaporization, and is easily measured by elementary imetey, Welet «4 1 molecule is transferred from the liquid 3), and (14) t9 obtain ne as) his is known as the Clausius-Clapeyron ‘The derivation of this equation was a rem hermodynamies. Both sides of (18) ace i has been verified « acly useful form of (15) if we make two approx ty the volume eccupied by an atom ianor the vapor pressure equation 0 At atmospheric pressure u/s; = 10°, and the approximation is very good. (b) We assume that the ideat gas law so that (16) may be written es Ay = in i) With these approximations the vapor pressare equation becomes 202a Chapee 10 Phase Teas whence Bp = ~ Loft + constants where py is a constant, We defined Lo a5 the fone molecule, If Ly refers instead to om Ed = poexpl ct 20) lent heat of vaporization of PAT) = pocxp(—Lo/RT) , en where Ris the g2s constr latent heat atthe 00°C, a sebstontal variation vapor pressure of water and of i versus 1/7. The curve is near over subs R & Nog, where No is the Avogadro constant. For bid-gas transition is 2485 J g~* at O°C and 2260 regions, consistent wi x Kceticat pin i Liquid water atm 0G 1 . | tee oy 20 25°30 35 40 a5 50 10/7, in Ko Desvation ofthe Coexistence Carey Versus ¢ Pressure, in mm Hg Figure 104 Vapor presure versus temperature fr “He Aller H. van Dif fal, Journal of Research ofthe Nations Bureau of Standatds GA 12 1955), approximate result (20). The vapor pressure of “He, plotted in Figure 10.4, is widely used in the measurement of temperatures between f and $ K. ie phase diagrant of *He at low temperatures was shown in Notice that the liquid: ure T., vexistence cures closely horizontal below 1.4K. ‘We infer from this and (11) thatthe entropy ofthe liquid is very neatly equal to the entropy of the solid in this the entropies lou be so similar, heeause a much mote disordered than a solid, o that the entropy of a normal liquid is considerably higher than tha 283284 liquid. For another quantum I idsolid curve is negative at low temperatures itropy ofthe liquid is fess than the enteopy thas more accessibie states than the liquid! low entropy for aliquid because i approxi has a low entropy when + « rp because of the atoms have t Trip po lee y= = ty Consider an equ enclosed volume somewhat pressure isthe u perature is not identical aimosph ig temperatures depend fs the melting temperature rium vapor pressure of the two condensed phases. For water the teple point temperature is 001K above the atmosphere Pressure melting temperature; T, = 001°C w 273,16K. The Kelvin scale ‘stined such that the tiple point of water i exactly 273.16: see Appendix Zatent heat and enthalpy, “The latent heat of a phase transformation, as from wid phase to the gas phase, is ea of the two phases at constant pressu difference of H = U + pV between enthalpy, The diffe s the entropy diffrence eat is also equal to the two phases, where H is called the isl is dE = dU + pd + Vilp. When we exoss the ie curve, the thermodynamic identity applies: ta = dU pa ~ N 2 On the cocristence curve jy =. constant pressure Lm tha = AU + pAV™ Oi oH, ~ H, ey Values of H are tabulated: at constint pressere: 2). aw Integration of the heat capacity Deviation ofthe Coesistonce Curesp Vers ¢ Hm Joye es oo st RES rater ey Example: Model system for gessoi euitr sextet inthe ground states, ub sate ib ~€g refered 0 foe stom attest 2.» Pearl~ ~ ce] = expel Levon) 5 eet 8) Theler ery Fis y= Uy 19, = ~clogZ,, en The Gibbs ee eeigy in the solid pe atom, G,= U,~ 9,49, = Ft m= Ie ea) ray be inthe gas. 285(Chapter 10: Phare Transformations Figure 106 States ofan tom boud sea quency a The fy ate ey tis ashimed 1 bee below that of he gas phase. in the Solid is equa to that of the ane with whi the sold phate is uch snale than the