Qc Sponsoring Etor: Peer Rene Project Eto: Naney ight Manuseript Eto: Rath Ves Designers: Gary A. Head and Shaten I, Sith Production Coontinatr: Frank Mickell ‘Mlastaton Coordinator: Batyoh Fanos Arts: Flin Coopee Conposior:SyisxIteratcoal DAA SS OK S2 ADSo c oby 4 Library of Congress Cataloging in Puiston Data Kitt, Charis, “Theta psc, Bibliography: Includes cx Hsrben 1928" oincauthor aL Tei QEIII.KS2 isxd 7 qp.tcen ISBN 67167-10889 (Copyright® 980 by W. H. Freinan and Company No pata ths book may be reprontcs by any ‘weshanical, photographie, oF eetraie process, off 1s form oF phonograph vecoeding. nar may be sored in retrieval ern aramid, cr hers ‘opie foe public or privat use without writen petmisson fromthe publics Printed inthe United Stat of Ameen ‘Twenty-fiest printing, 2000 Staite thermodyeunis, 1. Krome, About the Authors Charles Kittel has aught solid state physics at the University of California at Berkeley since 1951, having previously been at the Bell Laboratories, His undergraduate work in physics was done at MALT. and at the Cavendich Laboratory of Cambridge University. His Ph.D. research was in theoretical ‘nuclear physics with Professor Gregory Breit at the University of Wisconsin, He has been awarded three Guggenheim fellowships, the Olivet Buckley Prive ‘or Solid State Physics, and, for contributions to teaching, the Oersted Medal of the American Association of Physics Teachers. He is a member of "ie National Academy of Science and of the Ametican Academy of Arts a ‘Selnces. His research has been in magnetism, magnetic resonance, semi: ‘ductors, and the statistical mechanics of solids Hebert Krositer is Professor of Elzetrical Engincering at the University of Californie at Santa Varbara, His background ani training are in solid stave Dhysies, He receive a Ph.D. in physics in 1982 from the University of Cttingen in Germany with a thesis on hot electron effets in the then new keatsister From 1952 through 1968 he worked ia several semiconductor research lab foris in Germany and the United States. In 1968 he became Professor of [lectical Enginecring at the University of Colorado; he eame to UCSH fa 1976, tis research hus been in the physics and technology of semiconductors and semiconductor devices, including high-frequency transistors, negative: ‘nats effects in semiconductor, injection lasers, the Gunn effect, electron-hole «drops, and semiconductor heterojunctions.Preface ‘This book gives an elementary account of thermal physics. The subject is simple, the methods are powerful, and the results have broad applica tions, Probably no other physical theory is used more widely throughout science and engineering. ‘We have written for undergraduate students of physics and astronomy, and for electrical engineering students generally, ‘These fields for ove Purposes have strong common bonds, most notably a concem with Ferri ftses, whether in semiconductors, metals, slurs, oF nuclei, We develop methods (not original, Lut aut easily accessible elsewhere) that are well suited to these fields. We wrote the book in the fist place because we ‘were delighted by the clarity of the "new" methods as compared to those ‘we were tought when we were students ourselves. We have not emphasized several traditional wopies, some because they ‘are no longer useful and some because their eeliance on classical satisti- cal mechanics would make the course more difficult than we believe a first course should be, Also, we have avoided the use of combinatorial ‘methods where they are unnecessary. Notation aad units: We generally use the SI and CGS systems in parallel, We do not use the calorie. The kelvia teriperature T is related to the fundamental temperature 7 by += Fy7, aud the conventional entropy. 5 is telated to the fundamental entropy o by $ kya The symbol log, will denote natural logarithm throughout, simply because In is less ex Pressive when set in type, The notation (18) refers to Equation (18) of the current chapter, but (3.18) refers t0 Equation (18) of Chapter 3 The book is the successor fo course notes developed with the assist. ance of grinis by the University of California, Edveard M. Purcell con tributed many ideas to the first edition. We benefited from review of th secand edition by Seymour Geller, Paul L, Richards, and Nicholas Whecter. Help was given by Ibrahim adawi, Bemard Black, G. Domo- kos, Margaret Geller, Cameron Hayne, K. A. Jackson, S. Justi, Peter Kittel, Richard Kistler, Manin J, Klein, Ellen Leverene, Brice H. J. fcKellar, F. E. O'Meara, Norman E.Phillips, B. Roswell Russell, T. M.treface Sanders, B. Stozchly, John Verhoogen, Wichmann. We thenk Carol Tua Wilde for her help with the index. An clemeniary treatment of the greenhouse effect in the sphere was added in 1994 on page 115, following an at by Professor Richard Muller. A page on atomic gas experiments on the Bose-Einstein condensation was added 10 page 223 in 2000, For instructors who have adopted the course for classroom use, @ solutions manual is available via the freeman web site (hitpsshfrecman, ‘comu/hermalphysics). Joh Wheatley, and Eyvind wg for the typed manuscript and Sari aeth's skmo- rguiment suggested Berkeley and Santa Barbara Charles Kitel Herbert Kroemer Note to the Student mum coverage of the concepts presented in each chapter, the authors ‘ecommend the following exercises. Chapter 2: 1, 2,3; Chapter 3: 1.23.4, &, 14; Chapter 4:1, 2,4, 5, 6,8; Chapter 5: 1,3,4, 6, 8 Chapter 6: 14, 15; Chapter 7:2, 3.5, 6,7, 11; Chaptec 8: 1, 2,3, 5,6, 7; Chapter 9: i, 2,35 ‘Chapter 10: 1,2, 3; Chapter 11: 1,2, 3; Chapter 12: 3, 4 5; Chapter 13: 1,2, 3.7.8, 10; Chapter 14: 1,3, 4, 5; Chaptor 15: 2, 3,4, 6Contents Guide to Fundamental Definitions xiii General References xv Introduetion 1 Chapter 1 States ofa Model System 5 Chapter Enttopy und Temperature 27 Chapter Raltzmana Distribution end Hctuholiz Free Energy 55 Chapter 4 Thermal Radiation and Planck Distribution 87 Chapter 5 Chemical Potential and Gibbs Disuibution 117 Chapter6 Weal Gas 151 Chapter? Fermi and Bose Gases 181 Chapter8 Heat ahd Work 225 Chapter 9 Gibbs Free Energy and Chemical Reactions 261 Chapter 10 Phase Transformations 275, Chapter 11 Binary Mixtures 309 Chapter 12 Cryogenics 333 Chapter 13 Semiconductor Statistics 353 Chapter 14 Kinetie Theory 389 Chapter 15 Propagation 423 Appendiv. A Some Integrals Containing Appendix B Temperature Scales 445 xponentials 439 xAppendix © Appendix D Appendix Inder 465 Poisson Distribution 433 Pressure 459 Negative Temperature 460 Guide to Fundamental Definitions Absolute activity, 2 expt) 139 Accessible state 29 Boltzmann constant, by 25 Boltzmann factor, expl—e/s) 6 Boson 183, Chemical potential, 119 Classical regime, ce my 74 Ensemble of systems 31 Enthalpy, HH = Ut p¥ 246 Entropy,e 40 Fermion 183, Gibbs factor, expf(Nu — ele] 138 Gibbs free energy, G —rot py 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 Multiplicity, 7 Orbital 9 Partition function, Z 61 ‘aiGuide to Fundamental Defaitons Quantum concentration, ng = (Ma/2xh%? 73 Reversible process 64 Temperature, 41 ‘Thermal average 62 Thermal equilibrium — 39 Work, WW 227 General References ‘Thermodynamics A.B, Pippard, Elements of classical shermodnanics, Cambridge Univenity Press 196 M.W. Zemansky and R. H. Dittman, Heat and thermodynamics: an inermediare ‘exibook, 6 ed, MEGraw-Hil, 198) Suisical Mechanics BLK, Agaoval and M. Eisner, Staiteu! mechanics, Wiley, 1988 TL Mil Statsical mechanis: prncptes and selected applications, Dover Pubtica- inn, 987, 1956, © Kitt, Brocton staistcal pysce, Wiley, 1938, Pans 2 and 3 ea applications to noise and 10 elementary transport theory. Part thas been expanded into the R. Kubo, Statice! mechanic, North Hollnd, 1990, 1965, RR. Kubo, M. Tada, N. Hashitsime, Staniticalphysis 1! (Noneguilibrtu, Springer, 1983, 1. Landauand E, M.Liphit,Staristca physics, 3d ed by EM. LiShitgand LP Pitaersi, Pergamon, 1980, pat 1 Shang-Keog Ma, Staiic mackanics, Wosld Sientifc, 198. M, Toda, 8 Kubo, N. Suto, Statistical physice £ (Equilibrium), Springer, 1983 Mathematical tables HB. Deight, Tables of integrals and other mathematical data, th ed, Macmvittaa, 1961, A widely useful small collection, Applications Asteophysiss RJ. Taylon The star: their siictare and evohaton, Spingse, 1972, S. Weinbus, The fist thrce minuess a madern view of the ogi ofthe taverse, new fa, Bautsin Books, 1984 ‘Biophysics and macromolecules T.L Hil, Cooperatvityheory in bischenistry: steady state and equiltbeian systems, Springer, 1985General References CCoyopenies end low temperature physi. G. K, White, Experimental tetniques in low-temperature physics, 3d ed, Oxford Univesity Press, 1947, 1979 «pa, 4. Wika and D, 8. Beas, a intron tof guid helium, 2nd ed, Oxford Univesity Pres, 1987 Irreversible thermodynamics 2A McLennaa, Introductian 1 nom equ statistical mechanics Peete Mad, 1539, 1. Prgorine and 1, Stenger, Onder out of chaos: man's new dialog Random House, 1984, ee Kinetic theory aad transpon phenomena §.G.Bossh, The kind of motion we cll heat, North-Holland, 1986, e191. HL Smith and HHL Jensen, Transpar phenamena, Onfocd Univey Press, 1989, Plasma phases 1 Spitee I Physical proceses inthe intratllar miedvan, Wiley, 1978. Phase transitions PP. Peay and G. Toulouse, Snraduaion othe renormalization group end to teat phenomena, Wiles, 1977 HE Stanley, Jetceton to phase trsiions an eritical phenomena, Onferd Usk veaity Press, 1987. ‘Metals 2nd atlogs P. Hasen, Ppsical metllvgy, 20d el, Cambridge University Press, 1986, Superb, Bousdary value problems HS. Cardaw and J.C. Jaeger, Conduction of heat in solids, 2nd ed, Oxford Univer: sity Pres, 1986, ©1989, Semiconductor devices R, Dalen, Fzoducton co applied slid stare physics, Plenum, 1990, K Seeger, Semiconductor phyticr: on inraduction, Sth ed, Springer, 1594 SUM. Sze, Physics of semiconductor devices, 208 td, Wiley, (981. state physics C Kittel, Intracuction solid state physics, 6th ed, Wiley, 1986, Reeredtoas ISSP.Thermal PhysicsIntroduction Ourapproach tothermal physics diters fram the tradition follosed in beginning physics courses. Therefore we provide this introduction to Set out what we are ‘oing to do in the chapters that follow. We show the main lies ofthe logical structure: in thi subject all the physis comes from the loge, In ordee of their appearance, the leading characters in aur story are the entropy, the lemperature, the Boltzmann factor, the chemical potential, the Gibbs factor, and the eistribus sion fonctions ‘The entropy measures the number af quantum states accessible toa ystor A close system might be in any of these quantum states and (we assume) with ‘equal probability. The fundamentt statistic element, the fundamental logical assumption, i that quantum states are either accessible or inaccessible to the system, sd the system is equally ikely to be In any one accessbte state a8 any other accessible state. Given g accessible states, the entropy is defined as 2 = logg. The entropy thus defined will be a function of the energy U, the number of particles N, and the volume 1 of the system, because these param cers emter the determination of g2 other parameters may enter as well. The use of the logarithm is a mathematical eonvenionce: itis easier to write 102° than exp({0), and it is more natural for wo systems to speak of ay + oy than of gis ‘When two systems, each of specified energy, are brought into thermal coatact ‘hey may wansfer energy; their total energy remains constant, but the constraints, on their individual energies are lifted. A transfer of energy in one direction, or peshaps inthe other, may increase the product gg, that measures the number of accessible states of the combined systems. The fundamental assumption biases the outcome ia favor ofthat allocation ofthe total energy that maximizes the number of accessible states: more is better, and moe likely, This statement is the kernel ofthe law of increase of entropy, whict isthe general expression of the second law of theemody namics, ‘We have brought 1wo systems into thermal contact so that they may transfor 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 will increase. Eventually the entropy will reach @ maximum for ‘the given total energy. Is not dificult to show (Chapter 2) that the maximum, 1Invocton raitained when the value of @6/€U}.y for one system is equal to the value of the same quantity forthe sec "ond sjstem, Thisequality property fortwo systems aera contact isjentthe propery weexpect ofthe emperatue, Accordisly, We define the fundarncutal tesnpecature + by the telition 0 ‘The use ofl atsures that energy wil Now fom high +10 low r;n0 more come Pleated eelaton is eccded. It will follow thatthe Kelvin temperatore sisoty proportional to, with r = AyT, where ky isthe bolo he conventional enteony 8 is given by § = ine Now consider a very sinyle exsnupe ‘Chapter 3. et sasall syste with say eon the Melizmsnun factor treated jin ies, une a enerny @ a naray ¢ be placed in thermal contact with a arge system that we eat ihe fessrvoit. The total energy of the combined systems is Uss when the smell ‘yatem is in the state of energy 0, the reservoir has energy‘ Us and wil hneg atl ohstates accesible voit, When the small scm isin the state of enersy nha ‘Metvoie wil hse energy Up ~ eand will have gle ~ «states accesible to i By the fanamental assumption, the rato of the probability of finding the Small sytem with emery « 19 the probably of nding it wih energy Oe MO We ~ 9 ofelt—o] : Fo) oO” ~ expat ; ‘The ceservoirenicopy a nigy be expanded in & Taylot series: SIU, - = al) ~ Alef) = olUy) ~ sie, % Dy the defiition (1) of the temperature, Higher order ray be dropped. Cancellation of the term exglaiU, ‘numerator and denorninator of (2) after the sul terms i the expansion a} which occurs in the stitution of (3), leaves us with Peay expel. “ ‘This is Boltemann’s result, To show is us ‘erny (e) ofthe twa state system in ther perature ¢ , weealeulate the theemal average mal contact with a reservoir at tem- © = YaPe) = 0-700) + ew) w 6 Iuadecton Where we have imposed the normalization eondit abilities: ® on the sum of the probe PO) + Phe) = 1 0 ‘The argument ean be generalized immediatly to find the average eneray of a harmonic oscillator at temperature s, and we da this in Chapter 4 as the frst step in the derivation of the Planck radiation law. ‘The most important extension of the theory i to systems that can transfer particles a8 well as enerey with the reservoir, Fortwo systems in difusive and thermal contaet, the entropy will be a maximum with respect to the transior of particles as well a8 to the transfer of energy. Not only must (26/CU.» be ‘equ for the to systems, but (76/Nyy- must also be equ, where A fers 19 the womsbe of parties ofa given specks He new eulity eto i the son for the iatvenbuction fa nee qustity, the bal pte y o For two systems in thermal and difusive contact, ry = ry and ly = py. The sign in (7) cuosen to ensure that the direction of particle fow as equitbrium 's approached is front high chemical potential to low chemical potent “The Gibbs factor of Chapter 5 isan extension of the Boltzmann factor and allows «to treat systems that ean zransfer particles. The simplest example is System with two states, one withO particlesand 0 energy, and one with 1 particle and energy «. The system isin contact with a reervolr at temperature and shiemical potential . We extend (3) forthe reservoic entropy: {Ug ~ €:Ny = 1) = a(UaiNe) ~ elea!dv = 1 @efanig = a(UaiNe) ~ ut + af. 8 By analogy with (4), we have PU.ey POM) = expllu ~ ae), ° for the ratio of the probability the system is occupied by t putticle at energy & to the probability the system is unoccupied, with eneray 0. The result () after normalization is readily expressed as t Pe Ses aT 0)‘This particutae resus is known a6 the Fermi-Dirac distsibution function and is used partioularly in the theory of metals to describe the electron gas at low temperature and high concentration (Chapter 7}, “The classical distribution function used in the derivation ofthe ideal gas tas js just te Tit of 10) when the occupancy P(e) is much less than PQs) = expfln — av on “The properties ofthe ideal gas are developed from this result in Chapter 6 ‘The Helmholtz free energy Fm U — te appears as an important computa ‘ional function, because the relation (2F/ét)sy = —< offers the easiest method for finding tke entropy, once we ave found out how to calculate F from the energy eigenvalues (Chapter 3} Othor powerful tools for the calevation of thcrimodynsmic functions are developed in the text, Most ofthe remainder of the text concerns applications that ae usafil in their own right and that illum nate the meaning and utility ofthe principal thermodynainic anctions. ‘Thermal physies connects the world of everyday objects, of astro objects, and of chemical and biologie provesses withthe world af molecu tom, und eleetconieayatema. I ites the two pasts war wut ta misty scopie and the macroscopic. Chapter 1 States of a Model System BINARY MODEL SYSTEMS Enumeration of States and the Multigliity Function Binary Alloy System ‘Sharpness of the Multiplicity Function AVERAGE VALUES : Enorgy of the Binary Magnetic Systema Example: Multiplicity Funotion for Hatmonie Oscillators SUMMARY. » 6 6 18 2 2 2 261 Gibbs A theory ts the mre in more diferent kinds spplicabiliy. Therefore the deep ‘pan me. Iris the only physical theory of uniter vill necer be averdvown, within she, concepts. pressive the greater she sinplicty ofits premises, the of things it relaes, and the more extended ts area of inpression tha classical thermodynanies made content which Ian convinced Sronework of applicability of us basic A. Finstcin haper ts es of a Modet Sytem Thermal physics is the treit ofthe union of statistical and mechanical principles Mechanics tells us the meaning of work; thermal phsics ell us the meaning of heat, There are three ne¥ quantities in thermal physics that do aot appeat tn ordinary mechanies: entropy, temperature, and free energy. We shall motivate their definitions in the frst three chapters and deduce their consequences theceater Our point of departure fr the development f thermal physics is the concept of the stationary quantum states of sjstem of particles. When ve ean count the quantum states accessible to a system, we know the entiopy ofthe system, for the entropy is defined as the logirithm of the numberof states (Chapter 2) ‘The dependence ofthe entropy an the energy ofthe system defines the tempera. tore. From the entropy. the temparatucondihe heecctey we NG the pressure, the chemical potential, and all ther thermodynamic propeties of the systerm For system ina stationary quantum state al ebserable physical proserticg such as the energy and the nutnber of panicles are independent ofthe tine For bievity we usually omit the word stationary; the quantum states that we teet ars stationary except when we discuss transport processes in Chapters 4.15 The systems we discuss may be composed ofa single particle of, more often, ‘of many particles. The theory is developed to handle general systems of inten, acting patticles, but powerful simplifications ean be made in special problems for which the interactions may be neglected Each quantum state has a definite enesgy, States with identical energies ace said to belong to the same energy level. The multiplicity or degeneracy of an nerey level isthe number of quantum states with very nearly the same energy, {tis the umber of quantum states that is important in thermal physics, not the number ofenergy levels, Wes frequently deal with sums overall quantum states, Two states atthe same enerey must always be counted 38 tivo states, os one fevel Let ustook a the ysantun systems The simplest is hydrogen, with one ecciean stl one proton. The lowly ing ‘energy levels of hyrogen are shown in Figuce 1. The zero of energy in the figure is taken at the state of toxest energy. The number ef quantum states belonging to the ame energy level esa energy lvstvofseser ten isin parentheses. ta the