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No Chapter S: Choice es sn Gibbs Distribution ‘The Gibbs sum is writen as B-LEPewl-gia = Liew), (61) and the ensemble average number of pastcles (57) is kN) = AS beg. 2) This relation is useful, because in many actual problems we determine A by finding the value that will make (1) ome out equal to the given number of patties Energy. The thermal average enerey ofthe systern is Esexol an ~ e)] aS : () where we have temporarily introduced the notation write U for <6). Observe that Je. We shall usually Wy Ua ZS ne «3% = Zing. oy so that (59) and (63) may be combined to give onGs ‘A simpler expression that is more widely used in calculations was obtained ia ‘Chapter 3 in terms of te partition function Z. a a3 are Be ce : an) log (65) Example: Occupancy sro erens. A rotMooded example af @ system that may te ‘occupied by zeromolecales or by one molecules the heme Broup which may be vacant oF iy be occupied by one O, molecsle~and never by more thas one O; mec (Figure 5.10) A sogle heme group occurs inthe protein myoglobin, which ie responsible forthe ‘ed color of eat. fe isthe energy ofan adsorbed molecule of O, relative to Oat vest at Gibbs Factor and Gite Sum Mt Figwe S10. Adborption ofan O, by @ heme, MbO, whet eis theenergy ofan adored Oy {oan O, a ioiite separa C Nb infinite distance, then the Gibbs sun is ela expla (66 energy must be added t rove the atom fom the hme wl bs aegaive.The ttm 1 jn the sum arises fom occupancy 270; the tern expt ~e 1) arses fom singe occupancy ‘Those ate the ony possibilities We have Mb +O, or BIRO, present whese Ms denotes ‘myoglobin, a protein of mleeslr weight 17020 Experimental esl forthe factional occupancy versus the concentration af oxseen are show in Figure 11, Wecompate te observed oxen saturation curves oF tyorebin ad hemoglobin in Figure 512. Hemoglobin tbe oxsgen-eateying component of Sood. 1Wismade upof four molecule strands, eachstrand neal entet with the singe staed of ‘myoglobin, and each cpable of tindinga single oxygen molese. Mistoiealy. the case workon th adsorption ofoxygenby hemoglobin xasdoneby Cristian Bok, the the of [Niels Bohs. The eayeeasutoraton curve for hemoglobin (Hb) has wslwct deat Tow pressures, boas te binding enerey sins 0, toa molecule of Wh i lwer tsa for Mb. At higher pressures of oxygen the HD cure hs 4 teion that is concave upeads, ‘esause the binding eneray pe O,inieases fle the fist Oy is adsorbed. ‘The ©, molecules oa hemes sein egitim with the O, in the surrounding iui, so ‘hat the chemical potentials of O, ae equal onthe ryoglobin and in soltion: HMO) = p(O,): (M003) (02) wn where 4 expla/s From Chapter 3 find the value of Zin tems of the gs pressure Dy the elation ing fg (ss) ‘We assume the al gas ext apis to O, in solution. At constant temperature 700) ieetly proportional tothe pessuep. “The Faction fof Mb occupies by O, sound trom 6610 be 2expl=e)) t S° Ty hep(-eih” Pepe et * @) Teor the site energy aust be spplicd to detach the O, from the heme, thea evil be agateFigue S11 the easton of myoglobin Iho) molecute with oxygen may be viewed as the adsorption of a molecule of O, at a site a ‘ali faow a Langmuir oti gute Ney Each aogiinnetecdcess fe arb one 0, mates Thee sancsstow =| Aetacionfuyepobawibedsord Oo, [E Balinclonofeperit pesiecofOe? The cori sre human yeah in * soliton. Myoglobin found ao muscles: ie resgonsbi for the color of steik. Alter A, RossiFavall and E, Antonin, Atchines of iochemity aod Diophyses 7, 478 O95, o z + 6 ‘Concentration of Oy relative scale Figore 8.12. Saturation cures of, bound ‘0 mplubin (Mb) and bernogtobin (Hb) molecules insolation ia water, The pit eure of Oy js pote a8 the horitotal sis The eel ans gives the faction of ‘the mleeules of Mb whlch fs one bound ©; molecule, o he faction ofthe strands of Nb whi have one bowad O anu Hemoglobin has a mael lneger chine in ‘xygem content inthe pressure range between (Oe artes andthe veins, Tis citeumstance Sita the ation athe heart, vis a 2 pnp. The cure for myoglobin Bas the rite form Ge the ection Mb-+ Oy +> MbO,, Th eure be Hemoglobin hs a Sea ure form because ofaeractions between reer eee olcules bord 0 the fur strana ofthe Pressure of Oy i man Hg {ib moleete The deving ister JS. Peston an 8. Simmonds, General boheme, We, 1361, 2) bO, or HBO, Git Factor and Gibbs Sum NARs Bite ame as the Ferm-Diae distribution faction desived in Chapter 7. We subsiue (68) (68) 10 lain 1 P f° GamepRIT TT” geeTTG * Mie] th ps ata ay ‘etsw pis coustaat with respect fo prestre, bu depends onthe temperature The result. 7H iskoose asthe Langa adsorption soteem when use i describe the adsorsion of ses on the sure of wld, Example: lupus atom ionization ina semiconinctor. Atoms of nutierous chemical lems when presot as impurities a semiconductor may lene aneletvon by ioneren to the contetion band of ihe serconductr crystal, Inthe conduction baad the clacton moves about moh aft were are pattie, au the eect pa the contortion at ‘may fen be teated as an ideal gas The impiy atoms ae sill stems 8 in then a sie equa wih th lage reseroi formed by the vest of the cemioractey ‘he atoms exchange eesitons and cvergy withthe semiconductor, {st the ination enerey of the immpuity atom, We suppote that one, but oaly one, ‘Sesto can be bound te an inpuriy stom: eee orientation 1 0c {of the clcrom spa i accessible Therefore the ster has thee allowed sates one withost sn ceenorn Soeni amletton attached with spin [and one with an electron attached with spi 1 ‘Nhe § haszeiolscirons,theimpuriy atom sionized Wechoose the eto ofenerey of ‘sthisstai:theatherswo slates therefore have the common cueray € = 1, These cont sates of Sate summarized below. Stare aumbee Description Noe 1 Electzon detached o 68 2 Electron atthe. spin 1 3 Htottom athe spin fT ‘The Gibbs sum given by Se 14 Dexple tt) 0 waCheptor $2 Chemical Poteniaand Gibbs Dibation “The probability that $ Binieed( ois 1 1 ionized) « PI —— 3 Plonized) = POO = 3 = aeptiae aA io “The probablity he $ret unos P(neutsal) = PULT,—1) + PULA sy hich sunt = Pro) SUMMARY 1. The chemical potential is defined as (7.8) = found from y= (CU/EN), equilbsium 1 = yy. (CFHEN gy and may also be =WlofPN}cy. Two systems are in difusive 2. The chemical potential is made up of exo parts, external and internal. The ‘external part i the potential energy ofa particle in an external field of force, The internal pact is of Wiermal origin; for an ideal monatomic gas pint elog(wingl where nis the concentration and ng = (Mu2ah) isthe quan ‘wm concentration, 3. The Gibbs fetor PUN) = exon ~ eG. gives the probability that a system at chemical potential rand temperature ¢ ‘will have 1V particles and be ina quantum state « of eneray&, 4, The Gibbs sum, is taken overall stats for all numbers of particles. 'S. The absolute activity is defined by 2 = explut) (6. The thermal average number of pactiles is oo = 28 bea. | | | PROBLEMS. 4. Cenirifuge. A circular cylinder of radius R rotates about the long axis with angular velocity ©. The cylinder contains an ideal gas f atoms of mass Mf at temperature ¢, Find an expression for the dependence of the concestsation tl) on the radial distance r from the axis, ia terms of n{0) on the ania. Take 12s for an ideal gas, 2. Afotccutes inthe Eurth’s atmosphere. ICnisthe concentration of molecules at the surface of the Earth, Af the mass of molecule, and g the granitaional acceleration atthe surface, show that at constant temperature the total numer ‘of molecules in the atmosphere is N= Aeltexri-Metionf seeteolsttefra. 08) wih me red from the center ofthe Earth hore Ris the eaius of the Hae, The intewra diverges at the upper lint, so that NY eannot be bounded and the atmospltere cannot be in equilibrium. Molecules, particularly light molecules, are always escaping front the atmosphere. 3. Potential energy of gas in gravitational field, Cousiler a column of atoms cach of mass M at temperatuse ¢ ia a uniform gravitational field . Find the thermal average potential everey per atom, The theraial average kinetic enerey density is independent of height. Find the total heat eapicity per atom. The ‘otal heat capacity isthe sura of contributions fromm the kinetic enersy:and leon the potential energy, Take the zero of the gravitational enesgy at the bottom f= Oot the column, Integrate from h = O10 h = <0, 4. detive transport. The concentration of potassium K* ions in the interaat sap ofa plant eel (or example, a fesh water alga) may exceed bya factor of LO" the concentration of K." ions in the pond water in which the cell is growing, The chemical potential of the K iors is higher in the sap because thet con. centration 1 is higher there. Estimate the dilference in chemical potential at 300K and show that its equivalent to a voltage of 0.26 across the cell wall Take jas for an ideal gas. Because the values of the chemical potentials are Siferent, the ions in the cell and in the pond are notin diffusive equilibrium, The plant cell membrane is highly impermeable to the passive leakage of ions {rough il. Important questions in cell physics include there: How isthe high Concentration of ions built up within the ell? How is metabolic enerey applied to energize the active ion transport? 5. Magnetic concentration, Determine the ratio mis for which Figuee 5.6 is drawn, If T s 300K, how many Bohr magnetons jty © eh/2ue would the particles contain to give a magnetic concentration effect of the magnitude shown’? us(Ghaprer 5: Chemieat Potential and Gibbs Disrbution 5, Gibbs sum fora to level system. (8) Consider @ system that may be une ‘ccupied with energy zevo or occupied by ane particle in either of two states, ‘onc ofenergy ero and one ofenergy «Show thatthe Gibbs sum for this system i GSE HL + dexpl—eha, (7) ‘Our assumption excludes the possibilty of one particle in each state atthe same tine. Notice that we include in the summa term for N = Qasaparticularstate ofa system of a variable number of partite, (@) Show that the thermal average accupaney ofthe system is 24 Jexp(—e) ow m & (©) Show that the thermal average occupancy ofthe sate at energy eis ENO) = dexpl 0/3. 08 {s) Find an expression forthe thermal average oergy ofthe system. {e} Allow the possibility that the orbital at @and at emay be occupied each by fone particle atthe same time; show that HALA + Lewpl—efe) + Pespl-wsy= (1+ Alt + Aexe(—e)]. 9) Because 3 can be factored as shown, we have in effect wo independent systems, 7. States of postive and negative ionization, Consider a laitie of fixed hy- drogen atoms; suppose that each aom cam exist in four Stare Number of electrons Buergy Ground t 8 Pesiiveion ° w Negative om 2 y Excited 1 o ind the condition that the average number of electrons per atom be unity. ‘Ye condition will involve 5 2, saul 8. Carhan monoxide paivoning. neato monoxide poisening the CO iplaces the O, adsot bed! on hnoslabin (1b) mulccules i the bla Te show the elect, consider a model for which exch adsorption site on a heme may be scant of may be eeeupied either with energy é4 by ave molecule O, oF with energy ey by one motecule CO. Let ¥ fixed heise sites be in equilibrium with Problems (©; and CO in the gas phases at concentrations such that the activites ar Oy) = 1 x 10-§ and 3{CO} = Lx 10, all at body temperature 37°C. Neglect any spin multiplicity factors (a) First consider the system i the absence of CO. Evaluate cy such that 99 percent of the Hb sites ate occupied by Oy Expross the answer in eV per Os. (b) Now admit the CO under the specified Conditions. Find ty such that only 10 percent ofthe Hb sites are occupied by Oy. 9. Adsorption of O, ina magnetic feld. Suppose that at most one O, can be bound to a heme group (see Problem 8), and that when £{O,) = 10° we have 90 percent of the hemes occupied by O,. Consider O, as having a spin of 1 and amagnetic moment of 11g. How stronga magnetic field isneeded tochange the adsorption by I percent at T= 300K (The Gibts sum in the limit ofer0 magnetic field will difer fom that of Problem § because there the spin rultic plicit of the bound state was neglected.) 10, Concentiation fluctuations. The number of particles is nat constant in & system in diffusive contact with a reservoie. We have seen that 5): “ from (59). (a) Show that omy = ey ‘The mean-square deviation ((AN)*) of N from GV) is defined by AND?S = IV = CSD) = QNPY = 2QNDKND GND? = ENP) = GND or B-3@) (6) Show that this may CANT) = e2END/E 3) {tn Chapter 6 we apply ths sult to the lyst fil that any? ND 8) js the mean square fractional Ructuation in the population of am ideal gas in Uitfasive contact with a reservoir, I <.N) is of the order of 10? wtomns then the NrMe (Chaprer 5: ChemicelPotemal and Gibbs Discibuion Sactional Actuation is exceedingly small. In such a system the number of Pacticles is well defined even though it cannot be rigorously constant because diffusive contact is allowed with the reerveie, Whew (Nis lov, his gelation an be used in the experimental detecmination of the moleeslar Weight of lage ‘olecoles such as DNA of MIV 10" ~ 10'*; sce M. Weissman, H. Schindler, and G. Feher, Proc. Nat. Acad Sei 73, 2776 (196), 11, Equivalent defiition of chemical potential. The chemical potestial was defined by (5) as (2F/2N),,. An equivalent expression listed in Table 31 is Hs CUM, y. «9 Prove that this relation, which was used by Gibbs to define j,i equivalent to ‘he definition (5) that we have adopted. It will be convenient to make use ofthe ‘sults (01) and (35). Our reasons for treating(5) asthe definition of yi and (85) as 4 mathematical consequence, are two-fold. In practice, we need the chemi potential more often asa function ofthe temperature + than asa function ofthe entropy ¢. Operationally, a process in which a particle is added to a system hile the temperature of the system is kept constant is a more natural process "han one in which the entropy i kept constant; Adding a particle to s)steas st A finite temperature tends to increase its entropy unless we can keep each system (of the ensemble in a definite although new, quantum state. There is no natural laboratory process by which this can be done, Heace the dsfinition (3) oF (6), in which the chernical potential is expressed as the change in free enetay pet added particle under conditions of constant temperate, is operanionally the simples, We point out that (85) will nat give U = jeN on integration, because (N.0,¥) isa function of NY; compare with (9.13). 12, Ascent of sapin trees Find the maximum height to whieh water may rise ‘unde the sssimption thatthe ots stand in pool of wotee and the ‘opermost eaves ae in ar containing water vapor at a felatie humidity r= 09. The temperature is 25°C, I the elative busily sr, the seal concur tion of water vapor inthe ac atthe uppermost leaves is mp, whete mis the concentration in the situated air that stands immediately above the pool af water 13, Ieentrope expansion. (a) Show thatthe eotcopy of an ideal gos can be ‘expressed as a function only of the orbital occupancies. (0) From this result show that 72” is constant in an isatrepic expansion ofan ideal monatomic 0s. 14, Maliple binding of 0. A hemoglobin molecule can bind four Or rolecules, Assume that eis theenergy ofeach bound O3, relative t0 O, a rest a infinite distance Let denote the absolute activity exp) ofthe fee Os (in Selution).(a} What isthe probability tht one anid only on€ O, is adsorbed on a Probleas !hemoglobin molecule? Sketch the result qualitatively as.a function of (b) What is the probability that four and only four O, are adsorbed? Sketch this cesul ale, 415, External chemical potential, Consider a system at tempersture +, with 1X atoms of mass Af in volume V. Let (0) denote the value of the chemical potential at the surface of the earth. {a} Prove cacefully and honestly that the Value of the fotal chemical potential for the identical system when translated tosltitude his 1G) = (0) 4 AMgh where g is the acceleration of gravity. (b) Why is this result different from that applicable to the barometric equation of an isothermal atmosphere? wyChapter 6 Ideal Gas FERMI-DIRAC DISTRIBUTION FUNCTION BOSE-EINSTEIN DISTRIBUTION FUNCTION CLASSICAL LIMIT Chemical Potential Free Energy Pressure Energy Entropy Heat Capacity Example: Experimental Test ofthe Sackur-Tetrode Equation ‘Chemical Potential of Ideal Gas with Internal Degrees ot Freedom Example: Spin Entropy in Zero Magnetic Field Reversible Isothermal Expansion Reversible Expansion at Constant Entcopy Sudden Expansion into a Vacuum SUMMARY PROBLEMS 1. Derivative of Ferii-Dirac Function 2. Symmetey of Filled and Vacant Orbital 3. Distribution Function for Double Occupancy Statistios 4. Eneray of Gas of Extreme Relativistic Particls 5. Integration of the Thermodynamic Identity for an Tdcal Gas 6. Entropy of Mixing 7, Relation of Pressure and Energy Density 8, Time fora Large Fluctuation Cas of Atoms with Iaiernal Degive of Frecdom 10. Isenteopic Relations af Ideal Gas 11. Convective Isentcopie Equilibrium ofthe Atmosphere 12, Weal Gas in Twa Dimensions 13, Gibbs Sum for Ideal Gas 14, Ideal Gas Cateutations 1S, Diesel Engine Compression ast1s Chapter b: Idec! Gat The ideal gas is gas of noninteracting atoms in the limit oflow eoneenteation ‘The limit is defined below interme of the thermal average value ofthe number of particles that occupy an orbital. The thermal average occupancy is eatied the slistribution function, usually designated as fletyi). where ¢ is the encrey of the orbital. ‘An orbital isa state of the Schrddinger equation for only one particle. This term is widely used particulaly by chemists the interactions between pastistes are weak, the orbital model allows us 10 approximate an exset guantiey state ‘of the Schriinger equation ofa systems of N particles in hate quantum state that we consicuct by asigning the N pastels to otbials, with each orbitals solution of one-paticle Seheétinger equation. There are usually an infinite number of orbitals avsilable for occupancy. The teem “orbital” is esed even when there is no analogy to a classical orbit or to a Bolu orbit. The orbital mode! gives an exzet solution ofthe N-pactivle problem only if there are no interactions botveen the particles, Tis a fundamental result of quantum mechanics (the derivation of whieh would lead us astray fete} that all species af particles fll into two distinct lasses, fermions and bosons. Any pacticle with hallintegral spin isa. fermion, ‘and any particle with zevo or integcal spin is a bason, These ae no interme. diate classes. Composite purticies follow the same rule; an atom of He is composed of an odd number of partcies? electrons, 2 protons, I neutron — each of spin , so that *He must have hal-ategral spin and must be a fermion, An aiom of “He has one more neutron, so there are an even numberof particles cf spa}, and “He must bea boson The fermion of boson nature of the particle species that make up a manj- body system has a profound and important effect on the slates of the system ‘The results of quantum theory as applied tothe orbital mode! of noninteracting particles sppear as occupancy rules ms of an approxi- 1. An orbital ean be occupied by any integral umber of bosons of the sume species, including zero. 2. An orbital can be occupied by Or | fermion of the same species. ‘The second rule isa statement of the Paul exclusion principle, Thermal averages ‘of occupancies need not be integral or hal integral, but the orbilat occupancies ‘of any individual system must conform to one ot the other rule. Feamt-Dirue Disribution Function ‘The two different occupancy cules give rse to two diffrent Gibbs sums for sch orbital: there is a boson sum over al integral values of the orbital oceu- paney N, und there isa fermion sum ia which N = Qor N = | only. Different Gibbs sums lead to different quantum disteibution functions feta) for the ‘ermal average occupancy. ffconditions are such that f « 1, iwill not matter whether the occupancies Nv = 2,3,...are excluded of are allowed, Thus when £ & 1 the fermion and boson distribution fonctions saust be similar This fenit in which the orbitat occupancy is smal in compacison with unity i eaed the classical cegimne, We now teat the Fermi-Dirae distribution funetion for the thermat avécage ‘occupuney ofan orbital by fermions and the Bose-Einstein distribution fonction for the thereat average occupancy of an orbital by bosons. We show the squivalence ofthe we Functions in tbe init of low axcupaney, an we go on to treat the propertss of a gas in this limt-In Chapter 7 we treat the properties fof fermion and boson gases in the opposite limit, where the mature of the particles is absolutely crucial for the properties of the gas. FERMLDIRAC DISTRIBUTION FUNCTION We consider a system composed of a single orbital that may be occupied by a fermion. The system is placed in theraval and dilfusive contact with a fesecvoin, as in Figures 6. and 6.2. A real system may consist of a large number Ng of fermions, but itis very helpfal to focus on one orbital and call it the system, All other orbitals ofthe real system are thought ofa te reservois. Que prablem {s to find the thermal average occupancy of the orbital thus singled out, An orbital can be occupied by 2er0 or by ene fermion. No other occupancy is allowed by the Pauli exclusion principle. The energy of the system wil be taken to be zero ifthe orbital is unoccupied. The energy isc ithe orbital is occupied boy one fermion, ‘The Gibbs sum now is simple: from the definition in Chapter 5 we have Bett explo o “he tem T comes from the configuration with occupancy N= 0 and energy 4 > O.The term Aexp(—tfe) comes when the orbital is occu by one Fermion, so that N = 1 and the energy is The thermal average value of he occupancy of the orbital is the raifo of the term in the Gibbs sues with WV = 1 to the enuire Gibbs sum: expe) 1 MOD Ty expla)” Paap eT ° 1ast apr Hea Gas Reserve Reservoir Vacant : (Joss Ternion 0 fermions O energy Ny Fermions (My — 1 enions Uy Oe ens ave tp Peete A OIE Ae) SO eyo wate Uy My Hye EE Figore 64 We considers the systet a single ocbial that may be occupied a most by one fecnin, he systems in dhcmal an dfs contact wit the ceservoe at temperate The erny of he occupied obitl might be the Kinetic energy of ae electron of edeinte ‘in eresteton aod vnfued 10 « ke volume. Utne alowed quanto sates may be soasidered as forming the reserve. The reservoir wil contain No ermions ifthe s)sem is ‘unoccupied and Np ~ 1 fermions ifthe system is occupied by one eion, We introduce for the average occupangy the conventional symbol fle) that denotes the thermal average number of particles in an orbital of enerdy Slo) = «NU. Recall from Chapter 5 that 2 = explui), where wis the chemical potential We may write (2) in the standaed form et pleat Slo) isl ‘This result is known as the Fermi-Dirae distribution funetion.* Equation (4) Bives the average number of fermions in single orbital of energy e. The value _ 661 (19261, Snot hep ty Dust oer ens te chan a en 302 {12h}, and aL Dita, Procosingsulthe Ruy Sviy of Lona A Bash works drew on Pauls pape af the pete oral statement fe fora assumed by the Paul pace ons hy. Ferni-Dirae Distribution Fenetion Reservoir System Reservoir ” Figure 62_ (2) The obvious method of vewing 4 system of noaintesetng particles is shown here. The nergy etl eat eer an orb that ia solution of ele Dosti Schrier equation. The total eneigy of the sytem ie. 6a DM Iphete the number of putes in the orbital m of enrry «For fermions iy 2110) 8 nauc smpter thaw (a, and equally valid to eat 4 sng orl a fasten, The stem inthis scheme may be the orbital wof energy ny Al other eeorals ‘ate Need a8 the revo. The total energy ofthis one-orbial gatem i Maes where ‘z's the numberof patciss in the orbital, This deviee of using one orl the sustem works because the pactiles are supposed to interact only weakly withech othe. I'se think ofthe fermion system astocated withthe orbital these we tro Dossibiitis: her the sytem bas particles and eneepy Os he spes nd eney F. Thos, the Gibbs sum Consists of ely te esos, Bal + temper he fest term aries fom the orbital oecupuney Ny = 0, andthe secon teh arses from N= | hs par of f always lies between zero and one, The Fermi-Dirae distribu 4s plotted in Figure 63, In the field of solid state physics the chemical potential jis often called the Fermi level, The chemical potential usually depends on the temperature. The value of ion function 2210 feaypersturs is atten written as ep: that HG =O) HO) = ty. 8 We call ge the Fermi energy, not co be confused” with the Fermi fevel whieh Gui econ erator he symbol ei fen wed for at any temperate ‘hen cide Fen et BsChapter 6s Meal Gas Lop 08 7 og + a 07 06 c 1 104, oa | 03 | 02 on acy sF = pein oni Figure 6.3_ Plot ofthe Feemi:Dirae distribution function fle versus e — gin unite of the temperature, The value of fc zies the ection of bial st a given enerey which are ocupied wie the system isin thermal eqiibiams. Whet the systems hated from absolute 270, feratons ate ansere from the shaded region ate < 1 to the shaded region at eu > 1, For conduction electrans ina etal, might ‘eovespond to $0 000K. Js the temperature dependent js). Consider a system of many independent orbitals, 2s in Figure 64. Atthe temperatuse z = Gall orbitals of energy below the Fermi energy are occupied by exactly one fermion each, and sil orbitals of higher energy are unoccupied. At nonzero temperatures the value of the chemical potential y departs from the Fermi energy, a8 we will ce in Chapter 7 If there is an orbital of energy equal to the chemical potential (¢ = 4), the orbital is exaciy half filled, inthe sense ofa thermal average: fe= = @ Ortitels oflower energy are more than halffilled, and orbitals of higher energy are less than half fille, We shall discuss the physical consequences of the Fermi-Dirac distribution in Chapter 7, Right now we go on to discuss the distribution function af not Bose Finsteln Disibation Fnaton interacting bosons, and then we establish the iat gas law for both fermions ‘nd bosons in the appropiate lant BOSE-EINSTEIN DISTRIBUTION FUNCTION ‘A boson is a partite with aa integral value of the spin. The occupancy rule for bosons is that an orbital ean be occupied by aay number of bosons, 0 that bosons have an essentinly different quality than fermions, Systems of bosons tan have rather diferent physical properties than systems of fermions. Atoms of “His are bosons; atoms of "He ate fermions. The rematkable supertuid Droperties of the low temperature (T < 217K) phase of liquid helium can be attributed to the properties of a boson gas. There is @ sudden inerease in the Auidity and in the heat conductivity of liquid “He below this temperature, In experiments by Kapitza the low viscosity of “He below 217K was found to beless than 10°? ofthe viscosity ofthe liquid above 2.17 K. Photons (the quanta ofthe electromagnetic field) and phonons (the quanta of elastic waves in solids) can be considered 10 be bosons whose nurnber is ‘ot conserved, but itis simpler to think of photons and phonons as excitations of an oscillator, as we did in Chapter 4 ‘We consider the distribution function fora system of noninteracting bosons in thermat and diffusive contact with a reservoir. We assume the bosons are allofthe same species. Lete denote the energy of single orbital when occupied by one partite; when there'are W particles in the orbital, the energy is Ne, 4s in Figure 63, We reat one orbital asthe system and view all other orbitals 137 Figures.4 A convenient pictorial nay to think ofa system compose of inde ‘orbitals that do not interact with exh otc, bout interac with 3 common reseivoie.ist Chapeer 6: Heal Cae Vie 6 Ese eel chanson inerctng Son Herein ey Nessie enery ofthe sang erie wg Occ Nan hnp re hve Ein tcp hanes Thee oft eben eter no fran ans theoet tpn eee, ‘ep(nddrand the sqm cots neantagri esd eines indsoon TheGitstmingeree Foner) + Bene ye a5 part of the reservoie. An ‘The Gibbs sum taken for the orbital ig Y,.Pexol~ara ‘The upper limit on N should be the total umber of parties inthe combined Gruen and reservoir. However, the reservoir may be arbitrarily latg, so thot Nm rn from zero to init. The series (1) may be summed i close Let x a Lexp(—efs); then = Sapte is" Provided that Lex inequality: oherwis the Gibbs sum by use of 5.62) Smt Jrs3 arbitrary numberof particles may be inthe orbital = 21) < 1. Inll applications, Zexpl eft) will stay this ‘the number of bosons in the system would not be bounded, ‘The thermal average ofthe number of parties inthe orbital is fovnd evn ose Fintcin Distbaton Fenton Bose-Einstein fe Classica init. =r 0 t 2 in units of + Figure 6.6 Compavson of Bose-Finsten and Fermi-Dieae Aistibation functions The elsscal regime is tained for (6 ~ 3 » where the we astibutons become neal denial ‘We shall sein Chapier 7 that in the degenerate egies low ‘ermperature the chemical potenti fora FD disssbution fr positive, and changes to negative at high temperstre This defines the Rose-Eiastei distribution function ft difers mathematically Som the Fermi-Dirse distribution function only by having ~1 instead of +1 inthe denominator. The change can have very signiicent physical consequences, 8s we shall see in Chapter 7. The two distribution functions sre campared in Figure 6.6, The ideal gas represents the limit e — «3» rin which the wvo distr bution functions are approximately equal, as discussed below. The ehoice of the ze10 of the energy ¢ is always arbitrary. The paiticular choice made in aay problem will affect the valus of the ehemnial patential ja but dhe value of the uifercnee ¢ ~ 4 fas to be independent ofthe choice of the zro of. This point 's discussed turther in (20) below, A gas is in the classieal regime when the average number of atoms ia cach ‘orbital is much tess than one. The average orbital eccupancy for a gas st room ‘eonperature and atmospheric pressure is of the order of omy 10°®, safely in the slassical cegime, Differences between fermions (hafiategral spin} and bosons 13,reo Chapter: Hel Gor Table G1 Compatinon ofthe ebial occupancies inthe lassie and he quan egies uot Thecaal ances 065 scene oscupny radisle of any bial Fermion —Alsaye auch eth Toson”—Ahaays mck ec tha Quantum Ferion Boson ‘Close to bat tes tha one Ortitaloftowest energy has an occupa; much geeser than one. aise only for occupancies of the order of ane oF more, so that ja the classical resin their equilibrium properties are identical, The quantum regime is the ‘opposite ofthe classical regime. These characteris in Table 6. Features are surmmaized CLASSICAT Tur ‘An ideal gas is defined as a system of free noninteracting particles in the elasical regime, “Free” means confined in a box with na restrictions or external forces acting within the box. We develop the properties of an idval gas with the use ‘of the powerful method ofthe Gibbs sum. In Chapter 3 we treated the ideal gas by use ofthe partition function, but the identical particle problem encountered there was resolved by a method whose validity was not perfectly cleat ‘The FermiDirac and Bose-Einstein distribution functions in the classical Hint lead to the identical result forthe average number of atoms in an orbital. ‘Write fie) forthe average occupaney of an orbital at energy e. Here e is the ‘energy ofan orbital occupied by one particle; itis not the energy of system of 1 pautices, The Ferwi-Dirae (FD) and Bose-Einstein (BE) distribution func: tions are fc)» 1 $0 Sete RET an Where the plus sign is for the FD distribution and the minus sign for the BE istribution. inorder that f() be much smaller than unity or all orbi ‘must have in this classical eegime ls, we explle = pV > Ly 02) Chemical Potential for all e, When this inequality is satisfied we may neglect the tern £1 in the sen tor of (11) Then far ether fermions or bosons, the average occupancy ‘ofan orbital of energy eis Fed > espn ~ ave 4 dexpl~aft) | wy with Z © explu/e). The limiting result (13) is ealled the classical distribution function. 