volume ye of thesolidp, & Fy whence 2. expla) = Expl) = expl—togZ) = bs ent-fit~ at-top ‘We make the ideal gas approximation to describe the pas phase, and ve take the spin of the atom tobe zero. Then, fom Chapter 6, tate ka t(REy Go) ‘The gas isin equi sm withthe soli when 3, = 2y ot p= tngexp(—eq/t)[1 — exp(—her/t)]. GD i veinet nom (3.6) 7= (sia) Peo(—rft ~ e5(—ha 2) Vou Der Waals Equation of State VAN DER WAALS EQUATION OF STATE, ‘The simplest model fa Tiquid-gas phase teractions between atoms or molecules. By the argument thal was led 0 a modified equation of state ofthe form (P+ NqiV YY ~ Nb) = Ne, oy Known as the van der Waals equation of state, This is written for N atoms in volume V. The a, b are interaction constants to be defined; 1 meneure of the long active past of “The hard core repul he gas had available lume V — Nb, ‘bis the volume per molecule, We therefore replace the concentration n = N/V in 34) by NJ(V ~ NB) Thos, instead of (34), we have F ex —Neflog(ng(V — NbN] + 1} 03) is we now add a correction for the termolecular atractive forces tas a har, impenetrable cove Potential energy, & ar238 Chapter 10: Phase Transformations Mean Field Method ‘There exists @ taki He Approximate method, led the mean Feld method, for he etfect of weak tong range interactions fearon 0 [ave = ~200 6) hese ~2a denotes the ¥ intepral [4 9). The factor of two is 2 the hard core sphere of volume b fom the (36) we assume gas. That is, of the mean field ignore the increase ceneeay. In modern 18 correlations between approximation. By assuming uniform of concen 66) it follows that ie Interactions change the energy and the free energy of 8 gas of N’ moet les in volume ¥ by AF = aU = — it arranges th wo molecules is counted aly once i the total bonds is iva — (e109 The container of volume ¥ has N les, cach of value 8, The volume nat volume should be wed in pace of te coataner volume V. [o + NaIVY — Nb) = (40) in of stale, The terms in a the van der Waat ites 108 9, eal Points for the van der Waals Gas Weedetine the quai Rm aRT, Ym 3ND; x, = Bal2T,Chapter 102 Phace Transformations 3 a) temperature 5,. The equation may be written in terms of the dimensionless variables Bapins Wav; ted. Cy (Wee reo This result is known as the law of corresponding states. In terms of f, %, & all gases look alike—if they obey the van der Waals equation. Values of Gis Free Energy ofthe van der Weals Gar and b are usually obtained by fitting to the observed substances at the sane j, P, id. States of two are called corresponding states ofthe substances. ‘equation to high accuracy, point, the curve of f versus ¥ at constant # hat Porizontal point of infection. Here the local maximum and mii -V curve coincide, and there is no separation between the vapor phases. Ata horizontal point liquid pet; Pe teatwe ‘andthe critical pressure, critical volume, and critical temper Above 4.no phase separation ex Gibbs Pree Energy of the van der Waals Gas ‘The Gibbs free energy of the van der Waals gas exhi the liguid-gas phase ©. With G= F + ph, we NEY} + 1). (461 for Gare formas termes the phase coexistence The results of numerical ealevlations of G versus pare plotted for temperatures below and at the critical temperature. At any ‘temperature the lowest branch represents the stable phase; the other branches ‘present unstable phases. The pressure at which the branches eross determines the transition between gos and liquid; this pressure is called the eq ‘vapor pressure, Results for G versus x ate pl iguce 10.12. Figure 10.13 shows, on a p-V diagram, the region V < V, ia which only the quid phase exists and the region V > V, in which only the gas phase exists The phases coexist between ¥; and 14. The value of V, or Vis determi aby ‘he contion that (6.8) 