figure we overlook that the proton has a spin of Yh and has two indspendentofientations, paralelCompre Ve States of Sade Sper up 7 t | ew si a 2b ——u soe —w 5 4 + ——a tes ‘3 & 4 4 = — a J 3 2 y tof | eee Hydrogen ——a of —_w Lithium Boron Figure Lt Lowstying energy feels of atomishydrogts thin, snd boron. The ergs se given in electron vols with LeV = 1402 » 10°"? erp The numbers fo parentheses pve the numberof quactum sates having the Same cacy, with vo account laken ofthe spin of the nedeus. The eco a enerey inthe pure is tae for convenience at she lowest energy state of exch atom, rantiparallel to the direction ofan arbitrary external axis, such asthe dicetion, of a magnetic field. To take account ofthe wo orientations we should double the values ofthe multiplicities shown for atomic hydrogen, ‘An atom of lithiuen has three electcons which move about the nucleus. Each ‘lectron interacts with the nucleus, and each electron also interacts with all the leper 22 Stes of Mat Sten o mr Mubiptcity of quantuan nunbets —— « Soboiyaas -—— 6 sa ask -— 3 422 —— 332 t—— « s21 2s] —— 3 2430 f——— 3 ang h—— 3 322 os gad 1 222 -— > 314 3 224 3 zat Figure 1.2 Energy evel, clipes, and quantum numbers sty ofa parti coined 03 cube other electrons. The energies ofthe levels of lithium shown ia the figure are the collective energies ofthe entiesystem-The energy levels shown for boron, which thas five electrons, are also the energies of the entice system, “Theeneegy of systemisthe t nergy ofall particles kinetic plus potential, th account taken of interactions betwicen paticls. A quantum state ofthe system is a state of all particles. Quantum states of a one-particle system are called orbitals, The low-lying energy levels ofa single particle of mass M con- fined to a cube of side L are shoven in Figure 1.2. We shal find in Chapter 3wo % Particle can be charactsied by thee postive integral ‘The enesgy is quantum sumbersn, WP fx\? eB (Jot eat ens ® Tr eis ofthe letls ars incited inthe Rue. Te thee orbitals Tehetanteaunt ob) (ht) and (i s)alhaven? + m2 tas 8; the coresponding energy evel has the multipisiy 3, cate the statistical properties ofa system of panei extemal Sosened ee convenient arbitrary way, but two dieeat sate should ane Ce sssigned the same index 118 800d ides to start our program by studying the properties of simple Roel aatem or which the energies) can be cleulted exactly Wechoneg sound ate sinble binaty system Because the general satnicel peop Fuad fr the model system are believed ta apply equly well to aig see Ebsfal sstem. This assumption leads to predictions tat sluaye sere te seve e ata Eenera statistical properties are afconcer wil become ca 2s we goalong, BINARY MODEL SYSTEMS Pambicd OF snoscupied, z10 oF one, plus one or minus one. The ties ee phoniatat siles with dierent numbers are supposed nat to overlay ta Bisset soe: Youmight even thnk of hess as mumbuted prkitgseas ec Sat batking lot asin Figuce 14 Each pking ypocehas tostaten eoenng ‘occupied by one et Matever the nuture af our objects, we may designate the we sta cro ate only point straight up or stesight dn Ifthe magnet ping magne et he magnetic moment is +m. ithe magnet ins dove ihe ‘magnetic mement ism, Binary Model Systems 7 8 9 w te Figwe 13 Model system composed of 10 elementary magnets afte sites ona in, each having magnetic ‘moment +m. The aumbers shown ae attached io the sitess ch site has its own magnel. We assune tere ae ne Ieteractons among ths mapncs and theres no excceat ‘aeti eld. Each magnetic moment may te olen a {07a w75, up OF down, so that there ase 2" dine rangement of he 10 magoetic momseats shown inthe ‘gure. the arrangements are selected ina Fado process {he probability of ding the parila arrangement showy mine, | Number of the sit 2 Fine 14 State ofa parkieg lot with 10 numbered parking sp3ei. The ©'s denote spaces ocaied bya ans the O's oe vacant spaces This partis state equate to hat shown in Figure 13, Now consisr W dierent sts, each of which beats a moment that may issue the values tin. Each moment may be oriented ia two ways with & Probsbility independ of the orientation of all other moatents, The totsl nanber of arrangements of the N moments is 2x 2x 2x02 a2 4 stale ofthe systems is pacified hy giving the oricutatfon ofthe sito: thete are 2* states We any slate of the system of W sites lomeat on each ¥ vse the following simple notation for a single tnunitt @(Chapter Is States of Mosel System He L3 The four diferent states of meee || || || | I ‘The sites themselves are assumed to be arranged in a definite order. We may ‘namberthem in sequence fom left to right, as we di in Figure 13 According to this convention the state (2)also ean be weitten a8 Ifalalalstetatatotso eo Both sis of symbols (2) and (3) denote the same state of the system, the state in which the magnetic moment on sitet i +m on site 2, the moment is +m ‘onsite 3, the moment is ~ ry; and go forth, kis not hard to convince yourself that every distinet state ofthe system fs sontained ina symubullc product of factors (he + Wl + LMS Fe ta bed 6 ‘The multiplication rue is defined by (hth +) sit tlt hte + hb. 6 ‘The function (4) on multiplication generates 3 sum of 2" terms, one for each of ‘the 2Y possible states. Bach term isa product of N individual magnetic moment symbols, with one symbol for each elementary magnet on the line. Each term denotes an independent state of the system auld is @ simple product ofthe form Tefal "Ty, for example. Fora system of two elementary magnets, we multiply (Ty + L,)by (ts + La) to obtain the four possible states of Figure 1.5 (a FAs +1) Tila tele + Lata # dele © ‘The sumis nota statebut isa way of isting the four possiblestates of thesystern. ‘The product on the let-tand side ofthe equation iscalled a generating function: it generates the states of the system, Binary Moet ‘The genecoting function for the tates ofa system of theee magnets is (hy # Lita Lala + La ‘This expression on moltiplication generates 2” = 8 aiferent states ‘Three magnets up ht Twomsgnetsup: fytals Tilaly —nfat Onemagnetup: Tylaly Lataly —falats None up: Alas. ‘The total magnetic moment of ovr chedel system of N magnets each of ‘magnetic moment m willbe denoted by Af, whieh we will relate to the energy ina magneticield, The value of M varies from Nin to ~ Niu. The set of possible values is given by A= Nom, (N= 2pm, 49m, (N= Oe, Km ‘The set of possible values of Mis obtained if we start with the tate for which ail ‘mogaets are up(M = Nin)and reverse one ata time. Wemay reverse N magnets to obiain the uhimate state for which all magnets are down (M = — Nn). ‘There are N + 1 possible values of the totat moment, whereas there ate 2° states. When N21, we have 2° > N+ 1. There are many mote states than values ofthe total moment, IFN = 10, there are 2°° = 1024 staes dsieibuted Among 11 different values ofthe total magnetic moment. For lerge N’ many different states of the system may have the same valve of the total moment A. We will elculae in the next section how many states have s given value of M. Only one state ofa system has the moment Af s: Nor: that state i ttt tit 6 re N ways to form a state with one magnet down: Mites ttt ° is one such state; anothoe fs titan (10)“ Chapter: Stores "Model Sytem And the other states with one magnet down are form ed from (8) by reversing any single ignet The states (9) and (10) have total moment Af = N, Enumeration of States and the Multiplicity Funct ‘Nese the word spin s a shorthand fr elementaty magaet tis convenient to assume that N isan even number. We necd a mathematical expression for the {aber of states with Ny ~ AN 4 s magnets up and N= Ws magnets Govsn, where an integer. When we turn one magnet fom the upto the cows orientation, WY + s goes to UN +5— 1 and $N ~s goes oN — sat Tie dilfecence (number up ~ number dovn) changes om 2s 102s 3. The dierence Ny-M,= 2s ay jected the spaecess, The spin exces ofthe 4 states in Figuee 1.362.040, ~2, {am eto sit. The factor of nH) appcirs to bea nuisance a this sage Dut twill prove to he convenient. ‘The product jn (4) may be written symbolically as be ‘We may drop the ste tabels (the subicrpts) from (4) when we are interested only in how many of the magnets in a state ate up oF down, and not in which brticular sites have magnets up or down. {t we drop the labels and neglect ‘he order in sich the arrows appear in a given produet, then (5) becomes (HM Tr ate ty further, es tits se att + Uy We find (F + )* forarbitcary N by the binomial expansion aa AN NSIT & AN — Doty? goog ye (2) Enumeration of Sates and he Biutipity Function We may write the exponents of x and yin a lightly different, but equivalent form by replacing ¢ with 4 — 3 dnl FS (ety airy (3) With this result the symbolic expression (f+ 1)* becomes Pee nt ses pave = Ser arcgel ro) ‘The coefficient of the term in) {s the number of states having x, iN + § magnots up and Ny = 4 — s magnets down. This class of states has spin excess Ny ~ WY, = 25 and net magnetic moment Jom Let us tlenote the numberof states in this class by g(Ns), for a system of magnets a5) ‘Thus (14 s written as ae ANS) AY 9) ‘We al cat (the multiplicity function; tis the number of states having the same value of s. The reason for our definition emerges when a magnetic field is applied tothe spin system: in a magnetic fel, states of diferent values of S have diferent values of the enexgy, so that our gis equal to the multiplicity ofan energy level in a magnetic field. Until we introduce a magnet field, alt states ofthe model system have the same energy, which may be taken as zero, Note feom (16) thatthe total numberof states is given by wy XY aitts) = + 1 = 2% an 9 Examples related to g(N.s) for = 10 are given in Figures 1.6 and £2. Fora coin, “heads” could stand for “magnet up” and “xails" could stand for “magnet down” B16 Chapter I: Stoter ofa Model Sytem 210} [210 Fee 16 Number of distinct aerangemenss 2f5 4 sspins upand 3 ~ sins dwn, Volos of gia) efor N= TOs where is the spineauess NT WL The total aber of| i” 120 E ati0.. ‘The values ofthe sare taken froma table oF the bizomis coe eins io | | L apoRae aw Spin excess 26 Binary Alloy System To illustrate that the exact nature ofthe Wyo states on each sites irrelevant to the result, we consider an alternate ssstem—an alloy crystal with WN distinct sites, numbered from 1 through 12 in Figure L8, Each sites occupied by ether ‘an atom of chemical species A or an atom of ches sion for vacant sites, In brass, A could be single state ofthe alloy system can be ical species B, with no provi- ‘copper and B zine. In analogy to (3), ADBIBSADBSAGDBeDyA yA Ars > = 08) Binary Ay Sytem ” | ven namber of heads occurred fh CTisasereow Number of heads igure 17m expzroen was Gone a wien 18 pennies wee thrown 100 times The number ofteads in eh Shrove was econ, ©0080 © OO) @ Serene ‘ccupy dintinet numtere sterates of e Moule Sytem Every distinet state of a binary alloy system on NV sites is contained in the symbolic product of W factors: (Qc # BIA + BAL + BY y 4B), (9) in analogy to (4). The average composition of a binary alloy is specified con= ventionally by the chemical formula A, B,, which means that out ofa total of N atoms, the number of A atoms is Ny = (1 —sN and the number of B atoms is Ng = AN. Here x lies between D nd | ‘The symbolic expression wt (A + By = J ar 2" 8 Le ia {is analogous to the result (12). The coefficient of the term in AY“! BY gives the hhumber 20%, of possible arcangements of states of N— atoms A and 1 atonts B on N sites ae Wom" yy en which s identical tothe result (15) for the pin model system, except for notation ‘Sharpness of the Meltiplicity Funetion We know fiom common experience that systems held at constant temperature ‘usually have well-defined properties; this stability of physical properties is a ‘major prediction of thermal physics. The stability follows a8 a consequence of Ubeexceedingly sharp peak in the multiplicity function and of the steep variation ‘of that function away from the peak, We can show explicitly that for a very large system, the function g(¥,s) defined by (15) is peaked very sharply about the value s = 9, We look for an approsimation that allows us to examine the form of g{N.s) versus s when N>> 1 and {sfc N. We cannot fook up these Values in tables: common tables of fetorials do not go above N = 100, sid we ‘may be interested in = 10° ofthe ander of the number of atoms in a solid specimen big enaush to be seen and fel. An approximation is clearly needed, andl a good one is avaiable, 1k is convenient 10 work with logg. Becept where atherwine spot afl Fogatitans are understood to be log base, writen heres log. The international standacd usage is Infor fog base e, but itis clearer ta write fog when there ig no ambiguity whatever. When you confront a very, very large number such is Sharpness ofthe Mattiplisiy Function 10° isa simplification tolook atthe Logarithm ofthe number. se the logarithm of both sides of (15) 0 obtain og aN. fog! — log(h + 3) ~ tog = 91, (22) by virwe ofthe characteristic property ofthe logarithm ofa product. logay = logs + logy; tog(vs) = tose ~ logy, (23) With he notation Nees My en for the number of magnets up end down, (22) appears as legets) BN! — log Ny! ~ log Nut e9 We evaluate the logarithm of WH in 25) by use of the according to which log anpensinnation, resto sel) st 2aNENM exp Nb Y2N) + 1 6) for N > 1. This result is derived in Appendix A, For sufficiently large N, the terms 1,121) + +> in the argument may be neglacted in comparison with N. We take the logarithm of bath sides of (26) 10 obtain log! & Hlog2e + (N + S)logN — N. en Similarly logy! & Hog2n + (Ny + NlogM, — Ns (8; logit = Hogle + (Mi + Dloga ~ Me. (2) Aller rearcangement of (27), log! & Hosea Eth +L N+ logy = (Ny ND, wesliave uss for (25) BN fesubteact ta (29) from GO}tw obtain ogg & Hog(l/2nN) - ON, + HlogiNy/A) = OW + HlogN uN OH »0 Copter): States ofa Model System This may be simplified because FoulNUN) = log {Cl + 291N) = —log? + foglt + 2s!) log? + (2578) ~ s4/N4) (32) by virtue of the expansion logll + x) ex fst valid for x & 1 Sinularly, lop(N./N) = log ~ 25/8) = log? — 251M) - GS/NR, 03) (On subsiution in (31) we obtain ogg & {log(/xN) + Ntog2 - 224)v, 04) We write this esutt as [ a AN Dhexpl—29)N} , 03) where (0.0) = (fey, 26) Such 8 distribution of values of sis called a Gaussian distribution. The integeal™ (0 (35) over the runge ~ co to +00 for s gives the correct valve 2Mor the total umber of states. Several useful integeas are treated in Appendix A, ‘Thc exact value of g(N,0) is given by (15) with s w Tm OW ot 1B asco sm by a8 neat seh oC. fl Mavs doesnt nade ‘ict erre Foreampla thecal nt eh x 44M) to Meds = $n Inequaliot 4 UM, which approaches 1a. appecactes 0, Sharpness ofthe Matiplsy: Faection » Figore 19. The Gaussian approximation to tne binomial coeFicents lM} pated on a linea sale On tis stale not possible ssingush onthe drawing the approsimation from the exact vals evs the range os plotted The entire range of sis rom ~ SO10 “+50. The dashed line redrawn fom the points a je of he simon alu of (100, For N = 50, the value of (500) fs 1.264 > 10, from (37), The approximate value from (30)is 1.270 x 10" The distribution plotted in Figure 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)? , 29) the valve ofg is e°* of (NO) The quantity (1/20) is thus a reasonable mea sure of the fcactional widlh of the distbution. For N= 10%, the fractional ‘width is ofthe order of 10°"! When Nis very lage, the distribution is exceed ingly sharply defined in a relative sens. Ik is this sharp peak and the continued sharp variation of the multiplicity function fr from the peak that will ead to 2 prediction that the physical properties of systems in thermal equilibrium ate well defined. We now consider one such property the mean value of 2,a (Chapter I: States ofa Model System AVERAGE VALUES ‘Tis rege value or mean value, ofa fiction fs) taken aver a probabitity ‘stibution function P(s) is defined as P= Esorre) , 69) ‘Provided that the distribution function is normalized to unity LP 1 40) ‘The binomial distribution (15) has the property (17) that Lava) = 2, (4) nd is not normalized to unity. Hall states ae e GIN.32, nd we have SPs) willbe "ally probable, thea P(s} = = 1. The average of 3) aver this distribution D =F M9 PW, 2) ‘Consider the function ts) = 3. in the approximation that led to (38) and (4, we replace in (2) the sum Y, over s by an integral [+ ds between = and +, Then 1 _ CUA? 2° fide exp 25409 a fasten : BreAy (AIM F deers Pa CM yay, whence GP =A «aH 483) The quantity <7) is the mean square spn exces. The root mean square : spin excess is QsPy'? = WN, (44) Energy of he Binary Magnctic Sytem 45) ‘The larger N is, the smaller isthe fractional actuation. This meens that the ental peak of the distribution faction becomes relatively mose sharply defined as the size of the system increases, the size being measured by the Dumber of sites W. For 10° particles, # = 10-4, which is very small ‘Bnergy of the Binary Magnetic System ‘The thermal properties of the model sysem become phy the elementary magnets are placed in a magnetic field for then the cneteie of the diferent states are no longer il equal. Ftheensrgy ef the system is specie then ouly the states having this energy way eacuts The encryy af interstion ‘of single magnetic moment m with a fixed external magnetic eld Bi Cs =m, 40) hiss the potential energy of inthe itd For the model system of 2° ceseatary magnets, each with two allowed orientations ina uniform magnetic fc 8, the total poteatial energy U is De 30 = 0: Fm, 2) a, the expression M for the total magnetic moment 2am In this example the spectrum of values of the energy U is discrete. We shall see later that 2 con- ‘inuous or quasi-continuous specicum wil create no dificulty. Furthermore, the spacing between adjacent snergy levels of this model is constant, as in Figute 110. Constant spacing is a special fextute of the particulur move, bu this feature will not restrict the generality of the ar tive following sections, ‘The ealue of the energy for momeets What interact only with the external magnetic ticid i comeletcly determined by the value of s. This funetional Sependence ws wcicatia by writing UUs) Reversing a single moment lowers 2s by ~2, lowers the total magnatie moment by nd rises the enerey by 2mB. The energy dillerence between adjacent levels is donoted by de, where iment that i developed in Ae = Uy) Uls $1) = 2m «sy 2Chapter 1a States ofa Blake Systems : Lorna 56) tog sts) “St o wa “a tsa tty E535 o——— 9 om 553 FE s35, 9 was st Ht ao Ht ° Figure 1.10 Energy hve of the mode system of 10 ‘netic momeatsm ina magnetie eld The eels sv abso Uy st sale, whete 251s the spn teen “SAN + 95 + 515 he numberof up spi The ‘encebes U() and lips fate shown Fo his problem the engy leveled egy we Separation Az = Ill betwosnsjesot ene Example: Muliticy funtion for barmoic ocilaters, sysen isthe simplest problem for which an tacts “nowa, Another exactly solvable preblemis the hao ‘The problam ofthe binary mode ion for the multiplicity function is icosilator, for which the souton where the quanturs number sisa the exilatr. The umbe of Bato = ho (0) Expy ofthe Binary Megnatc Syters ‘an be distributed among the esilatrs, That ig, we wan the mliplisiy function la) foc the ocintocs. The ossitator mulpiity function not the Samet the spin lis plist asction found esti, We begin the aoaysisby ging back tothe makipiity fncion fro single ent forshich gl) = [forall atuetof the quantum numbers bereidenical ton Totove he rable of (3) below, we teed a fancion to repretcut or fscrae the sees othane = Fe co) AI ra fom Oto oo. Here ris just & temporary tol tha sil help us Gnd the cess (53) but does not appear in the final eesslt The answers (32) Provided we assume |< 1. For the problem of N oscitatrs, the geetating fonction is the tesa the ber of ways en am aa it the HA pos is pely sur of etal ways ia eich de integer mean be faces the smb N nomena inegers ‘Weiner that Wy 8 oe sin = tin (EY ava 1 (dy yx = ton (f) 9 = EM EO OO 6 “That for the system of ssilators, Nan witW =O! (59) (08) = "Ths res willbe needed in solving a problem in he next hapler Fy26 (Chapter 1: States of « Model Syne SUMMARY 1, The moltiplieity function for asystem of N magnets with spin excess 25 = Ny Mis i “NINE waa Ji the limit <1, with A'2» 1, we have the Gaussian approximation ats) = 7 N}AD exp ~25/N), 2 tall states of th i #€ modet spin system are equally likely, the verage value of 4s Lesa] f* asain =, in the Gaussian approximation 3 The factional Huctuation of st is defined as C425! pnt 4. Theeneray oft IN and is equal 10 vodel spin system in a state of spin excess 2sis UG) =, sn, ‘here mis the magnetic moment of one spin and B isthe magnetic fed Chapter 2 Entropy and Temperature FUNDAMENTAL ASSUMPTION » PROBABILITY a Example: Construction of an Ensemble 2 Most Probable Configuration a Example: Two Spin Systems in Thermal Contact 2 ‘THERMAL EQUILIBRIUM » ‘TEMPERATURE ENTROFY Example: Entropy tncrease on Heat Flow 4 Law of Increase of Enttopy 4“ LAWS OF THERMODYNAMICS, 4“ Enteopy as a Logarithm 0 Example: Perpetual Motion of the Second Kind 50 SUMMARY st PROBLEMS 1. Entropy and Temperature 2. Poramagnetisin 2 3. Quantum Harmonie Oscilator 2 4. The Meaning of "Never" 3 5. Aduitivity ofthe Entropy for Two Spin Systems 3 6. Integrated Deviation St by Probons 3 edo aotempPs Chapter 2: Eniopy and Temperature ne shoul nor tmagine the 0 gees i a 0.1 Her container, il is, then agin after a few days separa, : te contary, one fins... 19° years will hereby a recom int mice, then mis again on forth. On hot not unitate ens ng compared ts ny dceable nny af the gosee. One my that this is practically equivalent to never. : 7 1 Botcmae Ye wish 0 find in rational mechanics an a of thermodynamics, cntropy. prior foundation forthe principles Ne must Seek mechanical definitions of temperature and A.W. Gibbs The aeneral conection horween enorgy and temperature nuiy nly be esrabtshed by probability considerations. [Two systems} are hn seats! equilorium when ‘transfer of energy does not increase the prababliny M, Planck Fundamental aasumgtion We stun this chapter with a definiion of probability that enables us 1 defiae the average value of a physical property of a system, We then consider systems in thermal equilibrium, the definition of entropy, and the definition of temperature. The second iaw of thermodynamics will appear as the law of increase of entropy. This chapter is perhaps the most abstract in the book. The chapters that follow ssl apply the eoneepis to physical problems. FUNDAMENTAL ASSUMPTION ‘The fundamental assumption of thermal physis is that a closed system is equally likely to be in any of the quantum states accesible to it, Al accessible quartunt states re assumed to be equally prudable—sheve & Hu HeaseR 4O prefer some accessible states over other accessibe states, A closed sy hhave constant energy, 2 constant number of particles, constant volume, and constant values of all external parameters that may influence the system, including gravitational, electric, and magnetic feds. quantum state is accessible if ils properties are compatible with the plysical specification ofthe system: the energy of the state must be in the range within which the energy ofthe system is specified and the number of particles must be jn the range within which the numberof particles is specified, With lage systems ‘we can never know either of these exactly, but it will sufice to have BUJU « 1 and BN/N 1 Unusual properties of a system may sometimes make it impossible for cxttain sates tobe accessible during the time the tysier is under observation. For example, the states of the erystaline form of SiO, are inaccessible at low temperatures in any observation that starts with the glassy oF amorphous {orm: fused silica will not convert to quartzin our lifetime ina low-temperature caperiment. You will recognize many exclusions of this type by common sense, We treat all quantum states as accessible unless they are excluded by the specification ofthe system (Figure 2.1) and the time scale of the measurement Process, States that are not accessible ae std to have zero probability. Of cours, i is possible to specify the configuration of a closed system to a point that its statistical properties as such are of no interest. Ifwespecify that the »2 (Chapter 2s Entropy and Temperate Wig 2A pu oma ceieseis an csc quant atc ofa ed pe, The {urdanestalssngtion of sutra pei etn ‘tem eal iy tote imanpotine eae ne Accs ti, The emay cts epee os ey Ina ace not acess bcs the poperon oo roioee shespeciction of hess oie ns ingame std spo system i exactly ina stationary qua the problem, ania PROBABILITY Suppose we have a closed system that we know is equally likely to be in ofthe g accessible quantum states, Let she general sate late fan wot one ‘the spin excess The probability (9) of finding the system inthis se any hall 7 Mo w ithe states is acocesible and P() = 0 atherwse consent with the fun damental assumption. We shall be concered fle with syste that ae ane closed, for which the energy U and particle number N may tay. For thee ‘stems PO)will no bea constant asin} but willhavesfunetonal dependence on U and on N. Probubity The sum Ps) ofthe probability ove all sates is aways equal to unly, because the total probability thatthe system isin some state iy Leet rH The probabilities defined by (1} lead to the definition of the average value of any physical property. Suppose that the physical property X has the valve X(} when the system isin the state s. Here X might denote magnetic moment, ‘nergy, square of the energy charge density near a point r,o¢ any property that ‘san be observed when the system isin a quanturn state, Then the average of the observations of the quantity X taken over a system described by the proba. bilities Pu is mao CD = Exits, | a ‘This equation defines the average vatue of X. Mere P(x is the probability hat the system is in the state s. The angular brackets (+) are used to denote average value, Fora closod system, the average value of X'is baer ot = = EXC. co) because now all g accessible states are equally likely, with PC) = Vg. The ‘average in (4) ig an elementary example of what aay be called an ensenbte average: ke imagine g similar systems, one in each accessible quantum state uch a group of systems constructed alike is called an ensemble of systems. The average of any property over the group is called the ensemble average of that propery. = ve0'$ ‘Aa mile of spstems I composed of many systems, all constructed alike. Each system in the ensemble is replica of the actual system in one of the santum states accessible 10 the system If there are g accessible states, then {here will be g systems inthe ensemble, one system for each state. Each ssn in the ensembic is equivalent for all practical purposes to the actwal system, Each system satisfies all external requirements placed on the original system ‘and in this sense is “just as good” as the actual system, Every quantum state aChapter 2s Eneopy ond Temperate At ft Vigwe 22 Th of 10 spins ‘The shitty gt ‘rer in which the various systems in the embe ee lise aso sgniiance Accessible fo the acta syster is represented in the weensemble by one system in a Stationary quantum st as in Figure 22. We assume that the ensemble ‘epresens the rea system —thissimplied inthe fundamental assumption, Example: Consracion of n ensenSle. We consruct in Figuse 23 an ensemble to ‘sheen closed sytem of fie spins. ach system wth spin encess 2 = I, The eeray of chin mugneic itd is ~mB. (Do not coatoe the use of in spin exces eaten reswen us fata tate ins or abel) Each ple repesets en ofthe muipls of \ Mose Probable Cofguration Figwe23 Theensemble repesetsa system wth N = S spins and sin exces 2s « | 2 opal stuanon ‘uso states a thisenetgs, The number such tess given bythe multi function cs a= 9%, m0, SN = yyy 0 The 1Osystsms shown in Fgute 23 wake wp the cnsemb ahs ener nthe magnetic fal wee sul hate \hcensebke ts in Figure 24 romp heblaticn gS eauahand the new ensembe oat reeset 2 ysl of wih $ systems ave 25 35 10 systems have 2e= 1 10 sjstcas have fave 26 “3; and Lyeona has 2s 3 hale Most Probable Configuration et two systems $1 and $3 be brought into contact so that energy can be wansfereed freely (fom one tothe othce. This is called thermal contact (Figure 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 encray of one system is greater than the energy of the other, because theas Chaper 23 Entropy and Temperaare Two dosed [Uy tem aot |], incomact |]. gy Tnslation The systems sre in Therast contact lesulstiag The#mal conductor allows ‘vchangs of energy Fine? Estbtsbment of her contat betwcin to systems 8, ant ‘ystems can be diferent in siz and constitution. A constant total energy can be shared in many ways between two systems, The most probable division of the tal en system has the maxiniin aumabs accessible states af two models ergy sthat for Which the combined eof ccesibe states. We shall enumerate the ystems an then siady what characteries the Systema when in dermal contact, We fist sole in detail the prablein of thermal contact between vo spinsystes, land 2,ina magnetic ld which is introduced in order to define the ener. The numbers of pins, Np may bs diferent, and the values of the spin excess 2,, 25, may be diferent forthe two systems, All spins have magnetic moment m, The aemateschange of energy might take place ‘ia Some weak (residual) coupling between the spins near the interfce between the two systems, We assume that the quaniutn states of the total system $ ean be represented accurately by a combination of any tate of 8, with any state of ‘Sr We keep iY, Ny constant, but the valves ofthe spin excess are allowed to change. The spin excess of sate ofthe combinsd system wll be denoted by 25, wheres = 5, + sy. The eneigy of theeombined system is directly proportional to the total spin excess \ U0) = Usted + Us) = ~ Bs, + 83 Bs, 6 ‘The total number of pacicles is N= Ny 4 Ny ‘Most Probable Configuration ‘Wenssume that the energy splittings between adjuceit energy levels are equal 0 2m in both systems, so that the magnetic energy given up by system 1 when one spin is reverse can be taken up by the reversil af one spin ofsysiem 2 in the opposite sense. Any large physical system will have enough diverse modes of nergy storage so that encigy exchange with another system is always possible, ‘The value of s = 5, 4+ 5, is constant because the total energy is constae. but when the two systems are brought into thermal contact a redistribution is permitted in the separate values of s,, 5, and thus inthe energies Uy, Us. ‘The multiplicity function g(W3} of the combined system $ is related 19 the product of the multiplicity functions of the individual systems 4 and Sy by the relation ats) = DadM sills — 50. 6) ‘where the multiplicity functions 9,, 9, are given by expressions of the form of (1.13), The range of 5 in the summation is from ~4N, 10 40. iC Ny < Ny ‘To soe how (6) comes about, consider fest that config system for which the Fics system has spin excess 2s, and the socond system has spin excess 255. configuration is defined asthe st ofall states with specified values of and 52. The fist system has 9 (V5) accessible states, each of which 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 is given by the product g\(N,,5,)9,(N,s1) of the multiplicity functions of 8, and S,, Because s, = s ~ s, the product of the g's may be written as bf the combined gala slgtNas = 5p. o This product forms one term of the sum (6) Different configurations of the combined system are characterized by different ‘aloes of. Wesum over alt possible values of, to obtain the total number of ates ofall the configurations with Bxed ¢ or fred energy. We thus absain (6), Where g{N.s) is the number of accessible states of the combined sysein in the sum we hold 3, Ny, and 1, constant, as part of the specification of sheseyal The result (6) isa sum of products ofthe form (7) Suc a product will be a ‘maximum for some value of, say 8), 10 be read as “sy hat” of “3, caret” ‘The configuration for which gq, 1 a maximum it ealled the most probable ‘configuration; the mumber of states in itis 9lVas)9IN 3 ~ 54) @ eagle f? k e hove ob a46 Chaps 2: Entropy ant Tenperatare BC, UD Xap UU 0 Eo uy Thermal equilibeium Figure 26. Schematic representation of the dependence ofthe ‘onfigucation mtiptity onthe diision ofthe tla ence becwsen wo systems 3, and Sy If the systems are large, the maniinum with respect to changes ia s, will be ‘atemelyshacp, as in Figute 2. A eatively small numberof configu will dominate the statistical properties of the combined system. Th Probable configuration alone will describe iany ofthese properties, Such a sharp maximum isa property of every realistic type of lage system {or which exact solutions areavailabl; we postulate thst isa general property ‘of all large systems. From the sharpness property it follows that fucuoeatony, ‘about the most probable configuration are small, in a sense that we will define [The jnportant result folons thatthe values ofthe average physical properties of lange system in thermal contact with another large sytem are acewately oyfiitiel) + o,f) ‘As 2 consequence of (2), we see that S and g are connected by a scale facto c 1 SH hyo. (0) La We will call § the conventional entropy. ‘The more sites that are accessible, the greater the entropy. Inthe definition of (NU) we have indicated a functional dependence of the entropy on the ‘umber of patictes in the system and on the energy ofthe system. The enteopy ‘may depend on additional independent variables: she enteopy ofa gas (Chapter 3) depends on the volume, Jn the early history of thermal physics the physical signifisnce of theenteopy was not known, Thus the author of she article on thermodynamics in the Encyclopaedia Britanuico, {1th ed. (1905), wrote: “The wility of the conception of entropy «is tinited by the fact that it does not coeresporid directly to any atirectly measurable physical property, but is merely a mathematical function of the definition of absolute temperature.” We now know what absolute physical property the enfropy measures, An example of the comparison af the experi= mental determination and theoretieal calculation of the entropy is discussed in Chapter 6 Consider the total entropy change Ag when we remove pasitive amount of energy AU from 1 and ad the same amount of energy to 2, as in Figure 27Chapter 2: Enron and Fenperatre “The total entropy change is Jean + s0 that the total change of entropy is positive when the dtection af energy flow is fom the system with the higher temperature to the system with the lower temperature cs Exumpl: Entropy invens om het flows “Thisexarple makes se of fanulasy with heat and specie heat, {@) Leva ig speeimen ofcappeeat a temperature of 350K be placed i With an sential specimen ata termperatare of 241K, Let vs find the quay of energy seafetrdwhe hs tn species spac in contact nd come to equi at he fal tmperature T,. The specifi heat metalic copper over the lemperature range 15°C {9 100°C is approtinatey 0389 9°" K", according to a standard handbook ‘The cisigy ince of these pee seu oe energy YORE OT MMe tt ‘hc energy ineease of the second specimen yin joules, Au = 391 Tp — 290%) = BAIIK-NGSOK ~ TPs where the tempeeateres ate in Kalvin. The Raa tempsiare ascents i Ty = $090 + 290) 20K. AU, = QS9EK™(—30K) = 1173, and AU, = AU, = 171. Wh the change fentrpy ofthe vo spesinens wen a tras of 1 hat sen nya iy ar ect? Nee tr ea fae of teal ners aera at above Bese he enc ance ‘Seed aal we ay spe the specter ae apraimaey ate al eng turer of and 20K, The enrony ofthe fin body eres by 285 104K 7 Law of rere of Eneapy 6 ‘Tre sateopy ofthe second body isinereassd by on dy Bo 7 98S «OK The etl eatopy increases by AS, + AS, 286 4 345) x WYK! 059 x LOUK Js fundamsnit wits the inciease of entropy 059. 1074 iy be on heise Bottzmano constaat. This result micas that the number af accessible ater ofthe swo.pstems lnceass by the fata expe} = expiOd 10}, Law of focreass of Entropy We can show thet the total enteopy altvays increases when two systems are have just demonstrated this ina special ease + Uz is constant, the total multiplicity after the systems are in thermal contact is Drought into theraal contact. Well I die ota energy Um Uy AY) ~ Fata = oy), @) by (18) This expression contains the cerm g,(Uye)gy(U — Ugg) forthe initial ‘ultipliciy before contact and many other terms besides. Here Uyy is the ‘nikal energy system t and U — U9 isthe initial energy of system 2 Because al feems in (3) are positive numbers the multiplicity is always increased by ‘establishment of thermal contact between two systems. This is a proof of the law of increase of entropy for a well-defined operation, ‘The significant effect of contact, the effet th ogacithin of the multiplicity, isnot just thatthe numberof tems in the sunmmas ‘lon is lage, but thatthe largest single term ia the summation may be very, very ‘ouch larger than the fitial multiplicity. That is, at stands out even after taking the Gi) # 04(0,)9,(U — B,) oH“ (Chopree 2: Emropy and Temperature ce) Energy Entropy Time Time te2K A spstom wit twa prs, El 2. pone tra ine with Uy = Onl U; = U. Exchange of ence takes place between two partsand pesenly the sytem will ound norco othe most Probable configuration. The entopy inceeass 8 he system atains configurations ofinereasieg mulpiity o probability. The entropy ‘ventaly teaches the enlopy aU) ofthe most probable configrition may be very, very much larger than the initial term gilUsolasU ~ Used. 05) Hse 0, denotes the value of U, for which the product 9,9) is @ maximum, ‘The essential effec is that the systems afier contact evolve from their iit configurations to their final configurations. The Gundsinental assumption implies that evolution inthis operation will always take place, with all accessible Final states equsily probable, The statement int ~ 8G, Osbace ® Seat ~ 1031040 of the Law of netease of entropy: the entropy of a tends to remain constant of to igersase shen a constant intern to the syste is removed. The operation of establishing thermal contact is equivalent to the removal of the coostraint that Uy, Uy each be constant; after contact only U, + U, need be constant ‘The evolution of the combined system towards the Final thermal equilibrium configuration takes & certain time, Ife separate the two systems before they Lav of ncease of Entropy ” Ways to inrcose the entopy |Add panicles —d a AU energy Naa Incrsane the volume 3 a? Decompose molecules Leta linear polymer eudl up Figure 29, Operations that tend increase the entcopy ofa syste. ‘each this configuration, we will obiain an intermediate configuration with iermediate energies and an intermeuiate entropy. It's thevefore meat ‘ew the entropy asa function of the time that has elapead since temosal of constraint, called the time of evolution in Figure 23. Processes that tend to increase the entropy of a systein are shown in Fipuse 29; he arguments in support ofeach process will be developed in the chapters that follow,a Chapter 2 ane Tomer / Fora large system* (in thermal contuct with another large systerr thote will sever ovcur spontaneously significant ferences between the actual value ofthe ‘entropy and the value of the entropy ofthe most probsble configuration of the system, Weshowsd this forthe model spinsystemtin thearguntent fllowina(17}; ‘seuused “never” in the sense of not once inthe entire age of the universe, 10!" ‘We can only find a significant difevence between the actual entcopy and the sntcopy of the most probable eanfiguration of the macroscopic system very shortly after we have changed the nature of the contact between 160 systema, which implies that we had prepared the system initially in some special Way. Special preparation could consist of fining up all he spinsin one system parallel to one another or collecting all the molecules in the ait of the room