1 is the Fimit of the Fermi-Dieae and Bose-Einstein distribution functions when the average occupancy fl) is very small in comparison with unity. Equation (13), ahough called classical, is still a result for particles describes by quanturm mechanics: we shal find thatthe expression for 2 oF gt always involves the quantum constant & Any theory whieh contains fe caamat be a classical theory. ‘We use the classesl distribution function fte) = Zexp(—/s) to study the therml properties ofthe ideat gas. There ate many topics of imporiance: the entropy, chemical potential, Reat capacity, the pressure-volume-temperature reltion, and the distribution of atomic velocities. Ta obtain results from the classical disteibution function, we need st to fad the chemical potential in terms ofthe concentration f ators Chemical Potential ‘The chemical potential is found from the condition that the therma> average ‘of he (otal number of atoms equals the number of atomss known to be present This auniber must be the sum aver all orbital ofthe distribution function ft, Nn «w= TSG y (a) where sf the index of an orbital of energy c,. We start with a monatomic gas of N identical atoms of zero spin, and later we include spin and molecular modes of mation. The total number of atoms is the sum of the average number ‘of atoms in each orbital, We use (13) in (14) t0 obtain N= WZexp(-eo «3 “To evaluate this sum, observe that the summation over fice partite orbitals is just the partition function Z, for a single fre atom in volume ¥, whence N= iZy ut1 Chapter 6: Meat Gar is Chapter 3 it was shown that Z, = ngV, where ng (Me/2nh) is the ‘quentum concentration. Thus Ns az, inhi Una¥ = hing as in terms ofthe number density = NY. Finally, (a 1 3 = explujs) = nltg , | a sich it squa to the number of atoms inthe quantum volume Ig. Inthe classial regime wing is «1. The chemical potential of the ideal menatonte gasis = vote) | (8) J in agreement with (5.123) obtained in another way. The result may be written out to give = iflog —togY ~ flog + Hog(2at®/\)} a3) We see that the chemical potential increases a8 the concentration increases and decreases asthe temperature increases, Comment: The spl expression (18) forthe chenical potential canbe subject to sence odications. We mertien four ecamnplss. (3) H the zero ofthe energy seae shied by an energy so thatthe zero of the kinctie ‘hergy ofan orbital lisa ey = A insend ofa ey» 0, then HA + rlogining (20) (©) theatoms tare sin S the numberof bits inthe sum in 15) apie by the ‘in sultipoty 25 + 1 Forspin itisdoubled the sala ofthe parton nection zy | sublet; mg wil be ceased everynheze by tn. and the rghthoed side orth wil ase an added tort) ~rlog2, The efit ofthe spin on the emopy is nested Elo (6) If the easisn0t sonatomi, dhe incera enepy states asecated with rotational and ‘ration motion will ener sh pation faction, and the ehemieal potental ree Energy have an added term ~tlogZ.. pet (48) below, where Zs the patti function of he internal depres of eedom of one molecule (61 I the aa it nonieat, the test for» may be considerably more complicated: ee {Chapter 10 forthe relatively simple van det Waals approtiwaton to gis of inet, sting stom Free Energy ‘The chemical potentials related to the fee energy by GFN an) sccoing to Chater 5. From hig, Feta) = [avanevy=s[Mavposw 64, 2) \here the integrand is found in brackets in(19). Now fdvlog x = xlogx — so that (logA I~ togY ~ Hogs + Bog2ni/AN)], 03) [ = stony 4 eo ‘The free energy increases with concentration and decreases with temperature, Comments The integral in (22) should sircly bea sum, because Visa discrete vane Tas, om 5, Fovat) = Sut) 05) hich lies om the repr only in he term in tog. 9) or Buoy att e2edieemetnat, as 163us Chapter 6 Moat Gas whote the intepal pave os 23) Bot for large the Steling epprestnaion tog NlogN = N en ‘may be vse and now (25) the same as23) ners Prossure ‘The pressure is related to the free enerey by (349) p= CFV) .5 3) With 23) for F we have pasar: oven. ) Which isthe iat gas law, a8 derived in Chapter 3 Energy ‘The thermal energy U is found feom F a U ~ te, oF Warrier aang (24) 00 ‘With (23) for F we have @0),--2. i [was | oa ‘The factor J arises from the exponent oft in ny Because the gas is in thees dimensions; if mg were in one oF two dimensions, the factor would be $ or 1, ‘respectively. The average kinetic energy of translational motion in the lassical Timi is equal to fr or $yT per teansational degree of freedom of an atom, ‘The principe ofquipacttion ofenergyamong degiees of feedom was discussed fn Chapter 3 Heat Cpacity A polyatomic molecule has rotational degrees of freedom, and the average energy of each rotational degree of freedom is J when the temperature i high jn comparison with the enengy dilferences beween the rotational enctay Kevels of the molecule. The rotational energy is kinetic. A linear molecule has 1wo degrees of rotational freedom which can be excited; a nonlinear molecule has throv degcees of rotational freedom, Entropy ‘The entropy is related to the fee energy by FO ey From (23) for F we have the entropy of an ideal gas e= Moxon + a | 9 ‘Thie is identist with ou cuties sell (3.76) ti he enatcat epIMNE mg <1, 0 that logltg/n is positive. The eesul (34) is known asthe Saekur-Tetvde ‘uation for the absotute entropy of a monatomic ideal gas. It is important Aistorically and is esseatial in the thermodysamies of chemical reactions, Even {hough the equation contains f, the result was inferved from experiments an vapor pressure and on equilibrium in ehenvial reuctions long before the uantum-mechanical basis was fully understood. It was a great challenge to theoretical physicists to explain the Sackur-Tetcode equation, and many un successful attempts to do s0 were made in the eatly years ofthis century. We shall encounter applications of the result in later chapters, ‘The enteopy of the ideal gas is directly proportional to the number of particles \N if their concentration n is constant, as we see from (34). When two identicsl ‘Bases at identical conditions ars placed side by side, each system having entropy the total entropy is 2a, Derause N is doubled If valve that connects the systems is opened, the entropy is unchanged. We see thatthe entropy scales as the size ofthe system: the entropy is linear in the numberof particles, a constant concentration. Ifthe gases are not identical, the enteopy increases when the valve is opened (Problem 6) Heat Capacity, ‘The heat capacity at constant volume is defined in Chapter 3 as & (Gof. 05) 1s106 Claprr 6: Hest Gas We can ealeuate the derivative diveely from the entropy (3) of an ideal sas ‘shen the expression for ng is writen out: Ge. E Games From this, for an ideal gos “Ww, 66) oF Cy = BWky in conventional units. ‘he heat capacity at constant pressure is larger than Cy because additional beat must be added to perform the work needed to expand the volume of the 35 against the constont pressure p, a8 discussed in detail in Chapter &. We use the thermodynamic Meutty ta = dU + pdV to obtoin eo fet av) (2) “ @, + (&)- en eneety of deat ga dspends oily on the temperate, so that @U 20, Pihsvethe same valueas(@U fed, which ijust C bythe argument of 1784 pees eal gas law V = Nef, 30 thatthe team pl@Viary m N. thas 1) becomes (82) in fundamental units, or CeO tay (338) is conventional units. We notice again the different dimensions that heat ‘apacites have in the wvo systems of units. For one mole, ky usually writen 4 R, called the gas constant, ‘The results (38,6) are writen for an ideal gas without spin or other intemal degrees of fieedom of a molecule, For an atom Cy = 4N, <0 that C= Wew ai (686) in fundamental units, o C= ik (384) ‘nconventional its, The ratio Cy/Cyiswsten as, the Greck ter gemma, ste) ~ oO) [eC ©) ee Oana ike enropy atthe lowest cmperatte attained in the measurements HaCr, Ie thtd aw of thermodynamics sugges that (0) may best equal eee ‘ere are multiplicities not removed atthe lowest temperature atinned Ie can eae ie eattony of momatomie eat gv by wie ake Sack Teode ere K-41 K) = 723 x 108erg = —254, 7 “spansion at constant entropy. The work done by nergy of the gas, which is Uy — U, = 234 ‘Sudden Expansion lato @ Vacuum Lot the gas expand sutdenly into a-va ‘final volume of tees, This isan When a hole is opened inthe patti How much work is done in the expansion? No means of doing exteral work is provided, so that the work done zero. Zero wotk is not necessarily a characterise af all mermasban processes, but the work is zero for expansion into a vacuurn, What ts the temperature after expansion? No work is done and no heat is added inthe expansion: Ww 9,9 = O,and Us = Us s 0. Because the energy is unchanged, the ‘emperature of the ideal the eeatanet The energy of areal yas may change inthe proces hac ‘he atoms are moved free apar, which alets thet mene energy, What isthe change of ewropy tn the expansion? (The increase of sntropy when the volume is doubled at constant temperature ' given by (56) Ao a) For the expansion into a vacuum Q = 0, [Desusion ito a vacuum i ota reversible proces the system isnot in the ‘Nest Frobableoqulibrany) contigration at every sage ofthe expansion Onty us6 Chapter 6: Hest Gar Reversible iohermsl expansion Reversible } 1263 Summary of ileal monatomic gas expansion xpevinenis expansion Fereversite ‘expansion into the inital configuration before removal of the partition and the final con- guration after equilibration ase most probable configurations. At intermediate stages the distribution in concentration and Kinetic energy of atoms between the two regions into which the system is divided does not correspond to ai, equilibrium distribution. The central results of these calculations are sum- marized i Table 6.3 SUMMARY: STEPS LEADING TO THE IDEAL GAS LAW FOR SPINLESS MONATOMIC GAS, (@) flo = dexpl—u) ‘Occupancy of an obits in the | clas Timi of fl 1. Mae Lari Given N, this equation determines Sena en is eauton dete 2in the classieal limit. Energy ofa free particle orbital of quantum number a in 2 cube of volume ¥. | (0) Beso ess dx [dant expe) Transformation ofthe sumn tan i ° integra | (9 1= Wingy Result ofthe intpration (afer | substation in b) i (ng = (Meah2™ Definition of the quantum | concentration ' I Pte ©) pe Host) OW) Fm faryesier) on Nalloe(ag) (FIV. = NYY PROBLEMS 1. Devivative of Fermi-Divac func Fermi level ¢ = has the value (42) steeper the slope ofthe Fermi-Dirae Show that —éffée evaluated at the Thus the lower the temperature, the 2. Symmeny of filled and vacant orbitals. Let & pears as flye + 8b Show that Se + Bd fly = 3 7) “Thus the probability thatan orbital S above the Ferm level i occupied sequal {othe probability an orbital 5 below the Fermi level is vacant. A vacant orbitals sometimes known as a hole 1 8, $0 that fe) ape 2. Dinwibution function for double occupancy statstes. Let us tmaginea new ‘machtanics in which the allowed occupancies of an oxbital arc 0, 1, and 2. The values of the energy associated with these occupancies are assumed 10 be D, and 2, respectively, (a) Derive an expression for the ensemble average occupancy (IN), when the system composed of this orbital is in thermal and diffusive contact with a reservoir at temperature ¢ and chemical potential {8) Return now to the usual quantum mechanics, and derive an expression for the ensemble average occupancy of an energy level which is doubly de- generate; that is, two orbitals have the identical energy e. If both orbitals are ‘occupied the total energy is 2e 4. Energy of gas of extreme relatiistic particles. Extceme relativistic parti cles have momenta p such that pe >> M2, where M is the rest mass of the particle. The de Broglie relation 2 = hi/p forthe quantumn wavelength continues ‘o apply. Showr that the mean energy per pastcle ofan exteere relativistic ideal isis 3eife > pein conteast to fe forthe noncelativstic problem. (Aa interesting, Niriety of relativistic problems are discussed by E. Feri in Notes on Then» slynasnics end Statistics, University of Chisago Press, 1966, paperback) J. Integration of the thermodynamic identity for an ideal gas. From the ther- modynamic identity at constant number of particles we have ay, a 12) 4, 10 yy 4 BY to Nas LGRer + ) raa aa Chapter 6 Hest Gas Show by integration that for an ideal gas the entropy is Cyloge + NiogY + 01, 79 Where ois constant, independent of ¢ and V. we gelume: Show that afer ditusive eqilibriam is reached the total entropy Srna fest lo82. The entropy increase 2N logis known asthe entropy okrmixing. 1 the atoms are identical (A mB), show that there is no ners sWropy when diffusive contact i established. The dference in the results ag been called the Gibbs paradox, ce eaten of Pressure and energy density. (a) Show thatthe average pres Sarena system in thermal contact witha heat reservoir is given by Dee dEV beet ele pa 7 Iie the sui i overall states ofthe system. (b) Show for aga of re particles that 7% 41a sult of the boundary conditions of the problem, The result holds equally Wisther e,cefers to a state of N noninteracting patticles orto an orbital) Shore "at for a gas of free nonrelativistic particles 2upy , (79) ‘where U is the thermal average energy of the system. This result isnot limites {o the cassical regime; it holds equally for fermion and bason particles, os long as they are nonrelativistic, &. Tine fora large fluctuation, We quoted Boltzmann to the ffct that (wo gases 20 liter container will unmix only in atime etortnously long compared {a 107° years, We shall investigate telated problem: we let a gas el sterms of “He occupy a container of volume of. liter at 300 K and a pressuse of | ate and we ask how loag it will be before the atoms assume a configuration in Which all are in one-half ofthe container, (a) Estimate the number of states accessible to the system in this inital condition Probtens {0) The esis compressed isthermally toa volume of 005 lier. Flow many states are accessible now? (©) For the system inthe 01 titer container, estimate the value of the ratio umber of states for which all afoms are in one-half of umber of states for which mare any ‘toms are anywhere in the volun (2) A the collision rate of an atom is = 10's", what isthe total number of olisions of all atoms in the system ina year? We use this asa ere eatinae ofthe fequency with which the state ofthe system changes {0} Estimate the number of years you would expect to wait before all atoms are in one-half of the volume, starting from the cauilibsium confguaation 9 Gus of atoms with internal degree of feetom, Consider an ideal mon. ‘stomic gas, but one for which the atom has two internal energy states. one aa Shorey A above the other. There are NW atoms in volume ¥ st temperate 2 Find the () clic potential; (b) tres energy, fe) enltony: We) proccrey (6) heat capacity at constant pressure 12: entropic relations of ideal gas, (a) Show that the diferentis changes for ‘ideal gas in an isentropic process satsly ie ae oa Tron pao 2 0. 180) pF where 7 = C,/Cy; these relations apply even if the molecutes have internal slegrees of freedom. (b) The isentropic and isothermal bulk modutiare defined as Bow —ViepiVi,; B= ~VeepaV),. 8) ‘Show that for an ideal gas B = 3p; B, = p. The velocity of sound in sven by ¢ = (Bylp)*?; there is vety litle heat transfer in a sound wave. For an eal gas of molecules of mass M we have p = pr/M, so that ¢ = (ye/M}2, Here pis the mass density JI. Convective isentropic equilibrium of the atmosphere. The lover 10-15 km Of the atmosphere—the troposphere—is often ia 4 convective steady state at constant enteopy, not constant temperature, in such equilibrium pl independent of altinude, where » = CyiCy, Use the condition of mecha ‘auilbriue ina unifoom gravitational field to: (a) Show that dT/d: = constant, here «is the altitude. This quantity, important in meteorology, is call the ‘dry adiabatic lapse rate, (Do not use the Barometric pressure eelation that was etived in Chapter S for an isothermal atmosphere) (6) Estimate ui, in °C per kin, Take 7 = 1/5 (0) Show that p 2 p%, where pig the mass dens 1180 Chapter 6: Mest Gos ature gradient is greater than the isentiopie gradient, the ‘tunosphere may be unstable with respect to convection, 12. Hat gas in two dimensions. (a) Find the chemical potent ‘monatomic gos in Wvo dimensions, with I atoms confined to a squate of area A = 12, The spin is zero. (b) Find an expression for the enorgy U of the gas, (6) Find an expression forthe enteopy a. T of an ideal 13, Gibbs sum for ideal gas. (@) With the help of Ze ugl)S/N1 feo Chapter 3, show that the Gibbs sum for an ileal gas of iGentical atoms is 3 = expling¥) (b) Show that the probability thece are N atoms in the gas in Solume 1 ia diffusive contact ha reservoir Puy exp omisal potential y, for fee eletron Feri {85a oe and thee dmeasions. fn common ‘ets ey OL at goom lemperatre so tat is elosty equal to gy, Thve curves were In conventional units, 6s) tea om sere asnsions fines We found thatthe density of orbitals atthe Fecm energy is Dey) = 3N/2ep = SNP 69 — {ora Fee eecion gas, with ty gp. Do not be deceived by the notation ¢p itisnot the temper ure ofthe Fermi gas, but onlya convenient reference point {or r, the gas isin the classical eagine Thus (4) becomes Weset xm (e~ epife, ey [ Caste vs | on ‘and it follows feom (29) and (30) that In conventional units there is an extra factor ky, so that e ery Ca Deer) [dex 6 Cas PANRGTTy os Where ka7'p & éy. Again, T, is not an actual temperature but only a reference point, We can give a physical explanation of the form of the result (37). When the specimen is heated from absolute zero, chiefly those electrons in states within We may safely replace the lower limit by ~oo because the factor e* in the integrand is aleeady negligible at x = ~ey/t if we are cancemed with tow ‘emperatures suck tht e7/¢ ~ 100 or more, The integral® becomes 7 an energy range + of the Festi level ate excited thermally, because the FD Thus the occupation of he fst exci orbit a | mk 16 0 that the ration of the pats that ae in this orbital is f,N = $10" 10% 5 10°, hich very small. Wesee thatthe oooupancy of the fstencited orbitals low Temperatures relatively very much lower than would be expec at fist sgh lem the simple Boltemann factor (6), The Bose-Einstein distribution is guile stange i fava a situation in wha the greatest pat ofthe population sft in the ground obit ats. ieoty tow temperatres. The prtcsin the grousd orbital a long their amber s >. axe called the those-Eimtein condensate, The atoms in the conse at quite iferently from the atoms in excited states. How do we understand the existence of the condensate? Suppose the atoms were governed by the Planck distribation (Chapter 4), which makes to provision for holding ‘onstaat the total numberof prtles, sated, the thermal average suber of pointe ‘increases wit empstatureat".asfoundin Preble 41th lnsofeatue resect the ‘otal aomber of porns ta value N, we would my tat the gown aril the photo ss contained the diterence Mg = I~ N(epbeten the substan the tuber {hermally excited. The Ng noescted photons would be described a condense a the rownd orbital but Ng becomes essentially zero ata temperate, sch hall photons ace enced There fo actual sonsusiut um the wl tse Of photon; hone hee bea constraiat onthe total number N of material boson, such "Ihe tom a a spe. ‘This consent is the origin ofthe condensation iio the ground orbital Te uitrenee between the Planck distribution andthe Bose-Einscindstebution is tht the ter wil conserve the total umber of panics, dependent of repeats, 30 tht nonexstl stom are really in the ground stute condensate Ft Orbital Occupancy Versus Temperature \We sain (9) that the number of ke pats bias pr uit ence anes v0 = a(R)" oy ‘The total number of atoms ofhelium-t inthe ground and excited orbitals is given by the Sum of the accapancies of all orbitals: fora particle of spin ze N= Tho Nalel + N40) = Nelo) + [ de Dae (68) We have separated the sum over into two parts. Here No(s has been writen for f(0.%, the number of atoms in the ground orbital at temperature t, The integral in (66) gives the number of atoms N.fr) in all excited orbitals, with Orbit Occuponey Vera Temperature 5 1 4 | | | 3] i | wn | Ji | 2 7 _| 1 a 7] °y aE at 06 Figwre7.10_ Pt ofthe boson distibution fusion for wo temperatures, with scent paticls present to eosuce 2 = 1. The integral of the dstrioution times the eens of ‘ates gives the number N, of panies in excited arial; the ret ofthe pales preset sre condented into the ground sate exbital. The valve of Nis too lage fo be showa on the pl ‘Slex) as the Bose-Einstein distribution fanetion. The integral gives only the umber of sioms in excited orbitals and excludes the atoms in the ground orbital, because the function Dle)is zero ate = 0. To count the atoms correctly we must count separately the occupancy Np ofthe orbital with e = 0. Although only a single orbital is involved, the value of Ng may be very large ia a gas of bosons. We shall call Ng the number of atoms in the condensed phase ad My the number of atoms in the normal phase. The whole secret of the result which followsis that at low temperatures the chemical potential pis very much closer in energy to the ground state orbital than the first excited orbital is to the ‘round state orbital. This tloseness of p to the ground orbital loads most of the population of the system into the ground orbital (Figure 7.10). an204 (Chapter 7: Ferm and Bose Gases ny lowe Binsein distebution function when welten forthe orbital at Nao = gat (6 28 in (54), where 2 will depend on the temperature f. The in all excited orbitals increases as 232; V2.) 0 ea sao =z) prepa aT number of partictes or, with x 5 af, 149 Eo fae, o Notes the facor <1" which give the temperature dependence of N, iL aattcently low temperatures the numberof partcies ia the ground state Milde a very larar ourbar, Equation (67) el Usthat must be very close oy Unity whetiever Ny is > 1. Then dis very accurately constant, besnuse eae Tepe tale of Ne ores 2 to he close to nity, The condition forthe valigy ‘ofthe calculation that Na>> 1, and itis not requeed that Na fv Win, + in the integrand, the valve of the integcand is insensitive to small devin Mons of fom Iso that we can set wt ia (68) although notin 67) c integral in (68) is, when 2 50a co) [ras FEES « fravatnern (ire ass with 2 ff troxs—at Einstein Contemation Tenperaiure ‘Thus the number of atoms in excited states is Li0sy Aer ne SEE (ae) = 2612V, (70) Tot et)" again he qantun oncrtiation. We vide N, by ‘No obtain the faction of atoms in excited orbitals NGI = 12g VIN = 2612ng/n om in an excited orbital or in the ground orbital. The number in Ghcted onbitals is relatively insensitive to small changes in J, ba the sea oe Re nartiles have to be in the ground orbital. To asute thie we met che Tress fo 1 ong a8 No isa large number. Even 10° isa large montane ihe occupancy of an orbital. Yet within Arise ~ 10° of the uamivon en 12st by (72) below, the occupancy of the ground orbital i > 10" sone Si Bite concentration ofigud te This our argument highly as MA, = 10°S, Einstein Condensation Temperature Wee te Einstein condensation temperate gab the temperatute for TREK the number of atoms in excited states is equal to the tual nomen oy Ronn, That is Nils) = N. Above 1g the occupancy of the pround webnal Coe mie number: below tthe occupancy is macroscopie, Fron (70) ‘with W for N, we find forthe condensation temperature (72) Now (71) may be written as : 7 NaN Sha? san where Nis the total number of tome The number of atoms in excited orbitals varies as at tempers ures below ry,28 shown in Figure 7.11. The alculated Walls of 7 for atoms of*He ig =3.K "A Ht, Ade er Wiener Be, Sungei 1,26; 18954 20s6 (Chapter 7: Ferm amd Bose Gases 16) Me ) ‘We subtract (79) from (77) to obtain 1 beat aaa Ik (0) ‘There isa lowest value of the magnitude of the velocity V for which this ‘equation con be saliscd, The lowest value will aceur whim the erection of k is parallel to that of V. This critical velocity is given by Lage at aye ¥,= minimum of Me eh ‘The condition is a lite simpler to express if we let the mass My of the body become very large, for then 2) A body moving with atower velocity than V, will not beable to cresteexcitations {nthe liquid, so that the motion willbe resistanceless. The viscosity wil appear to be zero. A body moving with higher velocity will encounter resistance because of the generation of excitations. “There isa simple geometrical construction for (82). We make a plot of the ‘energy ty ofan elementary excitation as a fartion of the momentum hk ofthe excitation. We construct the stcaight Line from the origin which just touches Quasipnicts aad Supe tte the curve from below. The slope ofthis Hine is equal tothe critical velocity. If 5 = JEKYIM, a5 for the excitation of a free atom, the straight fine has zero slope and the crtieal velocity is zero Free atoms: Y= minimum of hkj281 = 0, 3) ‘The eneepy of a low energy phonon in liquid He H is q = hey = yk in the frequency region ofsound waves where the product of wavelength and frequency is equal to the velocity of sound v,, or where the cieular frequency «, is equal to the product ofv, times the wavevector k, Now the critical velocity is Phonons: Ke imum of hk = vy 4) ‘The eritical velocity ¥, is equal to the velocity of sound if (84) is valid for all waevecior, which itis not in liguid helium 11, The observed critical low velocities are indeed nonzero, but considerably 1bwer than the velocity of sound !nd usually lower than the sold straight line a Figure 7.17, presontably because the plot of «versus hk may turn dowavard at very high Nk ‘The actual spectrum of elementary eeriatinns in figuid belive 11 hae been determined by the observations on the inelastic sesttering of slow neuicons ‘The experimental results re shown in Figure 7.17. The solid straight tine is the indau critical velocity for the range af wavevectors covered by the neulzoa experiments, and (Or this line the ertical velocity is Km Aitky 510 cms", 69 where A and t, are identified on the figure. Charged ions of helium in Solution in Squid helium If under certain experi- ‘meatal conditions of pressure and temperature have been abserved* to move ‘atmos like fre particles and to have alimitingdsit velocity near S x 10° cms“ closely equal to the calculated value of (85). Under other experimental condi- tions the motion of the ions is limited at a lower velacty by the creation of Vortex rings. Such vortex rings are transverse modes of motion and do not appear in the Longitudinal modes covered by Figure 7.17, (Our result (88) for @ necessary condition for the critical velocity is more al than the cleulation we have given. Our ealeulation demonstrates that 4 body will move without resistance through liquid He Il at absolute zero if the velocity V of the body is less than the critical velocity ¥, However, at * LeMeyerand Reif Pigs Re 123,727 (1961, G. Wald Phys Rey, eters 6, 9340965, 2s16 Chopter 7: Fermi end Bose Cases 0) Free partite. 2 Energy. in units of 1.38 10" erp Wavevector, in units of 108 emt FeWG7H7, Eocigy venus waveretr of domentary a ytd Bel at 112 K-Thepabtccur sng Deut ocr the epion of over intheseoerinnane ep PG. Henshaw aad A.D. B, Woods, Phys. Ren hs Lee HO {emperatures above absolute zero, but below the Einstein temperature, there Nil bea normal Bud component of elementary exe Houid flows out dhrough a fine tube in the side fluid component may remain betind in Component lcuks out without resistance, of & container. The normal ‘he conisiner while the supesSuid ‘The derivation we have given of the Summary hid roan tS Bold for this situation, with Vas the velocity ofthe super Neate oe aete Se walls ofthe tui; Mg isthe mas of the ald. Exon ould be created above ¥, by the interaction between the flows and any mechanical irsegularty in the wally of the liquid ‘Superfluid Phases of "He Thoce superfluid phases of tiquid > contrast fo liquid “He—with teansit The superfisid phases are believed 0 be qualitative conducting state of electrons in metals, sere alti surfce fort a typeof bound state known asa Cooper pt sechn Puck attatively ike a diatorsic molecule, but the radius of the moleevic inertia the average iterlcton spacing ina mal of Ihe averane interpattcle spacing in liquid "Ye nm Superconductiviy the two elections that form a Cooper pair are {23 nonmagnetic (singlet) spin stale. In the superfluid sinine of guid tie see So that aes tm a pai ae in the triplet spin states ofthe two He noce, tone gghtge magnetic superfuids are posible corresponding to spin even, sapere eat =1, or mires of these thiee sates The magnet Sipeaibids have been explored experimentally, and both the magnet Supotluid properties have been confirmed, SUMMARY ‘+ Compared toa slssical gas, Fermi ga at fow tempetature hs hth binetie SorED SH fressure, ane tow heat capacity The entropy ofthe Fesm gas Bs 2ero in the ground state. The enerey of the highest filled orbital wy che Hround slate of a tree particle ges of femions of spin | % The votal Kinet energy inthe ground state is Us = Ber ISMN) 8 1G Wha. Phys Tay, Featy 1916.9. Legg ese Whee UTS sod 1.8 Heck, Pics dlinay Sug For taoeeee SSEC Whee Re Sod Phas 75 SHS nd AJ Lge es Med Pa Sher ee 20728 Chapter 7: Feeni and Bose Gases oR The density of orbitals at 6p is Be) = 3N/Pey 4. The beat capacity ofan election gas at r & yi Cam RE Oepe = Nejep in fundamental units 5. Fora Bose gas at r < te the fraction of atoms in excited orbitals is NIN = 2612igin = (vise? ? 