46) along the horizontal ¥, and 4. This wil osu ifthe shaded area below the ine i equal to the shaded atce a2 Chapter 10: Phase Teanfor 040 04} Iti, oss oF 03 Pet Tig GN cerita pei 04) i Gas above the line. To soe this, consider dG = mole + Vip + ual We have dG ~ Vip at ea iference of G between @ jotal umber of particles. The 8) 2.436, ~ 240 ome, ~ 244 oa rail L n Soe a.a8 Cr lee o versus temperature fr van der Waals equation 085 p, Courtesy ofA. Mantis, 230 Fete aoe <0 one, -20 — : cat 10 -anl_t : . \ 8x0 aa 0s wn 6 12) Gibbs fee energy versus temperature for van dr Waals esuation of state atthe etc pressure pya a Feramsgretion ea (Chapter 10: Phase Tansfermations : a T = constant the suface fees energy per unit area or ses tension te liquid fow when Gi < Gy An unsble maximum of AG fs atained aio AAOMR = Om ~ 428 H Ay + Say , (50) Re= 2m 6 K must be overcome by a thermat ation inorder fr a nucleus to grow beyond Ris found hy sue (): of (AG), = (L6x/)fy (2) Ue assume th to express ay as ‘he vapor behaves lke an ideal gas, we can use Chapice § Aut clostofpeg « tegrali just the sum of theshaded areas, one negative and one positive. tudes of 60) = Gils) 1 horizont 1 dravn in the Biguce. Ine in the gas phase and p, the equilibrium vapor ~ ©). We use 7 = Merge” (9 estimate R, Pato bel x 10-%em, Dressuts of the bulk liquid (& for water at 300K and p = Let oy = 9 aro ~ ve, the by have a lower free energy than e moe tbl suc ee energy a ged drops postive and lends eens coca of in Ti At smal dapat the suc abe oan epconteuisewiheqetto tens Wectateiecanenctis 1 ire -rgy when a drop of radius R forms. If», is the concentration of molecu ih, Percomagnetisan A ferromagnet has a spontaneous imap Fo moment even in zero ap he gas, Howeres, i, mation to the toiporatute dependence of rmagnticmomentperunitvaon ibbs i _ (53) ac = . P here 2a cons = Gy = —/R may + 4284 @ Le We take the external applied feld as zero,296 Chapter 10: Phase Tronsfon ag. isoy, ~oa Figure 10.14 Excess fee energy of drop in of drop radius R, beth a educed uit, The eo is supersaturated because the gud has the lower free energy for this curve as drawn, but the euttaceenecay of sl drop ereates an energy bait that inhibits the growth of nucl ofthe iid phase. Thermal actuation eventually may earty nucle ver the bare Consider a system wi In Chapter 3 we found an ex: (M = nutanh(B)) In the mean field approximation (83) this becomes, fora ferromagnet, Mo mptant(ylM/) , ‘ concentration n of magnetic atoms, each of spin $ ‘ result for the (4) 3 ro) Feeromegretion 207 02 04 06 GS 10 oprinte forthe paramagnetic repon there vo eutenal applied mag ercomagnti region and ine mat bout m = 094 nye As ves up tom = 1, so that ed up a absolute ze. 8 transcendental equation for M. We shall sce that solutions of this equation with nonzero M enistin the temperature range between 0 andr, To solve (55) we write itin terms of the reduced magnetization m = Mjny and the eeduced femperature t's enu2, whence sm = tanh 66) We plot the right and left sides of as in Figure 10.15. Th temperature of interest. The eri ‘curves of M versus x obai is equation separately as functions of m {Wo Curves gives tle value of m at the temperature is t= 1, or t, = ny?d. The way reproduce roughly the features of the28 03 on Sos + jeation ot = together heoretal curve farspia fonike — ga _—_ oo a 0 Oi 04 06 08 ho we experimental results, as shown in Figure 10.16 for nickel: As magnetization decreases smo reases the led the Curte temperature, LANDAU THEORY OF PHASE TRANSITIONS Landau gavea systematic formulation ofthe mean applicable to large varity of systems! consider systems at const. theory of phase transi= ransitions. We mperature, 0 that their Helmholtz fees energy F = U = xo is a minimum