into the sytem formed by a small volume in one corner of the room, Such extreme sitwations never arise naturally in systems let uudisturbed, but ase feom ntficiat operations performed on the system. Consies the ys in a room: the gas ia onchalf of the room might be prepared iniially with afow value of the average energy per molecule, while the gas in the other haf ofthe room might be prepared intially with a higher valve of the average energy per molecule. Ifthe gas in the two lslves is now allowed to imtosest by removal of a postition, the gas molecules wll come ¥ery quickly" toa most probable configuration in which the molecules in both hale of the room have the same average energy. Nothing else will ever be observed to hhappen. We willnever observe the system to feave the most probable configura ‘ion and reappeat later in the intial specially prepared configuration, Thisis true even though the equations of mation of physics ace reversible in time and do not distinguish past and futur, LAWS OF THERMODYNAMICS When thesmodynamics is studied as a nonstatistical subject, four postulates, fae introduced. These postulates ate called the laws of thermodynarsics. In cessenee, these laws ate contained within our statistical formation of thermal physics, but ii useful fo exhibie them as separate statements Zeroth law, 1 two systems are in thermal equilibrium with a thied system, they must be in thermal equilibrium with each other. This aw isa consequence { Alaegcor mooie stem ay betslentote ope sth marethan 10" o¢ 1" ston "These of he ine egal othe prnenagsly «pen i hydredyssc, Lev of Thermadynanies ‘of the condition (296) for equilibrium in therm: Boss) (eloga, elogg: wy), Us de) AU Ie In other words, ro 4, and tp = £5 imply ry = ty Flest law, Hes ) ‘sa form of energy. This law is no more than a statement of the principle of conservation ofenergy. Chapter & discusses what form of eneray oa is Second law, There are many equivalent statements of the second law. We shall se the statistical statement, whieh we have called the Inv of increase of entropy, applicable when a constraint interna oa closed systems removed The commonly usedstatement ofthe law ofinerease ofentrops is: "Ifa closed systems ‘sina configuration that snot the cuits iuon configuration dhe ant probate consoquence Will be thatthe entropy ofthe systein will inerease menotonicaly in successive instants of tims.” This a fooser statement tite the one We gave with Eg. (36) above, ‘Ths traditional thermodynamic statement is the Kelvin-Planck formulation ‘uf secon law of thermodynamics: “It is impossible far any cyclic process to occur whose sole effet isthe extraction of heat from a reservoir aid the pete formance of an equivalent amount of work" An engine that volutes the second lave by extracting the energy of one heat reservar is said to be performing Perpetual motion ofthe second kind, We will se ia Chapiee & thatthe Kelvine Planck formulation isa consequence of the statisti! statement ‘Thirdtay. The eatropy of a system approaches a constant valve as the ‘emperature approaches ze. The earliest statement ofthis la, dueto Nernst, is that at the absolute zero the entropy diference disappears Between all those configurations of s)sterm which are in internal thermal equilibsium. The third Jaw follows ffom the statistical definition of the entopy, provided that the {round state of the system has a well-defined multiplicity. Wf the ground state multiplicity is 9(0), the corresponding entropy i (0) = loggi0) as ¢ -0 From a quantum point of view, the law does not appear to say miuch that is ‘not implicit in the definition of entropy, provided, however, that the system is in its towest se of quantum states at absolute zero, Except for glasses, there Would not be any objection to affirming that g(0) isa small number and a(0) is essentially zero. Glasses have a frozen-in disorder, and for them 2(0) can be substantial, ofthe order of the number of atoms N. What the thicd law tells ws 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 / Entropy as.a Logarithm Several useful properties follow fiom the defini ition of the entropy as the toga: Fithey of the number of accessie states, instead of asthe number of accessing slates itself First, the entropy of two independent systems fs the sum of the separate entropies, Sccond, the entropy is entirely insensiive—for afl practical purposes—to the precision SU with which the energy ofa closed system is defined. We have ‘ever meant to imply thatthe system energy is known exactly, a eizcumstance ‘hat for a discrete spectrum of energy eigenvalues would make the number of seeessble sates depend erratically on the energy. We have simply not paid much attention tothe precision, whether it be determined by the uncertainty Principle 5U d(tine} ~ b, or determined otherwise, Define O(U) 38 de number of accessible states por Unit energy range; O(U) ean be a suitable smoathed average centered at U. Then y(U) = O(U}3U is the umber of accesibte states in the range SU at U, The entropy is OU) = lop D1L).4U = log OU) + fogsU, on ‘Typically a forthe system of 1 spins, the total numberof states will be of the frder of 2. Ifthe toral enerey is ofthe order of N times some sverage one particle energy A then 9(U) ~ 248A, Thus a) = Ni tog NA + logsU, 38) Let N= 102; 4 10" exgsand 5U = 10°" erg, 9(U) = 0.69 x 10° — 1382 ~ 23. 09) Wesee from this example thatthe value ofthe entropy is dominated overwhelm ingly by the value of NV; the precision SU is without perceptible effect on the result. Inthe problem of fre paiticlesin a box, the number ofstates is propor- tional to something like U*3U, whence @ ~ WlogU + logsU. Agsin the ' in N is dominant, @ conclusion independent of even the system of units sed for the energy twat orton of te second Kid. Esty in our stay of physics we exme to tsrstand the ansbiity of perp ution machine, a aching at il ge oth more encrsy th abort — Summary sn Equally imposible fa per Et ‘8 perpttal motion machine of the gsond kin, asi called ja Patt of theenvironment and delivered to nother pvt = emperatue dus established being used to power heck enesgy necessary to fom the ow temperstve ocran vo 4 Sip would dstease te total enttony of the combine lation of the tw of inexeas of entropy. propel the ship, The spontaneous trans of enti highes temperature bole on the ‘stems aed would thos te in ie SUMMARY 1 The fundamental assumption is that a ctosed system is equally likely to be ‘i any of the quantum states accessible to i 2 IEP()is the probability that a system isin the state 5, thea ‘ouantity X is age value ofa 6) = Exar, alike 4 Menenberofaccsnblesaesoftecombined sens tand2is es 9) = Lavelars ~ 51), Ss , os wheres, + 52 5, & S. The entropy o(N.U) = logg(N,U). The relation § e kyo connects the ‘conventional entropy S with the fundamental entropy o: 6, The fundamental temporatuce tis defined by Yew ee ‘The relation «= hyT connects the fundamental temperature and the cone ventional temperature 7. The law of increase of enteo fends to remain constant or system is moved, PY states that the entropy of a closed system to increase when a constraint internal to the2 (Chapter 2: Entropy ond Tewperatce ) ‘The thermnat equilibrium values of the physical properties of a syste defined as averages over all sates accesible when the system isin contact ‘vith wlargeaystem or reserve the ist syseny also fe lage, Me thermal ‘equilibrium propecies ae given accurately by consietion of the states in ‘the most probable configuration alone. PROBLEMS 1. Entropy and tempecatare, Suppase gW) = CU, where Cis a constant and N is the mumber of particles 1) Shows that U = JW. (8) Show that (@o/PUgis wegative This form of gtU actully ap tania, 2. Paramagnetisns. Find the equiltium value at temporatuee tof the free tional mag M Nar 2eay/N ofthe system of N spins cach ofuaguetic monient avi a magneite eld B.-The spin exeess is 25. Take the entzopy as the logactbithm of the muiplicity g(N,9) as given in (1.38): (5) = loo gX.0} 2M, a) for [p< N. Hint: Show that io this approximation o(U} = 69 ~ Ua BAN ay ‘with 9 = logg(N.0), Further, show that t/e = — Uj? BN, wh UD, the thermal average eneees 2 U de 3. Quantum harmonic oscttaor. (a) Find the entropy of a set of N osciators of equency «a8 a function ofthe total quantum number n. Use the multiplicity fonction (1.95) and make the Stirling approximation log N! = Nlog iN — N. Replace N~ 1 by NV (b) Let U denote the total energy ihe ofthe excilators Express the entropy 4s o(U,N). Show that the total energy at temperature is Ns U = Sahai) i ‘This isthe Planck results it is derived again in Chapter 4 by @ powerful method ‘hat Uoes not require us to find the mulipicity function, Prodens 4, The meaning of “never.” 1c has been stid® that “sie monkeys, se to sirum ‘uniutelligentty on typewsiters for millions of years, would be bond i tine to write all the books in the British Museum.” This statement is nonsense, for it ives a misleading conclusion about very, vey large numbers. Coeld all the ‘monkeys in the world have typed out a single spocitied book in the age of the Suppose that 10*° monkeys have bron seated at typewriters throughout the age ofthe universe, 10° s. This number of monkeys is aboot these times greater ‘han the present huntan population* of the eatth, We suppose that a monkey can hit 10 typewriter keys per second. A typewriter may have 44 keys: we accept lowecease Fetters in place of capital leters. Assuming that Shakespeare's Horiter bas 10° characters, will the monkeys hit wpa Hannlet? 2) Show that the probability that any given sequengs of 10* characters {yped at esnvion will eome out ie the eorreet sequent (he neuen of Heer) iso the onler of . (tater one 2 grist ade, where we have used logig 44 ~ 1.64345, (6) Show thet Ute probebility hava monkes-Hantet wil be typed in the age fof the universe is approximately 107'64"%, The probability of Handler is ‘therefore zero in any operational sense ofan event, so that the original statement atthe beginaing ofthis problem is nonsense: one book, muich less a library, ill never occur in the total literary production ofthe monkeys S. Aditivity of entropy fortwo spin systems, Given wo systems of Ny = 1 = 10% spins with multiplicity functions gy(Ny.s) end 93(N'39 ~ the Product gy93 85 «function of, is relatively sharply peaked at sy = §,.Fot 4 + 10" the produet gig, is reduced by 10°" Irom its peak vali. Use the ‘Gaussian approximation to the multipicty function; the form {17} may be sel {a) Compute 9,02/10,9ihun for s, = 5, + 10" and s = 0. (6) For s = 10°", by what factor must you multiply (g,¢slun to make it equal to Dy, aM isil0AN3,5 ~ s3)5 give the factor to the nearest order of magaituds, 1 Jeans yer waves, Cole Univesity Pres, 198,p.4 The sateen atte rot arelted mathemati trary say, ee“TheLiacyo Batt” by he per dong tic orp eciane, Grove Pres: Erte pspebact 1962, pp. "or etry person sow ave, some they prtne have scenes Th gue usted by A.C. Clarke in 301 We ae grail ete Popstaion RetrenceUaresu 2019 Dr. Reyer Revel or ‘elation ofthe evidence. The eamlatne number of manscconds 2 IGM wc take the ‘erage lite a5 2x 10" andthe wumber of Ives 10 ec of he cams ich et han the nub f onke-cconds 10) tgnin he rcblo, ss(6) How large is factor? 6, Integrated deviation, For the example that gave the result (17), caleulate 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, fractional error in the entropy when you ignore this cana) fem) 1 smal ems Chapter 3 Boltzmann Distribution and Helmholtz Free Energy BOLTZMANN FACTOR Partition Function Example: Energy and Heat Capacity of @ Two State System Definition: Reversible Process PRESSURE ‘Thermodynamic Wentity HELMHOLTZ FREE ENERGY Example: Minimum Property of the Free Enctey of a Paramageetie Systemn Ditterential Rettions Manvel Relation Clewtation of Ffcom 2 IDEAL GAS: A FIRST LOOK (One Atom in a Box Example: 4’ Atoms in a Box Energy Example: Equipaetiion of Energy Example: Entropy of Mixing SUMMARY PROBLEMS 1. Free Energy of a Two State System 2, Magnetic Suscepubility 3. Free Energy of a Harmonic Ocitaror 4. Energy Fluctuations 5. Overhauser Effect 6. Rotation of Diatomic Molecules 7 Zippee Pesbem 8 Quantum Concentration 856 (Chapter 3: Boltzmann Di ion aod Hetatois Fie Enrsy 9, Partition Funetion far Two Systems ts 10, Elasticity of Polymers 86 1 One-Dimensional Gas 86 Unis: Ternodsnamic teats cam ealy be watsed from fun Sane eso comentoaal unis The oa yaoi tat wil nse iis athe hot sapieg, eed book ei Mand) = eu sin fadanent ent and gs Clone) = Tees Pa wo quinn be for Class kyClood) : Chapter 3: Rotemann Distribution and Hetbolte Free Energy ” The laws of thermodynamics may easily Be obtained from the principles of Statistical mechanics, of which they are the incomplete expression, iste Weare able to distinguish in mechanical seems the thermal action of one systems (on another from thar which we eall mechanical in the narrower sense. so as to specify cases of thermal action and cases of mechanical action, istsIn this chaytee we devetop the principles that permit us 0 calculate the values # the physical properties of a system as a function of the temperature: We assume thatthe system Sof interest to {arge system Gt called the roserwuir, The system and the receivers wil here common temperature « because they are in thermal eomace ZThe total systein 8 + $ is a closed system, insulated from all external fnflusnces, as in Figure 3.1. The total eneray Uy = Um + Uy is comtant ta Pattie ifthe system i in a state energy, then Uy ~ ia the energy of Toul sytem Constant enerey U, Figure 34 Representation ofa closed teal ster decompose into'a ‘esse tin hucmal contd witha astern 8 BOLTZMANN FACTOR ‘ central problem of thermal physics isto fad the probability thatthe system § ‘ill be in. spciis quantum state sof energy This probability i propor ‘ional to the Boltzanana factor. ‘When we specify that 8 should be in the state 5, the number of accesible ‘ates of the total system is reduced to the number of accessible states of the reservoir l, at the appropriate energy. That is, the number ga, of states s Boltzmann Factor 8 co) Figure 32. The chaece ofentropy whun the aU) a reservoir iransers energy cto the systrn The fractional eect ofthe tansfer onthe reset is small when the reserva ang, because a lange reservoir will hive high entops Entropy of the reser Energy ofthe reservoir——— accessible oR +8 is aX may 0 ‘because for our present purposes we have specified the state of $ Jf the system energy is the reservoir energy is Up Gj. The number of states accessible to the reservoir inthis condition sgq(Up — e)asin Figure 3.2. ‘The ratio ofthe probability that the system is in quantum state t at enersy 4 to the probability that the system isin quantum state 2 at energy eis the ratio of the to multiplicities: le) _ Multiplicity of at eneray Ug = 2, WYa= PG.) ~ Multiplicity of 0 at ex tay Uo = @ gly — #3) eo This result is @ direst consequence of shat we have called the fundamental assumption. The twa situations are shown in Figure 3.3. Although questions about the system depend on the constitution af the reservoir, we shall se that the dependence is only on the temperntare of the reserve ihe reservoirs are very lange, the multiplicities are very, very large numbers, We write (2) in terms of te entropy of the reservoir Hed _ oles =A) estes 6) ~ elle in conformity with common practice; U will now refer to the system 4nd not, as earlier, to the system + exervoir, Example: Energy and est caput of at le with vo states, one of enegy a With a reece at temperate system as a fonction of the temper the particle ig Weweata system of one oei= on of corey The pute thermal comet fe wa0t to find the energy and the heat capil of the lute + The patton fanstion forthe two Mats of S019 + ene —e) = 1 4 explain 03) The average energy i Ua = SRE, ,_exrl-ae) T+ eloead uy ‘This fonction i pln in Figure 3.4 {ewe sh the aro of energy an tak the energy of the to tes. as —Leand +45 instead ofas.O ante, the esate appei difecnly We have Z = explaf2e) + expla) = Deoshley?9), us, Poston Fuction and dey = TOHCAD + UederD(—w!29 sinker 7 z Reoshled = =tetaninen, 06) ‘The heat capacity Cy ofa system at constant volume is deine as Cymaraley , (7a) which by the thermodynamic deny (34a) derived below isequvaout to the shernate Aebnition Cy = (UH. ub) Wehold ¥ constant cause the value of theenegy ae alcuated for asysematapcified solume. Prom (14) and (17), at fey expen : oeamenein() emer) he same result fellows rom (86, I conventional usits Cy isin 25 TWS/ET, or (UsOT whence con {In fardamentl unis the heat capacity ie dinensonles; in contentionsl unite ths he inersions of ensray pee Uehin, The pei het i dstined as he eat enpacy por wnt “Thebumpinhe poco tet expacily vers tompcratuein guests aScothy vomily. Fors» ¢ the heat cacy (18) becomes contention) (sb) Cy = et 419) ‘otis that Cy or +”? in this high temporatre ff the Tow lempeatuse Fit the ‘emperatore i smal in compatson with the egy level spacing «For t< ee have Cv = (ele expl—c/ eo Theesponenta fxplef} reduces C opdly a dereaes boausessgl is) 0 ssn 0,(Cloprer 3: Bolsnans Distbatio end Helabais Free Energy A process is reversible ifcarried out in such a the system is always infinitesimally close to the equilibrium condition, ‘amply ifthe entropy isa function of the volume, any change of volume mast be carried out so slowly that the enttony a any volume V is elosey equal {0 the equilibrium entropy o(¥). Thus, the entropy is well defined at every stage ofa reversible process, and by reversing the direction ofthe change tte sytem will be reluened to its initial condition. In «condition ofthe system is well defined at all tiie, in contrast to rreverable brocesses, where usually we will not knove what s going on during the process, We cannot apply the mathematical methods of thermal physics to systems whose condition is undefined. ‘A woluine change that leaves the system in the same quantum state is an xaruple ofan isentropic reversible process, the system always mains in the sme state the entropy change will be 2ero between any two stages ofthe pro. «e=35, becouse the number of satesin an ensemble (p. 31) of similar systems does ot change. Any process in which the entropy change vanishes is an isentropic reversible process, But reversible processes are not limited to isentropic pro- ets, nd we shall havea special interest alsoin isothermal reversible processes Definition: Kerersible process, sible processes, the ta fat Consider a system in the quantum state + of enerey e, We assume function of the volume of the system. The volume is decreased slowly from V to V = AV by apolication of an external force. Let the volume change take place sufcintly slowly thatthe system remains in the same quantum state 3 throughout the compression. The “same” state may be characterized by its ‘quantum numbers (Figure 35) oF by the number of 2105 ia the wavefunction, ‘The energy of the states after the reversible volume change is tobe a 5? = AP) = aft) — (dea + en Consider a pressure p, applied normal to all faces of a cube. The mechanical Work done on the system by the pressure in @ contraction (Figure 3.6) of the ‘cube volume from ¥ to V ~ AV appears as the change of energy af the systems UW — AY) = UY) = AU = —(dedY)AY. 22) Presse “ woe n 6 w 3 3 03 Sy Woe 24 3 Pos Mo TJ] 6 p+, D 0 as 18 is 20 Volume, setatve cae ite3.5_ Dependence of earey'onvelame, forthe enety ves of fee atte confined toa cube. The curves ae label by nt =n 4 mb my in Figwe 12. The mukipies 9 ate alo given The volume change here Isisouopic: 5 eube remains «cube, The energy rags eof the stes repeesentel in an eisebie of ssn wil nccae in 2 severe ‘ompresion, but we how fmm the dscssion i Chapter 2 thatthe width the energy range sei of no practi important ithe change it the average energy hat ie inpovtant, e36 Volume change ~ AW in wniform compression ofa cube66 (Chapter 4: Bolrmann Distribution amd elaoles Fee Energy Here U denotes the energy of the system, Let A he the area of one face of the cube; then Ala + Ay + av, @ ifall inceements AV and Ax = Ay = Az are taken as positive in the compres: sion. The work done in the compression is au AUX + Ay & A) = pay, ey £0 that, on comparison with (22 deg ro) isthe pressure on a system in the states Weaverage (25) over al states ofthe ensemble to btain the average pressure | (63) iscalled the quantum concentration. ti the concentration assoeiated with one ‘of side equal to the thermal average de Brostis wavelength, ‘which ie length roughly equal to A/M ce) ~ M(ME)!2, Here C1) isa thermal average velociy. This concentration will keep turning up in the thermal physics ‘of gases, ia semioanidutor theory, ad inthe theory of chemical reactions For helium at atmospheric pressure at room temperature, n = 25 x 10"em™? and i = O8 x 108*em™, Thus, wig = 3 x 10°% which is very 1”a (Chopir 3: Bottzmaon Distribution and telat Free Energy ‘mall compares to unity, so that helium is very dilute under norinel conditions, Mihenever hg 1 we say tha he ges isin the clastat regime. An ideal gas 's defined as a gas of noninteracting atoms inthe classical regime. ‘The thermal average energy ofthe atom in the box is, asin (123, Severpl—eie) oF - oz, v Dy oy because 2," exp(~e/e}s the probability the system isin the tate n, From (62), Jog Z, = —flog(l/e) + terms independent of « , sottt one gsofone tom [uk 69 Me = lyf, where ky is the Boltamann constant, then Us MT, the well ‘known result for the energy per atom of an ideal ges. ‘The thermal avexage occupancy ofa free puctcle orbital satistice the ine equality 1 Nenpl—fe) < Ze = lng. Which sets an upper init of 4 x 10°® for the occupancy of an orbital by a Nelinm ators at standard concentration and temperature. For the lasscal ‘egime to apply, this occupancy must be 41. We note that, a8 defined by (59) isalways positive fora fee stom, Vatams ina hor. There fllows now 8 ticky argument that we will use poratity until we develop in Chaps 6 a powesfl method 1 dal with the problem of ‘many noninteracting ideiical atoms na bos. Weft tat an eal pas of tonnsa box, all tons of dierent spies o¢ diferent isotopes. This sa simple eatension of the ‘ne atom rest. Westen sscus the nae coercion fst that rae when all tons ne ‘ential ofthe same isotope ofthe sume species, JOOGS0o roy Fige3.7 Any, baclse system of te patees with one patie in each of Boxee The "eee is imes tht fe one pte i one box Figue38 Atoms ctaifecent species ia singe box. cree ar acne som in each of dtnet bows (gue 3. the pation farcvion ithe ‘rvdct ofthe separate ene ator panition encooee 2rnna’ = Zl) 2,2) ZN), 6) Tena the product on the righthand side ictus every independent sate of the A boxes such 2 the ste of energy. 