6. The Einstein condensation temperature of gas of noninteracting boxons is FSM ei, PROBLEMS 1. Density of erbitas in one and two dimensions. (a) Show that the density of orbitals ofa free elecivon in one dimension is Duo = (Lin2mmtg"? , 66) where Lis the length ofthe line. (b) Show that in wo dimensions, fora square ofacea A, Dye) Ampah? 67) Independent of 2. Energy of relarisistc Fermi gas. For electrons with an energy ¢ > me?, here m isthe rest mass ofthe electron, the energy is given by ¢ = pc, where pis the momentum. For electrons in a cube of volume V = L? the momentum 's of the form (wit), multiplied by (uy! + 1,2 + n,2)"2, exactly as for the nongelativistic limit (2) Show that inthis extreme relativistic limit the Fermi ‘energy of a gas of N electcons i given by pm hne(Snfn)" 89) Problems where n = N/¥.(b} Shove that the total energy ofthe ground state of the gas is Uy = Nes (89) “The general problem is treated by F_Bittner, Zltschift fe Physik 47,542(1928), 3. Pressure and entropy of degenerate Fern gas cloctron gas inthe ground state exerte a pressure = SEH (MY 0 In a uniform decrease of the volume of = cube every orbital has is energy ruled: The energy of an orbital is proportional to W/L? or to V2, (b} Find aan expression for the eutropy of 3 Ferm! elztron gs in the tegion ¢ « ey Notice that a + O as + -+ 0. (@) Show that a Fermi 4. Chemical potential versus temperature. Explain graphically why the nitist ‘curvature of 1 versus + is upwatd for a fermion gas in one dimension and sdovnward in three dimensions (Figure 77) Hint: The D,(e) and Dale) curves are diferent, where ®, is given in Problem 1.1 wil be found usefol to set up the integral Tor N, the puntber of particles, and to consider from the eraphs the behavior ofthe integrand between 2210 temperature and a finite temperature S. Liquid He as a Fermi gas, Thestom Hehas spin I = {and isa fermion. (@) Calculate as in Table 71 the Fermi sphere parameters op, er. and Ty for *He at absolute zero, viewed as a gus of noninteracting fermions ‘The density ‘ofthe liquid is 0081 gem”. (b) Cafeutate the heat capacity at low temperatures T a Tyand compare with the experimental value Cy = 289NkgT as observed for T£O1K by A.C, Anderson, W. Reese and J. C. Wheatley, Phys. Rev 130, 495 (1963); see also Figure 7.18, Excelent surveys of the propertics of liquid *He ate given by J. Wilks, Properties of liquid and solid heliw, Oxford, 1967, and by J.C. Wheatley, “Dilute solutions of "He in *He at fow tem: peratutes,” American Journal of Physies 35, 181-210 (1968). The principles of reftigerators based on *He-“He miatures are reviewed in Chapter 12 09 exyogenics; such refrigerators produce steady temperatures down to O01 K ‘in continuously acting operation, 16. Mass-radius relationship for white dwarfs. Consider a white wart of mass ‘Mand radius R. Let the electrons be degenerate but nonrelativistic; the protons are nondegenerate. (a) Show that the order of magnitude of the gravitational self-energy is —GM/R, where G is the gravitational constant. (If the mass density is constant within the sphere of radius R, the exact potential energy is 2920 (Chapter 7: Ferd ond Bose Genes Probes ay so 2 & Pure He 20 z to] man : SPP repose 2 Fare 7.19 Heat capacity ofan ea for § MMe in te e Ensen gus at constant vehne Sas a a | PS a9 10d 300 a Tempera Q wt 2 Fite 718 Meat capacity ofigid “He and ofa 3 percent sltion of 7 Hein gwd te, The eo pte un the veel an 8 C/P, aid thehorizon alexis is 7, Thos fora Fermi gas in the degenerate lermperatare 3 tegion the theoretical curves of C/F at constant volume ate horizons Tea ee hat ofthe Sun @ x 10 ‘The curve for pure He is aken a constant pressure, Which sceounts Or aan? (6) Its believed that po the ight slope. The cure forthe sluton of He that the "ein solution acs as Ferm gas: the deg lempersture goss over tothe nondegenerate egion Thess bet, = h what the deny ofthe ite sae ats compose ofa cold denener ene fasof nesions Show that fea necon sar MR = 10" Scan Whee vacate en the alu ofthe aus fra netron star with a masa equal to that a ine Soe? thiher orate, Expres the et in fan nog ine ayer ont ote sion aaa at ih strain hecieanton rn Consier a science fition wverse jn which the less assis ttea a 238th ofan toa Ne eens ruber of photons isconstant a consntation of 10a Theses Sfer1.6 Whee Arb Pos See) thermally excted photons wesc pve by the teal of Probing ‘hich Ne 240474 Fi he cial eperaute in K flow whl Nec Mths excess ~ N, wil be ine photon made oflonet hegsenon the exes might be desited a a photon condensate ta Which tere eee def magnitude ofthe kinetic enerey ofthe concent ofphowonsia helo mode neal tere nomen that the tal number OF photons be constant, hence there is no photon contensite 7. Photon condensation. 3647/58), (B) Show that the 0 ‘lsetcoas in the ground state is nays un? ays : &. Energy, heat capacity, ant entropy of degenerate boson gas. Find expres: i sions a8 9 fustion of temperature in the Fegion ¢ -< ry fa the enetey, heat expaciy, and entcopy of gs oF V neniateraetiny bosons of spin era ied where m isthe mass of an electron and My isthe mass of @ proton. (e) Show ou volume ¥. Put the definite imtogel in dimensionless forms it ced not be {hat the gravitational and kinetic energies ace ofthe same order of magnitude Cvaluated. The calculated heat capacity abave and below te is shown ia (as requited by the virial theorem ofmechamies), "R22 10° 3"! em. (a) ifthe Figure 7.19, The experimental curve was shown in Figure 712 The difeconceChaptee 7: Fermi and Base Ges between the two curves is marked is ascribed to the effect of interactions Dtecen the ators 9. Boson gas in one dimension. Calculate the integrat for N,@) for a one: dimensional gas of noninteracting bosons, an show that the integral doce not converge. This result suggests that a boson grovnd state condensate docs ‘not form ia one dimension. Take J = 1 forthe cafeulation.(The problem should ‘cally be treated by means ofa sum aver orbitals on a finite line) 10. Retativisie white dianf stars. of rest mass min sphere of such that the great Consider a Fersui gas of N electrons each ius R. Conditions in certain white dwarfs ace najority of electrons have extreme relativistic kinetic energies & = pe, whese p is the momentum. The de Broglie relation remains 2 2nh/p. Problem 2 gives the ground state kinetic energy of the N electrons fn the assumption that « = pe forall electrons. Treat the sphere as a cebe of equal volume (a) Use the standard vical theorem argument to predict the value of , Assume that the whole star i ionized hydrogen, but neglect the Kinetic encegy of the protors compared to that of the eleeitons. (6) Estimate the value of N. A carefol treatment by Chandrasekhat leads not to single valve of N, but to 2 limit above which a stable white dwaif cannot exist: se B.D Chaytan, Principles of sellr evtatin and nucleosynthesis, Meta Hil, 1968, p. 161; M. Harwit, Astrophysical concepts, Wiley, 1973 11, Fluctuations én a Fermi gas. Show fora single orbital of fermion system that ANFY = CNN 1, the factional fluctuations are Of the order of unity: ((AN)?)/QN)? = 1, so that the actual fluctuations can be enormous. It has been said that “bosons travel in flocks.” The fest edition of this text has an elementary discussion of the uctuations of photons, 13. Chemical potential versus concentration. (a) Sketch carefully the chemical Potential versus the number of particles for a boson gas in volume V at Problems temperature « Tnclode both classical and quantum regimes, (b) Dy the same for a system af fermions. 14. Two orbita boson system. Consider a system of N bosons of spin zero, ‘with orbitals a the single particle energies 0 and e, The chemical porential fs H, and the temperature is 7, Find 7 such that the thermal average population of the lowest orbital is twice the population of the orbital st €. Assume 7 L and make what approximations are reasonable, Hf the atoms ina gas have and nu ntegral spin (counting the sum of electronic spins), they can form a boson condensate when the gas is cooled below the Binstein condensation temperatore 7, given by (72) Fe = Gately)», For atoms in the vapor phase the Einstein’ condensation temperature is very low becouse the number densities are very low: In (1995) eaily successful ‘experiments were carried out at Boulder, MIT, and elsewhere. Such exper ments, Which are extraordinarily complex, matk the exciting forefront of the quanium gas fled, A large literature on BEC experiments and theory is on fhe Web, One set of experiments (MIT) started with beam of sodium atoms ‘exiting at oven at 600K at a concentration NIV of 10! em), What happens next is the result of a number of clever ticks with laser beams dizected on fone putt oF anosher of the beam of atoms, First the sfoms are slowed by one laser bean from an exit velocity of 800 m +! to about 30 m st, This is slow enough for 10! atoms to be tapped within a mag Father tricks, including o-optcsl trap evaporation, reduced the temperature of the gas to 2 AK, the ultralow temperature zy at which the condensate was formed. The concentration at re was again 10! gtomsfem’ ‘The atoms in the condensed phase ate in the ground orbital and expand ‘only slowly once released from the trap. The atoms in excited states move felitively rapidly out of their steady-siate positions. The positions of the toms can be recorded as a function of time after release, using a laser beam The number of atoms in excited orbitals is in good agreement with the + ‘as, (73). With this technique the signature of Bose-Einstein condensation is the sudden appearance of a sharp peak of atoms 2s the temperatore is Aecreased through rp, The peak comes from light scatered by atoms in the condensate; the wings of the Tine from light scattered by atoms in encited orbitals,Chapter 8 Heat and Work ENERGY AND ENTROPY TRANSFER: DEFINITION OF HEAT AND Work HEAT ENGINES: CONVERSION OF HEAT INTO Work Carnot Inequality Sources of Irceversibiity Refrigerators Air Conditioners and Heat Pumps Carat Cycle Example: Carnot Cycle for an Ideal Gas ietey Conversion and the Second Law of Theemodynamics Path Dependence of Heat and Work Irreversible Work Example: Sudden Expansion of an Ideal Gas HEAT AND WORK AT CONSTANT TEMPERATURE OR CONSTANT PRESSURE Isothermal Work Isobaric Heat and Work Example: Electrolysis and Fuel Cells Chemical Work Example: Chemical Work for an Ideat Gas ‘Magnetic Work and Superconductors SUMMARY PROBLEMS 1 Hewt Pump 2. Aborption Refiigerstor A. Photon Caruot Engine 4 Meat Engine— Refrigerator 3. ‘Thermal Pottution 6, Root Ait Conditionce cade 22s, as Das MT 20 231 a726 Captor 82 Heat and Work 17, Light Bulb in a Refrigerator 259 8. Geotheemat Energy 259 9, Cooling of Nonmetallic Solid to T= 0 259 10, lreversible Expansion of a Fetmi Gas 259 Stet xy he nn fey onein deve ht eae nee el ‘Thm smerny vote seco ele wih gba ne The ken “eersbe laa roms whi he combine entopy ofthe interacting pss enn eons. Energy end Entropy Transfer: Definition of Heat and ork ENERGY AND ENTROPY TRANSFER: DEFINITION OF HEAT AND WORK eat and work are two diferent forms of energy transfer. Heat is the transfer of energy to a system by thermal contact with a reservoir. Work isthe transfer of energy to a system by a change inthe external parameters that describe the system, The parameters may include volume, magnetic field, electric field, ot when we discuss energy conversion processes, The most important physical process in a modern energy-intensive eiviliza- lion is the conversion of heat into work. The Industrial Revolution was made possible by the steam engine, which converts heat to work. The internal com- bostion engine, which seems to dominate man as much as it serves him, fs a Levies to convert heat to work, The problem of understanding the limitations ofthe steam engine gave rise much of the development of thermodynamics Enetgy conversion remains one ofthe central applications of thermal physics because most electrical energy is generated from heat. ‘The fundamental difference between heat and work is the difference in the entropy transfer. Consider the energy transfer dU from a reservoir (o a system with Which the reserves fa thermal contact at temperature } an entropy luansfer de «= dUjr accompaties the energy transfer, according to the argument ‘of Chapter 2 This energy transfer is what we defined above as heat, and we see itis accompanied by entropy transfer. Work, being energy transfer by a change inexernal paramelers—such as the position of piston—-does not transfer any entropy to the system. There is no place for entropy to come from when only work is petformed or transferred, However, we must be carcful: the total energy ef two systems brought into ‘contact is conserved, but their total entropy is not necessarily conserved and ‘may increase. The entropy transfer between two systems in thermal contact is ‘welldefined only ifthe entropy of one system ineceases by asmuch as theentropy fof the other decreases. Let us restrict ourselves for the present to reversible processes such that the combined entropy ofthe interacting systems remains ‘constant Later we will generalize the discussion to irreversible processes which are processes in which the total entropy ofthe two systems increases, as in the heat flow example in Chapter 2.28 (Chapter Bs Hest and Work We can give ' quantitative expression to the distinction between heat and. work, Let dU bs the eneray change ofa system during reversible process: da isthe entropy change, and ti the temperatute, We define 0 = we co} As theheat received by the syst of encesy, the process. By the principle conservation dU = 4W + aQ, ey Mich says that the energy change is caused partly by work done on the system ‘and partly by heat added to the system from the reservoir, Then AW = WU ~ AQ = aU ~ we cy) i the work performed on the system in the reversible process. Our reasons for teltaling heat andl work by fQ and dW rather tha JQ and al ace captained below. Forda = 0, we have pure work; for J ~ eda, pure heat HEAT ENGINES: CONVERSION OF HEAT INTO WORK Fg Carnot ineguaits. Heat and work Have different roles in encrey conversion Processes because of the difference in entrapy transfer. Consider two cone ‘quences of the diference: G) All ypes of work ars feely convertible into mechanical work and into ach other, because the entropy transfer is zero, An ideal electrical motor, without mechanical friction or electrical resistance, is a device to convert cleciical work into mechanical work, An ideal electrical gencrator converts mechanical work into electrical work, Because all forms of work are freely convertible, they sxe thermedynasnically equivalent to each other and, particular, equivatent to mechanical work. The term work denotes all types of work. (8) Work can be completely converted into heat, But the inverse fs not trues heat cannot be completely converted into work, Entropy enters the system with the heat but docs not leave the system with the work. A device that generates work from heat must necessarily strip the entropy from the heat that has been converted to work. The entropy removed from the converted input heat cannot be peemited to pile up inside the device indefinitely; ths enteopy must ulti ‘mately be removed from the device, The only way to do this isto provide more a Meat Engines: Conversion of Heat ato Work 2» Entropy Ouiny urpet work w Orn, & Entropy Heat uiput ere Cnucopy and ene 2 flow in any continscusly opeeating reversible device p netting work fom buat. The emeopy sation ‘us equal the entopy inflow jeput heat than the arsount converted to work, and to ej Aetas waste at ata temperature lower han that ofthe‘nputheattiecece y Bestese dQido = «the cversible heat transfer accompanying ome cate oe Toa 8 shen by the temperature at whieh the heat is wanskvred. Ik folios hut only part ofthe input heat need be sce atte tower tompersen ve Soa any Al the enwrop-of the input heat, Only the diecenee bts ine ant! Output feat can be eonverted to work, To prevent the secomularer ct sag y here sist be some output heat: therefore its impossible to comet all he input heat to work! A prohibition against unlimited entropy accumu {ean entropy cannot accumolate temporarily ‘Femoved, Many practical energy-conversion dev ct the excess input ition in a device daes not provided that it is ultimately ices operate in cycles, and the20 Cine Hatank Work aud Be no covey contained inthe devie varies priogialy with tine. Such 2 opie sevice is called a heat engine, The internal eohtbdstion engine is an example: “Theentopy contained in each inde at anima nea he beganing of the ntake stoke sad a main rear the bepining ofthe ext stoke “haces wae of he entropy contest to which the deve retures jf, the catropy des nt pile up dsl ‘What faction oft inut heat taken in during one jee at the es higher temerature canbe converted into work? Theepot entropy stneatd with thelaput eats a » Oy/ To avid contsingsign, we den otis ces Sonal energy, ea, nd etopy oss poive whether he Hino or out ofthe system, eather than folowing the wus convention according fo hich ow postin into the sytem ad reptve ou ofthe ster, HQ, the waste oat Iavng the stom per eles the Hed lows tempers ‘he output eneopy pr sees = Qi, I # reversible proces this ost entropy i equal tobe inp nteopy Quits @ sothat = (6/00 o ‘The work generated during one cycle of a reversible process isthe difference between the heat added and the waste heat extracted: = [= (isla = aoe Weg 1 0 “The ratio of the work generated to the heat added in the reversible process is called the Carnot efficiency o “This quantity is named in honor of Sadi Carnot, who derived it in 1824, Tews 1 remarkable fet: the concept of entropy had not yet been invented, and ‘Carnot’ derivation preceded by some 15 years the recognition that heat is = form of energy. ‘The Carnot eficiency is the highest possible value of the energy conversion efficiency n = W/Q,, the ouput work per unit of input heat, in any eyclic heat” ms Enginets Comerion of Heat ino Work 231 ouipet swoek v Ootput Figwe Envopy an eney os ne! ht engine containing crest pce ew none a The ogy etow a lover tp get ie tony inflow at the higher temperature, 7 ned engine that operates between the temperatures zy and «Actual heat syand «, Actual heat engines have lower efficiencies because the processes taking place within the device are not perfectly reversible. Entropy willbe generated inside the device by irevers, ible processes. The energy-entropy flow disgram is modified as in We now have three inequalities 28.2, 4 Ons eo Or = Onleateads 9) We O.~ 0,5 9H nO tt)a Chapter 86 Hest and Work ‘The actual energy conversion efficiency obeys the Carnot inequality 7 1 [o- WIQ, 1 (rife) He. | iy Tt} We can have» = me only in the Fit of reversible oper takes in heat ats and eects beat ay The Carnot inequality isthe bse nfation on any hea engine that operates ina etic process, The result tls us tht imps to convert all input heat into work, For a given temperatire ratio s/s, the highest conversion eficieny i obtained under reversible operation, The limiting eine in creases wih ineteasing sf but ve aan 10D percent eiieney only when The low-temperature waste heat of any heal engine must alimately be cieste into the environment. s0 that 1, cannot be txlow the enveonmental temperate. ually abut IND K. High aseny mss vo np emparte 7, high eompated to 300 K. The usble postures im practice ae noms nately nite by various materials constants. tn powerplant steam turbines, ‘hich ae expected To operate continootsy for yours te upper tempeatare is curren Limited to about 600K by psblems with hestrength and eortosion of sec, With T; = 00K and 7, » 600K, the Carat eficeney is ne oF S0 percent Losses eased by unavoidable irveriblities rues this lcesey typically 1 about 40 percent. To obtain higher ellie sa problem in igh ‘cepertare metry jon ofa device that Sources of irreversibility. Figure 8,3 illustrates several common sources of inseversiblty: @)_ Part of the input heat Q, may flow ditcetly (0 the low temperature, by- passing the actual encigy conversion process, as in the heat flow into the ‘ylindée walls during the combustion eyele of the internal combustion engine, (b) Pact of the temperature difference #4 ~ ty niay not be available as tem- eonversion process, because of the temperature deop across teri resstanees in the path of the heat ow, [e}_ Part ofthe work genesated may be converted back to heat by mechanical fiction, (4) Gas may expand irreversibly without doing work, as in the ireversible expansion ofan idea gas into a viousns + Reiigerstore Hl ‘Thermal resistance Irreversible expansion without work Gr heat Net work ve || Thermal fesistance So82 Pour sources of ireversblity in heat engines: heat fow hg ne every conersion proces, thecal es stance in he ath fhe tet ow, tition lsies,and eo es itteversible expansions, TOLL Reiigerstors feigestorsate tet erines in reverse, Refi Bes fom ow temperatures 0 higher em ‘atopy How dig of a reverie hea Swkony is genetated ise the deve ie on SXaet reversal of the energy and entropy Ay. ‘emanate revered fos IOS consume work fo move ature e,. Consider theenergy- ne in Figure 8.1. Because no ion can be reversed, with an 5. Equat nas(Clapier 8: Heat und Work, ‘The energy ratio of intevet in a refrigerator is not dhe enexey coMversion ‘efficiency (7), but the ratio + = Q,/H of the heat exacted at dhe low tam Peraiure to the work consumed. This ratio is called the cveflcient of refrigerator performance; its Fimiting value in reversible operation is called the Carnot eeficient of refrigerator performance, denoted bye, Donot confuse} = Oy with = 1/0, for the energy conversion efcieney of a heat engine; although 18 V always, y can be >1 or xh Two of tem aze isentropic, om &y 10 and back. The shaded areas show {a} the work done dutiag the wo expansion stages, (the work done during the two ompression stages and (che net work dove during the eye. 2920 Chapter 83 Hest and Wook Path Dependence of Heat and Work 2 ‘opis finite ant is caval tothe aeaof he ectangle ia Figure BS. We have Q=M +0, + a1im We Mat hy Wye Wh m Wee We =H + Oa + Wouy = Moy = aploathyH) ey 9 = GG) fou ‘The heat absorbed fom, was given in (20,50 that 18/0, the Comet relation (1). (4 = Dae which jus emer: Device 2 Energy Conversion and the Second Law of Thermodynamics Gam) ‘The Carnot limits on the conversion of heat into work and on the performance HOM) = Om ~ HQ, of refrigerators ace direst consequences ofthe law of increase of eniropy. The entropy. We staicd the classical Kelvin-Planck formulation in Chapter 2: 1 ~ 130, otha marco sce promancttaneaaien ee petatures have the same energy conversion efficiency m = WW/Qy. Were this not tin) = Oy = 92, srnecol omtnene een ee ea ae in such a way (Figure 8.7) that device 1 with the lower cfliciency is operated in Figure: calf patna can ‘crergy conversion devices operating between the me ken dete eh pe nse enon wiht sremetisbe sent nth Onet trou (oh wel he eal es cess ievusttnoechey ceacteennomematns mess the annihilation of entropy and would violate the law of increase of entropy. to work, ‘Now that we have established that all eversibie devices that operate between the same temperatureshave the sime energy conversion eficiency, itis sufficient i {9 calculate this eliciency for any particular device to find the common value Sach that the heat Quy and the work Hy, veh that J i required to earty the system from a ‘The Carnot cycle devise leads t0 ye = (¢5 ~ pity forthe common value, Mate oH) toa state (oy K) are given bythe difeences in Q and Path Dependence of Heat and Work Qe * Ole) = Ole, 2 Wet) ‘Weave carefully used the words heat and work to characterize energy transfer cesses, and et CO characterize properties of the system itself Hie not ‘reaningfal to speak of the heat content or af the work content of a system We look at te Carnot eyete once more: Around a elosed Joop in the pA? plane, 2 net arnount of work is generated by dhe system, and a net amount of heat is consumed, But the system—on being taken once around the loop-—is feturned to precisely the initial condition: no property of the systsm has ‘hanged. This means that there cannot exist two functions Qie,)) and HV(@,¥) such functions existed, Yop necessarily would ty the net transfers of heat and of work around 9 closed ™ #80, and we have shown dit the transfers are not The transfers of beat and work betwee state la uth taken between the two st Wesay that heat and work aren And iree energy, heat and work increments 4Q and ait? ara state (b) depend on the ‘ates, This pati-dependence is expressed when ot state functions Unlie temperature, entropy, K are not intrisic attributes of the system, The at we introduced in (1}and (2) cannot be difeccntiatsmm (Chapter Bs Heat and Work 4 7 Figure8.8_ Two ievewsiie processes in which mechanical or eleesal potential neigy used to heat a yen ‘af mathematical finetions O(0,¥) and W(e,¥) For this reason we designated the increments by 4Q and dV, rather than by dQ and dW. Without the path ependence of heat and work there would not exist eyeical processes that permit the generation of work from heat. Irreversible Work We consider the energy transfer processes of igure 88. In each process 3 is a purely mechanical or electrical system that delivers pure work with zero entropy change. The eneray transferred to 8, is converted to heat, ether by mechanical fiction or by electecal resistance. The final state of $8, is the Same as if the energy had been added as heat in the frst place, The entropy of 8; is increased by dc, = dU,/t. This entropy is newly created entropy. Processes in which new entropy is created are irreversible because there is no way to reverse the process in order to desiroy the newly ereated entropy. fnewly created entropy arises by the conversion of wark to heat, we say thal ireeversible work has been performed, we look only atthe net change ina system, there is no way to tell whether the process that led to this change was reversible or irreversible. For a change {AU in energy and ds in entcopy, we can define a reversible heat dQ,q, and 3 reversible work A, a$ the amount of heat and work that would accomplish this change in a reversible process. If part of the work done on the system is irreversible, the actual work required to accomplish a given change is larger Ieeerenibie Work than the eversible work, a, .> dM 3) By conservation of energy MT = A ipe + AQyag = IMs AQ rs Qo oe ‘The actuat eat transferred in the irreversible process must be less than the reversible heat, : Example: Selden expansion ofan ideal ger. Asan example ofan reversible process we éonsider once mare the sun expansion ofan eal asinta a vacuum. Neither heat 20¢ ‘work is tanfered, so tht dU = O an de = 0 The ial sai identical wih he sate “hat results from a reversible isthermal expansion withthe g3s fn thera equilibria witha ese The work WY, dane on the ps nthe fvesible expansion rom volume 119 Yi om (657, MW, = = Nelog(V/¥) (9) ‘Thework done onthe gus snepativ; the as does pose work onthe piston nan amount qual ta the heat tans into the syste One = —Wog =O) Wig <0. en The enon changes pul Qa oF oy ~ 8) = Walt = Nlosta/M) 2) in the reverse poss of capsnson ft the vacuum hs eto new rend ‘enucopy because aetthr heat nor work Rows into the system rtm the outside! Gree = 0. Ftom (31) we obtain Wow > Woon — Qsner < Quer + 63) in agreement with (28) and (29) 2aMe Chapter 8: Heat and Work fe area 4, ea Ay Pty = Pedy Figore 89 Systems Setween which ony noth but no hat is transferred need not be atthe sie temper svre fer the process o be rexeribie, {n our discussion of irceversible work we assumed thot the new entropy eee sie the systerm during the deliver of work tothe syetom tyes Feat raeene 8 89t he only soucee af irreversibility in energy tramsen, Pore Rex tanser, not involving any work, sirreverible if takes plac bere Chane Sa having diferent temperatures. We worked out an example in Caper 2. this process heat is wanseted fm asjtem at ton system at the lower temperature ty. We have’ Wy = 0% dos aU, 10, = nde dQ, +40, =0. 34) The newly created entropy is oie = (doy + do) = dQyfty + dale, = ity ~ Vegan, = &. 10, 03) The heat flow is fromm h hegative, 0 that dei > 0. to low temperature: 40, is negatives ey — 4, is Je encrky transfor betweon two systems with diferent temperatures need not be reversible only work but no hex is ransiried (Figure 89) Al actual energy transfer processes ace invariably somewhat itveversble, th, nib processes remain the bsckbone of the theory of thermal physiee Je) consti a natural it, which i the eguiibsium lint of vesting SzugPy Beneration. We shal assume heater tat he wouds heat and work Without a frther qualities, refer to reversible processes ‘eet and Work ut Consent Temperature or Constant Pressere BRAT AND WORK AT CONSTANT TEMPERATURE OR CONSTANT PRESSURE ‘is equal to the increase in the Helmholte ree reo that 8StEM. For a reversible process d= se = dive), because dr = 0, so that AW dU ~ dQ = dl = dco) = dF. cy jis im such proceses the Helmholtz fee energy ie the eatural energetiz function, more appropriate than the energy U. When we teen a isotherms Nauman, Cis of the Helnholts fice energy, we automaticaly, selves ne Sraatonal work that is requted 10 make up for the heat torte pane Foe the et eee Often the heat transir is the major putt wt ean {or the ideal gas the energy U docs not change in an kethenaL process, and ‘the work done is equal to the heat trensfor erate, thes liga ols under atmospheric pressure, the vapor ‘opacing Ihe smosphere docs work aginst the atm promen asChapter: Heat and Work where the pressure on te piston is the external atmospheric pressure. Ifthe system changes its volume by dV, the work — pul” = —u(pW) is part of the total work done on the system. If positive this work is provided by the environs ment and is in this sense “Ire.” If negative, the work is dativered (0 the fenvironment and is not extractable (eom the system for other purposes. For this reason its often appropriate to subteact — dip!) from the total work, We thus obtaia the effective work performed on the system, defined as AW we WY $a aU + dlp) ~dQudtt~aQ, BT) where we have defined a new function Heute, (38) called the enthalpy whieh plays the role in processes at constant pressure that the energy U plays in processes at constant volume. The term pY in (38) is the work required to displace the surrounding atmosphere in order to vacute the space to be occupied by the system tmplicit in these afiitions isthe ion that there are other kinds of work besides that due to volume changes ‘Two classes of the constant pressure processes are particlarly important {a) Processesin which no lfetive workisdone. The heat transfer isd = dF, from (7). The evaporation of a Viguid (Chapter 10) from an open vessel is such a process, because no effective work is done, The heat of vaporization is the enthelpy difference beeween the vapor phase and the liquid phase (©) Processes at constant temperature and con int pressure. Then dQ = ula = dca) and the eltective werk performed on the system is, from (36) and en, AW’ = dF 4 dlp) = a6, @) where we have defined another new function G=F4pV=U4py—w, (40) the Gibbs free energy, ‘The elfective work performed in a reversible process at constent temperature and pressure is equal to the change in the Gibbs fire energy of the system. This is particulrly useful in chemical reactions ‘where the volume changes as the reaction proceeds at a constant pressure The Gibbs free energy is used extensively in Chapter 9, and the enthalpy is used in Chapter 10, Heat and Work et Consant Temperature or Constant Presere Evonple:tlctotyas ant fut cls. Elestolyses a proces thats both thermal and Ssoturis, Consider an ektrlyte af dilate suri sei in which ate inners pati slecrodes cht do not uct with the acid (Figure 8.11), The sulle acd dissociates ina 1 3nd S0,-~ ons H,S0, = 2H" 4 50,7 i ‘When x carcents passed through the ell the hydeogen ions move tothe negtivectsetods where hey take up eleeons an farm eslecular hydrogen gas 2H* $e Hy (wy The sult fons move fo the postive eeceodes where they detompose water with the ‘lease of molecular oxygen at and election SO.