in equi ‘The big qu respect to wh 0.consider all possible variables. We suppose system can be described by a single order parameter, the Greek tonina ferromagnetic in a ferroelectric system, the fraction of opy are tak not necessarily, Thee 1 ordee para rium value SoCs) is Lendan Theory of Phase Trenstions at makes Fy a m mata given rand the actual Helmboltz free energy of the system at + equal to that minimum FO = Fulfoc) S FUGA) it gy 658) ant, the Landa fee ne minimum, The towest of these determines the e9 fist order phase transition anothee mi vum becomes the lowest minimum as the Landau fanction is an even 1 Of in the absence of applied fields. Most ferromagnetic and ferto. ic systems are examples ofthis. We also assume that Fy.) ia sulin ved function of & that it ean be expanded in a power series in &— something that should not be taken for granted, For an even function of € as assumed, = gle) + Sash? + Again + lade +. (59), ‘The entire temperature dependence of F,(é) is contained in the expansion cooffcients go... sare matters for experiment or The simplest exariple of phase transition oe atemperatute ro. wwe take gi) Bale) ~ (© ~ rhe, (60) perature ange of interes ns, ures Because such & the thitd law, (FUR, = (© ~ ak + g45? = 0, (02) E=0 and = (ry ~ otaioa @)100 (Chapter 10: Phase Tramformations With a and 9, po energy fu ie root £ « O corresponds to temperatures above ro: here the Helmby num of the free 2 free energy is Fig) = gel 64 The other root, & = (xlatg ~ 1) corresponds to wum of the free {nergy function at temperatures below ro; here the Helmholtz free energy is FU) = els) = (2 Fe0ae ~ 20) 65) ‘The variation of F(e) with temperature is shown ia Figure 10.17. The variation of Fulgix) 25a function of for theee representative temperatures is shown in Figure 10.18, and the temperature dependence of the equilibrium value of § is shown in Figure 1 (Our model describes a phase trans ‘eter goes continuously to zer0 as the 1c order param. ‘ceased to. Theentropy Free energy Ar) fee energy Region of order 7 Region of parameter ¢>0 | Regions 0 order Figue 10.7 Temperature dependence ofthe fee enerey {or an idealized phase transition of the second onder. Landau fee energy te drops tlw fo etied by the logs 08 05} io 0) 04 7 02] —\4 a a rT) the Figere 1019 Spontaneous plat temperature, fora second-order pet that dfde-+ 0381 +0,a0 (Chapter 10: Phase Transformations Uhl is continuous at + = ze, s0 that there ig no latent heat atthe transition uperature éq. Such a transition is by definition a second order fons with a nonzero latent heat are called frst order siscuss them presenily, The real world coi second order transitions; conductors, ina remarkable diversity of best examples are ferromagnets and super. field approtination, Geromagaets satis the tom af magnetic moment pina magnetic fed, M1 2M a8 in (53), The iteracion energy densiy fy IMB = hae (66) rete he factor $s common to selene ey problems. The enteopy densi i given approxi by Problem 2235 O(N) ~ constant — AP nthe regime in which AY cep. Th © ee energy function pr unit volume is FM = ag —t 2) + terms ofhigher order. (68) ae Alte tasiton tempera the coefficient of AM? vanishes, shat lscussion folowing (6). cS characterizes fon at constant pressure is a First Onder Trassitons 303 Landau free energy Figure 1020. Landau Gceencegy fonction versus finite €as shown, For «below re laeger values of 38+ pees through x iseontinuous change in the pos extrema of this function are given by ute 10.0; roots of ef /2§ = 0 as in SC ~ tole = InslOe? # ae? = 0, ) Either g = Oor CE? + gek* = 0. (2 At the transition temperature the frce energies with § = O and wisos Chapter 10: Phase Transformations Fab! - 5.4 first order phase transition is characterize. CoN