2D EO) eet). wn whet A... snot the eri indice of atoms uso ives he puttin freien ‘ingle box Fie 8, inthe suvcsive Bote. The esl (65) "of N sowintraetiy atous al of wierenl speees trp 21) 2,1) 2,06) 24) , INS ein he sae problem because the ene igsnvalus ate sae fr (6h the ‘Rass of alhee diferent atoms happen to be the same the lal sini keaing ould be Z,% where Z, igen by (OL ches we constr ihe mate ccmmon prablem of M intial partic in one box, we have to crrest 2," bacause it oxerenunte the dita ster ate Sue Fatslesofa sige secs ars ot dsingentablesstsnoun da sot cany ee Sop mumburs. For wo ible patie @ sad ina snge toe the state uO) ey aii thestte ule) + 6401 are distinc states ad both combinations sane theruate eae ian Mostin, Bat fr ivo idea pots the st of creep eons te ache steas f+ sy andonyencentey isto be made ia he tatesun inthe peice Auncion erat pute16 Chapter: Bal nana Distribution and Hats Fre Energy hc orbital nae areal icon, exh ety wil eccur N kmes ia 2,4 whereas the ‘nity should occur onl enced aries ate cata TZ," onerouetsthestatesby afacior of and the carset pti funtion for iene ptt (63) in the casa regime Here ng = (Me 2ah°P* fron (6) “These isastep inthe argument whee we ssn hat al N oecupsd orbitals re aways sdecent ocbitats. 18 no simple mater to erluate dire the error intron’ by te sppcoximation, but ater we wll cost by another metho the validity of 8) fo the {asia ops ng The tor change theres fo the entony of the hes goo The cnopy is an experimentally messurabe uantiy, and it has bern coated hat the tacts corti this iw concentration Ln Sst Soe Energy. The energy of the ideal gas follows from the particle pation function by use of 12} (Clog Z 410 ie, 6) consistent with (68) for one partite, The fee energy is F = ~sloszy 11082," + tlog 70) With theearlier result Z, = ng = (MsP2xh?)V and the Stcing approxima tion logN! = NlogN ~ N, wehave Foo tN logiMe/25h2)!2¥] + eWtopi — aN, om 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, ~” pene, | a or eal Gass A Fe Lak Whit cafe the eal gosta, tn conventional units, 1 = Why, 0 “The entropy follows from (49) o> (FP oe = Nlog[tAtePaekPRP] + IN = Nope +N, (75) 4 Mlogtnle) +. 9 with the concenteation 9 equation forthe ent N/V. This result is known as the Sachur-Tetiode opy of a monatomic ideal gas, 1 agtess with experiment. ‘The result involves fr through the tern ng, so even forthe cassial ideal gas ' ths enteopy iwvulves 8 quantum concept, We shall derive these results spain in ‘Chapter 6by a dicest method that doesnot explicitly involve the N or identical particle argument. The energy (69) aso follows from U = F + roy ith use of (7) and (76) we have U = Ne of exergy. Theenergy U = IN from (Ds seb to cont: ‘ation from each “degree of eedom” ef each patie whee the numberof degser of ficedom isthe numberof dimensions ofthe space in which the atoms move: in th ‘example, In the essa! form of statisti! methanisy the pation fenton cotsns the ints enetay ofthe pasticles ina interal ovr the momentum eompaneatn, For one fee particle ae 21 fffesvt= (ot + 0,8 + PVM doedeydp, 7) ‘resol sir to (61) The timits of integration are 2p fr etch component The thermal 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 Ishomopeneousof degre 2in 3 canonical momentum componente sass lini othe 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otcoinn Distribution and Welnhats Face Energy | Vibration ak L 2 MW Rotation “Translation 4 102530 18105380 Sea" 1000” 2500. Sooo ‘Temperate, K Figure 39° Heat capaciy a constant woltine of one molsee of Hy fa ‘he is hase, The wea rte ia ademas eats sae goa in conventional units rouliply by fy, The contibution fom the thece ‘eansutiona depres of ieom isthe eatibution at high tempertores fem the 40 colatinal deers of reedars Isa he coneiburon Som he potential ad bins energy ofthe wbuational voto inthe Tigh tneratere int 1 The asia nts ate stained ten + > elvan esrgy kvl separations plies othe harmovieosiatoe i he easily The quanto ess forthe hae "otic oseilator and for the diatomierotaor ace deinen Potens and 6 esp ‘AC high temperautes the cassis hms ne sinioed a i Fig 3 Exanrle: Exons of mixing. In Chapter | we caleulated the umber of posible arrange Ineatsof A ani Bina soli made wpof — rates end ¢ toms B. We found ia 020) forthe aumber of arongsnents x y= 0 AN = aT oy “The enttopy assed with hese arrangements 3 {8,4 = logg(Nu) = log! ~ log — a! tose, 79) dis pote in Figure 310 for 0. Thiscontrbution othe tal entepy of a alloy eat a Fis took enropy 0 ae Alloy composition Ay. Dy Figure340_ Mixing entropy ofa random biauy alloy a8 function of the proportions ofthe enstivent atoms A aa 8. The er¥e plated as caleulated fora total of 20 atoms, We ee that iis enteopy iva maximom uhen A and B are present in csualpropottions (03), sind the entropy is Zev oe pure A ot pote system called the entropy of mining The eau (29 may be putin a more convenient orm by ue ofthe Sting approximation ON) = NlogN ~ N —(N ~ log —4.N =e ~rloge +1 = Nlog. — (N= t)logt — 0 = Hoge = UN = logit ~ x) — Hoga) , on with s =, ot) = ~XE(L ~ ajlog(t ~ a) + slog}. 10) ‘Tis tel ies che entropy of sving ofan alloy A,B, tested ss 3 eandom thor. steous sold sulin. The problem is rcpt in dealin Chae f We ask she homogeneous soit solution the egilibium conition ofa mister sf snd atoms, or isthe cquibciim a two-phase stem, sis a6 @ miu of esta of ue A and crystallites of pure The complete aaswer ithe isis of much of the s-2ace ‘of metstlngy the answer will depen onthe tengeratare and onthe inteatrns ser tion enegis Ugas Vay. ad Uy, he spdalcase tht theinteraetionenerge sn se ”‘0 (Chapter 3: Mattnaan Distribution ond Hetil: Fee Enos ‘NA, BM, an A neighbor pirat al aul, the hormogencous Solid solution will havea lower fie ency than the cocesponding misture of eyatalics of the pre elente The foc energy ofthe slid solaion A,B, Fe Fy = 104) Fa + Nofll ~ a)log(t ~ x) xlozx}, (81) ‘whi We ust compare mith Fa (l~ SF + xFy = Fy (82) for the mature ofA and 8 crystals in the proportion () ~ x to The entropy of mining {salays positise—all entropies are positive—ao tht the slit solution bas she lone, free energy inthis special ete There is tender for atest» very small proportion of any element B to dasoke ie any er element A, even fa strong eepusive energy exists between a atom aed the suttounng A ators. Let ths repulsive energy be denoted by U postine quantty es ‘ety smallpraportion x « 1B atoms i prety etal epusieenersy & eA. he Vis the suber of #8 atoms. The mining eneopy (80 bs approxinutcs o ~xN logs ns ats that te fee eneray is Fls) = NOU + exlogsl . ) Which nas minimum when EF lax = NW + tlogs + =O, 85) x= exp(—Hexpl= Up 66) ‘This shows there is maturlinpuiy conten inal eystas SUMMARY 1. The factor Pe) expla is the probability of finding a system in a state sofencegy e, when the system. Probtens s {sin thecmal contact with a lange reservoir at temperature t, The number of particles in the sjstem is assunied constant 2. The portton fonction is Tepe 3. The pressure is piven by pe Up), Caley ‘The Helmholtz fee energy is defined as F ‘qullibeium for a system field at constant, V. Sos -GFiéth: p= —(eF/20), 6 F = ~clogz. Thisresult is very useful ineatcilations of Fand of quantities such as pando derived fom F U = 18. 1818.8 minimum in For an ideal monatomic as of N atoms of spin zero, Zn = (ugh PINE, m= NIV «ny. The quantum concenteation ng = (Ar/2ah?), Further, P= Neo Nflogligh) +f]; Cy = aN. BA proces is reversible ifthe system remains infinitesimally close to the auilibrium state at ll tines dung the process, PROBLEMS 1, Five energy of «tea state system. (a) Find an expresion for the free ‘nerey 85a function of «of a system with two slates, one at encrey O and one st energy &{b) From the free every, find expressiows fr the energy aactentropy ‘of the system, The entropy is plotted in Figure Rt 2. Alageetic susceptibility. (a) Use the partition function to find in exact sspresion for the magnetization AL aud the susceptibility x = dM) as a function of temperature and magnetic field forthe model system of magntic ‘moments in @ magnetic field. The result for the magietization is Af ‘otanh(mBs, as derived in (46) by another method. Here n is the patticle2 ‘Chapeee 4: Rotman Disribaon and Het: Free Energy ; of : ; ; = Figwe3.10_ Enuopy ofa tnostate tem sea faction fe Notice that el) fog at? = 19) os 05 Figure 312. Plot ofthe total magostc moment a fonction ‘of, Notice hat at Tow nthe mmc iss Laci uncon {ij but at high mB he moment ends to caturae oncenteation. The result is plotted in Figure 812,(b) Find the free energy and xpress the result as fonction only of rand the parameter x = Aun (el Shoe sat the suseepabiity i 7 = wu in the init mB wc ~1 3: Pree enerey of harmonic osittor.& ore-tinersional harmonic osile ‘stor hasan infinite series of usly spaced enemy sates with = shor where Probtens i t 2 3 Pg Figure 3.13 Enirony versus temperature or harmonic ‘scat of eguency ex sis 0 positive integer oF zero, and os isthe classical fequency of the oseilator. We hove chosen the zero of eneryy at the state s = 0. (4) Show that for a hhaemonie ossillator the fre energy i F = rloyl exp(—heysy. wn ‘Note that at high temperatures such that ¢ > fs wwe may expand the argucnent ‘of the logarithm to obtain F = cloy(usjt).(b) From (81) show thatthe enttopy ~ loglt ~ exp(—h/). 89) ‘The entropy is shown in Figure 3.13 and the hen capacity in Figure .44 4. Energy flctoations. Consider a system of fixed volume in thermal contact with @ reservofe. Show that the mean squage Auctustion in the exergy of the system is Me = (OF) = HEU;EN,. 9) ere U is the conventional symbol for (¢), Hint: Use the pasttion function Z tw relate €U/2r 10 the mean square fluctuation, Also, multiply cut the term (oF Wote: The temperature «of a system isa quantity that by teaition dacsF109, Fiore Hoal pacity es tamperature L fhutmonic ovo of requ oThe ttl temperate athe igh temperature lini Gy fe i Fades talus mown asthe case Chapter Bote n Disiaton and Helle: Fee En in isa ha hich it see By ala the wits This Ato is ‘ot Actuate fa value when the system isi thermal contact with a eeservoir. ‘Aay ole attitude would be inconsistent with our definition ofthe teniperanuse ‘of a system, The energy of such a system may fuetuate, but the temperature ddo:s not Some workers do not adhere to rigorous definition of temperature, “Thus Lardy and Lifshite give the result a> = FIC, (00) but this show!d be viewed as just another form of (89) with Ae set equal to AUICy, We kaow that AU & CAs, whence (90) becomes (lAt/}') = Cy, Wwhich's our resalt (89) $. Overhauser efect. Suppose that by a suitable external mechanical or lecirital arrangement one can add ae to the energy of the heat reservoir whenever the reservoir passes tothe system the quantum of energy e The net increase ofenerey ofthe reservoir is (a — Ie. Here wis some numerical fctor, positive or nezative, Show thatthe effective Boltamane factor for this abnormal system is givea by Pea). exp (1 ~ adele} on) ‘This reasoning gives the statistical basis of the Overhauser effect wheseby the nuclear polarization in @ magnetic feld ean be enhanced above the thetmal ‘quilibsium polarization, Such a condition requires the active supply of energy to the system fcom an external source. The system is notin equilitrivm, Dut IS sig to be in 8 steady state, CLA. W. Overhauser, Phys. Rev. 92,411 (1953) 6, Rotation of diatomic moteeules. I our Best look atthe ideal gas we con: sidered only the translational energy ofthe partctes. But moleevles ean rotate, Prablems with kineti energy: The rotational motion is quanta ‘of adiatomie molecule ar ofthe form, and te energy levels eI + Ney 2) where is any positive integer including zero: = 0, 1,2 cof each rotational level is gi} = 2j + t(al Find the partition function 24() for the rotational states of one molecule. Remember that Z is @ sum over all Sales not overall kvels—this makes a uillerence. (6) Evaluate Zale) approxi ‘mately for + > ga, by converting the sur to at integral. (e) Do the sume for £ fa by truncating the sum afer the sscond tere, () Give enpresions for the energy UV and the heat capacity C, as fosetions of x, in both limits, Observe that the rotational contribution to the heat capacity of a diatomic molecule ‘smntoaches | (or. in convention units hl whgn > ey fe) Sheil the behsiog of Us) and Cia), showing the limiting betsvions for ¢-» 20 and ¢ 6 2. Zipper problem. zipper has N links; each link has a state in which itis «tose with energy O and state in which itis open with energy e We require, however, that the zipper can only unzip from the left end, and that the Tink ‘uuuuber s can only opp if a nhs tothe Ie (12. so I) areslecudy ope (a) Show that the partition fasion ea he sutumed fa the Farm ‘The motipticity 63) T= a (6) tn the limit ¢ » «. find the average mumber of open links. The model is @ ety simplified model of the unwinding of wo steanded DNA molecules-sce C. Kittel, Amer. J. Physics 37,917 (1989). 8. Quantuns concentration. Consider one particle confined to a cubs of side ‘ithe concentration in effet is = 1/1. Find the kinetic energy ofthe particle ‘when inthe ground orbital. There will bea value of the concentration for hich this zero-point quancoim kinetic energy is equal tothe temperature s.(At this concentration the occupaney ofthe lowest orbital sof the order of unity; the lowest oxbita alas has higher occupancy than any other orbital.) Show that the concentration tg thus defined is equal to the quantum concentration ng defined by (63), within factor ofthe order of unity 9. Partition function fortwo systems, Show that the pattition function U1 +2) of to independent systems I and 2 in thermal contact at a comition femperature xis equal to the product of the partition functions ofthe separate systems: Zl +2) = zz, 04)% Chapter 3: Botts Distebeton and Helnsoite Free Energy 10, Elasticity of polymers. The thermodynamicidentity for wone-dimensionsl system ie wu wu ~ pat 9 when J is the external force exerted on the line and sine. By analogy with (32) we form the derivative to find ‘The direction of the force is opposite to the conventional direction of the pressure We consider a polyuerie chain of N links each of length p, with each link ‘equally likely to be directed to therright and tothe left. (a) Show that the number ‘of arrangements that give a head-to-tail length of t= 2fp is the extension of the 2N! 906-3) + 008) = TN oy (61 For | « N show that a(t) = logt2gtN.0)] — Pap? s (6) Show thatthe force at extension Lis J = TING 9) The fores is propoctional 10 the tempersture, The force arises because the polymer wants to cutl up: the entropy is higher in a randoms coil than it an "uncoiled configuration. Warming @ rubber band makes it contract; warming & eel wire makes it expand. The theory of rubber elssticily is discussed by 1H. M. James and E. Guth, Journal of Chemical Physies 1, 455 (1943); Journal ‘of Polymer Science 4, 153 1949}; see also L. R. G. Treloar, Physics of rubber lusticity, Oxford, 1958, 11, One-dimensional gas. Consider an ideal gas of NY portcles, each of mass M, confined to one-cimensionat line oflength L, Find the eatropy a tempers tore e. The pastiles have spin zero. Chapter 4 Thermal Radiation and Planck Distribution ‘Eee aca anette orem near rene PLANCK DISTRIBUTION FUNCTION 9 PLANCK LAW AND STEFAN-HOLTZMANN LAW ” Emission and Absorption: Kirchhoff Law 56 Estimation of Sueface Temperature 1 Example: Cosmic Black Body Background Radiation 98 ELECTRICAL NOISE 98 PHONONS IN SOLIDS: DEBYE THEORY 102 Number of Phonon Modes: tot SUMMARY 109 PROBLEMS 110 1, Number of Thermal Photons na 2. Surface Ternperatuce of the Sun 10 5. Average Temperature ofthe Interior of the Sua Mt 4 Age of the Sun 5. Surface Temperature of the Earth i 6. Pressure of Thermal Radiation 1 1. Free Energy of a Photon Gas na 8. Heat Shields 12 9. Photon Gas in One Dimension mn 10, Heat Capacity of latergalactic Space U3 11. Heat Capacity of Solids in High Temperature Limit 1D 12, Heat Capacity of Photons and Phonons 13 15, Energy Fluctuations in a Solid at Lov Temperatures 13 Ls. Heat Capacity of Liguid “Hte at Low Temperatures 13 1S, Angular Distribution of Radiant Energy Flux 14 16, Image of a Radiant Object a4 17, Entropy and Occupancy 1 18, Tsentvopic Expansion of Photon Gas ua 19, Reflective Heat Shield and Kirehhof's Law us ‘SUPPLEMENT: GREENHOUSE EFFECT 1srn Chapter 4: Thermal Raslaron and Planck Pisibeton [i¥e consider] the distribution of the energy U among N oscillator of frequency SAP U is elewed as divisible without limit then on finite manber of distributions are possible, We consider howecer~and thi i the extenial point of the whole caleulation—U as made up ofan emirely determined number of Jinite equal ports, and we make use ofthe natural constant k-= 635 x 10" ‘ergrsec. This constant witen mutiplid by the common frequency «of the oscillators gives she element of energy & in ergs Planck Distribution Function PLANCK DISTRIBUTION FUNCTION “The Planck dsributiondeseribese spetrumot the elecromagnetic nation inthermal sour within actly. Appronimtely, it deseibes te emsion sfecttum ofthe Sun or of metal heated ba veldng ore, The Panck seb tion wet the fest applation of quantum thermal physics, Thermal eecco- smageetic ation often called Back body radiation The Planck distebution also describes the thermal energy spectrum of tatice vibrations in an clastic soli, “The word “mode” characterizes a particulaé oscillation amplitude pattern in ‘the eavty orn the fold. We shall always refer to wo = 2af as the frequency of the radiation. The characteristic feature of the radiation problem is that a mode of oscillation of frequency a may be excited only in units of the quantum of energy fa, Une energy &, of the state with s quanta i the mode is a= shu 0 ‘where sis zero or any postive integer (Figure 4.1). We omit the zero point energy He. “These cnergies ate the same asthe energies of a quantum harmonic oscillator of Frequency o, but there is a differenve bergen the concepls. A harmonic » Figue 44. Statesof39 oxeilator hat reprerent mode of requency w ofan ‘Shstvomajgnetie eld, When the ooilatr ihn the arbital of energy sho, the sate equivalent tos photons inthe mode saa |(Chapters Thermal Rediaion and Planck Diibution Fuge 42. Represeotaion in one tines viva of we socromagnete riod aand bof feguency «and. The ange of he dete: runctc il is suggested in the fires for one photon ai photon ‘ccurancy ofeach tata ‘oscillator isa localized oscillator, whereas the elecitic and magnetic energy of fn electromagnetic cavity mode is dstéibuted theoughout the inttior of the cavity (Figure 42), For both problens the energy eigenvalues ate integral ‘oultples of i, an this isthe reason forthe snilaity inthe thermal physics of the two problems. The language used to describe an excitation is diferent: s for the oscillator is called the quantum number, and s for the quantited electro. ‘magnetic mode is called the number af photons inthe mod We fist calculate the thermal average of the number of photons in'a mode, ‘when these photons are in thermal equilibrium witha reservoirata temperata «The pactition function (3.10) fs the sum over the states (1) a= Fears a This sum is of the form Sut with « = exp — h/t), Because x ia smaller than 1, the infinite series may be summed and has the value 1/(L ~ x), whence o Planch Law ond Siefum Bolten Law ‘The probability thatthe system is inthe state 2 sof enceay shao is given by the Boltzmann factor: Pf) a HSH) “ The thermal average value of sis 0 wi 7 ee - 0) © TS expt =i From (3) and (S} we find ‘ ‘ ©) Om Spina TS 7 This is the Planck distribution function for the thermal avecage number of Photons (Figure 43) in a single mode of frequency o Equally, itis the average number of phonons in the miode. The result applies to any Kind of wave field With energy in the form of (1). PLANCK LAW AND STEFA\ BOLTZMANN LAW The thermal average energy in the mode is ho 6» ho = 0 an2 (Chapter 4: Thermal Ration and anck Diaributon Planck Law and Stfom Botsnonn have 40) When weinser (9) into (10) and drop al common factors, we find the condition Este + Eyl + Ban, & nao ay Figue 43. Phock istibation aes fection othe edaced temperate ren Hive Cae | Fete thera stage of he number ef pltans inthe mode of Fegeeney o.