°> HO + H,SO/ 440, 4 26° wo ‘The sum ofthe above tres steps isthe Het ection equation inthe eel 1,04, lo, sy in a veel open fo the atmosphere he provers ie a coment resureand eunstan cenperature A Re par ofthe stra np poner aco FigureB4f_ An clectotyis ell An eletial cortent pasies through an elettroyie, such {sila sulfric acid. The overall result isthe decomposition of water into gaseous hydrogen and oxygen. The proces is an example of work being done at constant ‘emperature and constant pressure ww8 Chapter #2 Heat and Work ee eoite The eestive mock requ to decompose 1 mole of ‘water is telated tothe molae Gibbs es energies ofthe reson 17 = AG = G{H1,0} ~ G(tis) - 46(04) (4s) Chemica tabs fist temperature In elecrolsis this wosk sperformed by acurtent 5. I tis the inerequized 1 decompose one me of (Wot the heat) Basing through the el and ve bane % Gib fe energy diference AG as —237kIpermale at room hat fous under sn exert voltage water, Q = 1 Fis the ftal charge W = Ov, 49) Tenge 0h ee are tro decom nthe in decomposing one water molec ene Q = -2N,¢ = ~193 x 105 coulomb. a maa (510 ota he comin for etait plas Ts eters Dinu vatiage Wyn -agjan,e, (38) Pres22t ols A vlaus lng than ¥en Be applied o Oban afte eu Pesta ¥ alone mercy reduce to eo ihe potent barter beaneen he pe on SIGE othe testi uation (69, When” > Ve theences power 2 ieee ae be dsipated as eatin the eecolyte dino RE *E3e0n 8 wil recto igh te provided gaseous hydrogen is available at i and gascous oaygen al the negative elect, Tp ihe pana fe Between thetstrodes and. the eletrodesareconneced enteral cen cid {ove Thsarragcnkicaleda tadroyctonge lee, Ful ers mecancd coe, Reena! th Geni aed Apolo space and incidently produced deoting ‘ater for the astronouis Ja itp lchnologel ition of fe ealisis thee low cuzent per unit electrode See eue Apolo cellshe cures density was ontya ew hundeed mAents hee Looe AO tes ate reuied 1 pose ceasonabe cures The extent ings chee ER oat stestochemical sin its wo oprating ranges al el and a8 cece ll te shown in Figue 813 seattle ed Sand 0 sath tan Pn decree amd KOH cairn 50, TISSANE Fora tld destin, an moc tarmaton on fod ce he ese Eos ag BostesandS Sasa, Fa ls: Thi clectrochensny. McGee Woke ak Porous estos Figure 812 A fet ell isan electolysiscell operated in revere, with hyduogsn and oxygen supplied fle The {ul ats forse vue press teu pcos electra Seperated by an eletolye. The lydeogen snd onpuen ect to fom water the exces Gibbs ice energy melee ‘outside as cies energy. Water forma the posing testa andi removed tiers Current 1 f>——Fuet eet ——-L Etecsotyis-——— a Voltage 7 Figure 813° The curcstrainscharacteiniofanlestoytie ‘sll or fuel cll, indicatng he to operating fonges 720 (Chapter €: Meat and Chemical Work Work performed by the transfer of particles to a system is called chemical ark, because it is associated with the chemical potential When particles are transferred, the numberof particles in the system is one ‘ofthe independent variables on which the energy U depends. IU = Ulo,¥.N), then for a reversible process aw de = pV + pd, (9) by the thermodynamic identity of Chapter 5. Here we have replaced the partial ‘derivatives by thei familiar equivalents (Table 5.1). By our definition of heat, the tds ferm represents the transfr of heat and the —plV and judN terms represent the performance of work, all understood to be reversible: GW = —pl¥ + pl. (0) The ~ pd¥ term is mechanical work; the piN term s the chem iV, = wd, 6) Ifthere is no volume change, dV = 0. All the work is chemical In particle transfer there sre usually {wo systems involved, both in contact ‘witha heat reservoir, and the total chemical work isthe sum ofthe contributions from both systems Inthe arrangement of Figure 8.142 pump transfers particles from system 8, to system 35. The chemical potentials are yi and py. If dN dN, = AN, is the numberof particles transfered, the total chemical ‘work pesformed is AW, = dey 4 dW = dN + dN, = — mdIN. ——2) “The work that must be supplied to the pump is 18, ifthere is no volume work (UV, dV = D),and ial processes are reversible ‘The result (52} gives an additional messing of the chemical potentiat. We ‘summarize the properties f the chemical potential: (@)_ The chemical potential ofa system isthe work required to transfer one particle into the system, fem 2 reservoir at zero chemical potential. (©). The difference in chemical potential between two systems is equal to the ‘het work required to move a fartile from one system to the other. Pap Basta Me |S Figure 8.14 Chemical wook ithe work performs! when pasties ere mone reversibly trom one system to another, with the wo syst having dileeae ‘hema potential. ithe to vanes Jo notch mite work pure homicl work: the amount pr pals he Seon nce poten (2) the wo systems are in diffusive equilibrium they have the sane chemicat potential no Work is required to move a particle from one system to ie oder (4) The difference in internal chemical potential (Chapter 5) between io systems is equal but apposite to the potential barrier that maintains the systems in diffusive equilibrium, Es wple: Chemeal work foranieal pax. We consider the work per patie required 9 ‘move revecsibly the atoms ofa monatomic ideal pas fom 8, with conconteation my to ‘sith concetestion ng > n, both aytean bring tthe same tompetatre (Figure S43) AV =the work contain ony a chemical work erm, which oh be cess fon the ierence in ehesial potential, no rater how the proces ie setualy performed, The hema potential dlfletence between wo ila! ga ystems with ilerent concentrations ie Bam Me [logtazitig) ~ login,ina}] = tlos(a/n,). (53) “Tis res is equal to the mechaneal work por pide eyuied to compass the eas Jsothermally fot the concession my tothe easentation my. The work tequived (0 ‘compres 1 partes ofan ideal 8 rma ital vu Y, co aia volume Vs ee ee Hence the mechanical work per particle i slogan) ental to the esl (53) Thea2 Cheprer 8: Hest and Work cot ime b= ae cha ian oss not chang if he process is perf iothermally with bat spoce ee ‘hermal equltriur wih s common itge revrvols Bei ofthe chemical wonk with she rhea! consason work Sistas Ue eg Tence ot convenubty of dierent kinds of work Magnetic Work and Supercondactors An important form of work is magnetic work. The most important application of magnetic work is to superconductors, and this application is treated here Eslow some critical temperature T, that is usually less than 20K. many clectcical conductors undergo a transition from their noemnal state with a Rete ty and the evitieal magnetic field Sccreases, Everything else being equal, a high stabilization energy ia a ype 1 superconductor will ead to both a high critical temperature and a high ertical field. The highest critica fields are found amongst the superconductors with the highest critical temperatures, and sice versa Prodtens SUMMARY 1, Heat is the transfer of energ yy by thermal contact with a reservoir. In a reversible process dQ = eda. - Work isthe transfer of energy by a change in the external parameters that Aescribe the system. The entropy transfer in a reversible process is zero when ly work is performed and no heat is trensferred, 3. The Carnot energy conversion efficiency, ne = (64 ~ rity isthe upper Nimit tothe ratio H¥/Q, of the work generated to the heat added, The Carnot cocfticient of retigerator performance, 3p = nitty ~ this the upper Him to the ratio Qy/HV of the hest extracted to the work covsumed The total work performed on system at constant temperature ina reversible Process is equal o the change ia the Helisoltz five encigy P= Uta of the system, 6. The effective work performed on a system at constant tempmuature und Pressure in a reversible process is equal to the change ia the Gibbs frve energy G5 Ure + pv 1 ‘The chemical work performed on a system in the reversible transfer of. Particles to the system is pl 8. The change in the fice ence ty density ofa superconductor (oF type I) caused by am external magon is field is 8/2). in SI and 83,8x in CGS PROBLEMS J. Heat pun. (a) Show that fora reversbte heat pump the everay requited perunit of heat écivered inside the building i given by the Carnot efficiency (6): w a What happens if the heat purmp is not reversibto? (hj Assume tet he eeetesity consumed by a reversibie eat pusep must itsell e ei aicu by a Cattt ene» ‘operating between the temperatures zy and 1) What i the raid Quy Qys oF the hheat consumed at ry to the heat delivered at r,? Give numerical values for Tw = OOK; Ty = 300K; Ty = 270K. (@) Draw an enerey-enttopy flow sliapeaun (or the combination heat engiveshest pump, sina to Figures § 1, 82.and 84, but involving no external work at all. only enerey and enters flows at thee temperatures, 257a8 Chaprr 8: Heat and Werk 2. Absouption ceftigevator. Yn absorption retigerators the energy driving the Process is supplied nat as work, but as hea from a gas flame a a temperature 1a > £4, Mobile home and eabin eeigerators may bs ofthis type Wi uel. (a) Give an energy-enteopy flow diag such a retigerator, involving no work ata atthe three temperatuees hheatextractedat'¢ = 4, opzeation, propane ant simile to Figures 82 and 8.4 for but with energy and entropy flows it > 4 > 4 (b) Caleuate the ratio Q,/Qy, fOr the where is theheat input at = ty. ASSUME feversble 3. Photon Caruot engine. Consider a Carnot engine that uses asthe working Sobstance a photon gas. (a) Given x, and r, a8 well as Vy and V,, determine sand ¥,. (0) What isthe heat Q, taken up and the work dane by the gas during the first isothermal expansion’ Are they equcl to each other, as forthe deat gas? (6) Do the two isentropic siages cancel each other, as forthe ideal gas? (@) Caleu late the total work done by the gus dusing one eycle. Compare it with the feat taken up at 1, and show that the energy conversion elfiieney is the Cammot efciency. 4. Heat engine—refrigeratoreaseade. The efficiency of a heat engige is to be improved by lowering the temperature of its low-temperature reservoir to 2 ‘alue Belov the snvisouincntal temperature t, by means ofa reltigerator. The rebigerator consumes part of the work produced by the heat engine. Assume that both the heat engine and the reftigerator operate reversibly, Calculate the «tio of the net (available) work to the heat Qy supplied to the heat engine at {emperature t, 1st possible to obtain a higher net energy conversion eficieney in this way? S$. Thermal pollaion. & siver with a water tempereture T; = 20°C is to be sed a8 the low temperature reservoir ofa large power plant, witha steam femperatur of T, = SO0°C. if ecological consiecations lit the amount of ‘neat that can be dumped int the river to 1500 MW, that isthe largest electrical Outpt that ike plant can deliver? I improvements in hot steam technology Would permit raising T, by 100°C, what effect would this have on the plant capacity? 6. Room air conditioner. A room aic conditioner operates as @ Carnot eycle refrigerator between an outside temperature T, and a room at alower tempera tute Ty, The room gains heat from the outdoors at a rate A(T — Ty) this heat is removed by the ai conditioner, The power supplied to the cooling unit is P. (a) Show that the steady state temperature of the room is, 1, (Ty + PA) ~ [(T, + PRAP = TAY, {8) Ifthe outdoors is at 37°C and the room is maintained at 17°C by a cooling ower of 2KW, find the heat loss coeficint 4 of the room in WK". A good Frablome *moll Aa acid esd to eta 2 proton donor, The concentration fH" ions ‘increased by adding a aid to the water ad the conection of OH” Hons will decrease 4s requied to maitain the product (#1 [OH] conta, Snir, the concentration ‘of OH ionscan be increased by adding x basco he wate, and the Ht concentration wl ‘ccreaseaccoeigly The physical state of water is more complicated than the equation ofthe ionkztion process suggests—the H” ions are not bate protons, but are asiocnted with graups* of H,0 tmolcuss This doce na signifeaniy aes the ality of he easton ‘eyustion Its often eomenient wo express the acidity or alin ofa solution in tems the pt, Asfined 3s @ “Theplt ofa solution ithe negative of hearin base tenof they drogen ionconceatta ‘on inmoles per litrofsoltion. The pit of pure waters Tbecuse[}"] = 10°? moll” ‘Thesteongest aide stations have pH netrOor even neyatves an apple ayhave pH ~ 3 Human blood plasma hasa pi of 31075; basle [Exemyles Kinetic made of man action. Suppose that atoms A and B combine to form a molecule AB. We suppose that AB is med ina biome eolision of A and B Let iy gst dente the conceteations of A, Band AB respecte). The rate of change ofa Arya llt = City = Digy «) where the rte donstant C describes the formation of AB in a collision OFA with B, and he rate constant D descnibes the reverse procs the therzsh decay of AB ito is component ome A a 8, I thers 1, so that nN) ~ ng(N + 1) Find the concentration ratio (W + tY/[N] at room temperatuee if there is zet0 free ‘nergy change in the basic reaction step:that IAF = Fy.y ~ Fy ~ Fy = 0, Assume (1] — 10% un”, as for amine acia molecules it a bacterial cel The ‘molecular weight of the monomer is 200, (d) Show tht for the reaction to goin the dircetion of long moecules we need AF < ~O.6eV, approximately. This ‘condition is not satisfied in Nature, ut an ingenious pathway is followed that Simulates the condition. An elementary discussoa is given by C. Kittel, Am Phys. 40, 60 1972}, 4, Partcle-antiparticl egitim, (a) Find 2 quantitative expression forthe thermal equilibrium concentration in the partile-antipatle feaction A* + A” = O.The reactants may be tletrons and positons: protons and antiprotons; or electrons and holes in a semiconductor Let the mass of sither particle be MY, neglect the spins of the particles, The minimum eneipy felease when A* combines with A~is Take the ero ofthe enengy scale ashe ‘nergy with no partcies presen. (b] Estimate nin cm” for an electron for 8 hole) in a semiconductor T = 300K with a A such that A/c = 20. The hoe is viewed asthe antipartcletotheeletron. Assume thatthe electron concentttion is equal to the hole concentration; assume also that the pails are in the tlassieal regime. (¢) Corcect the result of a) to let each particle have a spin of Partstes that have autipatiles are usually fermions with spins of Chapter 10 Phase Transformations VAPOR PRESSURE EQUATION 6 Derivation of the Coexistence Curve, p Versus ¢ 78 Triple Point 28 Latent Heat and Enthalpy 284 Example: Model System for Gas-Sotid Equilibrium ras VAN DER WAALS EQUATION OF STATE. 237 Mean Field Method 28 Critical Points for the van der Waals Gas 289 Gibbs Free Energy of the van der Wuals Gas 21 Nucteation 2 Fecromagnetismn ass LANDAU THEORY OF PHASE TRANSITIONS 298 Example: Ferromagnets 302 First Order Transitions 302 SUMMARY, 04 PROBLEMS. 305 1. Entropy, Energy, and Enthalpy of van der Wasls Gas 305 2. Calculation of dT/dp for Water 305 3. Heat of Vaporization of tee 305 4, Gas Solid Equitibrium 305 5. Gas-Solid Equilibrium 305 6. ‘Thermodynamics ofthe Superconducting Transition 306 17. Simplified Mode of the Superconducting Transition, 307 8, First Order Crystal Transform: 307 ‘Nave: nthe ist Seton «dates o ibe magnetic momen! ofan ao the atopy pes atom Un the ston on etomagntim,Chapter 10: Phase Transformations VAPOR PRESSURE EQUATION The curve of pressure versus volume for a quantity of matter at constant lemperature is determined by the fee energy of the substance. The curve is falled an isotherm. We consider the isothsems ofa rel gas in which the ators oF rmolecules interact with one another and undee appropriate conditions can associate together in liquid oF solid Uhat is uniform in composition, ‘Two phases may coex Phase. A phase isa portion ofa system with adefinite boundary between them. An isotherm ‘fa seal gas may show a region inthe p-¥ plane in which liquid and gas cooxie {a equilibrium with cach other, Asin Figure 10.1, part of the volume contains ‘toms in the as phase. Thee> are ieotherme at low temporctures for witch Solidand liquid coexist and isotherms for which solidand gascocxist. Everything ‘we say for the liquid-gns equilibrium holds also forthe solid-ges equilibrium and the solid-liquid equitibrium. Liquid and vapor may coexist on a section of an isotherm only if the femperatuce of the isotherm lies below a critical temperature s,. Above the srtical temperature only a single phase—the Rid phase—exists, no matter hhow great the pressure. There is no more reason to call this ghase a gas than ‘liquid, so we avoid the issue and call ita fluid. Values ofthe critica temperature for several gases ere given in Table 101 Liquid and gas will never coexist along the entire extent of an isotherm from zero pressure to infinite pressures they coexist at most only along a Section of the isotherm. For a fixed temperature and fixed number of atoms, there will be a volume above which all atoms present are in the ges phase A seoall drop of water placed inanevacvated sealed bella at rooin temperature will evaporate enticey, leaving the bell jar filed with H,0 gas at some pressure A drop of water exposed to aie not already saturated with moisture may evaporate entirely. There is a concentration of water, howevce, above which the atoms from the vapor will bind thennselves into a liquid drop. The volume relations are suggested by Figure HL ‘The thermodynamic conditions for the coexistence of twa phases are the conditions for the equilibrium of two systems that are in thermal, difusive, * Vapor stro sed fora gas when the gt inn ets wth its gid o si fom Vapor Pestre Equation a Curve taken at \ Liquid + gas Tigeid Liquid ¥ gas Gas Figure 10.1 Prestuce-volume isoterm of set gas ata ‘smaperatre soc that figuid aed ges phases may coeast that 5 5 < te tothe two-phase region of quid + gis the presute ‘constant, but the volume may change. At given tespertune ‘ete i only ingle value ofthe ressve for which ligead sandits vapor ace in equi. [fat his peste we trove the Psion dow, some of the gas condensed a liga, bo the ‘ressue remains unchanged a long as any gas fens Table 10.1 Critical temporaires of gases Ta He ma Ne 140 ar 143 Ke sini Xe mo?Chapter 10: Phase Tramformations and mechanical contact, These conditions are that t, = <3) for liquid and gas, Heyl om i P= Pa w ‘where the subscripts 1 and g denote the liquid and gas phases. Note that the chemical potentials of the same chemical species in the two phases must be ‘qual ifthe phases coexist The chemical potentials are evaluated atthe eammon Dressure and common temperature ofthe liquid andgas, so that APA = 1400.9 | @ [Ata general point in the p-r plane the two phases do not coesist: If, < jy the liquid phase alone is stable, and if y, < 1 the gas phase alone is stable Metastable phases may occur, by supercoaling or superheating. A metastable phase aay have 2 transient existence, sometimes brief, sometimes long, at a temperature for which another and more etable phase of the same sulalene hhasa lower chemical potential, Derivation ofthe Coexistence Curve, p Versus ¢ Let po be the pressure for which two phases, liquid and gas, coexist at the temperature cg. Suppose that the two phases also coexist at the nearby point Po + do:so + de. The curve in the px plane along which the two phases coexist divide the p, x plane into a phase diagram, as given ini Figure 10.2 for 1,0. Iisa condition of coexistence that HlPo.te) = ppt) + 8 And also that Walbo + dp. to + dt) = plpe + do ty + dO, Equations (3) and (4) give a relationship between dp and de. ‘We make a seties expansion of exch side of (4 to obtain viesa + (ae « (Bas = ninss + (ar + (Bac een 280 150 sole 1 the volume cecupied by an atom in the gas phuse fs very much larger than in the liquid (or solid) phase, so that we may replace Av by vy experimentally, ani Susu = KIN, ag At atmospheric pressure u/s; = 10°, and the approximation is very good. (b) We assume that the ideat gas law pl Nye applies to the gas phase, so that (16) may be written es Ay = in i) With these approximations the vapor pressure equation becomes t t bn Lora k, “9 ‘shore Lis the latent heat per motecule, Giten Las a function of temperatura, ‘his equation may be integrated ta find the coevistence curve, fin addition, the latent heat L is independent of temperature over the femperature range of interest, we may take L.= Lg outside the integeal Thus hen we integrate (18) we obtain fe 4, 9) 20Figur 103 Vapor pressore of water sa oie plied versus 1/7. The vertical sale logarthic The dashed lise taiht ine. (Chapue 10: Phase Teasfornsions whence logp = ~La/t constant; pl = pocxel—Lefe) « 20) where py is constant, We defined Lp a5 the latent heat of vaporization of ‘one molecule, If refers instead to one mole, then PAT) = pocxp(—Lo/RT) , en where Ris the gas constant, oka, where No s the Avogadro constant. For «the latent heat at th liguid-gas transition ie 2485 J g™# at O°C and 2260) J g7# at 100°C, a sbstontal varistion with temperature. ‘The vapor pressure of water and of ie is plotted in Figure 10.3 as logp versus 1/7. The curve is tinear over substantial regions, consistent with the celica point Liquid water ise Pressure is mma Bg 0G 1S 20 2530 35 a0 as 50 10/7, in Ko Desvation ofthe Coexistence Carey Versus ¢ | = CE sao! | 7G. mt a 7 Pec eC AT is cco E eC ECUELT : aos +— 2 i - a 2 in equilibrium and coexist, Al os Tiguid or all vapor. AU inuch hig 02 |} |} 7 C “Temperature, in K Figure 1044 Vapor pressure versus temperatre fr “te Aer H. van Dijk fal, Journal of Research ofthe Nations Bureau of Standatds GA 12 1955), approximate result (20). The vapor pressure of “He, plotted in Figure 10.4, is widely used in the measurement of temperatures between f and $ K. ‘The phase diagram of *He at low temperatures wes shown in Figure 7.14, Notice hat the tiqui-solid cocxistence curve is closely horizontal below LA K. ‘We infer from this and (11) thatthe entropy ofthe liquid is very neatly equal {0 the entropy ofthe solid inthis region I is remarkable thatthe entropies should be co similar, bsause a no«mal liquid fs much more disordered than a solid, o that the entropy of a norma liquid is considerably higher than that 283284 Chapter 10: Phase Temsformations ofa normal solid, But “He is @ Sie, the slope of the (Figure 7.15), and inthis (of the solid, The so quantum liquid, For another quantum liquid, ‘widsolid curve is negative at low temperatur sion the entropy of the liquid is less than the entrony hhas more accessibie states than the liquid! Liquid "He wropy for a liquid because it approximates « Fermi gos, tow entropy when + « tp because a large proportion. ‘momenta ordered into the Fermi sphere of Chapter 7, Tilepoint. The tsiple point ¢ of a substance is that potint px in the p-e plane at which all thee phases, vapor, liquid, and soli, are fa equliiom Hy Consider an equilibsium mixture offiquid and solid phases chelosed in a volume somewhat larger than that occupied by the mixtare jlone, The remaining volume will contain only the vapor, in equlibriom with both condensed phases, and at a pressure equal to the common equiltsiors ‘vepor pressure of both phases. This pressure is the triple point pressure, “he triple point temperature isnot identical with the melting temperature Of the substanes at atmospheris pressure. Melting temperatures depend Somewiat on pressure; the ple point remperature isthe melting empersioe str the common cquilirium Vapor pressue ofthe two condensed phases For water the teple point temperature is 001K above the atmosphere pressure melting temperature; T, = 001°C w 273,16K. The Kelvin seals is ‘stined such that the tiple point of water i exactly 273.16: see Appendix Zetent heat and enthalpy. “The latent heat of a phase transformation, as fom the liquid phase to the gas phase, is equal to t times the entropy siference Gt the two phases at constant pressure. The latent heat is alsa equal to the difetence of H = U ++ pY between the two phases, where Hf i called the cathalpy. The differential is dtf = dU + pd¥ + Vdp. When we crows the ‘Soexistence curve the thermodynamic identity applies of the atoms have their de UU sb PAV ~ (uy = mgd, 2 On the coexistence curve i Thus at constant pressure Lethe = AU + pAVm AHH, Hy ey ‘Values of & are tabulated; they are found by miegration of the heat capacity at constint pressere: ea Deviation ofthe Coesistonce Curesp Vers ¢ Exempla: Mod system for gersoidequllvin, We construe simple model to de- ‘cre a sli in equiri with aga asin Figue 105. We ean easly desi te steer ‘rss cve fot this model. Roughly the sae model would apply a lan, Imagine the solid to consist of N atoms, each bout as a haemae osilator of fee guency toa fixed etter of force, The binding energy ofeach atom inthe proved sais {tha is the energy ofan atem in is ground state is ey telered to alee atom at ee ‘The encray states oa single esitator are aluy ~ rg, where nis posite ineyer oreo (Einue 106) For the ake of ipl we suppose that each atom can anllate soy tro V, in which only the gas phase exists The phases coexist between ¥; and K. The value of V, ot ¥; is determined by the condition that (6) = s4(se) along the horizontal line between ¥, and Ys. This will occur ifthe shaded area below the line is equal fo the shaded ateaes pte 10 Phat ranformaos 0m + 044) z cm ‘ {vapor peur os a -03 GIN, I criicat point I L- & cof bd a Fal w Figure 11 (a) Gibbs fee encgy versus pressure for van det Waals equation of sate: ¢ = 09S, Courtesy of, Cahn, (@1 Gibbs fre energy sess prewire for van dee Waals equation of ‘above the line. To soe this, consider dG = mole + Vip + ual @ We have dG ~ Vp at constant r end constant total number of particles, The ference of G between ¥, and V, is G= fur, a) 2.436, ~ 7 p= 0.5 L gh = 4 Liquid -2.40 Ginna ome, EF ~ 244 oa rail L n Soe a.a8 Cr lee o Figure 10.128 Gibbs tge energy versus temperature fr van der Waals eaation csatest p= 095 p, Couey of Manche =2.20 Geto ee nob -2.0 | ON — o as 20 aml. \ 1 ‘ 399 08s 00 tn Figure 10.120 Gibbs fre energy versus temperatre for vn dec Wasl equation of state atthe etc pressure pyvy Y, v Figure 0.13, Tsotherm of van der Wanls gas ata teoigerature below the eriteal temperature Fo vues less than V, only the iid phace ents fr volumes above Fy only the gus phase exist Between Ha the sytem in stable equilibrium lie slong the coexistence and isan inhomogeneeus mistute of twa phases. The liquid and gas phages coexist The proportion ofthe liquid sed gas phases mist be such that the sun of hee volumes equals the volume ¥ hati avai ‘but the integrals just che sum ofthe shaded areas, oncnegetive and one postive When the magnitudes of the areas are equal, Gy(t} = G(s) and y,(se) = ‘4(0) along the horizontal coexistence line drawn in the figuze. In euilibriom werequire p, = yy Necleation, Let Ope = sty ~ be the chemical potential diference between {he vapor surrounding a small Liquid droplet and the Liquid in bulk (an infinitely large dcop), If duis positive, the butk liquid will have a lower free energy than the xs and thus the liquid will be more stable than the gas. However, surface free energy of a liquid drop is postive and tends to inérease the free ‘nergy of the liquid. At small drop radi the surface can be dominant and the rop can be unstable with respect to the gas, We calculate the change in Gibbs free energy when 2 drop of radius R forms If isthe concentration of molecuiet inthe quid, AG = Gy ~ Gy = —(4x/3) m,n + 428% = am a Feramageesions Where isthe sucuce f ‘drop will grow when G, % 0 | Resionot 0 order Figue 10.7 Temperature dependence ofthe fee enerey {or an idealized phase transition of the second onder. Figure 10.18 Landau fce energy aneion vers at ‘epresenstive emperaturen At he temperate dope BION theif value a§ gently poston othe exisigut ofthe ee : 19) 08 05} wo, 0) 04 oa a a rT) the Figere 1019 Spontaneous polarization versus temperature, fora second-order phase tacsition The ire isnot realistic at low temperatures Because ofthe ‘eof Ea. (60): the tied law of theraodyramice requires that dfde-+ 0381 +0,a0 (Chapter 10: Phase Transformations Uhl is continuous at + = ze, s0 that there ig no latent heat atthe transition Semperature to, Such a transition is by definition a second order transition Tarstions with a nonzero tatent heat are called fst order transitions we seuss them presently. The real world contains a remarkable diversity of Second order transitions; the best examples are ferromagnets and super conductors, na Ferromagacts. In the mean field approximation, frcomageets siily the {Anda theory To show tis, consider an atom ofmagneie moment pina magnetic field whieh we salt equal to the mean eld £4 a in (83) The ntracionenegydensiy U0) = IMB = haa 66 rete he factor $s common to selene ey problems. The enteopy densi i given approxi ‘ately by Problem 22 a5 (Mf) » constant — Any, (6) nthe regime in which Af «ny. Thus thee energy fonction per unt volume fs FA(M) ~ constant ~ ves at + terms of higher order, (68) ie A ihe transition temperature the conficient of M? vanihes so shat tome, () jnagrexmen wth he discussion fotiowing (6). rem First Order Transitions A latent heat characterizes a fist order phase transition. The liquid. gos trans ton a€ constant pressure isa first order transition, Inthe physies of solids frst ‘onder transitions are common in feroelsctrie erysats and in phase traosformna ons in metals and alloys. The Landaw function describes fist otder transition When the expansion coefficient g, is negative and gis positive. We considct FUEGO) = gole) + bale — 20S? ~ Nostale 4 70) First Onder Trassitons 