hysteresis, PROBLEMS id by a a | 4 enthalpy of van der Waals gas. (3) Show th aa ryinK tropy of the van dee Ws 3) and the order parameter & (Figure 10.21) does not go continuously to zero at + These results difer from those in the second order phase transition treated : cartier, where & went to ze10 continuously at to e te A fist onder transfor Ue grew i mation may show hysteresis, as in supercooling or supersaturation, but no hysteresis exists in second order transit « he eathalpy He U ++ pris HiGV) = Ne + NYY = Wait; es) SUMMARY Mig) = Ne + Nip — 2M « 1. The coexistence curve in the per plane between two plas Clausius Clapeyron e st satisfy the elk ae Tho ‘where Lis the latent heat and Av isthe volume dilference per atom between ton of ice, The pressureofwater vapor over ice is 3.88 mm the two phases, Hig at ~2°C and 4.58 mm Hig at 0°C, Estimate in Jumol™! the heat of vaporiza- tion ofice at =F 2. The latent heat = Hy — Hy, where H =U + pl isthe enthaty. c 3. The van der Wass equation of state is 4. Gas-sotid equilibria. Consider a version ofthe example (26}-(32) in which \We let the oscillators inthe solid move in three dimensions. () Show that regime (> fa) the vapor pressure is > (pe MalV IV ~ NB) = Ne 4 tshetantsen seo 2 (RY Bata o FAGs) & UGA) ~ 0189), Oana or fent heat per atom is ry ~ 4. 5. Gas-solid equilibrium. Consider the gas-solid equilibrium under the ex- sme assumption that the entropy ofthe said may be neglected over the tem- erature range of interest. Let ~tp be the cohesive energy of the solid, per atom, the energy and entropy are taken when the order parameter has the specified value &, not necessarily the thermal equilibrium value fo. The function Fi, ‘a minimum with respect to & when the system is in thermal equilibrium,Chapter 10: Phase Transformations Problems 307 Treat the ga8.as ideal and monatomic: Make the approxima accessible to the gas is the volume ¥ of * F, died by the solid, = ‘yen goal — i Noval PRE + Em Neg + NyLlosiN Vig) — 1), (8) @ og, = conductor ‘where the total number ofstoms, N = B Seeral thum othetee energy wthrcpct to F 04 S : testo | fy = tg exp(~to/t) 09) © Los — (0) Find the cour vapor pesue, tLe 85g 6 Mermadsnomics ofthe sapecondutivg wansiion (0) Show hat Temperature, K 1 4B2)_ 2, , “Red ee () 8 temperature Ty = L180 K the fee energy lower in the superconducting state The i hake ra of tansition at T,) The curve Fy is meas messed ina magaetic fi for B,. Because 8, decreases 7. The superconduc ‘so latent heat 2210 magreti sulicent co put the speci ia the nous isthe more 0 t0 zero, consistent eurveot B, versus 2? following conse merge, as shown UsGr). (3) Ther What tr bat © {wo enetgies are the same: Uy(s) = st associated wit fon when cartied out in a magnetic field 2 Simplified model ofthe superconducting transition. The Byli)curvesofmost the heat capa i: superconductors have shapes close to bolas. Suppose that BAe) = Bold ~ (alt) (83) Bm C5 = Cy = =e Assume that Cs vanishes fester than lineadly as x ~+ 0. Assume also that Cy is ‘sas for a Fermi gas (Chapter 7). Draw on the res id plot the reps %5 T? and shows that Cy decreases much faster the latent heat ofthe eereasing t, while Cy decreases as 74, For t « zy OC mn. Show that Cylr, Cy 8. Fiest order exystal transformation, Consider aceys of two structures, denoted by a and fl. We suppose low temperature form is the stable (2) form of the substance, 1 the is taken as Separated atoms a UO) at r= 008 Chapter 10: Phase Tratsfermatons negative. The phase sta 40) < Uf) the ve 1 phase, corresp alc O will have the lower valve of UtO ty of sound ry inthe B phase is lower than ng to Tower values of the elastic, ns in the ff phase will have larger amy phase. The larger the per the ent the free energy. So