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Thermal Physics - Kittel PDF
Thermal Physics - Kittel PDF
. The ent number of states in we have deseribed. We the pressure on a systern mai ‘Welook for other expressions for the pressure cutrapy depend only om U and on ¥, for a fixed number of particles, 30 t only the two variables U and V describe the system. The eiffeensial of UU) = (3) we en i difforential change of the entropy for arbitrary independent chats WU and dV, Assume no Thermodynamle enity «cancel. The overall entropy change do will be zero. If we denote these \ependent values of JU and d¥ by (SU), and (SV), the entropy change w be ze: o= (2) un. « (S)n. es Air division by (GV), °=(a)ent * GB), ” But the ratio GU, /BV), i constant a: respect to Guy, l= (2U/av),. 69) With this and the defi ion Ife = (2o/2U)., Ea, (29) becomes (9-0) ” and side of 31) =p. whence Pp» (), 02) donlav stay, 63) or oros Chapter Bottonann Dis ‘This useful reation wil be called the thetmody nan variable will oppear in (5.38) A simple AU = cdo ~ pl¥, of dU = Tas ~ pa. (G4) the actual process of change of stat of the system is reversible, we can identify edo asthe heat added to the system and ~ pV as the system, The increase of energy is caused in part by mec Part by the transfer of heat, Heat i defined as the transfe tio systems brought work done on work and of energy betwoen, HELMHOLTZ FREE ENERGY The function 6s) 8 the part in thermal ses at constant temperature that the energy U plays in ordinary mechanical hare always understood to be at constant entropy, because no 3 of state are allowed, Fy = dU, ~ tag 69 at constant temperature. But 1/r = (2ey/2Us)y, $0 that dUy = ede at com stant volume. Therefore (36) becomes aF,=0, ey Which is the condition for F to be an extremum with respect to ‘¢constant volumeand temperature. We lke F Because we cen calculate from ‘the energy eigenvalues ¢, ofthe system (se p. 72) Conmem, We can show Cyd Uy Thea th © oy + oy = eal ~ Uy) + o4lUs) & ot) ~ Usleag/ Ulin + aU Wekuow tat (ani?Uady = a soy) ~ Felts neigy ofthe syste Now oa( sayy ina get etd it~ Don whe “Thee energy fonction (tbe eed 1 ~ teh ov ),f racat~ aan (04am f(r tthe minimum of F632) withsexpect Goce energy eh Thats, Filed) ) = FB beens) ina ‘minima of F with espect othe pla eacrscscrs whet N+25 (Leahy = O= ~InB + clog ES Sy es)u($ +3) —(G= ol funetonbecomes equal is Pres Eseray 1 The tal ences fs U 08) 09) isconsants and we am sa maim wit respeet 10 Ue falls orn hemos probable energy af paramagnetic stent. Conse the 69(Chapter 3: Fotcmana Disnibation and Helmbols Free Energy ‘Thos in the magnetic field B ermal valu ofthe spin ences 2 ten by N+ Qo co = aaa ), a) Wo ea = PNB: ert &% on dividing numerator sn denominator by expln8th 25) = Neon 5) ++ exp(— mye) = 2eosh(n Bye, ro) Now ese the relation F = clog a derived below. Mull by to obtain the reul oC N magnets (The magnetiaation is derived more simply by the method of Prabion 2) (34a), dP = -odr ~ pdVs (48) (S--2 (B=. en Lo eee rewind ge of volume; contrast TT Caleaation of F from Z may be written a5, (0) by use of Fa U ~ ta, hand side of (50) represent ‘what wo may call the energy pressure and the entropy pressure, The energy pressure ~(6U/2V}, 1s dominant in most solies a (Opy pressure 20/2V), is dominant in gases and in elastic polymers such as rubber (Problem 10), The entropy contr the importance of the entrory’ the naive feeling from it AU JAY must tell everything bout the pressure is seriously incomplete