303 Landau free energy Figire 1020. Lanudau ce encegy fonction versus ina fest oder transition, a representative tempeatates. Att ‘he Landay function has eaual minima at €~ 9 nd ata finite €as shown, For r below the absolute minimis a laegr values of £38 «passes thiough «hore ciscontinuovs tang i the portion ofthe absclate ninimum The arcows mask the minima, The extrema of this function are given by the roots of OF 26 Oss in Figuee 1020: AE ~ tole = Las? + aoe? oy Either g = Oor ae ~ to) ~ alg? + ag = 0. (2 As fis transition temperatures the free enertcs will be equal fo the phases wih ¢= O and with the root € # 0, The value ofc, will not be equal 10 vg304 Figure 10.21 ‘typical fst onder phase rst, Chapter 10: Phase Transformations Dependence of on « = x for® and the order parameter ¢ (Figure 10.21) does not go continuously to 2er0 at ‘te These results differ from those in the second order phase transition treated earlier, where £ went to zer0 continuously at tq = tq A first order transfor mation may show hysteresis, as in supercooling or supersaturation, but no hysteresis exists in a second order transition SUMMARY 1. The coexistence curve in the p-r plane between two phases must stisty the (Clausius Clapeyron equation: ‘where Lis the latent heat and Av isthe volume dilference per atom between the two phases, 2, Thelatent heat [= Hy — where H = U + pis the enthalpy 3. The van der Wass equation of state is (p+ NAVY ~ NB) = Ne 4, Tn the Landau feee eneeey function Fulks) = UES) ~ vob theenergy and entropy arc taken when the order parameter has the specified value &, not necessarily the thermal equilibrium value fo. The function Fi, is a minimum with respect to & when the system isin thermal equilibrium. Problems 5.8 frst ord fe phase transition is characterized by a latent heat and by hysteresis, PROBLEMS 1. Entropy. energy, and enthalpy of von der Waals gas. (a) Show that ths « lropy of the van dee Waals gas is Ntlogingl? = NON] 4 4) oy {b) Show thatthe eneeyis Ue Wren Nig. 04) (6) Show thatthe enthalpy H we U 4 pis HUY) = 3Ne + Nhe — INP: es) Mrp) = Ne + Nh = Naples 6, All eesolts are given to fist order in the van dor Waals correstion teem a b 2, Caleulation of dT [dp for water, Calculate from the vapor pressure equa. tion the value of dTiip near p = 1 atm for the liquid-vapor equlibrivm of water. The heat of vaporization at 100°C is 22605 ¢-', Express the result in kelvin/aten, 4. Heat of vaporization of ice, The pressureotwater vapor over iceis 3.88 mim Hig at ~2°C and 4.58 mm Hig at 0°C, Estimate in Jumol™! the heat of vaporiza- tion ofioe at = °C. 4. Gas-sotid equilibria. Consider a version ofthe example (26}-(32) in which \We let the oscillators inthe solid move in three dimensions. (a) Show that in the high temperature regime ( > fa) the vapor pressure is = ()"Siertwn on () Explain why the latent heat per atom isto — Hr 5. Gas-solid equilibrium. Consider the gas-solid equilibrium under the ex- ‘treme assumption that thé entropy of the solid may be neglected over the tem erature range of interest. Let ~tp be the cohesive energy of the solid, per atom, 0s30 Chapter 10: Phase Transformations ‘Treat the ga8.as ideal and monatomic: Make the approxima accessible 0 the gas isthe volome ¥ of the contain, indy smallet volume occupied by the solid, (a} Show that the energy of the system is tion that thevolume pendent of the much, Total Helmholtz fee Fake kya, ste + N,tLlog(,Vig) — 1], (8) Bre th otal mumber ofatoms, N m+ Nis consant.b) Find the mine ‘nom ofthe eecnergy with respect to N,:show tatintheegullibriamenedies x nV exp(~ colt) (9) (6) Find the equilibrium vapor pressure, 6 Thermodynamics of the superconducting transition, (3) Show that Lda) _ Ban, ia de hg We (s = onyv = (so) in Sl units for 2. Because 8, decreases with increas Side i negative. The superconducting phase has te loNerenropysit ethene Crdered phase. AS + +0, the cniropyin both phases will go to cet, eorehenne ey athe thie taw. What docs this imply for theshape of the eurvet Ps veree cy (ALE = fo We have B, = Vand henes 25 = oy. Show that nieve he ihe ‘owing consequences: (1) The two five energy curves do nat css at bot Tee eat It Figure 10.22. (2) The two enceges ae the ames UC) WAG) Tete ie no latent heat associated with the transition at $2 SB the atca heat ofthe wanstion wien eeried out uta magnets fel, Bel © Show that Cs and Cy the heat capacities per unit volume, ate related by temperature, the right doe) AC = Cy = Cy = HE, sn AC m Cy ~ Cy = 5 ep Figure 8.18 is a plot of C/T" vs T? and shows that Cy decreases much faster than tneany with decreasing x, while Cy decreases as yx. Fort « vy Ae dominated by C,. Show that this implies (2) Problems 307 4 5 0a} & Normal @ fs s ‘Superconductor 3 ps 2 ~o6| S 3 1.180 x] g © Los so Temperature, K Figure 1022, Exceriments vatuoe ofthe es energy on «fasion of {empetature fr alumioum i the superconducting sate aad in the aosmal se, Helo the ransition temperature 7, L180 K the fee energy lower in the superconducting sat. The wo curves merge at the teansion fempeatur, so that the phase inition e second order (ere ho latent heat of eansition at T,) The curve Fis measured in eco magic Hel, and Peis Imeasuced ina magnetic eld suticent to pot the spect i the nova sate Courtesy of NE. Phils 2 Simplified model ofthe superconducting transition. The Byli)curvesofmost superconductors have shapes close to simple puraboles. Suppose that BA) = Balt ~ (o/rd"Y 83) Assume that Cy vanishes faster tham lineadly as + -» 0. Assume also that Cy is lineae in «as for @ Fecmi gas (Chapter 7), Draw on the results af Problem 6 to ‘aleulateand plot the rdepondences ofthe twocntropis, the two heat cay and the latent heat ofthe transition, Show that Cs(e,)!Cy(s,) = 3 8. Flrst order crystal transformation, Consider a crystal that can exist in either of two steuetures, denoted by w and f. We suppose thut the # struvtte i the Stable low temperature form and the f structure is the stable high temperature form ofthe substance, Ifthe zero of the energy scale is taken a the stote of Separated atoms at infinity, then the energy density U0) at += 0 will be08 Chapter 10: Phase Tratsfermatons ‘negative. The phase stable at z = 0 will have the lower value of U{O}; thus 440) < U4l0). 1 the velocity of sound tin the f phase is lower than vin the « phase, corresponding to lower values of the elastic modul for f then the thermal excitations in the phase will have lager amplitudes than in the 2 phase. The larger the thermal excitation, the larger the entropy and the lower the fee enexgy, Soit systems tend to be stable at high temperataces, haed Systems at Low. (a) Show from Chapter 4 thatthe fre energy density conterbuted bythe phononsina solid at a temperature much less than the Debye temperature is given by —x?r4/300%H, in the Debye approximation with v taken as the velocity ofall phonons. (b) Show that atthe transformation temperature (30 fa*VLE AO) — UO ep”? — 89) 89) ‘There will bea finite reat solution i < ey. This example is a simplified model of class of actual phase transformations i solids (c) The latent feat of trans formation is defied as the thermal enesey that must be supplied to carry the system through the transformation, Show thatthe latent heat for this model is L LU,10) — Us0H) «) In (84) and (85), U refers to nit volume Chapter 11 Binary Mixtures SOLUBILITY GAPS ENERGY AND ENTROPY OF MIXING Example: Binary Alloy with Neatest-Neighbor Interactions Example: Mixture of Two Solids with Different Crystal Structures, Example: Liquid He-*He Mixtures at Low Temperatures Phase Diagrams for Simple Solubility Gaps PHASE EQUILIBRIA BETWEEN LIQUID AND SOLID MIXTURES, Advanced Treat Buteties SUMMARY PROBLEMS, . Chemical Potentials in Two-Phase Equtinram 1 2. Mixing Energy in "He~tHe and Pb-Sn Mixtures 3. Segregation Coefficient of Impurities 4 5 . Solidification Range of Binary Alloy Alloying of Gold into Silicon ‘Noe Al compotion peerings ae sated in atom percent, 310 ey 318 319 320 mI 3 330 330 30 330 a3 331 331 09310 Chapter 1: Binary Mixcares Many applications of m: biophysics, are concerned have io of more phases in coexistence, Beautiful bhysical fects oceur in such ays in this chapter, with examples drawn fiom simple situation, SOLUBILITY Gaps ites are syslems of wo of more detent chemical pies Minary mixtrce Zave only two constituents, Mixtures with hee and foteconstiueme se cacy ceiee 7 ce staternary mixture, Ifthe constituents are atoms, end not mote, cules, the minture is ealled an alloy single homogeneous phase, The properties of mixtures differ from the Properties of pure substances, The ieking and solidification propcris of mixtures are of special interest Fetes Eiaous mistures may melt at lower temperatures than their constituents siser a goldsiticon alloy: pure Au mets at 105°C and pure Sixt 100", irre aarey the formation of any low-metting Av-Si compound: mictosconie investigation of the soidied mixture shows a two phase mivture of almost pure Au side by side with almost pure Si (Figure U1). Mixtures with such prorertiss ae common, and they are af practical importance precsey because cof their lowered melting points, What determines whether to substances form a homogeneous ot a hetero- ‘geneous miature? Wh, ti the composition of the phases that are in equilbriuna 'tecoueneous mixture? The properties of mintures can be Principle that any system at a fixed temperature will ration of minimum free energy. Two substances will Tego ch other and form a homogeneous mntreif that isthe configura ‘ion of lowest fre energy accesible 0 the components, The substances will Sotbilty Gaps ant 10 um 1S ULL Heterogeneous gldsilcon alloy. When 2 mivtate of 69 pct Aw and 32 pet. Siis meted andthe shied, the minture segregates into a phase of almost pure Aw ig phase) coeistent wit a phase of almost pure Si ark phase) Magnified stot 800 mes The composition given stat ofthe fowestomeling Aus Staats the Sorclld eutectic mature, a concept explained lace in the tent Photograph cotesy ofStephan Just form a heterogeneous minture if the combined free energy of the two separate phases sie by side is Toner than the fiee energy of the homogeneous misturet then we say thatthe mixture exhibits a sotubilty gap. A heterogeneous misture will melt at a lower temperature than the separate substances ifthe free energy of the homogeneous melt is lower than the com- bined free energies of the two separate solid phases. Tucougtout this chapter we assume for simplicity that the external pressure ‘may be neglected, and we set pV = 0. Then volume changes do not involve work, and the appropriate fees energy is the Helmholtz fee energy F rather than the Gibbs free energy 6. We will usually simply speak of the free enerey. We discuss binary mitures of constituents that do not form well-defined ‘compounds with each ather. Ou principal interest isin binary alloys. Considerao Chapter 1: Binory Mictares Many applications of materials science, and large parts of chemistry and biophysics, ate concerned with the properties af rmulticomponent systems that have two or more phases in coexistence. Beautiful, unexpected, and important Dhysical eects occur in such systems. We treat the fundamentals ofthe subject in this chapter, with examples drawn from simple situations SOLUBILITY GAPS Mixtures ae systems of wo or more different chemical species. Binary nintures have only two constituents. Mixtures with three and four constituents are called femary and quaternary mixtures. 1 the constituents are atoms, and not mole: cules, the mixture is called an alloy A mitture ishomogeneous whem its conslituents are intermixed on an atomnie Scale to forma single phase, asin a solution. A mixtuteishetecogencous when it Contains two or more distinct phases, such as oil and water. The everyday expression “oil and water do not mis” means that their mittsre does not form single homogeneous phase. ‘The properties of mixtures differ from the properties of pure substances. The ‘icting and solidification properties of mixtutes are of special interes. Hetero ‘geneous mixtures may melt at lower temperatures then their constituents, Consider a gold-siticon alloy: pure Au melts at 1053°C and pute Si at 04°C, Dut an alloy of 69 pct Au and 31 pet Simelts (and solidifies) at 370°C. This is not {he result of the formation of any low-melting Au-Si compound: microscopic investigation of the solidified mixture shows a two phase mixtute of almost Pure Au side by side with almost pure Si (Figore 11.1). Mixtures with such Properties are common, and they are of practical importance precisely because ‘of their lowered melting points. What determines whether two substances form a homogeneous of a hetero- -encous mature? What isthe composition ofthe phases that ae ineuilixium ‘with each other in @ heterogeneous mixture? The properties of mixtures can be understood from the principle that any system at a fixed temperature will evolve to the configuration of minimum free energy. Two substances will xg the 5 ‘The composi ) forthe liquid, are cauilibrium is a homogeneous liquid the system in equilibrium consists of two phases, a "8 sand a liquid phase of composition x, ystem in equilibrium is @ homogeneous sali, Ms xs and x, of «solid and a liquid phase in equilibrium are femperature dependent. As the temperaiure dectesses the fice energy of te valid deercases wore rapidly tis that of the figuid, The tangential pots in Figure 1191 move to the left This behavior i epresented by a phase diagram similae to the eaticerepressutation of the equilibrium composition curves for rmbstures with phase separation. In Figure 14.96 the curve for x, is called the Higuidus cunve; the Curve for x, 5 the solidus carve ‘The phase diagrams have been determined experimentally for vast sumbers Of binary mixtures, Those for mos! af the possible binaty alloys ate known? For most metal alloys the phate diagrams are more complicated than Figure 11.9, which was draw fora simple syste, germanium silicon, ‘When the temperature is lowered in 2 binary liquid mixture with the phase sliagram of Figure 119, solidification takes place over a finite temperature ‘ange, not just al a fixed teraperature, To see ths, considee a liguid with the initial composition x,, shown in Figute 11.1. As the temperature is lowered, Solidification begins at « = x, The composition of the solid formed is siren by xis, 80 that the composition of the remsining liguid is changed. In the ‘cxample ss > 2.,80 that the liquid moves towards lower values ofr, where the solidification temperature is lower. The temperature has to be lowered it solidification is to continue. The composition of the liquid moves along the liquidus curve until the solidification is completed at t= xy the equilibrium state of the system is homogeneous solid. tn the ist range the sold will have the crystal steueture in the second range the structure is . (©. For x41 < x < spp, the equilibrium state is @ homogeneous liquid. (0) and (6). For xy5 < x < Xp OF pu hich the liquid phase free energy touches the z Figure 11.44 a} Phase disgram of the PbSa system, ater Hansen, Ab) Microphotograph ai ‘of the Pb-Sn eutectic, magnified about 800 fianes. Cuartesy of J. D. Hunt and K. A aa0 (Chapter 11: Binary Mistures fangeat to the sotid phase curves lis between the compositions x, and xy, In Some systems this point les outside the interval, as if either fig and f. oF fos and J, were interchanged in Figure 11,12a, Such systems are called peritectic systens, SUMMARY 1, A minture exhibits solubility gap when the combined fee energy of two Separate phases side by side is lower than the cee energy af the homogeneous mixture, 2 The mixing entropy arises when atoms of diflerent species are interchanged in position. For the alloy A, 8, we have Sy = {C1 ~ splogll ~9 + xtog3?). 3. The misingeneray for neatse-neighhoe interactions it ag pall ~ Lean — Higa tel) 5 {or p nearest neighbors 4. The liquidus is the composition curve x, versus + for a liquid phase in equilibrium with a solid, The sclidus isthe composition curve xy ¥ersus t fora solid phase in equilibrium with a liquid ‘5. Mixtures with two branches to the liquidus curve are called eutecties, The ‘minimum solidification temperature is called the eutectic temperature PROBLEMS, J. Chemical potentials in neo-phese equilibrium. Show that the chemical po- tentials iq and pig of the two atomic species A and B of an equilirium two phase misture are given by theintercepts ofthe two-point tangent in Figure 11.2 With the vertical edges of the diagram at x = O and x = 1. 2. Mixing energy in*He—'He and Pb-Sn mixtures, The phase diagram of lig: vid He-*He mixtures in Figure 11.8 shows that the solubility of *He in “He emains Gnite (about 6 pet) as t+ 0. Similarly, the Pb-Sn phase diagram of Figure 11.14 shows a finite residual solubility of Pb in solid Sn with decreasing Problems What do such finite residual solubilities imply about the form ofthe function nto? 3. Segregation coefficient of impurities. Let Bean impurity in A. with x « 1 {inthis limit the nou-miing parts of the fee energy can be expressed as linear fanciions of x, as fls) = fel) + xfo(0}, for both liquid and solid phases ‘Assume thatthe iquid mistare isin equilibcium with the solid mixture, Calculate ‘he equilibrium concentration ratio Km x4/%q, called the segregation coefficient For many sjstems & « 1, and then a substance may be purified by melting and partial solidification, discarding a small fraction of the melt, Ths principle is widely used in the purification of materials as in the zone refining of sem conductors. Gives numerical value fork for fo’ ~ Jou’ = LeV and T = 1000. 4. Solidifeation range of a binary alloy. Consider the solidification ofa binary alloy with the phase diagram of Figure 1110, Show that, regardless of the inital ompostion, the melt will always become fully depleted in component B by the time the last remnant of the melt solidifies. That is, the solidification will not be complete until the temperature has dropped to Ty. 5. Alloying of gold into silicon. (a) Suppose a 1000 A layer of Axis evaporated, onto a Si enpstal, and subsequently heated to 400°C. From the Au-Si phase diagram, Figure TL, estimate how deep the gold will penetrate into the silicon erystal, The densities of Au and Si are 19.3 and 233gem”>, (b) Redo. the estimate ar 800°C. arCOOLING BY EXTERNAL WoRK IN AN EXPANSION ENGINE Gas Liquefaction by the Joule-Thomson Effect Example: Joule-Thomson Effect for van det Waals Gas Linde Cycle Evaporation Cooling: Pumped Helium, to 0.3 K Helium Dilution Refiigerator: Millidegrees ISENTROPIC DEMAGNETIZATION: ‘QUEST FOR ABSOLUTE 7FRO. Nuclear Demagnetization SUMMARY PROBLEMS 1. Helium as a van der Waals Gas 2, Ideal Carnot Liquefier 3. Claude Cycle Heliuin Liquefer 4, Evaporation Cooling Limit 5 Initial Temperature for Demagaetizaton Cooling cng 34 3i7 335 39 3 M2 346 8 380 350 390 3h 31 352 352(Chaper 12: Crogenies, CCoyogenics isthe physics and technology ofthe production aflow temperatures We discuss the physical principles of the most important cooling methods, down to the lowest temperatures, ‘The dominant principle oflow temperature generation down to 10m is the cooling of gas by letting it do work against a force during an expansion. The as employed may be a conventional gas; the free electron gas in a semicon ‘ductor; oF the vieual gas of ?He atoms dissolved in liquid “He. The fore against which work is done may be external or internal to the gas. Below 10mK the dominant cooling principle isthe isentropic demagnettz, paramagnetic substance, ion of 8 We diseuss the cooling methods ia the order in which they occur in a laboratory cooling chain that starts by liquefying helium and proceeds from there to the lowent laboratory temperatures, uoually 1OmK, zometimes 1k. Household cooling appliances and automobile air conditioners utilize the same evaporation cooling method that is used in the laboratory for cooling, Tiquid helium below is boiling temperature, to about 1K. COOLING BY EXTERNAL WORK IN AN EXPANSION ENGINE In the isentropic expansion of « monatomic ideal gas from pressure p to & Jower pressure pz, the temperature drops according to Tr = Theale, a ty (664 Soppore py = 32atm py = Hatm; and 7, = 300K; then the tem perature will drop to T, = 75K. We are chiely interested in betism as the working gs, and for helium (1) san exelent approximation i the cooing proces i reversible ‘The problems in implementing expansion cooling arise from the pail irreversibility of actual expansion processes. The problems are compotnded by the nonetstence of good low temperature Iibricanis. Actual expansion cooling cycles follow Figure 121. The compression and expansion parts of Cooling by Esterat Work in an Fapension Engine Heat ejection Heat cxclianger Expansion Working — volunie igute 1 Sinple expansion eeigeraior. A working goss ‘omptesed; the beat of compression i gested into the ‘environment. The compress com ferperatre as is brecooed further in the couateow hee exchanger I then does work ina expansion engine where itcoals toa ternperatare below that of the Working volume. Aer extracting teat rom the working volume the gas retuns thecompressor i the heat exchanger. ais26 Chapter 12: Cryogenics the cycle are separated, The compression is performed at or above room temperature. The hot compressed gas is cooled 10 near room tentperature bby geeting heat into the environment. The gas i further precooles in ¢ counter: flow heat exchanger by contact with the cold ceturn gas stream at the low temperature of the cooling load, The gos is then cooted to is lowest temperature jn the expansion engine, usually a low fiction turbine, The cold gas extracts heat from the cooling load and then returns to the compressor via the heat ‘exchartger. The heat exchanger greatly reduces the cooling requirements im- posed on the expansion engine. The desiga of the heat exchanger is as important as the design of the expansion engine. ‘The work extracted by the expansion engine is the enthalpy diference between the input and ouput gas: The Lotat energy flowing into the expansion ‘engine is the internal energy U, of the gas plus the displacement work p.¥% done by the compressor, where both U, and M, reler to a given mass of gas. ‘The toral energy leaving the engine with the gas is the energy U, of the gus plus the work pp required fo miove the gas against the pressure py. The work. ‘exeacted by the engie is the difference We (Us + mh) ~ (Us + aah) = Ty = Hh a For a monatomic ideal gas U= {Ne and p¥ = Ns, hence H = {Nx The ‘work performed on the engine by the gas is My =) 8 The counterilow heat exchanger is an enthalpy exchange device: it is an expansion engine which extracts no external work, Most gas liquefiets use expansion engines to precool the gas clase 10 its liquefaction temperature. It is impractical to carry the expansion cooling 10 tke point of liquefaction: the formation of a liquid phase inside expansion engines causes mechanical operating difficulties. The final Fiquefaction stage is usually a Joule-Thomson stage, discussed below. Helium and hydrogen liquefiecs usually contain two oF more expansion engines at successive tem peratures, with mufiple heat exchangers. The principle of cooling by isentcopic expansion ofan ideal gas is applicable to the electron gas in semiconductors, When electrons flow from a semir conductor with clectron cone high eleetzon couceatation into a semiconductor witha lower ration, the electron gas expands and docs work against the poteatil barrir between the two substances that equalizes the two chemical Potentials, The resulting elstroni cooling, called the Peter effect, is used Gas Liguefecton by the Joule Thomson Eece down to about 195K quite routinely; in multistage units temperatures down, {0 135K have been schioved. Gas Liquefaction by the Joule-Thomason Effect Intermolecular atteacive interactions cause the condensation ofall gases. At ‘smperatures slightly above the condensation temperature the interactions are strong enough that work against them during expansion causes significant cooling ofthe gas. Ifthe cooling is suffcin, pact of the gas will condense This process is foule-Thomison Hiquelacton, The practical implementation is simple. Gas at pressure py is forced theoug’ 4 constriction called an expansion valve into space with a lower pressure py, 48 in Figure 122. The work is the dilferenee batween the displacement werk ~Pud¥, dons on the gas in pushing it through the expansion valve and the displacement work +p, dV, recovered from the gas on the downstream side Hered, is negative and dV, is positive The overall process is at constant enthalpy, To see this, notice that the ‘sparaon valve avis ao au eapansion engine that extracts zero work, With §¥ = 0in 2) we have Hy = Hin the Joule-Thomson effect, For an ideal gas Hf ~ 4,0 that ¢y = 13 in the expansion, There is zero cooling effect for an ‘eal gas. Jn real gases a small temperature change occurs because of the internal ‘work done by the molccules duting expansion, The sign of the temperature A Pol Expsnsion valse Figue 2.2 The Jovle-Thomson elt A ga ie pushed ‘hough an expansion sale ff he gas is nonadea, chere will bbea temperature change during the expansion because of work done agains the intermolecelae force. Ifthe temperate is iy below a certain inversion temperate ys the gs ‘sil cool on Joul-Thomsaa expaasion, aae 12: Ceyoeries Table 2.1 Liquefaction dats fr tow blag gases ah te ai met | emtinot | wattctier 1 | ao8 | om as? | aaa aia mj) st | as) “ate |e 2 | 3 6) m3 ess | ie aa | m5 am | 6 ais | sion | 0 ee Sort: 7, = stmowheiepresure bolog tempering; T, = etal temperature: Toy ‘Thomod invesion temperate; Sif» marten heat of vporeaton |= moll vole of the liquid. Thelost caluna, Afi dicate best aca ta conte en op fre geet ‘onsenpion of ite per hou; Tn vlus i ptetse ate an dt Wass sles cele) irom Tyan net eased vaae ‘Cuton sowie slits when coped a atop estat, bosses rie point cies shove atmoyples fronure Soll, €O, hue snsy he Mane, Cll he Pid co Sstact of tora fs, which i tigseB n bug quan oe shins UNG foc Lage buyee and iron are separated in he iui of air For hsm, ge data Soh forte feomimon notope He ae fre change during a Joule-Thomson expansion depends on the intial temperatore, All gases have an inversion temperature tj, below which such an expansion ‘cools, above which it heats the gas. Inversion temperatures for common gases are listed in Table 12. Exonple:Joute-Thomson effet for van der Waals gar. We fou ix (19.23) tht Ho Ber (/NbE ~ 29) “ fora van der Waals gas, where a ad b ae postive constants, The fst wo terms ae the cottectons caused by th short range repulsion and the fng range aration. The cur tions have opposite sigas. THe tote earetion changes sgn al the tenpertaze © hese «the erica temperature, defined by (6045) “The temperature ry 6 the invesion temperature Fort < ty the enthalpy at Bed temperatre increases 3s the volume ineteses tee inexpansin te work done spans the alteactve interactions between molecules is omisan. Ina proces at consent enttalpy ‘his increases compensated bya decrease ofthe 4s team that, by cooing the gas FOr se Gas Liguefction by te Jule-Thomn Effect 30 £ > tay theentaly ata fed temperature decrcass beause now the werk dod by the Strong short range repulsive imerseione ie dominant: atthe higher lempotate the okeules penetrate fares into the repulsive region, Linde escle, In gas iqueliers the Joule-Thomnson expansion is combined with ® counterflow heat exchanger, as shown in Figure 123. The combination is called a Linde cycle, after Carl vo Linde who used such a eyele in 1895 to Tiquety air starting ftom room temperature, In our discussion we assume that the expanded gas returning from the heat exchanger is at the same temperature as the compressed gas entering it. We neglect any pressure diffrence between the output ofthe heat exchanger and the pressure above the liquid, To and from compressor ‘or precoaling stages i [IF see Figure 123 The Linde ete, Gas i auf by combining Joule Thomson pasion mith a countedlow heat exchanger. |__—sT expansion valve Liquefied gas30 Chapter 12: Cxyoperes 04, 03} “ant 02 Liquefuetion eve oa o 10 © w % Input pressure, atm Fare 1.4. Performance of hetivn tui operating bythe Linde yee, 3 fnction of he input pressure, rm oulpl press ot | alm ave {or various values ofthe input tempertuce, The solid euves give the ‘igufasion coset, The broken cuses ge. = H.-H, the ‘nteoat efigration load avaiable at 4.2 K ifthe load it placed nse the ieee ad the sill cold helium gas ba off bythe lad ie returned {trough te heat exchanger rather than bole into the stmaephore. See Problem 3 Afler AJ. Coo in Adtamed cryignis (CA, Bele, Plenum, 1971, 9.187 oe Eroporaton Cooling: Pumped Heim 0 043 K ne combination heat exchanger-eapansion vale i a constat enh spy Fection a isaaont ole of Bes enter the combination; suppore ine Fraction 2 is liquefied. Constant enthalpy requis thar Mg = 2g +S = Alte o rece MT and Hu HUT) 80 the enthalpies pee mete ot Sethe heat 204 Output pressures, Botha the common upper eames ofthe heat exchanges Hugi the enthalpy per mole of vid at its boiling tense erature under the pressure py. From (6) we obtain the fraction Fa Tg” " called the fiquefaction coefficient, Liquefaction takes place when Huu, > Has that ie, when, HT ePoud > WT « tray enthalpies atthe input temperature ofthe heat exchanger matter, tr the Joule‘Thomson expansion at this temperature coals the gon ecto’ will ake place, The thre enthalpies in (7) are knowa experimentally Viguefaction coefiient cateutated fom them for heli daeign Of in) and the inccesse ofthe denominator. To obtain vssulligue, ures below onethicd of the inversion {hs g24 by em expansion engine. The combination ofan expansion engine ond a Linde cycle is called a Claude eyes. The expansion engine ie invariably receded by another heat exchanger, as in Figure 121 Evaporation Cooling: Pusaped Metiumy, (00.3 K Steitng from liquid helium, the simplest route to fower tempotatures ix * ‘aportion cooking ofthe liquid helium, by pumping aWay hela vapor. 