& pot of (so) + fisalso hes, where isthe elective 259 point ocspaney othe modes the dashed line the clasicl asymptote Note that we This slates thatthe fekd vectors must be perpendicular to the vector m with {he components ny and n, 50 that the electeomageatic field inthe cavity isa twansversely polarized field, The polarization directions defined as thedicection, of Es, For a given triplet ms, polavzation diretions, «0 0s rn, we ean choose two mutially perpendiculae there ace two distinet modes for each triplet, “On substitution of) in he wave equation ay with ethe velocity of ight, we find The high temperstore limit © fe ie oft called the clasteal Timi. Hove cexplhcjt) may be approximated as 1 + hye +++", whence the classical average energy is i i | | 2 dt ne) = wD wy This determines the frequency eo of te mode in ferms ofthe tiple of integces yt He define ae ® adem tna, 04) ‘There isan infinite number of electromagnetic modes within any cavity. Each mode m has its own frequency @,. For radiation coafined within 9 pertely ‘hen hefteusnses are ofthe form conducting cavity in the form ofa cube of eige f, there is ast of modes ofthe form = melt 0s) ss Expsin or costagnsfL}sin(yny/L)sinfnzit) , (a) “The total energy ofthe photons in the eavly is, oom (7), E, = Eygsinetsinytx/Leostn,xy/L)sinns!L), (9b) i veyep ey le X60 = Fa plbest ba E, = ExgsinotsiolngexfL3sin(eyy/L cosas os) “The sum is over the triplet of integers n, 1h, n,- Positive integers alone will describe all independont modes of the form (2) We replace the sum o¥er Mi, ian, byan integral over the volume element dit, da, in the space ofthe mode Indices. That i, we set Here E., E, and E, are the theoe electric field components, and Exe, Eye and E,pate the corresponding armplitudes. The three components are not indepen= dont, because the field must be divergence-free: 26, | 08, |e, iv pm Me 4 OE y Es (- dive Fe a Ft a, 0) Ze na feu ant an* Chapter 4: Thermal Raton and Planck Disibation tay? By Wan dn Smeg TT a ‘Siplienaybay inthe) [> dew 418) with (15) for en. Standard Practice isto wransform the definite integral to one over a dimensionless vai West x = ahenjLs, and (18) becomes Ym tnthetyctiehay [dem 8 an fie geo d The definite integra has the value 315; ti ound in good standard tables Such as Dwight (ie in the genera ectorences the ently pt se ah uli ¥~ ise eo ty Wiih fhe volume V = 12. The result at he radand energy density is propor. onal tothe fourth power ofthe temperatures known asthe Stefan Boltamrane law of radiation. For many applications of this theory we decompose (20) into the spectead dersity of the radiation. The spectral density is defined asthe eneray per unt Jqve Ber unit frequency range, and is denoted as u,. We can fide from (18) rewitien in terms of w: Uv = fou, a so that the specteal density is SS kL on Snel o up 1 la 4 —f rot AL os a a caf L olf SI et 2 se Te fiafp—— edt Plot of Cie" ~ tj with x hoje. This Funston i involve in the Panik ration fw fo ths spect detnity ny The temperature ofa Hack boy may found am the feyueney tg at which the radiant nergy Sensi maimur, fo unit feguescy range, ‘This equeney is dtety proportional the ternpcatre ‘This result isthe Planck radiation lave it gives the frequency distribution of thermal radiation (Figure 44), Quantum theory begat here, The extropy of the thermal photons ean be found from the relation (3.344) At constant volume: ds = dU, whence from (20, ev sm ae Thus theenteopy is (0) = An? HAN ep a ‘The constant of integration is zero, fcom (3.55) and the relation between Pa oChapter 4: Thermal Raaton end Planck Diselbution {A process carted out at constant photon entcopy will have V4 “The measutement of hgh temperatures onstant ends on the Mux ofadiant energy fom a small hole ia the wall of a cavity maintained at the temperatore of ingetest, Such a hole is said to cadiate ae a black body—which means that the radiation emission is charseteristic ofa thermal equilibrium distribution, The energy Mux density Jy Is defined as the rate of energy emission pe unit area. The flux density is of the order of the energy contained in a column of unit area and length equal to the velocity of fight times the vnit of time. Thus, Jo [eURYV] + (geometseal factor, ey ‘The geometrical factor is equal to J; the derivation i the subjet of Problem 15, The final result forthe radiant energy Mux is, cui) _ tet fu = Ge eames es by use of 20) forthe eneray dencty LV The raul ie fion weriton a6 Jom ants en ‘the Stefan-Bottzmann constant aps ay! 60H (2a) has the value $670 x 10°* W m"® K~* or $670 x 10° exg em™? st K~* (Gexe 09 is not the entropy, A body that radiates at this rate is said to radiate «sa black body. A small hole ina cavity whose walls are in thermal equilibrium, at temperature T will radiate asa black body at the rate given in (26), The rate is independent of the physical constitution of the walls of the cavily and de- pends only on the temperature Emission and Absorption: Kirchholf Law ‘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 is dfined to be black ina given frequency range ifall electromagnetic radiation {incident upon itn that range is absorbed. By this definition a hoe in a cavity is, black ifthe hole is small enough that radiation incident through the hole will Estinaion of Serfice Temperate reflect enough times from the cavity walls to be absorbed in the cavity with negligible loss back through the hol. “The vadiant ensrgy flux density Jy from a black surface at temperature is ‘equal to the radiant energy Nux density Jy emitted from a small hole in a cavity ‘al the same temperature, To prove this, let us close the fle with the black surface, hereafier called the objet. In theca equiibvium the thermal average ‘energy flux from the Black object to the interior of the cavity must be equel, boat opposite, to the thermal average energy fut from the cavity to the black object. ‘We prove the following: If x non-black object at temperature + absorbs a faction ¢ ofthe radiation incident upon it, the radiation flux emitted by the ‘object wil be o times the radiation flux emitted by a black body at the same temperate. Let a denote the absorptivity and e the emissivity, whete the ssinty is defined so thatthe radiation Bus emitted by the objects e times the fas emitted by a black body at the same temperature. The object must emit ‘prov ifequilibsiom isto be maintained. 1 follows that hho law, For the special ease of a perfect reflector, ais oro, ehews ef cotu. A pesfeut vefleion dues wt satiate ‘The arguments ean be generalized to apply tothe radiation at any frequency, as botesn wand ca deo, We inserts filler Between the abjzet and the hole it the bisek body. Let the filer relet perfecily outside this fequency range, and Jet it tansmit perfectly withia this range. The fx equality arguments now apply (0 the transmitted spectral band, so that ao) = e(a) for any surfice Ja thermal equilibrium, =e This is the Estimation of Surface Temperature (One way 10 estimate the surface temperature of a hot body such asa star is from the fequency at which the maximum emission of radiant energy takes place (te Figure 44), What this frequency is depends on whether welook at the ‘eneray Alas per unit Frequeney range or per unit wavelength range, For tay the ‘energy density per unit frequency’ range, the maximum is given from the Planck law, Ea. 22) a5, as as laps 3exp(-a} ”os Chapter Thermal Rediaion and Planck Disvibtion ‘This equation may be solved numerically. The root is tae haT 282, en asin Figure 44, Example: Cosmic blackbody Background adi wolves acressible 9 us filed with eaion St 29K, The existence of tha radi me Amar recent discovery stat the spprosinaely the tbat of back Body Figure 43} isenportant eidene er Bg borg Seimelaia mod which asune shit hence begun and oalocanae ed regataton sk ont om an uly epoch neste unene tatsorpneel ony Sfeletrans aul pains a temperate of shina WDE. The plea eee rojo rel song wilh eaconsyrae saluting sal inate Reena Tee ter wu he Hk boy eaation weet snl equiva hy ee ‘he wniverschal evoked 10 000K, the ater wenger ‘This interats with black boy raion only ate Hines. Most ofthe back Body faation snergy ty mater, Thetcaler the radution evoteed whine inn nthe aes of tums tegen, 1 feueneics of the hyarogsn sata us as eicinde decouple foun tae Such a8 staiht,eacatdby the mate ince the decnping ‘superimposed on the cosmic Bich bod} radio, ELECTRICAL NOISE ‘48 an important exainpe of the Planck ta ia one dimension, we consider the ‘Pontansous thermal uctuations in voltage actos a esis, These lctustions, Trick ate called noise, were discotered by J.B. Johnson and expliined by HE Naquist* The characteristic progeny of Johason noise is that the mea, faMaEe nolse voltage is proportional ta the value ofthe resistance Ras shown ‘y Phgure 46, We shall sor that <2) is also dieeetly propowsiona to the tem, +H. Sguit Ps Rev 52, 10023 eps esnon igen by C. Rt, lout statin ea osha Wis, 1935 Sections Fh Elecuial Noise om Microwave | tovecstetar CN Cx measurements Spoceal flex ( 29K Black bouy—~ oor ar 1 is iio Frequency (em) gue 4S Experimental measuremens ofthe pes ofthe cose Hak i radion Obstet fas woe eadeuah isons tee rece at frequencies below the pet, ete Sede fom opal mesnencns ofthe spear a ntertlat CN molecules ea the ea and were meserel ‘sith flloon bore inated specteoeler ot eguenees above te pk ‘Coutesy of. Liha erature cand the bandwidth Af of the cccui. (This gestion presunies 9 knowl edge of electromagnetic wave propagation at the intermediate level) The Nyquist theorem gives « quantitative expression forthe thermal noise ‘oltage generated by a resistor in thermal equilibrium, The theorem is therefore ceded in any estimate ofthe limiting signal-to-noise ratio of an experinental ”(Choper és Theat Rasiaton and Planck Disibaton sx 10 Z| eke bo | axes ‘Or ae Resistance compotent, ia MA sgunted veo resistence fr various 1 Be dohan, apparatus. In the original form the Nyquist theorem states that the mean square voltage across a resisor of resistance K in thermal equilibria at reat | es 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 bya rsstor toa matched load is ¢ the factor 4 enters where it docs becuse fa the circuit of Figure 47, the power jered to-an arbitiaey resistive load is 9) which at match (R’ = Ris CV*Y/AR. nhs seen the word guys eye pe eit and not aan peri tie. Blecrca Noise Noise generator Rermination : resistance) Figwe 4 Equivalent ccut ora resistance & with 4 gzerator of thermal nos ht divers power toa load Rt Thecurent so that the mean power dissipated i the lost is Po (rn = Se OR Te aE ‘which sa marie wih respect to R when R’ = R Te this conston the fod sh to be rated 0 the power supply At match, 2 = 0 js the subject of Frobiain IL Several celated thermodynamic fonetions for a Debye solid are siven in Tabls 4.2 and are plotted in Figure 4.12, versus 770 is dey Plsk 38, 7990919), St Botan, KSemi, Py static Zech Bar(bintrwesusn, Naber of Phonon Modes Sm i Pa 1 Na | Pm | v_| x 27 2 2 é 2 la a8lo e a agile | an Pr P co Nore: The subscript zo on ted denies low tone wor108 Chapter 4: Thermal Radision ond Planck Diseibaion | Suramary 3 Ey Figure 411 Heat expaciy Cy ofa solid, actos tothe Debyeapproximation, The ‘ewizl sale isin Jmol"! KO. The Hoviaonl sea i the txmperture normalized tothe Debye temporatare 0, The region ofthe Flaw is below O10. The ssjnptti wale thigh sales of 7) 29K J mol" Ke FE _ ~20}- a 30} —— an “oar od as Oso : ~ = oes ooo 20 oe nas 86 oe on 1 ahs Seat 35 8 Me 5000 itis SUMMARY 8388 en 38 a7 Bas ais a ae ae a 1. The Panck distibution function is 9396 sas ws 19 Bn 3H ike t hs aa a © Sect! 2 2059 18.30 ss Poh 3 i633 wn Fr : a a7! 7 forthe thermal average numberof photons in a cavity mode of fequency o 3 3 ‘ot oe é A uh a 2 The Stefn-Boltemann tw is 7 a6 im ois 3 338, 12 ons 7 5 233, tis 005 eet 0 Test dis oie is 0598 nse ous for the radiant energy density ina cavity at temperature x.(Chapter 4: Therml Relietion and Planck Disrbation 3. The Planck radiation law is PC explliayty — 1" ‘or the radiation energy per unit volume per unit range of frequency, 4, The Mux density of radiant enere Boltemann constant xk {60H%C', Ju oaT*, where oy is the Stefan- 5. The Debye low temperature limit of the heat capacity of a dielectric solid is, in conventional units, (7. 0 Ue jhyhGat N/V) 12atNky Cy where the Debye temperature PROBLEMS, 1, Number of thermal photons. Show that the number of photons <5) in ‘quilibeium at temperature rin a cavity of voluine Vis WN = 2408" (/he)* (3) From (23) the entcopy is o = (4x*V/4S}ajhe) whence o/N = 3602, It is believed that the total nwmber of photons in the Universe is 10® larger than the {otal number of nucleons (protons, aeuteons). Because both entropies are of the onder of the respective number of particles (see Eq, 3.76), the photons provide the dominant contribution to the entropy of the universe, elthough the particles dominas «i total energy. We belive that the entropy of the photons is essentially constant, so hat the entropy of the universe is approxi mately constant with time, temtn of he Eanh The eben value ingrtel over i eats ne solar constant = 0.136)s"*em™2, (49) Problems (@) Show thatthe total rate of energy generation of the Sun is 4 x 102° Js~t, (©) From ‘this result and the Stefan-Boltzmann constant ay = 56? x 20°12 43°! cm”? KS, show that the eflective temperature ofthe surface of the Sun treated as a black body is T = 6000 K. Tske the distance ofthe Eavih freee the Sun as 15 x 10" cm and the radius ofthe Sun as? 10" ore 3+ Average temperature ofthe interior of the Sun. (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. {ational constant Gis 66 x 10° dsnecm® g~* The self-energy will be negative referred (o atoms at rest at infinite separation. (b) Assume thatthe total thermal Kinetic energy of the atoms in the Sun is equal to ~{ times the gravitational ‘enotey. This isthe result of the virial theorem of mechanics. Fstimate the average temperature ofthe Sun. Take the numberof particles as 1x 10°? This estimate fives somewhat f00 low a temperature, because the density of the Sun is for from uniform, “The range in central temperature for different stars, excluding ply those composed of degenerate matter for which the law of perfect gases does not hold (white dwar ) and those which have excessively svall average vonaities (giants and supergians), Is between 19 and 30 x 10" degrees (0. Struve B.Lynds, and 11. Pillans Elementary asironomy, Oxford, 1959) 4. Age ofthe Sun. Suppose 4 x 10°*5. raulites energy atthe present time. (a) Find the total energy of the Sun available for radiation, on the rough assamptione that the energy source the comersion (of hydrogen (atomic weight 10078) to helium (atomic weigh 10026) and thet the reaction stops when 10 percent of the original hydrogen has been converted to helium. Use the Binstein relation £ = (A.\Ne?.(b} Use (a) to estimate the Ife expectancy of the Sun. It is believed that the age of the wniverse fs about 10 x 10? years. (A good discussion is given in the books by Peebles and by Weinberg, cited i the general references) is the total rate at which the Sun &. Suiface temperature ofthe Earth. Calculate the temperature ofthe surface ‘of the Eaith on the assumption that asa black body in thermal equilibrium it ‘orate as muel thermal radiation hat the surf eyele Use To 15 x 10% om, as it receives from the Su, Assume also fof the Earth is at a constant temperature avse the day-night S800K; Ro = 7 x 10! em: and the Barth Sn estanes of 6. Pressure of thermal vadiation. Show fora photon gas that {a} p= (CULV), = ~S sided) , (50) mmChapeee 4s Thermal Ration and Planck Distibuton ‘whore §, isthe umber of photons in the mots ” day = wv; on © p= Up. (9) Thus the radiation pressure is equal to} x (enerey density), (} Compare the pressuce of thermal radiation with the kinetic pressure of 2208 of H atoms at a concentration of | molecm™? characteristic of the Sun. ‘AL what temperature (coughly) are the two pressures equal? ‘The average Temperature of the Sun i believed to be nese 2 x 107K. The concentration s highly nonuniform and rises to near 100motecm”? at the center, where the kinetic pressure is considerably higher than the radiation pressure. 7. Free encrgy of photon gas. (s} Show that the partition function of a photon gas is given by ZeT]{ eine", re where the product is over the modes n.