fora process atc erature, because the entropy can change in response to the valume change cv ‘nergy is independent of votume, as far an i (ole), = pee obvious, Other Maxwell ations by similar arguments. The methodology of of namie relations is discussed by R. Gila, 3. Chem, Phys. 5,596 where 2 ”85) satislies the 6 lfeeatia equation 32), would appear possible for Fx to contain an additive constant « such F = =rlogZ + at, How entropy must reduce to loggy when temperature isso lowe Z = expl— Fn 69 1) for the occupancy probit of a quantum sales = expl(F - 23/4). sn, IDEAL GAS: A FIRST LOOK One a ina box. We calevlate he partion fonction Z, of one atom of ‘mass M ffee to move ina cubical box of volume ¥ = £2. The orbitals ofthe fee particle wave equation ~(iPM1)6%9 = bare Wyre) = A sin(agns L)siniylL)sin(n.nz/L) 658) where M, not give tegrs, as in Chapter 1. Negative integers do jon, The enecey ne) 69) ler structure of the atom, so that a state of the he valves Of Malan: A Fst bagk By Provided the spacing of adjacent eneesy values is small ws may replace the summations by integrations: 20 fam, Ma, [da enel a n comparison w Thenotation a? = may be ‘i'x*/2ML3zis introduced for convenionce, The exponential asthe product of three factors expla? hexpl— 2% Vexpl= 2, 4 = cr fraconine) ae, By ry = mgY = @ + yar = Nav = Malm» terms ofthe concentration n = 1/¥. Here No = (Mspaany | (63) om ina cubs of side equal to 1 . ‘which i @fength roughly equal to W/ALCe) ~ HA", Here Ce) isa therm miconductor theory, and For helium at atmospheric pressure at room temperature, m= 25 x 10"em™? and i = O8 x 108*em™, Thus, wig = 3 x 10°% which is veryhae fatemen Dito ed Het Fe Engg td Ga Fo Lk = ‘all cmpar io unity, so shat sum is vey ite unde noc ondtons : 7 > Whenever ng Vve say that the ge inte hea ree, Wea : : Sedofied ana go of nniterating soa lathe dea hk ‘ae then aseage energy of the atom inthe bon ! Foret? Aa. pace stn fe ties nh oe pen enh Yeveipl—eie) ofS boxes Toecrtapng forone pale ance vn» aang zea, co because 2,~" expt ey 1 probability the system isin the state n.From(62), Figue38 Atoms ctaifecent species ia Jog Z, = —flog(l/e) + terms independent of « , single box, ‘so that for an idea! gas of one atom [p=] ea He = byT, whece ky is the Boltemann constant, ‘known result for the energy per atom of an ideal ges. ‘The thermal stom ineachof di he patton fasctionis the separate one atom pact Zena Zt) Zi) ZN) , (65) ‘cause the product om the right id side includes every independent state of the N boxes such 2 the ste of energy. equality FADE oI wn whore x Bs it of 4 x 10°* for the occupancy of an lard 60 ‘occupancy must he «1, We note that ey as de fora feee stom, 21) 2,1) 2,06) 24) , ‘ental, ofthe16 (Chapter: Roltomann Disebuton and Hetil Fee Energy in the casa regime, Here ng = (Me2aK° “Thete isa sep inthe si se stways rot introduced by this Energy. The energy of the ideal gas function by use of 12} U = H(elogZ,/02) = Ne , 6) '5)for one purticle, The fre energy is F = ~1logZy = ~rlog 2," + clog 70) With thea V = (Mfe?2eh4)>2V and the w approxima Fo ~eNlog{Me/2sh!