1 Seert hea of saporiantion of the tguid elm isexteacted alongwith the va, The hea exestion atses the further cooling: work is done agains! the nic atomic forees that eaused the helium to Hguely ia the fest place. In Jom 7a8 Chapter 12 Cepapenice Yatte122.Temperttes inhi. a shih she opr press of Hees PHe reach specified values: a Tet =e pion wo? wo sie | 036086 om ose tHe =| 023 O06 a ‘The lowest temperature accessible by evaporation cvoling of liquid helium isa problem in vacuum technology (Chapter 14) As the temperature drops, the cquilibrium vapor pressure drops (Table 12.2) and so does the rate at which hhclium gas and its heat of vaporization can be extracted fcom the tiquid helivrs bath, Evaporation cooting is the dominant cooting principle in everyday cooling Sevioes such as houschold refrigerators and freezers and in ai cowditioners “The only difference is in the working substance, Helium Dilution Reftigerat idegrees (Once the esuilibxium vapor pressure of liguid "He has dropped to 10°*tors, lassie sefigeration principles lose thei uit. The temperatute range from 06K to 001K is dominated by the helium dilution refrigerator, which is an ‘evaporation refrigerator in a very dever quantum dieguise® We saw in Chapter 7 that ‘He atoms are bosons, while He atoms ae f Iwions. This distinction is not important at temperatures appresiably higher han the supeduid transition temperatute of ‘Hs, 217K. However, the two dsotopes behave as altogether diferent substances at lower emperatuts, Belo 87K liquid He and “He are immiscible over a wide composition range, like cil and water. This was discussed in Chapter It and is shown in the phase siagram of PHe-*Hle mixtures ia Figure 11.7. A miature with composition in the range labeled unstable will decompose into to separate phoses whose ‘compositions are given by the two branches of the curve enclosing tat ates The concentrated *He phase floats on top ofthe elilute He phase. As T-» 0, the "He concentration ofthe phase dilute in He drops to about ‘pet an the phase rich in He becomes essentially pure He. Consider liquid odrerews, DS Bets, Contemporary Pyscs9,97{ 18): ).C. Wheatley. Am. iy 1960 fc general eve of oaligecnigus brow 1 Ke Wl. Hosap ad ©. esis. Prop. Baye 36, 49) 179), OV. Lounsmnaa, Eugene procs ead AIR Racin eaten van dhe hvcydencuny ams V Lesage ‘Scicatife American 221, 26 (1969), 7 oN etiam Ditton Refizerter itegrees ane “evaporation” nee Figure 2.8 Cooling principle of th hiv dilution reiserstor. Lgl Plein equibriam with a He-+He mtu When “He is de tothe rmixtre, He evaporates (om the pure "He Mul and abc Bet inthe proces, SHe~*He miature with more than 6 pet *He at a temperature in the millidegree range, nea the bottom of Figure 11.7. At these temperatures almost all the “He _aloms have condensed into the ground stat orbital. Their entropy is negligible ‘compared to that ofthe remaining "He atoms, which then behave asithey were present alone, asa gas occupying the volume ofthe mixture. I'the *Hle concen ration exceeds 6p, the excess condenses into concentrated liguid *He and latent heat is Hberated. If concentrated liquid *He is evaporated into the *He rich phase, the latent heat is consumed. The principle of evaporation cooling, «an again be applied: this isthe basis ofthe helium dilution refrigerator. “To see how the solution of "He can be employed to obtain refrigeration, consider the equilibrium between the concentrated ?He liquiel phase and the dilute *He gas-like phase (Figure 12.5) Suppose that the "He:*He ratio of the dilute phase is decreased, as by dilution with pure *He. In order to restore the equilibrium conceattation, *He atoms wll evaporate from the concentrated Ht liquid. Cooting will result. “To obtain a cyclie process the *He-*He mixture must be separated again, ‘The most common method is by distillation, using the diffrent equilibrium vapor pressures of *He and ‘He (Table 12.2). Figure 126 shows a schematic agcam of a reltgerator built on these principles. The diagram is highly ‘oversimplified. In particulse, in actual refeigerators the heat exchanger between themixingchamber and the sillhas an elaborate multistage design. An alternate imethod™ to separate the "He-‘He mixture utilizes the superluidity of *He below 217K. For a variety of practical reasons itis less commonly used, although its performance i excellent, aeai Chapter 12 Coyogenics He pomp loop To pump Pumped “He bath iE | Heat exchanger eel Miniag chamber. Ite wr Nv wwe LU a 42> Vacuum HT shietds Key quid | is Liguia a 7 ‘agua rs ate - le oe eta Ditton Refigeraar:Miltegrees chet oem dlaon eget, Precoklgld He eset ing opornion eg eset ie siemBy whee esting tke pee fy ae The guna alts He stonsinto the denser Heit mined phew ene Wen Regt oH stone doled nui Heth de hens acounterfow MAGNETO aA. Thc the esc tom he Leet teeee Iu eas punoad ol To obtain a stl ie eapoion aed gon terra a ed the sito ruses epee sbou OK hich eae ie ‘He vapor presureisstil uch stalee Tan the “ede SOE Rm Apoteibe extn: he He moresihoupha enayeectenee {Selttound of He. The numpedaif eis cused othe yes eed rsd consti nat Beeoled 0 about 1K by contact witha pumped te bol nee Srclonan lt the condense ater p the exces press geened Spike fein AD ove Ue pressure ia he ull The ied "He coset forge, changer, tens ns sousow het cans, seeing te ing chante, However, Femoving 40,\V at 80 mK. Temperatures bslow SmK exn be achicved by single shot operation, A, in these Remo fieuce 126 weshut of the He supply atersome ntcofoscation ther i no necd t9 cool the incoming He ill and the temperate of the rd shamber drops below its steady state value, untl all He hos boos removed from the chamber ‘he dilation ekigerator i not the only cooling mncthod in the milikelvin {ange that uilizes the peculiar properties of He, An alternate method, keoen 3s Pomeranchls cooing utes the phase diagram of He, se shown in Ph std it HS negative slope ofthe phase boundary between tiguid arc 0M TM The lerested reader is refered tothe ceviens by Huiskomp and Lounasmaa, and by Lounssmaa, cited earl ashi (AMBER He Bere abot KW. Toon ys B08 (576 ad Physi 0 24 on yigy ie46 Chapte 1 ISENTROPIC DEMAGNETIZATION: QUEST FOR ABSOLUTE ZERO Below 0.01 K the dominant cooling prosess i the isentropic (adiabatic) dena netization of a paramagnetic substance, By this process, temporatutes of nk hnave been attained with electronic paramagnetic systems and IK with nuclear Paramagnetic systems. The method depends on the fact that at fixed tempera {rc the entropy ofa system of magnetic moments is lowered by application ofa magnetic field essentially because fewer states are accessible to the system. ‘when the level splitting is large than when the level spliting is small, Examples ‘of the dependence ofthe entropy on the magnetic field were given in Chapters 2 and 3, ‘Wefirst apply a magnetic field B, at constant temperature r,. The spin excess will ttain a value appropriate tothe value of y/¢, the magnetic ald i then reduced to B, without changing the entropy ofthe spin system, the spin excess will remain unchanged, which means that By/t, will equal B,)c,. If, +, Substances with @ gap of moze than about 25eV are usually insulators Table 1341 gives the energy gaps for selected ‘eplconductors ogetber with other properties needed ae, {att denote the concentration of conduction electrons and 1 the con. Suton holes, Ina pure semiconductor the two will be eal, a =m, Q ithe eta is electrically neutral remeamikondactors as used in devices have ben ntetonly doped wth temperate fy Become thermlly ionized ia the semicondarior eee Ponta gambles that give an electron to the eysal end tee POMS charged inthe process) are called donors. Impuritin: tat accept Energy Bands; Fem Level Electrons and Hotes Table BU Bind suture data ofsomeimportast semiconductors fn | Qunwacmeaion | Denies | Diane Be rs tenet | NSS [ele os 8 ae Tree iw ae Gu] 2g | ees ceee > | om | Shige Be | Bos 8G wo | See et ees an clesiron (fom the valence band (and become negatively charged in the process) are called acceptors, het ni" be the contention of positively banged donors and 1,” the concentration of negatively charged acceptors The diference bn 8) Eealled the net fonized donor concentration, The electrical neutrality condition becomes Mom ong a, @ Which specifies the diference between electron and hole concentrations {The clevtron concentration may be calculated from the Fermi-Ditae dise tribution function of Chapter 6: 1 oo ‘) eplle— Ry et 7 ists fis the chemical potential of the electrons. The subscript e refers to cleetcons, tn semigondector theory the electron chemical potential is always called the Fermi level. Further, in semiconductor theoty the character vie almast always reserved for the electron and hole mobilities, and the Fermi level is designated by sy or by {. To avoid confusion with the Fermi energy of 8 mci which we designated a5 ¢, and which stands for the Form level Hn the Fini t+ 0, we shall maintin ove previous usage ofthe letter p forthe chemical potential st any temperature, 39ase Chapter 13: Semleondactor States Given js and t, the number of conduction electrons is obtained by summing ‘she distribution function J.) over all conduction band orbitals: Nem Sto 6 The number of holes is M= ED = LE 60. o ‘where the suraniation is overall valence band orbitals. Here wehave introduced the quantity - ~ Sat RIFT 7 fio) Which is the probability that an orbital at energy & is unoccupied, We say {hat the unoccupied orbital is “occupied by a hale” then {fois the detibution Function for holes just as {cis the distribution function for electcons. Com. parison of (8) with (5) shows that the hole occupation probably involves # = where the electron occupation probability involves e ~ 4x ‘The concentrations n= NyV and m= N/V depend on the Fermi level But what is the value of the Fermi level? It is determined by the electrical neutrality requirement (4), now written as (i) = miu) = An. This ie an ‘implicit equation for sto solve the equation we must determine the fanctionel ependences n,) and ny) Classical Regime We assume that both electron and hole concentrations are in the classical regime defined by the requirements that f, « 1 and fy « 1, a8 in Chapter 6 ‘This will be true if as im Figure 132, the Ferm level lies inside the energy gap ‘and is separated from both band edges by energies large enough thet expt, ~ ie) 1; expf—( ~ ave) « 1 ° To satisly (9) both (@, ~ p) and (y. — 6) have to be positive and at least a few times larger than x, Such a semiconductor is called nondegenerate, The inequalities (9) place upper limits on the electron and hole concentrations and {are satisfied in many applications. With (9) the two occupation probabilities Sdo) and le) reduce to classical distributions: er hasicat Regine a9 Conduction ban a Figure 132 Occupancy of orbitals at a Gite terperatue, according tothe Fess Dirac distribution funtion. The condvetion and valence bands may be represented fa ters oftemperature-dependent elective aumbers WV, of degenerate orbs located atthe wo Ba edges yf The nn ate the Corespouding quantum La =exl-C- Me] He ep-u ar} 0) ‘We use (6) and (10) 10 write the total number of conduction electrons in the form New Foot -te-nlk] “eel —t6,- a expt (e~ aaah . Ny = Neexpl(6- id (a)360 Chapter 14: Sesicondstor Staies where we define Nee Sexpl ~~ aye) (2) Here e ~ eis the ene band edge ¢, as origin, Fae tBtesion for N, has the mathematica form of pactton faction fer one letron inthe conduction band In Chapter 3 ween similar sn gated thereby Z,, and we an adap tha result othe prose problem, wd asa ProNimate moilication fr band sic eects, Deane the ares Gaesass of exp —(e ~ ei] asc inceases above ls mnie at, rioters he sbuton af orbitals within a range of few ¢ abone really sums in (12). The orbitals high in the band thes etlbible contribution, The importa points that nen the bet edge the electrons behave very much like fy 1 particles. Not only ate the electrons Tama iti causes the conductivity of the semiondocon, bar she energy distribution of the o tals near the band edge usually difers from that of tree Pastos only by « proportionality facto inthe energy asd eventually in the sun for Z, eg Git ttanee for a suitable propononaly ctor by use of a device alle he density afstates efetve mos, For free particles we cateoice ne oat ato 2: (36) bux foe zero spin, For panies of epie the ‘result larger by a factor of 2,50 that (12) becomes "ay of conduction electron referred t0 the conduction N, ag = Bone anspry, 03) Numerically, this gives Nel¥ % 2509 x 10! x (TOOK) em"? , 04 Where T'is in kelvin petiantity N, for actual semiconductors exhiis the same temperature dependence as (13, but ders in maguitede bya proporianslay here We SSS this Formally by writing in anaogy to (13), Loyrrprade py , as) meena fale the densiyotstates eecive mass for eletons, Exper ental valves are given in Table 1.1. The introduction of effective mene "Smore than a formality tn the tory of electeans in erysals i is shown that ee Classical Regine racelttmieal behavior of electrons and holes, under the inuenc of external (pice Ruch select Hel, is that of particles with efecive asce safc wrench ee cletron mass. The dyonmizal masses usualy are efron! hag the density-ofstates masses, however, Weedefine the quantum concentration 1, for conduction electrons ax By (11) the conduction clecton concenteation n, | Me = neexpl —(e, — pM. | (17) ion (9) is equivalent 10 the assumption that 1, sng 50 thant conduction electrons act a8 an ideal ps. Axa ad to menor, oy rhe Naas arising rom N, orbitals at, with the Fermi level at, rag In the semiconductor literature , is invariably called the efectine demitg of sates of the conduction bund. Similac reasoning gives the numberof holes in the valence band (16) The earlier assump Yew Ue — ae] = Morel tu — eae) 0 With the definition Ns Dewl te = a 419) We define the quantum concentration n, for hotes as ny 3 NV Aoytefdahe ps, | 0) ere mh i the density-ofstates effective mass for holes. By (18) the hole concentration my = Ny/V is [ = nexpl (i ~ e\fth ey 36Chapter 132 Semsondactor Suisics Like (17), this gives the cartier concentration in terms of the quantum con cznteation and the position of the Fermi level relative to the valeace band edge. tn the semiconductor literature n, ie called the effective dcusiy of states of the valence band Law of Mass Action ‘The product nis independent ofthe Fecmi level go longas the concentrations are in the classical regime. Then nay = noncexpl ~(te— eit) nyexpls,/0) (2) Where the energy gap ¢ = ¢, ~ fy. Ina pure semiconductor we have n= Hy, {and the common value ofthe two concenteations i called the iattasieearviee concentration n, ofthe semiconductor. By (223), (22) ‘The Fermi level independence of the product non, means that this product ‘stains its value even when ng # my, as in the presence ofelecticlly charged ‘importy atoms, provided both concentrations remain ia the classical revime, ‘We may then write 223) as may = ne (220) ‘The value of the product depends only on the temperature, This result is the ‘mass action law of semiconductors, similae to the chemical mass action law (Chapter 9) Intrinsic Feri Level For an intrinsic semiconductor ng =n, and we may equate the right-hand siées of (17) and (226): meexpl (ee — pdt] = (nan expat e Insert = , ~ 6, and divide by nexp(—a/0: expluis) = (nfo) explics + 2/24) Donors and Aeceptors ‘Wetale logarithms to obtain We Mee + e+ Frloglaytn) = Hee +e) + deloginnt yout), 24) by use of(16) and (20), The Fermi level for an inteinsie semiconductor lies near ‘he middle of the forbidden gap, but displaced from the exact middle by aa, amicunt that is usually smal ncTYPE, AND p-T'YPE SEMICONDUCTORS Dozors and Acceptors PPurs semiconductors are an idealization of little practical interest. Semicon. ucors used in devices usualy have impurities intentionally added in order to increase the concentration of either conductian electrans or holes. A semicon. ‘ductor with more conduction electrons than holes is called type: @ semi conductor with more holes than electrons is called p-type, The letters mand p sigely negative and postive majority canriets. Consider a silicon crystal in ri sonte of the St atoms have been substituted by phosphorus atoms Phosphorus is just to the right of Si in the periodic table, hence each P has ‘exactly one electron more than the Si i replaces. These extra clecteous donot Svinte the filed valence tard ence a Sicrystal with some P atoms willeoniain oie conduction electrons and, by the law of mass action, sect hols than pure Si crystal. Next consider aluminum atoms, Abuminvin is just 10 the left of Si in the periodic table, hence Al has exaesly one electean fever than the Si it replaces Asa result, Al atomis increase the number of holes anu deerease the ‘number of conduction electrons, Most impurities inthe sume columns of the petiodie table as P and Al will behave ia Si jst as P and Al behave. What matters is the number of valence slectrons relative to Si and not the total number of electrons on the atom. Impurities from other eotumans ofthe periodic table will not behave so simply. Similar easoning can be applied to other semiconductors, for example GaAs, Forthe present we assume that each donor atom contcibutes one electron which ‘may enter the conduction band oF fill one hole in the valence band. We also sssume that each acceptor atom removes one electron, either from the valence band or from the conduction band. These assumptions ace called the approni- mation of fully ionized impurities: all impurities when ionized are either posi- tively charged donors D* or nezatively charged acceptors A~ ‘The electrical neutrality condition (4 told us that Ann — ment = 05) sas468 Chapter 18: Semiconductor States Because n, ~ npn, from the ‘equation for n, matsaction av, wesce that (28) feuds to aquadratic NP mdm ng °8) “The postive root i 31Cean? + nz + an) ma and because, = hy ~ Anwe have am Hoan aneyt— ay, 75) ‘Most often the doping conce atration is large compared to Centration, 60 that either n, o ny i rch larger than ny ful > ny, ‘This condition defines a extn emfeotunon The Sguate roo in (27) can tien be expanded Elan? + énaye = if any ye [nf + 2nd 2) Jan ntype semiconductor dn is postive and (21) becomes An + nin = An: ry mln oy 0) ‘©. Ptype semiconductor Anis negative and (27) becomes 8 HOM m Sa + ni Ja en The majority carrier concenteation inthe esteinsie lim the magnitude of Aa, while the minor Proportional 10 Jan it (28) is nearly equal to ‘ty cartier concentration is inversely Fen -evel in Extrinsic Senicondvetor By use ofthe mas uetion law we calcul hhaving to caleulate the Fermi lve fast, 1m by solving (17) oF (21) frp ted the cartier concentrations without The Fermi level is obtained from 1, oF Degenerate Semiceniactore type, An Sorin 1 Sos] E04 303 1 ag * on cr) 0 i 2a, Tink Figote 13.3 The Pee level in icon asf ‘atl doping concea\atons. The Fertle (he band edges. smal decrease ofthe enon boon negleced ction of eaperatre, fo ts ae exprested elaine to BY Bop with emperatute has Hem 6, ~ rlogtiind = 6+ elogtnn 6 eae tow 886 QP to ind wa «faction of tempertuce and doping les] 4, Figure 13.3 gives numerical results for $i Wi Fermi level in an extrinsic semicon the valence band edge, ith decreasing temperature the iuctor approaches ether the conduction os Degenerate Semiconductors When one of the carrier concent turn concenization, we may no I cartier. The calculation of thee ations is increased and approaches the quan longer use the classical dsteibution (10) for that artier concentration now follows the trea States times the disteibution function: Nea faoiape, By a 465is Chapter 14: SeniconductoeStatisies where for free particles of mass m the density of states i ral P10 (FR) 9 That is, Dlcis i the number of orbitals in the energy interval (ee + de). To sake the transition to conduction clectrons in semiconductors we replace NV by nim by m,*; and eby ¢ ~ a We obtain see (2m2)" pa dele ~ eg 7 al i) Ore eae aa haa Let (€~ eran = (4 ~ at, We use the definition (16) of 40 obiain potest 7 =o a6 V+ expix — 9) bd ‘ne integral it (36) is known as the Fermi-Dirac integral When ¢ — 4 rwehave —y > 1, so that exp(x — 9) > L la this limit alte . 2 t [Pdcenty? mF Tae explw ee, 37) £ A ti ve the familiar result for the ideal gas. In semiconductors the electron concentration rately exceeds several times ‘the quantum concentcation n,. The deviation between the value ofp from (38) and the approximation (37) then can be expanded into a rapidly conversing poser series ofthe ratio r nn, called the Joyce-Dixon approximation:* ~G-Bp i rent Figure 13.4 compates the exact relation (36] wth the approximations (37) and 9). os) {8B Joye and RW, Dison, Appl Phys. Le. 3,35(J97I the ht side of i writen SAY te is low concn ey = 553853 9 0" Ay ea 9I00 HD Ay Teds Wo “se « To of u oak oo oon ait ae co 1G Oh z 5 3 6 Figer 134 Electron concenetion as 2 fncion of Fem ev, frp near OF above conection band ege The dashed curve epescat theft Term ofthe Joyee Dixon approximation 3).364 (Chapter 13: Semiconductor Statics When 9, is 0 ton, ‘er small omparci ton, the expression ofthe mass action law must be madi dt Problem 4 se ask the reider to show that any = nd expl mlfBig + | (39) Jfthe gp itslfdepends wn the cartier concentration, the value of to be wed bere will depend on concentration, Impurity Levets Fhe addition of impurities to a semiconductor moves some orbitals ce band into the energy gap, where the orbitals now ap Mt states. We consider phosphorous ina silicon crystal, tthe weed its extra electron to the Si conduction band, the atom olumin V donors in $i and Ge. The lowest orbital of an electron bowed tog donor corresponds ¢o an energy lvl Ac, = ¢, ~ tq below the edge at the seaaietion band (Figure 135). Thee is one set of bound orbitals for every fonar. A parallel argument applies to holes and acceptors. Orbitls are split off from the valence band, asin Figure 135. For each accept atom there is one ‘ct fbound orbitals with anjonization energy As, =, ~ ¢,,ofthe same order 3s Ate Tonization energies for column IN acceptors in Site listed in Table 132, |nGaAs the ionization energies fr all columsn VI don «lose to 6 meV. For zing, the most important acceptor, 1s except oxygen are ay = 24 meV. Some Table 13.2 ovizaton ener wfeutanw Vdanoes snd ofum HI seepioss in Sand Gn me’ Acceptare BoA Geta oT ese fos 102 fos ne Bonar PO ae si fas” Ge} a 1a Occupation of Donor Levels 369 Figure B85 Dororand accpto sep efasemiontactor capuity feel inthe energy Impurities generate orbitals deep inside the forbidden gap, sometimes with ‘multiple orbitals correspording to different ionization states, Occupation of Donor Levels A donot level can be occupied by an electron with either spin up or spin dowa. Hence there are two different orbitals with the same energy, However, the ceccupations ofthese two orbitals are not independent of each other: Once the level is occupies by one electron, the donor cannot bind a second electron with ‘opposite spin. As a result, the occupation probability for & donor level is not given by the simple Fermi-Dirae distribution function, but by a function {tcated in Chapter 5. We write the probability that the donor orbital is vacant, 50 that the donor i ionized, in & form slightly diferent from (5.73) SO") = (40) + dexplie Here ¢y isthe energy ofa singly occupied donor o*bital relaive to the origin ofthe encray. The probability that the donor orbital is oecupied by an electron, 0 that the danoe is neutral is given by (5.73) {0 = Tp = aya0 Chepter 18: Semiconductor Static Acceptors require extra thought. in the fonized con ach of the chemical bonds bewween the aceptor atoms and the surrounding Semiconductor atoms contains a pair of electrons with antiparallel spins There § only one such state, hence the ionized condition contributes only ane term, ‘exp{(u ~ al/¢] to the Gibbs sum for she acceptor. In the neutral condition A OF the acceptor, one electron is missing from the surrounding bonds. Becauve {hetmissing electron may have either spin up o spin down, the neutral condition '5 represented twice in the Gibbs sum for the acceptor, by a term 2 x 1 = 2 Hence the thermal average occupancy is say =, 20lle = aey 24 eaplix = eR] ~ TF Dem ition A of the acoeptor, (22) ‘The neutral condition A, with the acceptor orbits! unoccupied, occurs with reobability 2 1 (0-3 Seale aR Tia ‘The value of An = ny* — n,~ ihe ulerence of concentrations of D* and A From (40) or (42) we have nef") = “4 EMSA) ee (4 8 ratte a (63) ‘The neutrality condition (4) may be rewritten as We nen em my a, 46) ‘This expression may be visualized by a logasthmie plot of i and? as func tions of the position of the Fermi level (Figure 13.6), The four dashed lines ‘epresent the four terms in ($6); the two solid lines repcesent the sua ofall positive and all negative charges. The actual Feim) level occurs where the total positive charges equal the total negative charges. For my — a." > ny as in Figure 13.6, the holes can be neglected; for ne” = 14" > my the electrons can be neglected. If one of the two impurity species can be neglecied, the majority carrier concentration caa be calculated in closed form. Consider an n-type semiconductor with no acceptors, The Fr Figure 136 Graphica determination of Ferm levc and electron concentration i an mype semiconductor containing both donors and acceptors, ‘euteality point in Figure’ 12.6 is now given by the intersection point ofthe w* curve with the n, curve. Ifthe donor concentration isnot too high, the inter- section will be on the straight portion ofthe n, curve, along which the approxi- mation (17) holds. We rewrite this as explult) = (ndndexpleysh: “ explle ~ ie] = (n/ngenpfle, ~ ee] = 48)mn Chapter 12: Semiconductor Sates” where acorn U6 = aie neexp(~ Seyi) 49) i th eleton concentration tat would be pe the Fermi level coincided with the donor level He fonization energy. ‘We insect (48) into (44) and set ay nt in the conduetion band if lore Aty =, ~ és the donor =" to obtain a (0) 9 Ament = Ainge on) ‘This sa quadratic equation in nthe positive solution is He = INH + Brinn? — F For shallow donor leet tis lange and close ton, the doping is sufficiently oak that Sy < my * the square root may be expanded by use of (tal eieepe ye (9 fore 1. With x = Siyin* we obtdia ning nl = 2 64 seni tei inthe parentheses gives theft order departwe rom compete Table ty kame, for P in Si at 300K, we have do) = 1.14 from Toni 132. co that nyt = 17S, rom (48). I == Ola, Ee 34) pedi hat ILA pat of the donors cemain unionized, The linit of wesk loonie the subject of Problem 6, Coutl pore GaAs be prepuce t would have miperstuc of, = 10cm * With soca low ctl the conductivity would be closet to at seagate, haa 103 conventional smcondectn Inisisc Guat wowld be wena Ther dg aus 00 which to prepa thin tyes of doped Ganson needed ey ee ‘These does nol exist a technology to patiy any subwanee to 10 ener pee soncentraton of easier, 10" es than a Poa Junctions Sith ce ati achieve near asc cater consettions in Gadsby doping Tren eetaeatons (10-10 en ofexysen and chromium teeter roc or SEALE icc mpurty tess aco he mile ofthe eneety ep Onaee eas SISRIRAE oor Is Gads as expected fom the positon sf O ithe areas a Sahel As the cetyl isabout 07 eV blames Chromiom inane ines nergy level sbout 88eY below ayiscalled semi-insulting GaAs andi used exteosvely eiamet ently OO" 1 1" Oem) state fr GaAs devices A sna dong pe ‘lute posible in t, with on taking the ple of cheousaaee p-n MINCTIONS, Semiconductors used in devices are almost never uniformly doped. An under sanding of devices requires an understanding of nonuniformly doped semis conductors, particulary of structures called p-n junetions in which the d foping ‘changes with position fram pty Pe Comtype within the same crystal. We conaidor 2 semiconductor crystal inside which the doping changes abruptly at + 0 from a uniform donor concentration ng to a uniform acceptor eoncentertion in Figure 13.7. This isan example of a p-n junction, More complicated \evioe structures are made up from simple junctions: a bipolar tunsinis hag ‘wo closely sped pn junctions of the sequence p-n-p of pon a junctions contain 2 built-in electrostatic potentit step Va even in the absence of an exterally applied vohiage (Figure 13.78). With no externally Applied voltage, the electrons on the two sides ofthe junction ace in difsive ssuilibrium, which means that the chemical potentials (Fermi levels) ofthe two Sides are the same, Because the position of the Fecmi level within the band Seucture depends on the focal doping, constancy of the Fermi level forces a hit in he electcon energy bands in ccossng the junction (Figure (3.7), Th INS el The potential step of eight e¥, isan example ofthe potemtial sep seauited to equatize the total chemical potential of two systems when the intrinsic ehemest potentials are unequal, as discussed in Chapter 5. 8 Zecca J-Apyt Phys. 4,197 (9TH). The encey assign issomeuhat uncertain aoO ot) © © @ Figure 137A p-»juscion. (6) Doping distribution eis assumed at the doping changes abruptly fom w-yge ta pype. The two oping levels ar usually diferent. Elestestatic penal The builtin volage Vy establishes difuive equilxiom betwsen the ‘wo sides with diferent electron concenratsns.a wel as hole ‘concentrations () Energy bands Besaute the Feri level must be ‘onstant throughout the stactre the bands on the two sien sre ‘tied relative to eachother.) Space charge dole required to ‘everate the builtin voltage and to shit the energy bands ‘We assume that the wo doping concentrations ny, nie in the extrinsic but nondegenerate range, a8 defined by Meme NS ME MK Hy 5) Ifthe donors are fully ionized on the m side and the aeceplors fully fonized on the p side, then the electron and hole concentrations satisfy mM WEN, (65) fone on the n side and the other on the p side. (We have dropped the superscripts -£ from ny 1g) The conduction band energies on the w and p sides follow fram (1: fa =H = toto “n fie = = elon) = j= elonindngy). 6s) by 020, Hence eV = clogtnngin?) (59) lost (60) For doping concentrations ny ~ G01n, and n, ~ O0Ln,, wend eM ~ ¢, 92, ‘whieh is 091 eV in silicon at room temperature, A stop inelectrostatic poteatal is required to shift the band edge energies on the two sides of the junction relative to each other. The electrostatic potential ‘9(2) must satisfy the Poisson equation ee & (sy . (61) ‘shere pis the space charge density and ¢ the permittivity ofthe semiconductor. ‘Space charge must be present whenever @ varies. In the vicinity of the junction, the charge carriers no fonger neuteaize the impurities asin the bulk material ‘The space charge must be positive on the w side and negative on the p side (Figure 13.74). Positive space charge on the m side means that the electron concentration is less than the donor concentration, Indeed, as the conduction usa6 Chapter 13: Semicondacor Staisies Aeverse-iesed Abrupt pon Jncton a band edge is ated relative tothe fed Fermi level, (17 predicts sn exponentiat decrease ofthe electron concenteation ,, ‘The field £ isthe same a Take the origin ofthe electrostatic potential atx = — Sifon the n-type side all electrons had been depleted Then (x) = 6,(— co) — ep(x), and (17) becomes : 7 7 7 nie= neato o mE -(Zm-u) w=218)". 