iperature much less than the Debye temperatuee '¢00, in the Debye approximation velocity ofall phonons. (b) Show that atthe transforma rE = GOI /a*V[U4O) — UsON ey? — 0%) (69) simplified modet ids. (c) The latent heat of rans: ray that mst be supplied to carry the ransformation, Show that the latent hea for this model is 1 = 4{U40)— U0) (85) In (84) and (85), U refers to nit volume system through Chapter 11 Binary Mixtures SOLUBILITY GAPS ENERGY AND ENTROPY OF ME Example: Binary Alloy with Neatest-Neighbor Inter Example: Mixture of Two Solids with Different Cryst Example: Liquid He-*He Mixtures at Low Temperatures Phase Diagrams for Simple Solubility Gaps PHASE EQUILIBRIA BETWEEN LIQUID AND SOLID MIXTURES, Advanced Treat SUMMARY PROBLEMS, ‘Noe Al compotion peerings ae sated in atom percent, 310 ey 318 319 320 mI 3 ms 330 330 30 330 a3 331 331 09310 Chapter 1: Binary Mixcares hhave to of more pha phys 1A ral such as fon “oil and water do not «single homogeneous phase, The propert Sotbilty Gaps combined free energy of the to sepa fice energy of the homogeneous m geneous 5 of the (Ko separate solid phas antChapter 1: Binory Mictares ‘The properties of mixt melting and solidifica ¥ formation of any low-me mn of the solidified mi pure Au side by side wi i they are of pra ‘of their lowered melting poi What determines whe ‘ substances form a homogeneous of he composition of the phases tha ‘heterogeneous mixture? The properties of Understood from the principle that any system at a fixed tery the configuration of minimum free energy. Two sul ach other and form a homogencous mixture if that is the configu ton of lowest fice energy accessible to the components, The substances will form a heterogeneous mi Dhases side by side is u fice energies of the two separ Nughout this chapter we assume far sim atsn Chapter: Binary Mixtures use of Ny atoms of substance A und Ny stoms of substance B, The number of atoms is al Nm NA+ Mp o ‘We express the composition of the system in terms ofthe faction sof x= NIN: x= NaN, ® Suppose the system forms homogensous slat peratom given by with an average free energy Sa FN, Q Suppose further that f(x) has the func nal form shown in Figure 11.2. Because ive dfidx? is negative, [ecan draw alive tangent tothe curve a two points at x = x, and x = xy Free energy curves of this shape ace common, and we will see later what may ‘cause this shape. Any homogeneous mixture in ion range xcxexy « is unstable wi respect to two Eeparite phases of composition x, and xp. We shall show that the average tee enerky per atom of the segeegated mixture is iven by the point ine connecting the points «and f. Thus nthe Segregated system has a lower fre energy than the homogeneous system. Proof: The fice energy ofa segregated miature ofthe two phases x and pis Fm NSU) + NGS) « t where Nand. These numbers @ o Sotubily Gaps oy mogencous mature his «shape sich ‘hat touches he curve at to di ‘ange between the vo po ‘composition in ange will decompose iat tuo shases > Xan xy, The fees energy iver by e point onthe sta From (3) we obtain Meee) #0 SOM, wear in x and is a Ifwesetx = x, ory, we see that the line docs po Sa and f. Thus, the point on the staga Chapter 11s Binary Mistores Wehavenot yetmade use ofthe assumption that the straight ine fs tangent to J(3) at the points = and f, and there itholds for any steaight that has two points x and ff ia common with f(s} But fora given value of x st free eneray is obtained by di lowest free energy, the two phases must be to both atomic species, so that Ho Hae: tiven by the intercepts ofthe two- poink tangent with the two vertical edges of the f(s) plot at x w Oand x = 1, asin Figure ENERGY AND ENTROPY OF MIXING ‘The Helmholtz free energy F = U ~ to has conteibutions from the energy and from the entropy. We teat the effect of mixing two components A and B on both terms. Le! In uaa yy ude ao) which defines a straight line ia the wx re 113, The average eneray per atom of the homogeneous miature may be larget or smaller than for the separate constituents. Inthe exemple of Figute 11.3, the energy of w energy of the separate constituents. 