}32¥)] 4 eWog a ~ en, a From the free energy we ean calculate the entropy and the pressure ofthe ideal ‘8 of N atoms. The pressure follows from (9) P= ~(CF/OV), = NYY, ~ or pene, | 7 eal Gass Firs Look scaled the eal gos fay my “The entzopy follows fromm {49} ° NaN, (13 o = Nilosiraie) + i] ro) with the concentration n = N/V. This result is known as the Sackur-Tetrode equation for the entcopy ofa monatomic esl gas Teagrees ‘The result involves fr through lg, 80 even for the cassical ideal the entcopy involves quantum concept. We shall decive tl ‘Chapter 6 by a direct method that doesnot expl argument. The energy (9) also follows fom Um F + x0; with use of th experima (7) and (76) we have U = Ne 7 of entry. ‘Theenerey U = 4Nefsom! ‘ution $s rom each “degree of feedom of each freedom ithe numberof eimensions ofthe space in whic Se In the class fom of ic ener ofthe particles ina For one fee particle 21 fffesvt= (ot + 0,8 + PVM doedeydp, 7) on are 00 for enh component, The thera average energy may be ealeuated by wr of 12) sn is equal o fe ‘Tae result generalize inthe lassical theory. Whenever the haritonian of thesystece {shomopeneousof degre 2in 3 canonical momentum componente sass lini et. thermal average kinetic energy associated with that enmmentn wil be fe Frthey ithe ‘amitonan s homogeneous of degre 2a postion eordiatecomporent the heal ‘sverige potential energy asocated with that eoardiate wil als be fe The cet thuss Chapter 32 Wend Hells Foce Enory Neal Gass A Fst took Vibe Rotation Mixing entropy 253015103250 Seo" 1000” 2500 So0g ‘Temperate, K Figure 39° Heat capciy a constant volume of one molesee of H. ‘he os pase. The veri ele ia fname in convemional units ruliply by hy. The cor Srarslations dee enemies eae ya fem thetno coaional epes ininom when Aad Bae presenta ext popatns (2 09, sind the entropy is Zev oe pure A ot pote ON) = NlogN ~ N —(N ~ log —4.N =e ~rloge +1 = Nlog. ~ (N ~ 1)logtv = 0 = togr = UN = logit ~ x) — Hoga) , In Chapter we calculated the number of posible arrange Bina solidimadeupot ¥ ~ ratoms A sad ¢stom B, We ound ia U2), ananen ot) = = = 9 4) + vlogs 180) aN = a oy = ‘This result gives the entropy of, “Thee hese arrangements {8,4 = logg(Nu) = log! ~ log — a! tose, 79) dis la n Figure 310 for ~ 28. This contribution ote total1 ” Pootens Foe Fo cols) = Fo + Nell ~ s)loglt ~9) + slosx] , : Ye must compa wih Fa(t~ fe tty Fe presuce piven by P= CURRY), = Hef 4 The Helmholtz fice energy is defined as F =x U — stant, V. oe» ~sNlogs (8 tec eoery is Zu = (QV PINE, Fl) = MOU + slo ee = NV «x mg. The quantum conc 5 (M/26h"P, Further, whic nasa mini when PY = Ne; Cr = aN. GFldx = NU + loge + x) =O, @) 8 is reve infinitesimatty close to the 7 ium state at X= expl—Hexpl= Ufa, (6 PROBLEMS aa 1, Fiee energy of a teo state system (a) Find an expression for the free \rBy a8 2 function oft of a system w SUMMARY Plo) = expe) temperature and magnetic field for the iS in @ magnetic field. The result for the magnetization is Af 3), a8 derived in (46) by another method. Her is the probability of finding a system in a state sofencegy e, when the system.a 10) as a tam sea fonction 05 18 is ‘Note that at high temperatures such ‘of the logarithm to obtain F = rlog(4u/r).(b) From (87) sow that The entropy is shown in Figure 3.13 and the heat capa 4. Energy flcteations. Pron " F z| 2 x t z 3 thom Figwe3.13 Entropy sero temperate fr harmon eater of fgucocy enuy or the ree energy & Fe tox{t ~ enh) sn hat «> hea we may expand thearguncat entropy 6 ay ~ Hoult ~ exot—). ro) Con: jut the term {by defnition docsim Chaper Prablems here to a rigorous definition of temperature, wx give the result a> = FIC, 0) but this shou!d be viewed as just another form of (89) with Ae set equ AUIC,, We kaow that AU & Cy As, whence (90) becomes {(AU}'> = 1 which he average number of open links, The n ‘of tworsteanded DNA molecsles—sce sts 37,817 (1969). mechanical or