09 ‘The Poisson equation (61) is wrth no depletion at] > w,. The distance misused i semiconductor device ae 7 {hsofy 884 measure ofthe depth of penetration ofthe space charge naming Re bund] = S41 ~ epleoia 69 layer into the msde, 7 : Similarly, on the p side, Multiply by 24d to obtain * i ~ 290)". ay do d* ‘dy? ' eres (2) iia ze ve exter} ad ‘The total depletion width vs, + wes Integrate with the initit condition g{~ cc) » 0 200 1 2 cen 7 Hfiveassume n, = ny = 10'Scm~3;¢ m Heaiand Vis — 2cfe = 1 volt we tind At the interface x = Owe assume that 425 x 10*Vem™' and w = 4.10 x 10cm, ~ #0) = > fe, (66) Reverse-ased Abrupt p-n Junction bets Ys that part ofthe built-in electrostatic potential drop that occurs on eresbttad ie tetida at i : St t voltage V be spplied toa p-n junction, of such sign thal the p side is ata ‘hen side. The exponential en the right-hand side of (65) can be neglected, and negative votage clave tothe olde ate ee V raises the potential laid {terey ofthe clectronson he pside. This vltage wll drive condition electrons Es [enfeh, ~ spe]? (6) from the p side (othe » side, and hols fom the m se to the p side. But the _Psids in bulk containsa very low concentration ofconduction elections and the n side contains a very low concentration of holes, consistemt with the mass Action law. As a result, very lite curent flows. The distributions of electrons, [Oem ~ yey, 6s) Roles and potential are approximately the sme ifthe builtin voliage nore F_inereased by the applied voltage, Figuce 138, The fel the mee ene given by ‘orale component ofthe ceettc field # = ~dyis atthe atesfue, Similatl, ‘hers, is that pact ofthe builtin electrostatic potential drop that occurs om {he pads, The Ww Eels mus bs the same; from this and fom Vz 4 ¥, = We find (Fete 200)” ) U1 a= ava)”, ) etmus Chapter 13: Semiconductor States Figure 1.8 Reverebised Pu junction, showing the quasi-Feem eves and pp. and the junetion thickaess is given by v= GPU ag” 2A + Yiu = 2ofe} fen 2) (74) In the semiconductor device literature we often find (73) and (74) without the term 2r/e, because certain approximations ha ‘charge and field distribution; we have solved ‘correct electron distribution (62, Wve been made about the space the Poisson equation with the Carrent Flo: Deifiont Dison NONEQUILIBRIUM SEMICONDUCTORS, Quasi-Fesmt Levets When a semiconductor is iluminated with fi ight of quantum energy greater ‘than the energy gap, lectrons are raised from the valence band to the cand. tion band. The electron and the hole concentrations created by illumination fare larger than their equilibrium concenteations, Similar nonequilibriuin con. centrations arise when a forwatd-biased p-n junction injects electrons into a P-type semiconductor or holes into an mtype semiconductor, The elect charge astociated with the injected carrier type attraets oppositely charged cavriers foom the external electrodes of the semiconductor so that both carrie concentrations increase. The excess carriers eventually recombine with each other. The recombination 8 vary greatly with the semiconductor, from less than 10° sto longer than 10"?s, Recombination times in high parity Siare near 10-2, Even the shortest recombination times are much longer than the times (~ 10s) required at Foom temperature for ths conduction electrons to reach thecmal equilibriom with each other in the conduction band, and for the holes to reach thermal fi. (7) ‘Wit the quasiFermi distibuions (19 this condition i expressed as Bo BP em ey 38) 3a Chapter 13: Seuisontater Staite Election now Figure 13.9 Double heterostuctre injection laser lets flow fom the ‘igh inte the active layer, wheve they frm degenerate econ pa. The potential barrier provided by the wide energy gap onthe pide prcients the {lecrons fom escaping tothe lef. Holes fw from te ef ito the sctive layer but cannot estape tothe right, When (88 i atained, laser neon becomes posible. For laser action the quesiFesmi levels must be separated by more than the energy sap. ‘The condition (8) requires that at east ene ofthe quanti levels inside he bos to which it sefers This is necessary, but cota sullen condition for lasee operation ‘An important additional condition is thatthe cnecgy gap fa ditect gap ether than #2 indivctenp. The distinction is teted in slid state physics texts, The most important semiconductors wit a dcec gap are Gans an InP. “The population inversion is max easly achioved inthe double heerostroctuce of Fig ‘e139; ere the lasing semiconducoris embedded between two wider gap semiconductor tseions of opposite doping. An exemple is GaAs embedded in ALAS. In Such a tdcute there is «potenti! barter that preveis the oxfiow of electron tothe pye region, and ‘an opposite poteatat barcist that prevents the oullow of holes (othe nigger rege, Exoept forthe current eavsed by the recombination al, the clestonsin te serie yee ‘cin dilusve equilibrium with the electrons in the m contact, and the cectton guess. Fecmitevel inthe active aye ies up with dhe Fer level in the cotac. Silay, he Yalener band quas-Ferm level lines up with the Fe level in the peoniact Iavecion ‘in be achieved if we apply a bss voltage large than the vlloge equllent ofthese layer enery gap, Most injection lasers uz this double etersiuctre principle, Sem Examples Cater recombination though aniparty ler ‘combine ether by an election falling iecly ino 4 Hole or tiey can recombine deough an inpirty lev! ithe ene ‘dominant silicon. Wediseus the processas an nstrctivectamplcofqussteaciiorcg, seoicosdestor statics. Comider an impurity ¢ecombination etl at chery gat Figure 13.10, Foue transition process are indicated in the figue. We assume thatthe ste Rat which conduction elections all nto the recoabination abies descbed 3 law ofthe form Eletromt anid holes can se- ith the emission of photon gy wap. The impuity process = Dndte (89) Inbete J the fraction of recombination orbitals already occupied by an elton fad hee not availabe, and is 2 characerste time constant forthe capture proces, We assume the everse proces proceeds atthe re R, fbi, (90) heres the ime constant forthe reverse mess We tte ssnttatfon of conduction desiens, beeaase we au rethatn, fi (a) Find the net ionized impurity concentration dn for ‘which the conductivity is # minimum. Give @ mathematical expression for this ‘minlimurn conductivity. (b) By what factor isi lower than the conductivity ofan intrinsic semiconductor’ (e) Give numerical values at 300K for Si for which the mobilities ae j, © 1350 and 7 = 480m! V"s" and for InSb, for whieh the mobiites ate 7, = 77000 and fi, = 7S0cm?V"!s~*, Calculate missing ‘data fom Table 13.1 2. Resistivity and impurity concentration, A manufacturer specifies the te- siatvity p ~ Ho of u Ge crystal as 20 ohm em. Take ip = 390m" V's * and fig 1900em? V! 5~?, What is the net impurity concentration a) ifthe ‘exystal is n-type; b) if he crystal is p-type? 4. Mass action law for high electron concentrations. Derive (39), which is the form of the law of mass action whea 1, is no longer small compared to 1. 5. Elvetron and hole concentrations in InSb. Calculate tg ny, and js ~ efor inype InSb at 300K, assuming n> = 46 x 10!%em™> = m, Because of the high ratio n/a, and the narrow energy gap, the hole concentration is not negligible under these conditions, nor is the nondegenerate approximation n,n, applicable. Use the generalized mats action law (39). Solve the tan scendental equation for n, by eration o graphically 6. Incomplete ionization of deep impurities, Find the fraction of ionized donor impurities ifthe donor ionization energy is large enough that Ae, is larger than rlor(nj8n) by several times «. The result explains why substances with large impurity ionization energies remain insulators, even if impure.388 Ohepar 18 Semiconductor Stasis 7. Built etd for exponential doping profile semiconducior tie jon and falls off exponential built-in cectie fee in the i 10° and x, — xy Suppose that in a paype ag MELO concentration atv = xy ism," ane soe Hy 40 a value 2," = 1m ab xm ws What is ne serval (xi? Give numerical valuts for n/n = 0; ea Assume T = 300K. Impurity distributions sich Tesin cea te bate rsion of many n-p-n teansatory The bane field ‘aids in driving the injected electrons across the hace &. Einscin relation for high electron concentrations approximation (38) 10 give & series expansion of the ‘concentrations spproaching or exceeding Use the Joyce-Dixon ratio Dyfi, for electron oti laser. Use the Joyee-Dixon approximation to cateulete aT 300K the electron-hole Pair concentration ia Gas that satisfies the inversion ‘ondition (88), assuming no ionized impurities 10. Minority carver lifetime, inasemiconduetorare raised by minority carrie lifetime t by eattiee concentrations ng and ny; ‘expressed Uy ny* anc my and the seul and very large values of Bu, Under what dent of bn? U1, Electron hole pair generation, electrons and Inside a reverse biased pon junction both pl.out, (a) Calculate the cleciron-hole pait tions, assuming n,* = my* and t, = 1, eneration rate is higher than the genetation fom which the holes have been swept out, ation remains equal to 1° 3 m, (e) Give 4 Siwith n° = 108% cm" Chapter 14 Kinetic Theory KINETIC THEORY OF THE IDEAL Gas LAW Maxwell Distibution of Velocities Experimental Verification Collision Cross Sections and Mean Free Paths ‘TRANSPORT PROCESSES Pacticke Dittsion ‘Thermal Conductivity Viscosity Generalized Forces Einstein Relation KINETICS OF DETAILED BALANCE, ADVANCED TREATMENT: BOLTZMANN TRANSPORT EQUATION Particle Diffusion Ctasscal Distribution Fermi-Dirac Distribution Electrical Conductivity LAWS OF RAREFIED GASES Flow of Motecules Through a Hole Example: Flow Through a Long Tube ‘speed of a Pump SUMMARY PROBLEMS 1. Mean Speeds in « Maasetlian Distitution 2. Mean Kinetic Energy in a Beam, 3. Ratio of Thermal to Electrical Conductivity 4. Thermal Conductivity of Metals 5. Holtzmann Equation aad Thermal Conductivity sceamuceces 301 an 394 395 aT 399 407 08 409 410 aul 4B 413 aus 416 417 419 419 20 20 20 at90 Chapter 18: Kintic Theory 6. Flow Through a Tube a2 1 Speed of a Tube 421 Tami conscious of being dnly an individual struggling weakly against she siream Of tine, But tall remains in my power to contribute in such a way that, when the theory of gases is again recived, not too much will have tobe rediscorered 1. Boltzmann Kinetic Theory ofthe Ideal Gos Law In this chapter we give a Kinetic derivation of the ideal gas law, the distribution. of velocities of gas molecules, and transport processes in uses: diffsion, ‘thermal conductivity, and viscosity. The Bolizmann transport equation is lscussed. We also teat gases st very low pressures, with reference to vacuum ‘Pumps. The chapter is essentially classical physics because the quantum theory of transport is difficult, KINETIC THEORY OF THE IDEAL GAS LAW ‘Weapply the kinetic method to obtain an elementary derivation of the ileal gas tow, pY = Ne. Consider moleiles that sista 2 unit aren of the wall uf container Let, denote the velocity component normal othe pane ofthe wal sin Figure 141. 1a molecule of mass Ari reflected specully (ntcor ke} from the wall the change of momentum ofthe molecule ss 2M 0 “This gives an impulse 24 0 the wall, by Newton's second law of motion, The pressure on the wall i 2 (Prcae") ("tar aeate ps JP rmopaa\e, = M f o,atedMe, 8) ‘The integral on the right is the thermal average of times the concenteation, s0 that p= Mnco?>, The average value of $Me? is fr, by equipartition of wtwn Figue tt tolecole of velocity «which is elected from the wal ofthe container is Chepter He Baste Theory was The change of momentum ofa energy (Chapter 3). Thus the pressure is PRIM) = n= (NM); pm Ne @ This isthe ideal gos taw, ‘The essumprion of specular reflstion isconvenent, but itis immatetial tothe Tea hat Comes into the suze mest go back, with the same dstibuting ‘thermal equiibsiwm isto be maintained Maxwell Distrib We now wansform the encrey distibution function of an ideal gos into a Jy erate + Sa Biad(— pir), 4) SAR Pe 3) Hore F, and F, are generalized forces defined by F Beadle); gradl~p/ 66) as05 Elastein relation 1m an isothermal process F, in (46) may be writen es F, = (~1)2)aradp on, jn terms ofthe internal and external parts ofthe chemical potestial, as Fim (Uo faradjig + grad jy) a For an ideal ges jig ~ slog(nfng), so that gre jy, = (rn) grad for an lectrostatic potential grad gy = 4 grad @ = ~GE, Thus (Yen gradn = oF] (49) ‘Now the particle fux density also has two terms, written as Sym —Dygradn + nf . 9) where D, is the diffusivity and 2 isthe mobility, which isthe drift velocity per unit electri feld, The ratio of the coefiients of grad. to E is Dy in 49) ‘and «/ng in (48. These ratios must be equal, so that Dy» sila (50) which is called the Einstein relation between the difusvity aad the mobility fora classical gas Comment. We sain an advantage, for reasons tated tothe thertodyeamcs of erevers ible processes, if we use F, and Fy in (6) a6 the devng forest the liseae onapert processes. We write We Luk + by See Laks + LaF, on ‘The Onsager dation of teeversibe thermodynamics is that 1,48) = Lyf-B) (2) whete B is the magnetic eld intensity. IfB = 0, hea Ly = Lg aways. For (52) to hold, ‘the driving forces F must be defined a in (46). Other defn: ofthe forces ste pte valid, such a the pat grad «and rad m, but donot neces lead to eon that satisty the Onsager relation. For a dev in the general references, see the book by Landau and List cited ines of Bette Batance KINETICS OF DETAILED BALANCE, ‘Consider a system with two states, one at energy A and one at energy ~A. In tn ensemble of NV such systems, N* are at A and N” are at A, with N N* + N7. To establish thermal equilibrium there must eaist some mechanisra whereby systems can pass between the two states, Consider the rate equation for transitions nto and out of the upper stat AN dt = aN” px, 653) Where a, may be functions of the temperature, The transition rate from — (0 + is directly proportional to the number of systems in the ~ state. The transi tion rate from + to ~ is directly proportional to the number of systems in the + slate, In thermal equilibrium CdN'* jdt) = 0, which can be satisfied only if AB = (NTYIENT) = exp 240, 69) ‘the Boltanann factor. This result expresses a relation between 2(s) and fe) that ‘must be satisfied by any and every mechanism that assists in the transitions. As an example, suppose that the transition + + ~ proceeds with the excitation of & harmonic oscillator from a state of energy se to a state of energy (s + Ne; in the inverse process ~~ 4 the oscillator goes from se to (s ~ UJe. In the ‘quantum mechanical theory of the oscillator i is shown that B_Probls-+s41) 541 BPs 1)" for the excitation and de-exctation of the oscillator, 2 result derived in most ‘exls on quantum theory. The valve of ¢5) i found fram the Planck disteibution: 1 expleie) Onset OF Saagy—T so that, with ¢ = 24 to conserve energy, GIB = (SKS +) = expl~2A/0, 65) ‘This satisfies the condition (54). ‘The principle ofdetaited balance emerges.as a generalization ofthisargument: in thermal equilibrium the rate of any process that leads to a given state must 40708 Chapter Hts Kinetic Theory equal exactly the rate of "tse process that leads from the state. One common application of the inple isto the Kischhof? law for the absor; Br Riston of ration by a oli aleeadydacussed in Chovies radiation sec, wavelength that is absorbed stcongly by a slid will co og emitted Trenulyatherwise the specimen would heat up becauseitcouldnor coe nto ‘heemal equilibrium with the radiation ADVANCED TREATMEN’ BOLTZMANN TRANSPORT EQUATION Te clsscal theory of transport processes is based on the Bolan transport selon rast Qtk in the si-dimensional space of Cartesian coordinates ond “stosity The cssical distribution function fis) is defined by ihe ehatoe Aesde de = number of particles in dey, 50 Fis Boltzmann equation i derived by the following argument. We conser Te GUE ofa tine sisplscement dwn the dstibutionRinction: The Leek, theorem of lasseat mechanics tells ws that ifwe follow a volune element along A flowline the distribution is conserved: SOF die dey + a) = flee), 657) in the absence of collisions. With collisions JOH Ate dt + aN) = S089) = ANETIED tn (58) Thus AMELIE + be grad, Fd grad foe (39) Let adenote the acceleration dvd; then rad Fa gad, f= (eA) (60) ‘This fs the Boltemana transport equation Jn many problems the collision term 2), may be treated bythe nto tion ofa relaxation time r,(¢3), defined by the equation Cid = ~~ fale (61) Tae PariteDiffesion © HF Ne note that Jo/et = O by definition ofthe equilibrium distribution, This {equation has the solution F~ I= UF ~ foroesml—ie)) (@y tis not excluded that 5, may be a function ofr and ¥. Tee SGmPIne (59. 60, and (6) 10 obtain he Hotemann transport equation in the relaxation time approximation: oH In the steady state ft = 0 by definition, Paiticle Diffusion Consider an isothermal system with a gradie int of the particle concentration, ‘he steady-state Boltamann transport ejuation i the telanation ie approxi: mation becomes eadflts = Af ~ fete 5 63) [kere the nonequilibrium distribution function f varies along the x dicetion We may write (65) 0 frst order as Lee h~ trdhelle (66) iste we have replaced dix by dafde. We ean iterate to obtain higher onder solutions when desired, Thus the second onder solution fg Si fo~ vathlds fy ~ cells + 0.22 olde. 67) The iteration is necessary forthe treatment of nonlinear effects,10 Chapter Ms Kinetic Theory Classica! Distetation [Let fo be the distcibution function inthe classical limit So=expllu~ eye}, (6) as in Chapter 6 We are at liberty to take whatever normalization for the ‘istribution function is most convenient because the transport equation is linear in f and fo, We can take the normalization as in (68) rath than as ia (681. Then Loli: = (Wy fduNeylas) = (foods), © ‘nd the frst order solution (66) for the nonequilibrium disteibution becomes L = fo~ ey hal Mepis). (70) ‘The particle Mux density inthe x dveeton f Je = foro, om ‘here Dies the density of orbitals per unit volume per nit energy range De) (rye. fy 48 n (7.65) for & particle of spin zero. Thus AF = fofoDonte ~ cytes) [los feOiate ce) The fist integral vanishes because o, isan odd function and fa ian even fan: tion of v,. This confirms that the net particle flux vanishes for the equilibrium distribution fe. The second integral will not vanish Belore evaluating the second integral, we have an opportucity to make use ‘of what we may know about the velocity dependence of the relaxation time t, Only for the sake of example we assume that r, is constant, independent of velocity; may then be taken out of the integral. ~Guldyes) fof Dee. a4) FerniDirae Diaribuion ‘The integral may be wri 4 feVOleMe = a JeMereDede = nt, 03) because the integral is just the kinetic energy density $nr of the particles, Here {Bunt = ns the concemteation. The pate fon density is Jet = (0A dull) = (eed MK , 2) because = slog + constant. The result (76) is ofthe form of the diffesion ‘equation with the difusivity D> tam KD co) Another possible assumption about the relaxation time is that itis inversely proportional tothe velocity, asin Instead of (14) we have Ifo, where the mean free path fis constant. Sm —Cdnfasytey FlochafoD(ede , 78) ‘nd now the integral may be written as 4 foeDiade = Je « where? is the average speed. Thus Jaf = —MlEn/s\dufdx) = —fletdnjdx) , (80) and the diisviy is D= Ye. (81) FeemiDirac Dis bation ‘The distribution function is fo Sees WET (62) anm (Chapter 14: Kinetic Thery ‘To form die a8 in (60) we need ie ervatve dg. We argue below tat oldu = dle ~y). ®) iow temperatures «, it fole tows that ODN = (MY gf"? ry20 Chapter Me Binet Theory tee fsullscan also be obtained directly from the expression in Chapter 3 for value ef aes ine energy ofan ideal gas. (8) Show tat the mont eae value of the speed gy is = Quay (129) drerbere table vale of the speed we mean the sasinun of the Maxvelt Speeds” 854 fometion of Notice that soy < ya 6) Show th eee speed 2 is 2m [oon (Brann, 2y ‘The mean speed may also be writen a (|). The ratio Caml? = 1.086, (122) (2) Show that %, the me "an of the absolute value of the 2 component af the velocity of an atom, is fed = Fe = Qrimag. ay ‘slosty component normal tothe axis of emission, What i the nea re Sreney Comet: Toe molecule in the bexm dost collide snd are not nse ‘ermal equilibrium afer they have exited from the oven, The gos et ena down ar ected with respect to fast molecules, andthe residual gas will col dlown its not reheated by heat Rowing in tough the walls ofthe oven, Panter oftHevial to electrical conductivity. Show for 2 classical gas of particles of charge q that Kita = ¥2q?, or K/To m Skyhp29? (124) ‘conventional units for K and 7. Thisis now asthe Wiedemann-Franz rato, Sculermal conducrisity of metas. ‘The thermal conductivity of copper at patsmperatute is taegely cari by the conduction electors, one per stom, “Themean free path ofthe electrons at SUOK is of the order of 400 10. Bom Probiems The Conduction electron concentration is 8 x 108 perem?, Estimate (a) the Owhen the temperature ofthe planer « (is varied periodically vith time as 110.) ~ Ogcoewr a Which is the real part of Opexp( fa, for real @y, Then in the medium 2 > 0 the temperature is Os8) = Oo Refexpfit: — wt} = OaRefexpli®(o/D)"*2 — fet) , wy where Re denotes real part snd 197 = (j — 1YWY5. Thus, with 6 = (20/0), tex) = 0 Referp(—='S)expLHsi6) ~ iat} exp —/8)costeat ~ 2/5, «3 ‘The quantity 5 = (2D/e)"* has the dimensions of len characteristic penetration depth of the temperature variat amplitude of the oscillations of@ is reduced by e~'. The characteristic depth ie called the skin depth if we are dealing with the eddy curvent equation, The ‘wave is highly damped in the medium—the wave amplitude decreases by e°* jn distance equal to a wavelength/2x. I the thermal difusivity of sol is taken as D = 1 x 10°2em?e~' penetration depth of the diurnal eycte of heatin, Cooling ofthe ground by the night sky ( th and represents the on: at this depth the thea the ig ofthe ground by the sun and 013 x 10°* 5") 15, L(Giucnat) (20fa)"* = Sem, For the annual eycle, Hannval) = 1m, Development ofa Pulte A layer af 10cm of earth on top of a cellar will tend to average out day a ight variations of surface tempera , but the sunmuc/wsinsr Garsation atthe kop of the cellar requires several meters of earth, Actual values of the therm Lifusivity are sensitive to the composition and conultion of the soil or rock Notice that a figure of merit for cellar consteuction inva! Giftusivty, and not the conductivity atone jes the thermal Development ofa Pulse Inaddition to the wavel © solutions of the form (9), the diffusion equation has Several other useful forms of solutions. We confirm by insertion in (8) that Ols.t) = RDN“ expl—x44Do) a isa solution. The proportionality fuctor has been chosen so that Siac = 1 as ‘The solution (14) corresponds to the time development ofa pulse which att = 0 has the form ofa Dirac delta function (a), sharply localize at x » 0, and 22%0, celsewnere, ‘The pulse might be a temperature pulse, as when a pulsed laser or pulsed clectron beam heats a surlace briefly. Let 0 be the quantity of heat deposited on the surface, per unit area. The temperature distribution is then given by 0) = Q0/Cy\seDY-* exp(—x"/4D 0, a) where Cy is the heat capacity per unit volume of the material, The fonction is plotted in Figure 15.1. The factor 2 arises because all heat is assumed to Now inwards from the surfice, while for the solution (14) symmettcal flow was assumed, Another example ofthe application of (4s the diffusion of impurities deposited on the surface of a semiconductor, to Form a p-n junction inside the semiconductor. The ple spreads ou with increasing ine, The mean square value of xf sien by 6» Jorasante fasts» 200, on after evaluating the Gaussian integrals. The root mean square valve is Sim) = Gx)! = RDM. 419) a7Tine tndependent Distribution 29 a8 Ditfasion with a Fixed Boundsey Condition at = 0 IF & solution of (8) is diferentiated or integrated with respect to any of its independent variables the result may again bea solution. Animportant example is obtained by integrating (14) with respect to x: 0 = (uD Pacexpl—etA09 \ we [Lasexp(—s) = feta, 20} ve ‘where a = 3/(400", Here we have introduced the error function dfsed by erfu he expl—s4h en ‘Tables of the error function are readily available, The eerarfanetan has the properties ecf(0) = 0; tim ec = 1 2) OF particular practical interest is the difusion of heat or of pasticles into an infinite sold from a surface at x ~ 0, wih the fixed boundary condition 0 = Og Fime ISA Plot spread of temperate pulse wil ing foe 4a os 4 solution is from Ea (86). Ate = Othe pulse sa delis oenon’ : » ae 80) = BoE ~ exfbxjt40n)!”9) 03) fo 3 Again we see that the distance at which O(x,) reaches a specified value is propor- ml ‘ional 1)", The application of this solution the diffusion of impurities Feral gS sons tha te wid of dgebtionnmenser at? ta areas gipleation ahs ston Feoalth = (2Dig)"7NU , a9) Vw 0, a4) Tr ees Slacrent is proportional to the sua sot of he number of steps ioe Srowsisa motion, the random motion of finite medium bounded by the plane : = 0 and extending ; along the positive z ais Let the temperature vary sinusoidally inthe bouedaty plane: This i the test observed ia ss of ‘sespensions of small pasties in igus, 23)00 Chapter 15: Peepapation ‘The solution of 24) in the mediuea is Axa) = Oosin kxexp( ka), 0° ‘The temperature variation is damped exponentially with the distance from the boundary plane. The temperature distribution inthe time-independent problem ust be maintained by constant heat sources on the boundary plane 2 = 0, PROPAGATION OF SOUND WAVES IN GASES Results developed enter inthis book can be applied tothe study ofsound waves in gases, Thermal effects are important in this problem, Let dp(x) denote the Pressure associated with the sound wave; the form of the wave may be wtitten 4p = Spoceplitkx ~ ex) , ey where kis the wavevector and ois the an in the x direction, We suppose the equation of state i that of an ideal gas gular frequency. The wave propagates PY= Nr, or ps pyMt, ) where p = NAI/V is the mass density, and M is the mass of a molecule. The force equation referred to unit volume is £20 pe as ox Max eo Here u is the x component of the velocity of volun element. The motion is subject to the equation of costinity dplor + div(pn) = 0, eo) ‘rin one dimension, Aploe + Apuljax an ‘The thermodynamic identity is aU + paV = ede, (2) Propegation of Sound Wares in Gases which cam also be written aoa vteye 62) Hf we assume (pending discussion below) that there is no entropy exchange ‘uring the passage of a sound wave, Eq. (526) becomes Cuesta) + (ni Me ren = 0, (3) where Cy isthe heat capacity at constant volume, per unit volume, We can re- ‘rite the second term in terns of 2f2t because p = NM/V and(L/V\(QVj61) = ~(Up\@e/61). Now the thermodynamic identity appears as Cutes/60) ~ ipipneplen) = 0. (4) Letus define the factional deviations 5, @ by prrllta: rm alt, os ‘where po toate the density and temperature in the absence of the sound wave, Weassume that us, have the form ofa teaveling wave: expfilke — wl]. The ‘hsee equations (2), (31), (34) that govern the motion now become ~iope + iLspo/Ms + (pra/Mi0) = 0; 69) ips + IM(pous + pu) % O; en ~icwteCy8 + i(p/p)pgs = 0. (38) ‘We assume that at sufficiently small wave amplitudes it is a good appeoxima- tion (o neglect ia these equations terms in the squates and eross products of 4.s,and 9, Foresample, pu m pg(t + shu becomes pyuit the cvoss product suis neglected, The equations thus reduce to, with the subscripts dropped {rom pands, ou ~ (be/M)s = (&e/ANO 9) os — ku = 0; (40) CO ps0; or G8 = ms «a arar Chapter 15: Propagation ‘here is the concentration, These equations have a solution only it © Guayte, @ where = (Cr+ miCy =» Cy, in our units-The velocity of sounds = cry) ay eset pple to monatomic gases fom the lowest fequencies up to bigh {sihensis ited ony by the requirement thatthe seoustcwarceneinane Ue uh larger than the mean fice path o he slows This ruinonenr ae Fe on Lo the applicability ofthe hydrodynamic approach embodied inthe force equation 29} ‘Thermal Relaxation Iuih polyatomic gases (43) i valid at fw frequents, but a8 the frequency is Sateased there isa transition frequency region above whith me velocity uf quency peepee i Hao region beeen low fequensy and heh fe ‘WUeNY Propagation is associated with relaxation effects “Vhermal relaxation describes the establishatent of thermal equilibrium ina team Eneray cssipation esos when al paris ofa ysten aay same Seaperatare; the dissipation i strongest when the period af ae heating and near ib Balfssele inthe sound wave i comparable with hence requiced for Hex exchange between the diferent degrees of eedon of wee system. In Polyatomi gases under standaed conditions there are tine lays of the order role te Wanser of energy beteen the meena vibrator en ofa ‘molecule and the external transtation states, [etthebeat capacity andtemperaturery = cll + 8,)reorto the fncernal bevanres Ne Gr and t= cat + 8) elec to the translational tees Thon GH becomes Caleeaset) + Cylerfe0) ~ (wyphapien = 0 , 9) of, in place of 9), ~ieteC, ~ iwraCy0 + etp/ppes = 0. «s snapose thatthe tcnsfer of nergy between the internal and exteena tates has ‘he characteriti tune delay fg such that fem —e— ny, 9) Thermal Retasation fo, = 0 ~ 8)ite «a (nero called the claration ine, These wil be separate relaxation time for ths sotatioaltrensstional raster and the vibrationaltenlational mre, ‘We combine (39), (40), (48) and (47) to obtain the dispersion tehatoe aaty CES 4 tata PO) a ee eB (a) ete Cr. Cy tle to the (anslational states atone tn the low fequency init te and Fs Me) LES spicy 1 With) SIE = fio « 169) Ter Ta ts lw tequeney Lint of the total heat capacity ratio (C, + C\)h (Cr + Ci). The tow frequency timit ofthe velocity of sounds 2,0 Goel M8, 50) In the high frequency limit wig > and A = OM MANCHIC) = witty oh. 61) Here ya sefers any to the translational states; thigh fequescies the internal Salsa not excited bythe sound wave. The high equsney limit ofthe eloty of sound is fo) = (nip 65) ‘Yoluss of 7 are given in Table 15.1; if mo interna states at all ate excited, ‘The waves atenusted when kis compen; the imaginary pact of k gies the Pressuce attenuation coefficient a. From (48) it i$ found that the menimuen Bbsorption per wavelength occurs when «w= 2x/ty and is given appeoninecty by (idan 6, ana8 Chapter 1: Propagation Tatle 154 Ratio C, Cy a yor gases Gar “Tenperatue,C ‘ie C 403 Ho 10 bu ny 1‘ vag 0; =181 vas 1s Naor 200 1395 200 1303 5 308 5 vest ~ 180 168 on: Fora mositenisideal gas, C/Cy = 39 = Le) foe Ai ane He ora dsome gar topcase High eoushoexcetheraraionamation Cor = 8 = 1 1 oe Ox and Hl a toom temperatures at ltnperateres Jute ih ie eile also the biatinal” motion GyiSp = B01 = 1a fr Oy a OO Trevaoer gel {ate int of fw Gequeaccs For very high eequney ‘ound wavs onl the Wandionl moien f eacied and Sis appican For CO, as at the elaxationtrequeney of 20kHtz under standard conditions the intensity is observed to decrease by I/e in about 4 wavelengths—a massive absorption, in agreement with theory. Example: Hest wansfer in sound wave, Equation (3) expresses the senteopi asuimp- Won: the equation neglect the thermal conductivity which gies rise to tome eesaaer of ‘ermal energy within the sound wase between successive avin ad cool half eytes The assumpionthat ds = Omuustbemedificdo ake account ot hen ow. Tacheat eandvetion ‘equation (5 may be writen as fact = n26/et. s) whore @ is the entropy devsty. The (04) becomes ColGs/B8) ~ (nlp K2o/80 = K(O*t/O8*) , tart ye + ops = = Kek29, 59) oe mraa( EH), 6 with 1 = Koa Atlow fequencies WA isawch smalls than Cy, sothatthesound socty is equal to the benteopi tlt s, = (¥/A0" a before The enditon WA! & Cy ental the eaition 2, where Ti the mlecuar mean fice path and 2 the wave length ofthe sound wave. The attenuation ofthe pestureosiation i given by the inary portatthe wavevecior kandi denoted by 2 The seul om (6) in thelow feqveney region WE? & Cy iethat, 2 big NoKutrere, , co ovhere Crees 0 unit sole SUMMARY 1. The heat conduction equation isthe patil diferential equation that follows when the phenomenological transport equation (here the Fourier few) is combined with the equation of contiauty. We obtain & pn Fawr; , 2. The time-dependent diffusion equation and the eddy current equation have the same fort, 20 that shee solutions may be translated from the solutions of the heat conduction equation, thes being often mote familiar in the Tierature. 