(b) The Helmbolt2 free energy is fou directly rom (33) as Ft Yogft ~ expt hoy} a) “Transform the sum to an integrals integrate by parts to find F eave site 69) 8, Heat shields. A black (nonrelleative) plane at temperature T, is parallel to a black plane at temperature 7), The net energy flux density in vacuum be- ‘ween the two planes is Jy = oy(T,* ~ 7), where gg isthe Stefan-Boltzmann constant used in (26). A third black plane is inserted between the ether two and is allowed to come to a steady state temperature T,. Find T. in terms of 7. and Ty, and show thatthe net energy fux density is cut in half because of the presence of this plane. This is the principle of the heat shield and is widely Used to reduce radiant heat transfer. Comment: ‘The resuk for N independent heat shielde floating in temperature between the planee and T; is that the ret encrgy fix density is Jy = e¢(Ty! — TM(N 1), 9. Photon ges in one dimension. Consider a teansmission line of length £08 which ‘electromagnetic waves satisfy the one-dimensional wave equation OEIC me GE(E0, where E is an electic eld component. Find the heat capacity ofthe photons onthe line, when in thermal equilibeium at temperature eee ee eee ee eeeer sree Peebles +. The enumeration of modes proceeds in the usual way for one dimeusion take the solutions as standing waves with zero anaplitune at cach end ofthe line. 10, Heat capacity of intergalactic space. Intergalactic space i believed to he ‘occupied by hydrogen atoms in a concentration = latomm™>. The space is also obcupied by thermal radiation at 29, from the Primitive Fireball Show thatthe ratio ofthe heat eapucty of matter to that of radiation fs = 10°? IL, Heat eapacity of sofis in high temperate fit. Show that in the timit T > the heat capacity of a solid gocs towards the Himit Cy -+ 3NAy. it conventional nits. To obtain higher accuracy when T is only moderately larger than 0, the heat capacity can be expanded as a power series in 1/T, of the form c= ania «ft ur] 06 Determine the frst nonvanishing term inthe sum, Check yourresultby inserting T= Ound comparing with Lable 42 12, Heat capacity of photons and phonows, Consider a vielectic slid with a Debye temperature equal to 100K and with 10°¥atomsem->, Estimate the temperature at which the photon contribution to the heat capacity would be ‘qual to the phonon conteibution evaluated at 1. 13. Energy fluctuations ina solid at love temperatures, Consider a solid of N toms in the temperature region in which the Debye > laveis valid. The sotid isin thermal contact: h aheat reservoir Use the results on energy fluctuations {om Chapter 3 10 show that the root mean square factional energy fluctuation > i given by - ayaa «007/02 fe ~ COP KO? = SE (5) on) Suppose that T = 10-?K;0 = 200K; and N = 10!5 for a particleO.01.em on @ side; then & = 0.02. At 107* K the fractional fluctuation in energy is of the ‘order of unity for aaeletrie patil of vlume lem 1. Heat capacity of fig *He at low temperaturce. The vslocity of longita inal sound waves in tguid “Heat temperatures below 0.6 K is2.383 x 10" em 51. There are no transverse sound waves in the liquid, The density is 0445 gem*. (a) Calevlate the Debye temperature. (b} Calculate the heat ‘capacity per gram on the Debye theory and compare with the experimental Value Cy = 00204 x 79,inJg-#K. The T? dependence of the experimental nsnt Chapter 4: Thermal Raistion ant Planch Disibation TERS sBetests that phonons are ste most important exeitations in liquid “He Fa 06 K. Note shat the experinsnta value has besn expressed pes ram of [atid The experiments are duc wo 3. Wibes, C. G. Nie Haieebg ioe H.C. Kramers, Physica 32, 625 11957} Se Ansar distribution of radiant energy lz. (a) Show that the special Genel of flte radiant cnorgy fax that arives in the solid angle ad iy Giuces dias, where Oi the angle the noma fo the unit area nekes wily theincident ray, and w, i thee that the sumn ofthis quantity ove 16. Image ofa radiant object. Let a ens image the hole in a cavity of area Aaron a black object of atea 4p. Use an equilibrium argument to relate the Product 4,0, 19 460, wher feat bt YHewed from the hole and fom the object. This genetal propery of focusing systems i easily decved ftom geometrical optics. It is also ie ah aeerenaa portant. Make the approximation that all rays ae nearly pavalfel (all axial angles smatt 22, Enrops and occupancy. We argued in this chapter that the entropy ofthe cosmic Mark bedy radiation hay not changed wih time because the peor cfihotons in each mode has not changed with time, although the frequency of cach mode has decreased as the wavelength has increased with the expansion of the universe. Establish the implied connection between entropy eed oc, tPsmey ofthe modes, by showing that for one mode of equeney he entropy js. function of te photon oceupariey-(s) only C54 Bplogés +1) = Gy lowes. (59) It is convenient to stat om the partition function 18 Isentropic expansion of photon gas, Consider the gas of photons of the thermal equilibeiuen radiation in a cube of volume V at temperatures Let the Savlly volume increas; the radiation pressure performs work ducing the expan, sion, and the temperature of the radiatian will deop. From the tell fog the ‘eatcopy we know that 7 is constant in such an expansion, (a) Assume that the temperature of the cosmic black-body radiation was decoupled rom the {temperature of the matter when both were at 3000 K. What was the radius of {he universe at that time, eomparcil to now? Ifthe radius as increased lncaly wwith time at what fraction ofthe present age ofthe universe dl the decoupling fake plaes?(b) Show thatthe work done by the photons during the expaysion Wwe. IBM Ae — 1p. The subscripts i and J refer to the intial and final wand gare the solid angles subtended by the Prottems U2. Mefectve heat sield and Kivehng?s law. Consider x plone sheet of mate- (at OFaDsOEPLNICY o eissicitye, and eellectiity » = 1 ~ a Lette sees fo ‘Higbee betwsen and parallel with two black shcets maintained at tempers, bree etn t; Show that the et Nox density of thermal radiation betwee the Uiacy sets is (0 ~ times the dux density when the intermediate sheet she Back asin Probes 8, which means witha =e Isr'= 0, Ligud hears {ents ate often insulated by many, perhaps 100, layers of an slomenscd Milar fl ealled Supcsinsutation, SUPPLEMENT: GREENHOUSE EFFECT. The Greenhouse Effet describes the warming of the sweface of the Earth SSS: BY the interposition ofan infrared absorbent layer of water, as vapor Ana in clouds, and of carbon dioxide in the atmosphere between the Suv ced Treen" The water may contribute as much 80 percent of the warming effect. Absent such a layer, the temperature of the surface of the Earth is determined primarily by the esquiresucut of energy balance between the fas of solar radiation incident on the Esrth and the lux of ceradiation fora 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 Gitte Garth and Teisthat of the Sun; here Rg isthe caus of the Sun and Dae is the Sun-Earth listance, The result of that problem is T_ = 280 K, assuming 7 ~ 5800 K. The in is much hotter than the Earth, but the geometry (the small sotid angle ‘ubtended bythe Sun) reduces the solae ux density incident atthe Earth ya factor of roughly (1/20) \We assume 26 an example that the atmosphere isa perfect greenhouse, {fined as an absorbent layer that transmits all of the vibe radiation that fullson it from the Sun, but absorbs and se-emits all the radiation (which lee inthe infared, from the surface ofthe Earth, We may idealize the problece by neglecting the absorption by the layer of the infrared portion of are jicident sole radiation, because the solar spectrum lies almost enisely at {ier fequencies, as evident from Figure 44, The layer will emi enewey fee Je.u? and 4, Gowen; the upward Mx wil balance the suiar un Ie so ist ALS ds, The net downward ux will be the sum of the solar Ox fe and the Hux, down from the layer, The latter increases the net thermal us incident atthe surface of the Earth, Thus pot h=Ny (59) wwhece dry isthe thermal flux from the Earth ia the presence of the perfect ns(Chapter 4 Termel Radiation and Planch Distibaton ‘recahiouss effect. Because the thermal fax varies as T*, the new temperature Of the surface of the Earth is Ty = 2Tg= (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 dacuons se Climate change a Climate chang 192, Casbridge UP. 1990 04 1992 J.T, Houghton etal, or. Chapter 5 Chemical Potential and Gibbs Distribution DEFINITION OF CHEMICAL. POTENTIAL Example: Chemical Potential of the Ideal Gas Internal and Total Chemical Potential Example: Variation of Barometric Pressure with Altitude Example: Chemical Potestial of Mobile Magnetic Particles ina Magnetic Field Example: Bauteries . Chemical Potential and Entropy ‘Thermodynamic Keniry GiBBS FACTOR AND. RRS SH Number of Particles Energy Example: Occupancy Zero or One Example: Impurity Atom fonieation in a Semiconductor SUMMARY PROBLEMS Centrituge Molecules ia the Earth's Atmosphere Potential Energy of Gas in a Gravitational Field ‘Active Transport Magnetic Concentration Gibbs Sum for a Two Level System, States of Positive and Negative fonization Carbon Mosoxide Poisoning Adsorption of O in a Magnetic Field Concentration Fluctuations Equivalent Definition of Chemical Potential Ascent of Sap in Trees Isentropic Expansion Multiple Binding of O, External Chemical Potential ng. 20 In ns ie 129 br bs a 10 140 0 irr 14 15, a5 145 las as 145 16 6 16 M7 137 148, 18 148, 18 149us Chopter : Chemical Potential and Gibbs Ditbution We eonsidered in Chapter 2 the properties of two systems in thermal contact, ide Were led naturally to the definition ofthe temperature. ithe wo system, have the same temperature, here is no net energy fow between ther Ifthe ‘cavpsratarss of Wo systems ae different, energy will ow from the systema with the higher temperature tothe system with the lower temperature Now consider systems that can exchange particles as well as energy. Such Ppstems are said to be in diffusive (and thermal) contact: molecules can move from one system to the other by diffusion through a permeable intecfase, Teg ‘stems are in equilibrium with respect to particle exchange when the net particle Now is zero. “The chemical potential governs the Now of pasiles between the sssems, just as the temperature goveins the Now of energy. If wo s)sems with & single chemical cpecioe ara at the souve semperature and have the same valve of re hemleat potential, there will be no net particle flow and no net energy flow between thein. 1f the chemical potentials of the two systems ave diferern, Particles will flow from the system at the higher chemical potential to the ‘stem atthe lower chemical potential Asan example, the chemical poteatial of electrons at one terminal of a storage battery is higher than at she other {etminal. When the terminals are connected by a wire, elections will ow in the Wire from high 10 low chemical potential Consider the establishment of difasive equilibrium between two systns 1 snd 8, that are in thermal and diffusive contact. We maintain t conse by placing bath systems in thermal contact (Figure 5) with a large reserves &. We found earlice that for a single system 5 in thermal equiliium with a seservole @, the Helaihottz free energy of & will assume the tnininura valac compatible with the common temperature + and with ether resteainis on the ‘stm, such as the volume and the number of particles. This resulh applies cauatly to the combined 8, + Sin equilibvion with &, In ditusive equilib, faim Between $, and S,, the pastcke dst ibution 2,.%s betwoun the sete makes the total Hetmboltz fee energy PRP AR =U 4 Us~ dle $09 0 4 nunimum, subject to N = N, + Ny = constant. Because N is constant the Helmholtz fee energy of the eombincd system i @ minim with respect te Pefiton of Chemist Petentiat a9 AN, vate dN, negative positive System 8, Reservoir & P~Enerey | Figure Sa Example oftwa systems, an vith a large reservoir tf Sew 5, cua be brought i dite ‘emperaice 2. The aeeous athe rom 8, 1085, Yeriations 5M, = —3N,. At the minimum, a PPLEN JIN, + (CFY/BN JAN, = 0 With Mi Fi also hetd constant, With Ny = —dNVy, we have AP = (EYER) ~ (CF YENI UN, $0 that ut equiibrium (PYeN,), = Fs DEFINITION OF CHEMICAL POTENTIAL We define the chemical potential as wsronn (2) | ind Sin thecal contact with exch other ving closed otal system. By opening the vale ne comact while remainiog atthe common vals have een drawn fora nc pti taster Jory wy 0ro (Chapter + ChemioatPatetal and Gidbs Discibuion whore js the Greek letter me. Then ‘expresses the condition for difusive equilibrium. If jt, > jn. We see from (3) that dF will be negative when dX, is negative: When particles are transferced fom 8 to 3, the value of dN, is negative, and dN is positive, Thus the fice energy decreases as particles Nlow from 8, to 3, that is, particles Nowe fom the system of high chemical potential to the system of low chemical potential. The strict definition of isin terms of a diflerence and not a deriva tive, because particles are not divisible: HoWN) = FleWN) ~ FIN = 0) © ‘The chemical potential regulates the particle transfer between systems i contact, and it i flly as important as the temperature, whieh regulates the energy transfer. Two systems that can exchange both eneray and particles are in combined thermal and difusive equilibrium when their temperatures and chemical potentials are equ ‘A difference in chemical potential acts as a driving force for the transfer of partiles just asa diference in temperature ets asa driving force for the sans of enerty, several chemical species are present, each has its own chemical potential. For species , o where the eiferenti forthe species j “sof all pacicles ae held constant except _Exampte: Chemlal potential ofthe ideal gar. In (370) we showed that the fee eneray fof he monatomic ideal gas F = ~sfNlogZ, ~ log] , ® Definition of Chemical Potential where a ng = (Me 20182 o isthe patton fonction fora single patie From (8 (19) Wve we the Sting appronimaton for Nand assume that we ean difrentint the ctrl we find a tag Nt a aes sv IN + DlogN = 8) ete glia ogN WV DLE Sy. UD) which approues log 4 neg Yass oF A. Memes the smb poeta oF Me Eis log Z, = logX) = elogt/2.) « ot, by (9), ry 9 where 1 — N/V is the concentration of particles and ng = (Mr/2xh*)?? is the quantum concentration define by (3.63) we sey = FON) — FUQ ~ 1)ftom (6) asthe defiiton of y, we donot need o wsethe Stiling eppronimation. From (8) We obtain = ~s[l08Z, ~ logN], which agrecs with (2) The rst depends on she concentation of patie, aot on ther ftal number ot on the bystem vollame separately, By use of tho ieal gos lave p = or we can write (12) 36 j= loglpfen (20) ‘Theches 1 penta increases a the coasentraton of particles increases This is what we expect intuitively: parila how fon higher o lowe chemical potenti fom higher to over concentration. Figure 32 shows the dependence on concentration ofan ideal gus composed of elections oF of helium atoms, bo temperatures, the boiling temperature a9 T T+ 7 Ty scr 4 4 Lytite tpt —[) classical boing pointe ae 10-009 atm -s =10) = fa -18 ~ ar u 4 L toe oo ten) Figure S2The concentration dependence of yf units ofr ofan ideal gas ‘composed of electrous or helium atoms, a 42 K and 300 Ko be in the ctasscal resine with n @ nga gas must havea valae of — pat east «For eleccon this satisfied oly for concentrations appeecably lets than these fa mea si the range of typical seniconducton, For gett ie avaye satisied veer natal conditions of fauid helium at atmospheric pressus, 4.2K, and oem temperatuse, 0K, Atomic aud molecular gases nays hase negate chee potest under plysalyreable ‘otions: at classical eancenirations such that tg & 1, we see fram (1) thats Internal and Total Chemical Potentih The best way to understand the chemical potential is to discuss difusive cquilibrium in the presence of a potential step that acts on the particles, This Internat and Total Chemical Poteriat te volagepotariy shown. th 5, broblemn has wide application and includes the semiconductor pu junction dlscussed in Chapter 13. We again consider to systems, 8, und $3, at the same temperature and capable of exchanging particles, but not yet in difusive ssuilibrium, We assume that intially py > j, and we denote the inital no equilibrium chemical potential ditference by Ay(initial) jeg — gt. Now let @ ilference in potential energy be established Betwesn the two systems, such that the potential energy of each particle in system 3, is raised by exactly Actiivial) above it inital valus, {Fale patticls carry a charge , one simple ‘say to establish this potential step isto apply between the two systems a voltage AW suc that GAY = ally ~ Vi) = Aatinitial), wp ‘ith the poly shown in Figure $3 A diference in gravitational potent slsocan sve asa potent difference: when we ae a system of partes onc of mass M by the eighth we esabish a potential iference fg, hee gh the gravitation ceteraton Ona potential te preset potenti ensey ofthe pats produved by step is ncaded in the energy U and inthe ee energy ofthe sytem Hin Figs 3.39 kesp the fee energy of system By el he stp rane the fc enensy of $y by Ny Apna) = Nya AV eetne tos al ce ta vhs lng slates tothe energy of ech state of 8, the potgta tnergy 8 Anita) has bean ad. The-ebee ofthe powcntel Wee “pss by (3) ses the estat penta 8, by Ay ae te ict petal of 3y ea ta a By lina) siti) + Cinta) ~ initia) finital) = p.ffnal) (4) FigereS.3 A potent step between two & sjstems of charged partises can bs established by applying voliage betwcen the stews. For ‘ncigy of positive paticice with charge g > 0 in sjstom §, would be raised by gAV with sespoet 10 3, The potential enety of negative patil would be fowered in 8, with respect(Chapter $2 Chemicat Potent end Gibbs Dstibation When the harrier was inserted, jy as fixed. Thus the barrier gAV = initial) ~ p,Cintiat) rings the two systems iatodilfasive equlibeium, eo ‘The chemical potential s equivalent to a tue potential energy: the difference in chemical potential between two systems is equal to the potential barrier that wil bring the to systems into diffusive equilibrium, ‘This statement gives vs a feling forthe physical effect ofthe chemical poten- tial, and it forms the basis forthe measurement of chemical patental dilleences Detween two systems. To measure qty — jy, We establish a pot ential step Detsicen two systems that can transfer particles, and we determine the step height at which the net particle teansfer vanishes Only differences of chemical potential havea physical meaning, The absolute value of the chemical potential depends on the zera of the potential energy scale. The ideal gos result (12) depends on the choice ofthe zer0 of energy of a (ces particle s equal to the zero of the kinetic energy ‘When external potential steps are present, we car express the Cota chemcat potential ofa system as the sum of two parts wee, Has + Haw as, Here 1, is the potential enoegy per particle in the external potential, and is the internal chemical potential* defined asthe chemical potential shat woud ‘os present ifthe external potential were 2ero. The term fy may be mechanical, lectical, magnetic, gravitational, ete. in ofigie. The equilibrium condition pa © my can be expressed a5 Aiea = AK is) Unfortunately, the distinction between external and internal chemical potential ‘Sometimes is not made in the literature. Some writers, particularly those working with charged particies in the fields of electrochemistry and of semiconductors, often mean the internal chemical potesial when they wse the words ehemsicat potential without a further qualifier. ‘The total chemical potential may be called the electrochemical potential if the potential barriers of interest are electrostatic. Although the term electro- Gib cate the potenti and he nei poten He copied that a vlineter mt- sures erences ng Inert and Total Chemical Pateniot bs system (2 FigureS4. A model ofthe variation of aumospiede pretete whale: Iwo sotumes of gis at etereat beige fn a unifoora feasitations eld in thera System chemical potenti is clear and unambiguous, we shall use “total chemical potential” The use of “chemical potential” without an adjective should be ‘voided in situations in which any confusion about its me: ng could occur Example: Vorit of barometric presre withaltiude. The singles, example of the Aifasive equibciom between systema fa iene eneral potatia the exilim btwcon ers at diferent heights of the Eats stapler, assumed 0 Be bother The eel atmaspoe tia inert equity: tie const pest by meteoric eects, both nthe form of macroscopic at movements nd of sean tempecause