heat reservo mm of energy & Hece is some numerical factor, tamane factor for this abnormal we can add 4 to the eneray of 1 ‘eservoir passes tothe system the qua increase of enery of ned toa cube of side ergy ofthe particle ‘occupancy of lowest oxbital always has higher occupancy ip thus defined is equal to defined by (63), within factor of 9. Partition funtion for ZU oft Pls) 2c exp[—U0 ~ oer} ves the statistical Dass ofthe Overhauser effect wheschy 1 4 magnetic field ean bee: systems, Show that the part systems I and 2 to the system ftom an external source, said to be in a steady state, Cl. A. W. Overt 6, Rotation of diatomic molceules. I our frst Wook atthe ideal gas we con. ional energy of the particles. But mozeules ean rotate, systems: Zi + y= 20z0, 04% ter 3 Botersann Distibution and Helmots Free Energy of polymers. The dimensions tls = du ~ ar 9 ine and dis the extension of the ‘eto find (96) ‘The direction of the force is opposite to the con. pressure 2Nt 5) = 7 Yo) NT a) (61 For sl << N show that 3 = 10) ~ Fane. 03) Ww thatthe force at extension Lis = kN Chapter 4 Thermal Radiation and Planck Distribution Hem amen atta sore maT PLANCK DISTRIBUTION FUNCTION » PLANCK LAW AND STEFAN-ROLTZMANN LAW ” Enision and Absorption: Ktchholf Law 56 Estimation of Suctace Temperature 7 Example: Cosme Black Body Background Radiation 58 ELECTRICAL NOISE 8 PHONONS IN SOLIDS: DEBYE THEORY wor Number of Phonon Modes ts SUMMARY 109 PROBLEMS 10 1, Number of Thermal Photons 2. Surface Temperature of the Sun 5. Average Temperature ofthe Interior of the Sua 4 Age of the Sun 5. Surface Temperature of 6 Pressure of Thermat Ri 1 8 9 Free Energy of a Photon Heat Shields of Solids in High Temperature Limit of Photons and Phono ions in a Solid at Low Temperatures of Liguid “He at Low T Isentropic Expansion of Photon Gas Rellective Heat Shield and Kivehhof’s Law ‘SUPPLEMENT: GREENHOUSE EFFECT arn Chapter 4: Therma Ra ton and Planck PLANCK DISTRIBUTION FUNCTION spectrum of the ina cavtty. Approximately, it describe heated by a welding torch. “mode” characterizes a particula ox the eavty orn the solid. We shall always refer to. = 2af a6 the radiation. The characteristic feature of the rad of osc fon problem is that a mode of frequency w may be excited only in units of the qua energy fia, The energy &, of the state with s quante is the mode is where sis 2er0 oF any p energy Hi. “These energies are the same asthe energies ofa quantum harm of Frequency o, but 4 maa fe States ofa osilatr that % reprerent mode of requency w ofan 22 Ghctomagneti | the orbit of energy » tos photons inthe mode 1 eat -l »ic energy of Intotior of th earal thermal physics of language used to describe an excitation is different: sfor or is called the quantum number, and s for the quantized electro- magnetic mode is called We fist calculate the mode, ‘when these photons ae in thermal equilibrium witha reservoirata temperature «The pation function (3.10) fs the sum over the sta 2 = ¥ erst e 1 2 eap(shaliy 0 Planch Law and Sicfon man Lave ‘The probability thatthe system is inthe state 2 sof encray shao is given by d Boltzmann factor: “The thermal anerage ale of sis 6) = E srt = 2 Ssexpl—stoyey. With y = for, the summation on the : ay. Ysewi-9) = - LY From (3) and (5) we find a asingle mode of frequency ev. Equs ner of phonons in the mode. The result applies to any energy in the orm of (1), PLANCK LAI AND STEFA BOLTZMANN LAW average rey se ho 6» ho = 0 an(Chapter 4: Thermal Ration and anck Diaributon