3. Frequently it is usefil to construct solutions in the form of superpositions of plane waves of the form expfithe = a) ‘The differential equation then gives the relation between «and, called the ‘ispersion relation of the problem. 4. The propagation of sound waves in gates depends on the rate ofexchange of energy between the translational, rotational, and vibrational motions of a moleculs. A low frequency sound wave is described by isentropio, and not ‘sothermal, parameters-a result thal seems paradoxical at first sight. ais6s Chapter 18: Propagation PROBLEMS 1 LGmter analysis of pulse. Consider a distribution that at the iii tie represented Sy en OF & Dirae dels funtion Ssh dlia Tunction ear ne Fepresented by a Fourier integral: O50) = dix) (68) tote times the pulse becomes Os dkexplitkx ~ wt)} , (59) on, by ws of (10), Osi) =}. avenptitx ~ Dk%p, oo) scans the intraral to cto th est (19). the method can be extend to describe the time development of any distribution given at L000) = fav foemse — x9, 1) ‘The time development of St ~ x) is Me ~ 2) = (xD)Feapl te — xy ADd 2 © U9) Thus at time the distribution f(:0) has evolved to Als) = (&ndy~* fds fo hexpl Ce = x)}/a0N (3) This isa powerful general solution 3 Bison in two and svceaintesions. (3) Show that the difsion equation jn two dimensions adhnits the solution 6, (Cyftlexpl rape) oa, and in three dimensions Bsf0) = (CP expl— (Ai (63) Prosems {D2 Gilaate the constants Cy and Cy. These solutions are analogous to (14) ‘and deserite the evolution of a delta inction at t= Reafemperatere vaviations in soit. Consider a hypothetical climate in which omnthedlyand theannua vaviations ofthe tempetatureare purely scarry Huh amplitudes 0, 10°C. The mean annual temperatats Be Hee eae shethermal ifsivity ofthesoit tobe |e 10cm? s-! Whatikthe isin ‘éepth at which water pipes should be buried in this climate? & Cooling ofa slab. Suppose a hot slab of thickness 2a and initial uniform (fmperature 0) is suddenly immersed into water of temperature 8, <0, Restby eeducig the temperature a the surface of the slab abruptly (0°2, and keeping it there. Expand the temperature in the slab in a Fourier series. After some time all but the longest wavelength Fourier component of the temperature will have decayed, and then the temperatuce distribution becomes sinusoidal Afr what time will the temperature diference between the center ofthe slab and its surfece decay to 001 of the initial diference 0, Og? 5, pn junction: difsion fom a fixed surface concentration, Suppose sili cou usta is ptype dopsd with a concentration of mz = 10%*em™* of boron ‘tons Ifthe eeytl slab is heated in an atmosphere containing phosphors ‘toms the latter wil dffse as donors with a concentration nats} inta the semis conductor. They will form a pn junction at that depth at which ny 2 Assume that the difusion conditions ace such thatthe phosphorus conser tion at the surface is maintsined at m0) = 10'7cme”. Take the ditescn cpeficient of donorstobe D = 10 .ems~ What isthe value of the sonstort C inthe equation x = Ce, where x is the depth of the pn junction and the time? 6: Heat difasion with internal sources. When internal heat sources ate pr ent, the continuity equation (5} must be modified to read (66) ‘whete , i the heat generation rate per unit volume. Examples include Joute heat generated in a wire; heat ffom the radioactive decay of trace elements {nse the Fart or the Moon. Give an expression for the temperature tise at he center off) eslindrical wie and (b) the spherical Eaith, on the assumption that g, i independent of position anu is constant with tine, 7. Ctl sce of mctear reactor. Extend the considerations ofthe preceuing {obi to particle diffusion, and assume tha there is a net particle generation ale y, that & proportional to the local particle concentration, g, = Wty, where ‘is ¢ characteristic time constant, Such behavior describes the neuteon gener ‘Hon in nuclear reactor. The value of ty depends on the concentration of 254) arus Chapter 18: Propagation nuclei if mo surtace losses took 5 expliffgh Consider a reactor i Ut surface losses pin the neut 4 (3) if augmented by a gene place, the neutron concentration would grow in the shape ofa cube of volume f and assume ison surface concentration at zero. Show that ation term 95 = ng, has solutions ofthe form NUE) explrt,)eos(k,r}eosth,s}eosth, 67 where Au. Kyl and kL are integer multiples of , Give the functional depen- dence of the net time constant ty On ky, fy. ke dd f, a0 show that for at feast one ofthe solutions ofthe form (67) the neuteon concentration grows with tine iC L exceeds a critical value boyy Expeess Ly a8 4 function of D, and te In ‘actual nuclear reactors this increase is ultimately halted because the neutron [Beneration rate g, decreases with increasing temperature, Appendix A Some Integrals Containing Exponential aw ‘THE GAUSS INTEGRAL Let fos [USempeestas = 2 fete o The following trick is used to evaluate Fo Write (1) in terms of a diferent integration variable: ten flew, @ Mul (1) nd (2) and conver the esl oa dosh integra Wha fDerpi—eids [Teapt—y dy = [27 [esp ~ (0 + pide oy) ‘This isan integral over the entre x-y plane. Convert to polar evordinates rand 4 a8 shown in Figure A.1. Then, x? + y* = 72, and the area element d= dy bevomes dA = rrp: I= Lt Sioesrt-r et = on fPexp( =r Because of dfexp(—r?)] = ~2expl—r)rr, the integrel over ris elementary’ Wena faencon = fea "Pexpl=x')de = 2 [2 expl—aide = x 0“0 ‘Some ftegrals Containing Espenentias The Stkng Approsiation a Form = 0,1 Js om (4) [tye ara = mis aneven integer, m = 21 > 0,nisa halFinteger, end. by repeated application of 7), with the aid of), that fy Frowe At Theares dement JA « edi fy 2 [Mexp(= sds = [Par terray “MEDC D ROAD debe Form = 1a = 0; = 2 Pxerp(—stydy = [fenrdy = Puy a1 (10) Ionian odd integer, w 214 1 & 1, nib an integer, m1 03nd we find stmiany, with the aid of 10), GENERALIZED GAUSS INTEGRALS, 1 2 fet exp(—atya = [verry AND GAMMA FUNCTION INTEGRALS Foor 2 fat tear(—atyds = [2 SMe Date (den 2xten an Inderal ofthe frm ‘The gamma rcton for postive integer argument i simply the fictoval ef n= 2 [Seerv(—x)dy, i> —1), o P the integer preceding the argument. \whete m need not be an integer, may be reduced tothe Widely tabulated gamma THE STIRLING APPROXIMATION ‘setion Tic by the substitutions x? = y, 2d = yt Foc rg valet oft can be approximated by he [oven erwey, ne > pp, 6 {he itearal in(8)may be viewed a the definition of) for noniateger positive (12) values of. q ‘The gamma function satisfies the recutson relation Mo +1) = aro o y Lift : logn! = Hogan + (n+ Slogn — n+ a +3) (1%) ei Resi obiined form > 0 om (6) by iteration by pri and its used to 7 entend the definition (6) of A Hays poate due gee ci ee ame Hew the e128 the st te of am expansion by powers of 1 and interval <2 <1 7 (Un stands for omitted higher order terms in this expansion, of ordse Iu?a Some Inecrals Containing Exponentats or Rizher to practice, even the term 1/12n is usually omitted is priscipal '8 to check on the accuracy of the a sortection introduces only a chan expression has the desired securacy. ‘To derive (12) we write, in secordance with (11), role :pproximation. If the effet of the 1/t2n, we below the desired accuraey, the entne [vets [etrie, 8 Se) = nlogs = x, ag We make the substitution nb ante nll bye, dem why a Then J) = nloen = m4 obs). i where (3) = aflogtt + 0°) — yur} « ‘With thes, exeL sO] = w'e-rexpfaun) . as) nim nl ite-* f°, explaty)d: 0 Tre function () has iis maxinwum at y = 0: gf} = 0. Using the Taylor expansion of the logarithm, log +s) s— hs ade bt pee, em) with s = (9/9), we expand 9()) atin SE eg) | = -b? + 08%. en The Stcing Approximation In the limit. -+ eo, #40, anch all but the first term in (21) vanish, end the integra in (19) becomes Faeelouny = [Pex 2) 2) With the sid of). 1 (22) is inserted into (19) the result is identical to (12a) except {or the correction term 1/12n. Its derivation is a bit tedious. We so ek with Joga! and write laeh= tees ae ne 2 40) ey ifwe replice n by n~ 1, loge = Dt = Hogzn + (n= slog = 1) — = 1) A soft tote (3) 235) We subtract (23b) from (233): Wn = os ~ Dt = wat = oan = (2+ Blogn ~ (1 — login — 1) = 1 Agape old), es ‘where all omitted terms are now at least of order I/n?, The two terms in A cam be combined: 4 TG) A 25) this is inserted into (24), we find 4. Dion By-1 + (5) 6 4“ Some Inteerale Containing Espanevtas =the ton en (a Hlog (28) {Chis is inserted in (26) we ste that A = 1/12, ‘We are often interested not in nl but only in tog, ‘uch thatthe relative error between an approximate ‘ue value decreases with incteasing Such sn a ‘eglecting all terms in (12b) that increase and only to an aceuracy Value of login! and the ximation is obtained by less eapidly than linearly with magn ~ (29) Appendix B Temperature Scales DEFINITION OF THE KELVIN SCALE lomerial values of temperaturet* are notexpressedin practice inteems ef the fundamental temperatarer, whose uit isthe unitofenergy, butonis absolute) by this defisiton, T, = 273.16K, exactly. This temperature 6001 K sbene “Tiuospheticpressure Geezing point of water (the ke point, Ty = 27M IS “The ile Point is mote easily nd accurately epeoducible than the ce poise ‘The triple point establishes isc automatically in any clean rower rat wattally backed with pute water aod cooled uatt port but natal ok IPs Neri ozen leading to an equilibrium between solid ies guid water ‘and the water vapor above the ice-water mistore “The Cebus temperature sealer is defined in tems of the Kelvin scale, by te T= 2315K, o ‘Temperatures om this sale are expressed in depres Celsius, symbl °C, Terme erature dflereness have the same value on bath Kelvin and Celsius Seales is conversion factor ky between the fundamental temperature ¢ and the Kelvin temperature, r. 2 [Ne tppssinte te asisance of Norman €. Pipe inthe preparation. {Ue lots suey ofthe vat af desogment ol plese tengo -custingsaeeitereaonalsjposimiahing pace sey ks joensen ae Teena ode aera ume roceeioge ate pute unde te H15C,0. Esch, ior: Reool, 1940 Tht whume lesion eae TG Gite Hes 185 Atbugh oa tngeedecng ihe ante aban nee ae eLeaie Deceeth today dicuutes of passe of san eatheoe cyacaraTets nat allo whi ate repeated he ner suum Ved Speen ae ref femba 892 Ferbane the mont ctl vlan bc of te aneinnay ae amatheearles meats ftengerstire measures Ya (Spay He Pose a oe anett Sosy of Ameri, Psbungh, 172 Most sic lr pecnnag ne Ran vat bods of tenpsatre meiitenen;consns er mtcdaceey ee a ‘han Vet his sppendin, smeaturement 6 she 4s5 Temperature Scales is called the Boltzmann constant. [ts numerical value must be determined expstimentally: the best current value ie he 1.350662 4. 0000044) x 10°! eg K a ‘The value of the Bol mann constant is determined with the aid of certain model systems whose structures are sufficiently simple that one can calculate the energy distribution of the quantum states, and from it the entropy as a function of the energy, @ = o(U). The fundamental temperature as a function, Of the energy is 1(U) = {Co/éUi)-'. Examples of model systems used ia the termination of by ace te following (4) Meat gas. In the limit of tow particle concentration all gases ideal pases, satisfyiog pV — hy iT: Onc obtains ky by measuring the p¥ product ofa known amount of gas at a known kelvin iemperature 7, extrapolated to ‘anishing pressure. The determination ofthe nuinber of particles N invariably involves the Avogdco constant N., independently known, ) Black boty radiation. We can obiain k by fitting she meusured speeteal ‘istibation of a black body of Known Kelvin temperature to the Planck ‘adistion law (Chapter 4) Because this kaw involves «through the tata haa/t = ‘alka, tis determination requires the independent knowledge of Planck's (© Spin parumognetise. tn the tinit of vanishing interaction the magnetic moment M of a system of ¥ spins in a magnetic field B, at temperature t's ives by Eq. (3.45). Various paramagnetic salts, such as cecous magnesiom nitrate (CMN) are good approximations to noninteracting spin systems if the temperature snot too low. By iting measured values of M asa function of B/T to (46) we can determine the ratio n/t ‘1 Whete in is the intrinsic magnetic ‘moment of the elesteon, now independently. Usually only the foweld Porton is used in which ease the number of pins must also be Known, Whi involves again Ng. Precision results require cortection for weak reid spin Interactions, salar to corrections for particle interactions in gos The fy valve given in 3) is weighted average of several determinations Withan uncertainty ofabou 32 pars permilion it sone ofthe least accurately ‘own fundamental constants, Mos of this uncertainty is due tothe diel’ of the measurements and tothe nonidealty of the systems used for these measurements About 5 parts per milion are due tothe limited acouacy with which and Ny are known SER Cohen and BN. Tayo, J Pips Chom Rfrence Data, No. 4(1979, Primary and Secondary Thermometers When expressing temperature as conventional Kelvin temperature T rather Yan fundamental temperature x, it i¢ customary to absorb the Boltzmann constant ito the definition of a conventional entropy 8, s “ The relation 49, de between reversible heat transfer and entropy transfer then becomes 4g = Tas, ° PRIMARY AND SECONDARY THERMOMETERS Any accurately measurable physical property X whose value is an accurataly ‘novsn function of the temperature, X= X(T). may be used asa thermornctrie Parameter to measure the temperature of the systein possessing the property X an of any system in therwial equilibrium with it. Used in this way, the Syatem with the peoporty X is m thecmueiet, THe principles andediving fe wiost commonly used thermometers ate listed in Tables Bub and B2. The {hsemomcters listed in Table B.2 are called secondary thermometers, defied 8 thermometers whose temperature dependence X(T) must be ealibrated ‘empisially, by comparison with another thermometer whose eatibeation is aleady known, The calibration ofall secondary thermometers must ultimately be traceable to a primary thermometer. But once calibrated, secondary thet- mometecs are easier to use and are more reproducible than the primary ther- ‘mometers available atthe same temperatuce Any calculable model system that can be used to determine the value ofthe Boltumenn constant kg can be used as a primary thermometer, and the three ‘model systcins discussed above are the mast important primaey thermometees (Table B.), ‘The precision and scouracy of thermometers vary greatly. Precision is ‘expressed by the variation A observed whenthe same temperatuce is measured a ferent times with the same instrument, Accuracy is expressed by the twnceriainty AT with which the thermometer reproduces the true Kelvin scale Secondary thermometers based on electrical resistance measurements may achieve @ precision of 3 part in 10%, ‘The precision of thermometers based on ‘mechanical pressure measurements is much poorer, particulary at low pres ‘ures, For example, helium vapor pressure theiniometers at the lower end of thei useful range have a precision of about | part in 103, The accuracy of secondary thermometers is limited by the accuracy ofthe primary thermometers we‘Table B.1 Principles ofthe most important primary thermometers “Temperature ange used Ex] equation z a sa gar +1400 220 7 2 é oooi-a -<0001-005, oon’ Metals: Cu, 7h, Pt By Nuslorsps Bleek body rad 1300 cocpeneneeste reesei sn Thermodsnanie Thermorcey TaileB2_ Principles of the sort important secondacy ermometers Physical property Thermoelectric valtage of thermocouples™ ‘Thermal expansion of liquid in glass Eisai estanee, octal Semiconductors (german! commercial estbon ester” spor pressure of Viqueed gas tte 7 He ‘ott: The rperatore ranges are approniane Bot inate imi, TEs838ntepoltinginsruen in the SPTS. wnat LEE Sot bert herman ach seinen ngs of ide wit, Ther ult them. The accuracy of primary thermometers i finite by thet elatively poor precision and by residual variations between dite, iheemometes. As a rough estimate, the present-day necursey of primary {hermometesis about | part in 10* above 100K, about | part in 10! armen 1K, and about 1 part in 10? near 0.01 K. THERMODYNAMIC THERMOMETRY {c's possible to perform primary thermometty without keying on the theoreti: cally Known propertis of simple model systems, by somehow utlzine the ‘elation (5). We give these examples, ) Carnot eyele. Consiloe a Carnot eyete opscating between a known tome serature T, and the unknown temperature [Because ofeatopy conservariey ihe Beat transfers atthe two temperatures Satisfy Qy/T, = Oy/Ts The we nowa tempessturs can be usterimined by measuring the ratio et ewan ‘cansfers, The method is not very practical, (8 Mapsetic calorimetry. Suppose a paramagnetic substance i italy {iow temperature Ty, ina magnetic fll 8, Let the substance be ete by ‘entropic demagnetization to the unknown temperature 7. Ifnow » tone480 “Temperstare Seles ‘mall amount dQ of heat is added to the substane, its entropy is raised by 4S = dQ/Ts, The substance is then isentropically resmaznstized, and the "magnetic Bela By is determined at which the temperature has returned exactly to Ty. The field f), will be found slightly diferent than 2:8, — By + a0 Entcopy conservation requires AS = AQIT, = S(T ,.By) ~ 5(T By) = (€5/60) 4B. 6 From the thermodyoatnic identity y for the Helmholtz fee energy for a magnetiz« able substance, dP a ~Sur — seo, o one obtuis, bythe usual crose-difecentation, the Maxwell relation (S120), = (OMIET ® ‘We insert (8) into (6) to find the expression forthe unknown temperature T, = eoUumyomyer), ®) ‘Thequantities (Oat T ~ TyanddBacT = 7, derivative of Mf at T a 7, and B = B, is easily measured. The method makes fo assumptions about the ideality of the paramagnetic substance, and it has therefore been used extensively at low temperattres, sare known, andthe temperature (©) Clausins-Clapeyron thermometry. Stance varies with pressure Chapter 10: The melting temperature T,, of « sub according to the Clausius-Clapeyron equation of AT gdp = TyAV/AH , 40) where AV is the volume change during melting, and AH the latent heat of fusion, IF both quantities have been measured as functions of pressure, (10) cat be integrate: Tait, =e [Maryam an ET, and p, ar known, a measurement of the pressure pat which the unknown Temperature Tis the equilibrium melting temperature permits calculation of International Pratieal Temperature Seale 1P7S) T, from (11). By utilization of the strona teinperniute dopendance of tolldifcation pressute of quid "He, the method has bees used as an alternative to magnetic thermometey at low temperatures INTERNATIONAL PRACTICAL TEMPERATURE, SCALE (IPTS) Many known ohase equilibrium temperatures ean be reproduced far more precisely than the accuracy with which ther exact location on the Kelvin scale ‘an be determined by primary thermometsy. To facilitate practical thermometty, number of easly reproducible phase equilibrium temperatures have been Setermined as accurately as possible and have been assigned best values to define an International Practical Temperature Scale (IPTS). On the 1PTS the selected equilibrium points ace tceated asi their temperatures were known to be exactly equal totheirassigned values. Intermediate temperatures are determined bby a precisely specified interpolation procedure that is chosen to reproduce the tue Kelvin scale a5 accurately as possible. The present version of the seale is HPTSO8, adopted in 1968 by international agreement, covering temperatures from the triple point of hydrogen (1381K) upward* Table B3 gives the assigned temperatures for IPTSES, In the range between 13.81 K and 90289, which is the melting point of antimony, a platinuin resistance thermometer is used as the interpolating {nstrunyest, Inthe range fom $03.89 K to 1337.88 K, the melting point of gold, 2 platinum-platinumythodium thermocouple is used. Above 133758 K black body radiation is used Beiow 13.81 K no precisely defined procedure has been agreed. {nthe range between $.2K and 1381K various seales based on the vapor pressure of hyclrogen are in practical use. Below 5.21 K, the critical point of *He, dossn to ‘bout 03K, the 1958 end 1962 helium scales* are widely used as de faclo exiensions of 1PTS68, The 1958 “He scale relates the vapor pressure of “He to the temperature T; the 1962 He scale uses the vapor pressure of He AAs the accuracy of primary temperature measurements improves, e€f0e8 in Practical scales such as IPTS become uncovered, leading eventually fo revision of the practical sales. Table B.3 lists some errors now believed to exist in IPTS68, 1 Se Gt eam, Amerion Ite of Pyles honloos, 2 of Mera Hi 1972; Seton eat MW. Zeman, elton Cntsing comple ona etches “stTemperature Scales able BS Assigned temperatures ofthe Laterationat Practical Temperature Sone uf 1968 Substance Type ink ‘hk fiydropen [> ina hystonen | 5050.00) | tron hydrogen | 2028 | neo ° 2202 | oxygen | se | oxygen | sos soler t TIS | exact ester 5 sais | boss fn £ sasuisi | oos sine L 2a | ooss silver r ‘ot old x 138 22% Easy fr ie pois ad eT ulna te oie ema ane ae pestonsasngs Palcgrint eaten at Bh teers tnd ssn pois sitar nota ae ee) Al ds rom te Jide. McGaw the lst colon eoeaing esses ftom Phys Today 29, a. 19 tmercwn bie if Physics hanook, B72; Seton tc Hes MW. Zemmey, Appendix C Poisson Distribution ‘The Poisson distribution taw is a famous result of probability theory, The result 's use in the design and analysis of counting experiments in physic, bistogy, ‘operations research, and enginecring, The statistical methods we have developed lend themselves to an elegant derivation of the Poisson law, whichis concerned with the occurrence of small numbers of objects in random sampling processes, {tis also called the law of small numbers. If on the average thece is one bad Penay in 4 thousand, what i the probability that N bad pennies will be found in ‘ given sample of one hundred pennies? The problem was first considered ond solved in a remarkable study of the role of luck in erieinal and civil law tials in France in the carly nineteenth century. We devive the Poisson dietsibution fay WHN Ie 310 of a model system that ‘onsite ofa large number R of independent lattcesitesin thermal and difusive contact with a gas, The gas serves as a reservoir. Each lattice site may adsorb 2210 oF one atom. We want to find the probabilities PO, POY PQ. POM. ‘ata total of G1, 2,...5 M,..., atoms ace adsorbed on the & sites, if we are siven the average number (2V) of adsorbed atoms over an ensemble of simitar systems, Consider system composed ofa single site tis convenient to set the binding energy of an atom to the site as zero. The identical form for the distribution ie found if a binding eneray is included in the calculation, The Gibbs sum is bea, a where the term 1 is proportional to the probability the site is occupied, and the term 1 is proportional tothe probability the sites vacant. Thus the absolute probability that the site is eccupied is fa @ ‘The actual value of 2 is determined by the condition of the gas in the reservoir, “ssa Poison Ditibation because for diffusive contact between the lattice and the reservair we must have attics) = Ae, ® by the argument of Chapter 5, The evaluation of 1 iver in Chapter 6. Wenowes (g25) for an ideal gas was tend the treatment to independent sites. Then Su Fede Fae @ By the argument used in Chapter 1 we know that the binomial expansion of (0 + @)For( + ay counts once and only once every state of the system of A sites, Bach site has two altenative states, namely © for vacant or @ for occupied, which cortesponds in the Gibbs sum to the term 1 for 2° and the term 3 for 3, In the low-oceupancy limit of f « 1 we have f whence AN) = R= AR o 's the average total number of adsorbed atoms, The Pofsson disteibution is concerned with this low-occupancy limit. We eatt now write (8) a aR Nyy ba- (AF (6 @Y. ® concemed with infeequent events! By the defiition of the exponential function wehave 0 so that Bus en) = gan = ‘The last step here isthe expansion of the exponential function in a power series Poison Disetution 45s ‘The term in 2 in Gua is proportional to the probability P(N) that N sit are occupied. With the Gibbs sum as the normalization fetor we have in the Tint of barge PR exp) an » or, Because 2R PUN) renew) (10) ‘This isthe Poisson distebution aw, "= Particular interest attaches to the probability P(0} that none of the sites is oceupied. From (10) we find, with (9° = band 0! = J, FCO) = EXP(—CNDI, 108 PCO) -(N). ay ‘Thus the probability of zero occupancy i simply related tothe average number 1 we have P(0) = expl—) 9) ln atcement wth (14), PROBLEMS 4, Random pulses. “A radioactive source emits alpha pacticles which are counted at an average rate of one per second. (a) What isthe probability of )/8 closely approaches a Gaussian function in foe for large (WV). That i, show when Ais lose to GN) that PUN) = Axel — BN ~ (NDF), where A, Bare quantities to be use the Stirling of (NS functions determined by you. Hint; Work with log PIN); proximation. [athe Gaussian form both Aand Bate functions in the development of the Poisson function you may find A, B are ‘Of, but the two forms ofA, Bae closely equivalent on Which the exponential factor has significant valet yer the range in Appendix D Pressure were Leta pressure p, be applied normal to the faces of a cube filed with a gas oF liquid ia quantum state s. By elementary mechanics (Chapter 3) the pressure is equal to Bm ~duyav , w where U, isthe energy ofthe system in the state s. We ean also write the pressure a Pam ~(@U/aV), @ where ((U/AV), denotes the expectation value of dU/dY over the state s at Yolume ¥. 1 is iuypovtam that we can cateulate p by (2) which is at a fixed volume with no ambiguity about the identity of the selected states, whereas (yinvotves following thestate through two volumes, Vand ¥ + d¥,with some possible doubt whether the state remains the same, The ensemble average bressure p is the average of p, over the states represented in the ensemble P= ke) = —KaUfa),) o Because the number ofstates inthe ensemble constant, theentropy isconstent, so that the derivative is at constant entropy. We may thetefore write p= (2 “ (or); ‘The result (4) uses the energy of the system expressed as Ule,¥,...); that is, ‘3 « function of the volume ¥ and the entropy o-not the temperature tI is the enttopy snd not the temperature that is to be held constant ia the diferentiation. The equivalence of (1) and @) i an example ofthe Hellmann Fey tnechanie according to which he deine af he hamfiniae se Se fespect 10 # pacar dae relied by dUfel = (Ufa. Toe derwaion maybe ued oo 102 oC. Coben-Tasnowd 8. Dis and F Late. Quantum mechanic, Wig, 111: e280 E Merabacher, Quantum mechani, tod ed, Wily, HE pa 49450 Appendix E Negative Temperature PY of a spin system as a function of the Ghiee Gegmetnelic Feld is pled herein Figure 1. Notice the region ig Sfuch ol?Uy a negative Figure £2} Negative means tha the porcine Of the upper states greater than the population ofthe lover state, When condition obtains we say that the population Figure E.3, The concept of negative tem that satisfies the following restr ipper bound on their energies, lom ofa particle can be ata negative tempera, ‘Thus only certain degrees of feed on r= 40 020d 8 Enessy U—— FigeteE.1 Entropy as faction of energy fora two sate system The sepatation ofthe sates ise = in ths example fn the {efthand sds of the gure ?6)2U is positive, so that «is postive On he right-hand sie ca/2U ie negetive and e & negative Negative Temperature wer + T t ! Leb | ~6 7 Figure E2 Temperature versus energy forthe avo sate stem, Here Gi 7 a), ee otc that the eney iso a min at Satisamaximumat eo {wre: the nuclear spin orientation in a magnetic field isthe degree of feedos: ‘ost commenly considered in experiments at negative temperatures. (6) The system must bein internal thermal equilibrium, This means the states ust have occupancies in accord with the Beltzmann factor taken for the appropriate negative emperatuce. (¢) The states that are ata negative temperature must be lated and inaesessibfe to those states of the body that are at 4 postive ‘temperature, The ordinary (anslaional and vibrational degrees of fredom ef « body have an entropy that increases without limit as the energy incteascs, in contrast ta the two state or spin system of Figure E.1, Ifa increases without limit, then ¢ slways positive: The exchange of energy between a system at a negative ‘emperature and a system that can only havea positive temperature use of402 Negative Temperorre VETTE ddd Figue £3 Posible sin disribotions for various postive and egatvetemperatar ‘The magnetic eld i diceced upward, The [ebalve sin temperatures cannot ae intnitaly bernie of weak ‘coupling between spins andthe atic. The late con only be ate Postve temperacure beaut its energy level spectum is Usbouraed (top. The downvarddtecied spins as at r= —rj,tuen over one by one thereby elasing energy tothe alice and opocaching

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