1 ‘energy excess is called the energy of mixing, Wthe ~ te term in the free energy ast s = 0,2 posit ‘enctay means that a homogeneous mixture isnot stable. Any suc ‘then separate into two phases. But ata finite temperature the — re term in the free energy of the homogeneous mixture always tends to lower the free energy, ‘Theentropy of amixturecontains aconuibution, called the entropy ofmixing, ‘that is not present in the entropies of the separate components, The mixing ‘entropy arises When atoms ofthe diferent species are interchanged in position; this operation generates a diferent state ofthe system. Because of such inter- Energy and Entropy of Mising system with po 8 the higher entropy. the mining entropy oy of a homogensous alloy ou = ~N[Q— sIlog{t ~ 9) + xtog2], any as plotted in Figure 114. The curve of oy veisus x that the slope at the ends of the composi portant property range is vertical. We have FEE = Hout — 3) = fogs = tog 7 (2) Which goes to eo as x 3 Oand to —co asx |, ats16 ‘hepter 11: Binary Mistures Chapter 11: Binary Bi Energy and Entropy of Micing a7 a os| doy = co Uoglde = an Figure 1.4 Mixing entropy. tn any mista of wo contents aa {aterchange of two atoms of diferent species leds io a sat ofthe ‘stem. The logarithm ofthe nur of sates elated i ths way the rixingenteopy. Figure HLS Free energy pera femperatuces, The curve fyi the fee ehersy pet atoms ‘mixing enttopycontcbution. Forllustration a paraba pendence is assumed, and the temperature dependence af. ‘seglesed. The thee slid eurves represent the ie energy in the ning entopy, forthe temperatres OF ty, 10 tu. aad 12 75, hese ty is the maximum temperature fr which thee isa Sl q 3p. The phase separation at O8 ty i apparent, fer mow the quantity fis) = S) ~ (6 = oul, 03) Wr argument this is ieelevant. Three important deductions follow from the bution, The Cconstcuction of the f(x) curves same for the Which isthe free energy per ator without the mi on-mixing part of the £{2) tums up at both ends of the composition te slope of the mixing temperature cy there is composition range within w jezative second derivative of the f(s) curve is sor ve second derivative of the ~ray contribution, thescby mal Possible wo draw a common tangent to f(x) at two different values of (9) Above ty the curve has a positive second desivative at 9 ~ ea) 10 f9), we obtain at Ss) curves shown in Figure LU. In drawing the 3 ‘temperature dependence of fis) itself, because for ‘compositions.na Chapcer 1: Binary Mistares ing energy will exhibit a ap below the temperature ty. The composition range of the gap ‘decreasing temperature, but the gap can reach t widens wi i obtained earlier in Chapter 3, The fs that the motual solubility is mixing energies arise indifferent ways, We now diseusstheee exa n beteea lite atoms. For simplicity we speak of the interactions as bonds. There ate diferent bonds: A~A, A~B, and B-B. Leta, sy and ina be te penta eneries of be negative with resp! ta separated atoms, ibe amang the lie sites, The average ty = = aa ban 4) wwhete(I ~ s}stheproportionofA and xis the propostion ofB. This result is ‘ean fed approximation of Chapter 10 Simlatly, for Batoms, by = (= Shiga + Ht 3) nergy is obtained by summing ver both atm types. Hench atom has p nearest he average energy pec atom is we Ail ~ ay + LL ~ ugg bell — has + uo) (16) ‘Thefacior fries because each bonds chareé