ay 0 Pia The high temperature limit + hus ie often called the class exp(ti/t) may be approximated as 1 + hule + average energy is in. Mere 1 whence the classical ae 6 ‘There isan infinite number of electromagnetic modes within any cavity, Each rode n has its own frequency o,. Far radiation confined within a perfectly conducting cavity in the form ofa cube of edge L, there isa st of modes ofthe form Jsin(n,ny/L)cos(neafL) (9) Here EE, and E, are clectrie field components, and E, E,p ate the corresponding amplitudes. The three components are dont, because the field must be divergence-free: Planch and Stefan Botznonn When weinser (9) into (10) and drop al common factors, we find the condition ay ilet of integers nest ‘hen the frequencies are of he form The ceneigy of the photoas inthe cavity is, 6 X66) = Epil) = T ad “The sum is over the triplet of integers Positive integers alone wil dsseribe all independent modes ofthe for (We replace the Hom O¥ET My ‘nym by an integral over the volume clement dh espace ofthe mode Indices. That i, we set xe A flomeant-9 a o* ‘octant of the space is Standard practice ist over a dimensionless variable, We set x = The defn © value Such as Dwight (cited in the gene ' the fourth powe of radiation. is defined as the eneray per us ange, and is denoted as u,, We can (2) “Theconstan Se Planch Law and Stfen-otts on as acy fe Taps ue %Chapter 4: Thermal Raiation end Planck a hole is said to radiate asa black body-—which ic of a thermal equilibrium dis rate of energy emission pet u Jo = [UY] (sors fst) en “The geometrical factor is equal to J; the der energy Bx is ation i the subject of Probh es by use of 20) forthe energy density U/V. The result is often writen a¢ Jy ants e, te Stefan-Boltzmano consta oa ay 60 (2a) has the value $670 x 10°* W m"® K~* or $670 x 10° exg em™? st K~* (Here 69 is not the entropy) A bods sa black body. A mia radiates at this rat is said to radiate jole ina cavity whose walls are in thermal equilibrium xe T will radiate as a black body atthe cate given in (26). The rate ion ofthe walls ofthe cavity and de- Emission and Absorpt ‘The ability of 2 surface to emit radiation is proportional to the ability of the surface to absorb radiation. We demonstrate this relation, frst ora black body or black surface and, second, for a surlace with arbitrary properties. An object ugh times front the cavity joss back though the hole. “The radiant ens energy flux from the Black object to the he thermal average energy fut from ‘We prove the following: If x non-black object at tem fraction 4 ofthe radiation incident upon it, the radi fed y a black body at the same ity, where the object ise times object must em a Mus emitted by U Fs to be we special ease of a parfect refisctor, ait ) = el) for any sueface ion of Surface Temperature One way to estimate the sutt temperature of a hot body suck as a star i from the fequency at which the maximum emission of radiant energy takes place (ste Figure 44), What this frequency is depends on whether we look atthe ‘energy Aux per unit frequency range or per ut energy density pr unt frequency cange, the maximum is given from th law, Ea. 22) a5, 3 - 3expl-x} = ”8 Chapter 2 Thermal Rai mand Planch Dsibuion eal Noi ‘This equation may be solved numerically. The root is T scone Permalhal Se 3282 | tester CN Cie measrements en asin Figure 44, ws oH eth radulion evolved inp cold by expaus eatops to atenperatute of? 9K T asin eatropy if the feguanc each mode the numberof photons each mode