sraicns (fam clout formation, and bssauts ef heat inp feo mate an approsinate meds of the ‘9s af Kea pics thotn mosphere by treating the dillent air fyete as sind ive eyiiun sith cach oe, illecat exiernal potentials Figace $4 If we place the rf the potential energy a round level, the potential energy permolecule a heaht his Ah where Mis the parle nas and the aviatonalaceection. The intemal cheesiest potential ofthe parties piven by (12). ‘The total chemical potential logting) + eh an Uw equltiony his most be independent of he bight Thea log{ntinfng] + Atgh = cloghOyg] + and the concentration ah at height satisfies n(h) = m(OJexpl—Afghfs) sy26 (Cheprer 82 Chemical Potential ad Gibbs Disiation 19) os 02 Zo Fiewe Ss Dacene sfumospharepessue $05 wit atte Th eosses represent he average ‘imosphere at spt on socket fights, ‘Tae connesing ssh line has a slope ‘cotrespoading toa temperature P= 227 K. ool LN 0! \ ove ove \ oxo Cr 5 Height i km Pressure, rl ‘The presse ofan ideal gatis proportional tothe conserrston; therefore the pressure st aliuds his PUI) = plOexpt~ Malye) = plO}exp(—by). «) Tis it the Marometete pressure cytaton. Te gies the deponnce ofthe pessuce on shitude in an inthermal sanosphst of single checcal species At the chatacerati eight he Mg the stmospsce pressure dereases by the fraction e- = O31, To eoinate the chacacevstis height, vonsder an isebermalaonosphere cooposed oF wittogennreevules ia molelr wight of 28 Theiansotan.v motets X 10" gen ha tenpetss twee vf 290K the valuc ofr = hyT i409 x 1 erg. Wig = $AOamia-3 the cheers Tete tcighe is &5hm, approximately $ miles Lighter toscules My sad Hes wl stand futher op, but these have largsly escape tom he amsphre: see Peableay 2 Hecate Enns sttosphoreintasuttely Botha ls iorceann tier chatior Figote 33 is. logit plot of peste data between 10 and 40 Ltometers, ‘3en on roet fights. The data poins ill ae await line, supgestng roustly io, Ices and Total Chemical Potential Tange ti ay estat ln connectng the data pins of Figute§Sapansa press as Mla = 1D over aualituterangefrom y= Theale eee omen, lis) _ Mo dog Md My, yy, ey ths) r ») eo STIR RERRE OE elie Aa whicheadstoT = hy = 227K Thenonimerscion Sree feu with he poi k= 2,0 = I cuted bye high cones tureat tower aiudes, rin amosahee Conse of more shan one species af gs fa atomic percent, the som, onto of yale asa level 38 pot N21 pet Oy. and 09 pat Arse eee seecata tan DM pet cach, The water vapor content ef the mone ee Fe tae ten atk 27 Gh a teas homily of 10 et corerponts vo hs othermal atmosphere cach gas would bei equlitriom with kesit The aa ithaseparateBoltemann actorof the formespt~ ght, Sak A the appropriate molecular mas. Because of the iteences ln oon ao ek ‘constitnis lof st dllerent ates Eouple: Chal potctal of motte magnetic parites in a magnetic field. Conder Sysco nia mets ach with « magnetic moneat an Fax simply supe aah moment is directed either paral or antiparallel |v an applied manners hag ea otal every of paises ~ ml, ad he poeta eet oft | pele ims. Wemayucatthe parties axbetnging othe odin chemical oocceslobehedy Tp hosewitewemalchenica potential pu) = ~mBanddeother with gett} c ol Tiepacils fand Lareas distinguishable se twodiferen iotopes ofan lene cece ‘Ffentekrments: we speak of | and Las distinc pees in equllibelim wih cach chen ‘ie tena chemical potential of the pacile siewed as ideal gases with concent yandn ate Holl) = elostifighs — ma) = slogtevng) en here = (8s 2c ese for bath pies. The tl hes potenti ae all) = tlogt ng) — mi @ Hall) = tosh ng) + md cs ne magnetic ares in ile over he vetaa of thesysen tee tua vang ver the vuln iad to nanan aetlantttalchamestics ode ay Sie he voted gm 56) (The ta checal punto species eewaa niga ‘Su of positon i thers fee dision of paises within the volume} Doras hese nayns (Chapter Cheniea! Potential and Gibhe Disnibuion rN 10 “oo CConcenztiosn, in patsles em-?—— To" ioe Figue 56 Dependence of te chemical potential ofa pus of magactie panics on the concentation at several wales of the magic held fntersiye fim 2 10" cov for B=, thon aa pot nbise 8 = 20 Siogause@ er} the concession willbe = 10? cm species in equitibium hace equa chemical potential Pal constant = pall} 3 “The deste glutons of 2) and (28) ace easly een by avbaution to be 4B) = AlOexplondye}s (8) = YoiOJespl—mBfe} (24) ‘where nO} sth total conceattation m+ my at a pois where the field B = 0, The totat onceatration ata point at magnetic Bld Bs 8) = mB) + 0,8) = Yn(Olexpio/e) + exp—me je]: HB) = neon) = ma +E ) es) ‘The result shows he erdency of maguele gates 1 concentrate in regions of high smageete fie intensity. The funcional form ofthe ret no lied Koes with wo sageetic orieettios, but is applieabe to fine feromagnetic pails in suspension in olla solution. Such suspensions are used inthe laboratory in the study of te magnetic fx surcture of superconductors and the domain srctre of eongnetic mater Ia engineering the suspensions are used to est for fie structural eck in high strength tel, suchas turbine blades and sircralt landing goat. Whenthese are coated witha eromagnetic | | Inraatand Total Chemical Poteet sspeton and placed in a magnetic Rl the pate concentration Becomes ens t Uelintenes eldest the edges ofthe crack, Tw the preceding discussion we added £0 jy the incenl chemisl potential of the patil. he parties wee el gus atoms, hy Boal be piven 12}. The Toga {oo foe pais not ested to ies gases, but 8a consequence of the conditions that the fatiles do not neract and thatthe eonceneation auc Tow. Hence (2) apis to macroscopic paris 36 well 28 to store that satiny thes assunptions, The only Aiesence isthe luc of he quagtun concetestion ny. We san therfore we Fig log a + constant 06) lst he constant ( ~ Tog) dace not depend on the concentration af de pts Example: Batteries. uc the vox vv exanpis cca psu and poeta stops fhe eetrocemical bare, tne mulated balery he negative electrode sss of mote ea, Pl, and the postive electra 8 yet fois Fad fxide, PUO,, on 3 PO subsite. Ths electron ate iamersst im alatad sults eid 1,50, whith is panially ionized ito H* fons (rots) aid SO, ons (Figure $7) lvthe discharge peoess both the metallic Mb of the negative elstrode atl the PHOS ofthe pastve elecvode are converted to Ia elt, POSD,, via the (eo ruetions Negative sfstode: Ph 4 SO,°" + POSO, + 22°; Positive electra: PLO, + 2H* + H,SO, + 2c” + PSO. + 2H,0. (276) ecause of (27s) he negative electrode aes a8 snk for S04" Sos, Lecping he inter ‘hemical potential p(SO,"~) ofthe sulfate ions a the surice of the newaive electrode Tower than inside the electrolyte Se Figore 5.70) Sinlaly, because of (270) the postive slecitode acts a6 a sink for H ions, keeping the interna chemical potential ") of the hydrogen ions lower atthe surfice ofthe pave eestrode than inside the electote. The chemical potential gradients drive the sons toward the eeceodes, and they dive the electrical euccens during the discharge process. I ahe battery terminals are ot connected, electons ace depleted fom the postive slestrode and accumulate in the eegativeeleceode, thereby charging Doth AS a rex, electrochemical potential steps deveion at the clecrode-lesolyte intertaes, steps of cxacly the contest magaitude to equalize the chemical potential steps and 1 slop the Aiesion ofions, which stops the chemical reaction om proceeding further fan external current is permitted to flow, the reactions resume. Electron fow telly through the clectrolyte Is negligible, because ofa negiibe leon canceteation in the electrolyte, "The teatons given arent rstons The actual eexton steps ae more complicit, nn30 Chapter 5: Chemist Potential and Gibb Dishibucon ~) ekewose (4) eleciode poo. } py « 7 S077 acy oe 28057 1 sath?) Figure 87 (a) The teabavl batery consists ofa Pb sid a POOselstove imrcried in Patsy ionized H1,50,. One SO, ~ ian converts one Pb atom to PUSOg Foe "0 Hons plus one uiioniaed SO, mateculssonvert one PEO, moleete na POSO4 + 24,0. uo wuning twa elcteons (4) The elestrochemical potent for $0; and” before the deselopment of itera potential baits tat stop thc dian {tthe chemi eesction,(} The eeteonatie potentials) afer the foranation ofthe baie (Chemical Potential and Entropy sig the charging peoess the reactions opposite to 2 esti oltge is pi that genset etre ufsich nape ast rence inl anes the drethon fio fo a) take place, because now an lestontate poten sey a he safe the sign of he otal heme putea praca Ne devote by AV. and AV, the difernces a ctestiostitie patent of the negative ad oie cette retaive tothe conivon eectlyte, Because the sollte ions envy so ogi charges, diasion wil stop when ~ 2 AV. = byl, (282) Diflusion othe H* ian wil stop when FGAV, Ault’) (286) [The to potentis AY ond AY are called halcell potentiate of falfeet! EME" {elstcomotie forces) thee magnitods ate kaown: SV = —Davol; ayy = 4 16vole ‘Ts teal clsstosttis putea dierence developed acr05 one full cll of th bate. a5 required to stop the difsion reaction, AV = AV, ~ AY. = 20voIt, 9) ‘Tisis the open oltage or EMF ofthe tery. drives the electrons fom the nega "ive terminal tothe postive tenia, whey the two ate commana Me have ignored fee electors in the eletolyte. The potential sep tend 10 dive ‘tesrons om the negative electrodes ino theelectelite, and fom the elects eto the Pesitveclctce, Such an electcon currents present, but hemagniide esa sally otee racially negligible, beause the concentation ef eetiros inthe electralyte fe mony orders of magnitude less than that ofthe ions. The only elective election ew path rough the external connection between te estou (Chemical Potential and Entropy mn G) we defined the chemical potential as a derivative of the Heleshottz ree AUHAY fe ; LI (20) oo ‘This expres the ratio w/e as & derivative ofthe entropy, similar to the way Yc was detined in Chapter 2 ntChapter 5: Chemica Potential end Gis Distribution “To derive (30), consider the entropy 28.8 function ofthe independent variables U, Vand 8. The differential a= (2) «(aro (aro ives the diferential change ofthe entropy for arbitrary, independent differential changes dU, d¥, and dN. Let dV = 0 for the processes under consideration. Further, select the ratios of da, dU, and dN in such a way that the overstl temperature change dz will be zero. If we denote these interdependent values of da, dU, and UN by (64), (5U), and (ON), then de = O when ae 80) aay ($5), © (&),e. Ae division by ON), Wa, _ for) OUy , (60° 7 torr = Galan * i), o The ratio (50) /(5N), is Ze/EX),, and (SU),jBN), 8 (BUJA4),, all st constant volume. With the original definition of Ij, we have Gi, > Ge Gi % “This expresses a derivative at constant U in terms of derivatives at constant. By the original defiaition of the chemical potential, r=) = Go - Gi, sand on comparison with (33) we obtain ra =e | o ‘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 a, Be Chemical Poremiat and Enopy a Tale Summary of elations exprenng the temperature the pressure py aad the chcoical potential im eae of ania devionves ofthe entropy othe every Uy an the ese energy F,with 2, U, and F given ae felons of thee nstutal Independent variables, aura Ue Fis independent Satie function offs natural independent variables «, ¥, and N, so that p appents as a funetion of the same variables, In (31) we assumed o = o(U,¥,N), so that (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 in Chapter 10 wederivea relation for as function of, p, and N. Table 5.4 compiles expressions for r, p, and seas derivatives of 6, U, and F. All forms have their uses, Thermodynamic identity. We can generalize the statement of the thermo: dynamic identity given in (3.34a} to include systems in which the number of particles is allowed to change. AS in (31), Gio oan de Diy use of the definition (2.26) of If, the relation (3.32) for pfs, and the relation (80) for = jf, we write da as da = dUje + pas ~ pdNje (8)ne Gibbs istribuion ‘This may be rearranged! to give [a le plV + nin, | 6% Which isa broader statement of the thermodynamic identity than we were able to develop in Chapter 3, GIBBS FACTOR AND GIBBS SUM ‘The Boltemann factor, derived in Chapter 3, allows us to give the ratio of the Probability that 2 system will be in state of energy cto the probability the ‘system will be in a state of energy es, fora sytem in thermal contact sith reservoir at temper prrreke Pie) expl—ey'e) exotney) (0 Fees * plea) bad ‘This is peas the best known result of statistical mechanics. The Gibs factor sthepeeety ofthe Boltzmann factor ta system in thermal and difosive ‘contact with a reservoir at temperature x and chemical potential. The arg ment retraces much of thet presented in Chapter 3 ‘We consider a very large body with constant energy Up end constant particle ‘number No. The body is composed of two parts, the very large rescevoie @ and {he system 8, in thermal and difusive contact (Figuee 58). They may exchange particles and energy. The contact assures that the temperature aud the chemical Potential ofthe system are equal to those ofthe reservoir. When the system has AM patios, the reservoir bas Ng ~ parties; whom the system hs eneigy & 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 + Feservolg, one copy foreach accessible quantum state ofthe combination, What is the probability in a given obseevation that the system will be found to con. tain NV particles and (o be ina sate s of enceey 2 ‘The states isa state ofa system having some specified number of pastices The enesgy Ey isthe enerty ofthe sates ofthe N-puctiele system; sometinies We write only tif the meaning i clear. When cat we write the energy of a system having X particles in an orbital as N times the energy of one particle in the orbital? Only when interactions beiwees the particles are neglected, so that the particles may be treated ss independent of exch other, Gis Factor and Gils Sune Resevoie Goes) a Figure 5.8 A system in her and ifsive contact with 4 large reservoir of energy an of particles Th total stems 1 + $s sulted (oom the externa world. so thatthe {otal energy and the total umber of paris ave sostant ‘The temperature of he system i cual toe temperature ‘ofthe reserve, and the chemical potential ofthe systems lta the chemical potential ofthe reservoir. The apse snay be as small as one atom of it may be mactoseopie, but the reserve i always to be thought of as much ger than he system. Let P(N.) denote the probably tht the system has N parties and isin & particular states. This probability is proportional tothe numberof aeesible states of the reservoir when the state of the sistem is exactly specified. That 48 ifwe specity the state of 8, the numiber of accesible states of @ + $ is just the number of accessible states of H+ 8} at) 1 a The factor 1 reminds us that we aretooking atthe system 3 ina ate, The g(t) states ofthe reservoir have Ny — N particles and have en Ug ~ by Because the system probability PUN) is proportional to the numlsct of accessible states of the reservoie, PUN) % gINo — Ne — 6). bsns Chapter 5: Chemical Potential and Gis Diseriation @ Panicles Ny — 5 Sie 1 Energy Up 0 ny ~ ey Particles % Particles Energy 6, Enea e Figue $9. The eservoie in thermal and difsive contact wih the system ff) the sssiem isin quantum state Land the weservic has gig ~ Ny, Uy ~ ey sates dense toi. In(6) the system i in quantum sate 2, andthe ceservit has ply ~ Nae Ug sales accesible to it Because we have specified the exact sate ofthe system, the tat umber of sttcs aoesible tot + 8s just the nuinber of states access tod. Here g refers to the ceservoir alone and depends on th in the reservoie and on the eaorgy of the racerveie We can express (42) as ratio of two probabilities, one that the system is in State 1 and the other that the system is in state 2: © umber of partites Pas) _ g\No = NuWa ~ 0) Fy)” Ge Nyy 6) ° e “here 9 relers tothe state of the reservoir. The situation is shown in Figure 59. By definition of the entropy StMoU) = explo(NoUa)] . ay so that the probability ratio in (43) may be written as, PWNaa) ~ explatile = NaUe~ al)’ “ Wee) = explolNo ~ Nyy ~ 1) — o(No ~ Ue - esd) = expla), 6) (Gils Factor and Gib Sure Here, Aa is the entcopy difference 9 © oly = Nyy ~ 61) ~ alo ~ NUe ~ a ‘he reservoir is very large in compacison with the system, and Az may be ‘approximated quite accurately by the fest order terms in a series expansion in the two quantities N and ethat relate tothe system. The enteopy of te reservol becomes AINy ~ NiUy~ 2) = ofXeUa) — + (38) For Ae defined by 47] we have, to the fist order in My — Ny and in ey Ts (56a) boy our original definition ofthe temperature. This is we bout the system will have the same temperature, Also, Ha (2% 50) iG), ‘89 by (G0) “The entcopy dilference (49) is en for the reservoir, on Here Ae refers tothe reservoir, but Ny, Nas est refer tothe system, The centeal ‘sult of statistical mechanics is found on eombining (46) and (51): Pas) _ expN — el] PUNat) expliNan = t/t] 9) aya8 (Chapter 5: Chemical Penta! and Gibbs Disribsion The probability is the ratio of wo exponential fictors, cach of the form ‘exp{l# ~ oft]. A term of this form is called a Gibbs actor, Ths Gibbs factor 5 wroportional to the probability thatthe system is in« state s of energy ey ‘and number of particles N. The result was first given by J. W. Gibbs, who referred t0 it as the grand canonical distribution, ‘The sum of Gibbs factors, taken over all tates ofthe system for all numbers of particles, is the normalizing factor that converts relative probabilities to absolute probabilities Blas) = FY espliny ~ egal Rowlsn - { | de | 69 | ‘This is called the Gibbs sum, or the grand sum, ofthe grand partition function, ‘The sum is to be cartied out over all states ofthe system for all numbers of Patties: this defines the abbreviation ASN, We have writen ¢, a8 tyay to emphasize the dependence of the state an the number of particles 8. Thos i, fag) 6 the energy of the state s(N) of the exact N-partice hamiltonian, The term N = 0 must be incladed; if we assiga its energy as zero, then the fist term in J willbe ‘The absolute probability that the system will be found in & state Ny, is siven by the Gibbs factor divided by the Gibbs sum: Puy) = SN = en) ‘ ay ‘This applies toa system that js at temperature r and chemical potential g. The fatio of any two P's is consistent with ovr central result (52) for the Gibbs factors. Thus (52) gives the correct relative probabilities for the states and N50 ofthe Nuts ‘The sum of the probabilities ofall states forall numbers of pasteles System is unity Sean = YEP) = Frey 63) by the Aefintion of Z. Thus (54) gives the eorreet als sobbiliy.® ised ect a poobabity theory wi oe Append Coe the Poin diebation tobe EARGIaY teint. The mshod ased ere 1a dee the Pabton daeibaen dope oe ee Gibbs Factor and Gibbs Sn Avenigs values over the systems in diffusive and thermal contact with a ssservoir are easily found. If XU) isthe valle of X when the system has N particles and isin the quantum states, then the thermal average of X over all, Nand al sis Rr Wserpltne = eave) ——. 56 XD = DOM gPIMe) We shall use this result to calculate thermal averages, Jed Number of particles. The number of particles in the system Gan vary because the system is in diffusive contact with a reservoir, The thermal average of the ‘number of particles in the system is ENeveliNn — eg] iy = Sn on according to (56). To obtain the numerator, each term in the Gibbs sum has ‘multiplied by the appropriate value of N, More convenient forms of CN’ «aa be obtained ffom the definition of BL wesstewn~ avd, 8) whence ny = 5 oP = ed. 9 me ‘The thermal average number of particles is easily found from the Gibbs sum & by direct use of (59). When no eosfusion arses, we shall weite N for the thermal average (N). When we speak later of the occupancy of an orbital, Lor Cf) will be viritten interchangeably for N or CN. We ofien employ the handy notation [ sew (60) where 2 is called the absolute setivity. Here J isthe Greek letter lamba. We See from (12) that for an ideal gas 2is directly propestional to the concenteation Le