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