Lept con ithe nuncberof photons in ech Spocteal ox (Wen? seradian ca“) ton 29K Black bouy—~ whieh ate called noise, were dis HL Nyquist? The the peak, and were measured balloon bore infared spectrometer at fequenies above the peak ason and explained by esy of PE. Riches, of Jobason noise 8:2 dep 1B3, Seesons 27°90 ”loo (Cheptcr 4 Threat Radiation and Planch sx toy 4 2 5) é 2 ZL. *Carbon filament $ 7 +Adva | v C050, ia HO Se ore intuing eecticlstes Alter Apparatus. In the original form the Ny square voltage across a resistor of resi temperature # given by raat. | eo where Af is the frequency* bandwidth within which the voltage @uetuations are measured; all frequency components outside the given range are ignored Weshow below that the thermal noise power per unit feequency range delivered toa matched load i he factor 4 enters where it docs because fa 47, the power delivered tan achilzarytesitve lod is ayy oe DR OR ER ad which at match (R’ = Ris CV*Y/AR. nhs scion the woe guy to es pet wi ine and nat to rine pretties Blecrca Noise resistance) Figwe 4 Equivalent ccut ora resistance & with rl non thal divers power toa load Rt Thecurent squat vllage fctuation applic. Consider as in Figure 48 losses ran teristic of feequency 2af, = 2na/L fom (15), 30 ‘quency range Frei, 60) where propagation velocity on the tne. E hwo Bplay) 1 wor10 Chapter 4: Thermal Rasiation and Planck Diss De AN) = WL Ale ‘The rate at which energy eames off the line in one dies + af 6) the line at one end is all absorbed in the terminal re reno reflections when the terminal impedance brim the load must emit energy to the temperature would rise, Thus the powee iaput The power coming of impedance R at matched to at the same rate, or else tothe lead is P= CPR= af, 69 = 2RI, so that (28) is obtained. The result has been used in low tempera- lure thermometry, in temperature regions (Figure 49) where itis more cot venient t0 measure <¥) than +. Jolinson noise is the noise accass a resistor here) appears nade current flows. PHONONS IN SOLIDS: DEBYE THEORY Phowons in Sods: Debye Theory 103 03-— B oa Figure 49 Meon square avis stage a gy} — 7 Aemperatue indicated thesmomict. Aller RR Gillan kA. We and J.C. Wheatley, J. Low Tern Physie 6 533,973 6 : 010 3050 P. Debye id is quantized just as the energy of an ic wave in a eavity is quantized, T) of eneray of annot account foe the ‘minimum of computation. ‘There are two important features ofthe experi ofa nant eed of the observed results in Chapter 7 er of possible electromagnetic modes in a cav ie modes ina finite solid is bounded. I'the solid consists three dogrees of freedom, the total number of modes is two transverse and ns ofan electron contrast tothe two possible pol ‘wave. Ina transverse inal wave the displace= {0 the propagation direction, The sum of a qué refactor 3, ment is pa ns. We want 10 fi to aN: 1 ffram re was no corcespor ‘austamary 10 write np, alter Debye, fr as Suet that the total number of elastic modes is equi = 3N, on In the umber of becomes Joton problens nodes, feng? = BN; ny = (62/0) 63) ‘The thermal energy of the phonons i, from (1 fo Ua LG = Desde Dee, 09) of Phonon Soues 69) a ay the volume V. Here, with (38), the uppee nofLe = (GRAN, EY, ra) usually weitten as Xo = UIT = bye. oy hots 0s called the Debye temperature: 0 = (hefner? Spon the integral is much ‘may be replaced by infinity. We note from Figure 44 bution to the BetNet _anthgT Sige = ap «6, Proportional to 7%. The heat capac «-(), fore « byl orT «6, (47a)