bythe wostomsit connects The can be written as veo Poll — ugg + 2taa) tm a7) Hew ye = PL = Vf — Han ) as) {she mixing energy. On this model the mining energy as function oie parabola sin Figue 115. : From 18) Page TGat = ~ Plena — Mona + wll ro) “The equal sig Consider ion. The stable eral tstute of ol entered cubiestrctre in which every ator ie surrounded by Wwelve equidistant hors. The sable crystal steucture of ican sucounded by op four equidistant nea oa «ofthe atoms by Si we ebiain a homogeneous minture Alyy tof A. Similar, ifin pure Si we replace a sm imsby Av, weabitn a homogeecous mature AM Shy but withthe diamond e4Stal ete of Si. Ther are wo diferent ee energies, ont fr each erystal truce (Figure 118} The two cuves misteross somewhet ia the composition range, or cee pure Auand Si would not cxystalizein dierent sructore. The eq ofthe lower OF the two cures with ink at the crossover point Soch a system exhibits a solubility 59 on either side of the cosiover comporiton, The carves shown in the igure are sche~ ‘matics inthe actual Au-Si system the unstable range exends «0 cloee {0 the edges cf Aiogram that it cannot be reeeseted oma fll cle pt extending from x = O to x the diamond steweture in which every neighbors. in pure Au wo ceplace & 41920 Chapter 1: Binary Mista i Ditoreat crystal aps in ey Phase Dingrans for S RL cm Unstable regime t Teng oo) 8 pure *He 0 A 50030830 bo percent *Hte pure ‘He FELT. Liquid mietues of He and He, second derivative 103 pose mixing eneey. Phase Diagrams for Simple Solubility Gaps 87 hose overall composi the curve is unstable asa homozenco am represents the temperature depen And xy branches merge at Esp eNists. Ata given tempers:Chapter: Riary Mixtures tempecatures cune. The PHASE EQUILIBRIA BETWEEN LIQUID AND SOLID MIXTURES, ‘When.a small fraction ofa homogeneous liquid miature freezes, the composition ‘of the soli that forms is almost always different from that of the liquid, The Phenomenon is readily understood from the fee energies for liquid and solid ‘mixtures. We consider a simple mode, under two assumptions: (a) Neither the Phase Equliia Between Liguid en Sold Miseares solid nor the liquid has a solubitity gap, (b) The mel constituent is lower than the melt ‘We consider a temperature bet ‘The feee energies per ator, fx) forthe solid and f(x) fo town qualitatively in Figure 11.93. The two curves intersect at some cone position. Let us draw a tangent common to both estves, touching eat x = np and fi at x = x,, We ean define three compos nal equilibria. ion ranges, each with diferent a) When x< xy, the system in eq (8) When x, x5 the system nt xy and x; of a sol ‘curve for x5 s the solidus care. ‘The phase diagrams have been determined experimentally for vast sumbers of binary mixtures. Those for most of the posible binaty alloys For most metal allays the phase diagrams are moze complicate 119, which was drawn fora simple system, gtmanium When the temperature is lowered in a binary liquid mixture with the of Figure 1159, solidification takes place over a faite temy jot just al a fixed temperature. To see composition xy, shown in Figure 11.10. As the temperature is fone Solidification bepins at x = «The composition of the Solid formed is given by xis, 80 that the composition of the remsining liguid is changed. In the ‘cxample ss > 2.,80 that the liquid moves towards lower values ofr, where the ‘on temperature is lower. The temperature has to be lowered if solidification is to continue. The compos liquidus eurve u ton is completed at « = eq. The solid formed ‘The solid may homoge- nize afterward by stomic diffusion, particularly if the temperature sema high for a long time. But for many solids atomic difsion is too slow, and ins “frozen in” indefinitely ay