COMPLEX THERMODYNAMIC SYSTEMS Vv. V. Sychey ,, WOW bs et caeg '¥PCC! MOSCOW 1994:BB. Carmen Moca, "Haya" Tuenaita AP Ns 063377 oF 22.05.94 Gopwar GOX8S/16, Thee. 15, San. N78, ‘Tupas 1000 2x2. Tisgerencerso "VPCC™ 111672 1. Moceaa, ya. Hosoxscmicxaa 27/174 Mocxoneraa run. Ne 4 Kouarrera PoP no now 129041, Mocksa, B.Tepescrancras, 48 ISBN s-80417-72-6 © V.V. Sychow, 1980 © Trandaton, E, Yankovsky, 1981 © “PCC”, 1994 (CHONCHBIE TEPMOMMHAMMTIECKME CHCTEMEI Jn memory of my father Foreword to the Third Russian Edition {With the intensive development of modern engineering, the role of Teubmal physies andy in particular, one of ils main branches, ther- imocynamice, is increas. ‘aihouga the basics of thermodynamics remain, naturally. un- changed the range of its practical realaation is constently broaden. {ngs a reel, modern thermodynamics ts separating into severs) elise engincoring thermodynamics, chowical thermodynamics, the felts Gamamics of systems with many variables (uch systems 826 Siem e en ihe eatier unfortunate mame "complex systems"), the oie, iyoumics of mixtures and solutions, the thermodyaamics of etme hte processes, and other fields. One mist bear in mindy how roe That ik discussing these diferent Golde 1 is important Yo vse $* aU + pa. 20) For systems in equilibria rasa +3 tere (126) a Tas = aU + pav + at, (ze) Tas =a + pw +baX, (4.280) For mass specific quantities we hava, respectively, rem du 3, teden (4.260) Tas=dut pav+ a, 2m Tde= du + pavt Ede (1.28) follows we will assume that work done by # system is wacom the apstem is negative. Correspondingly Berl ule thot the smoot of Beat ig peeitive when the system Fring Mase and negative when ie is leaiog heat. Nacoraily, the Be oeention is arbitrary, be must be retained in all thermo- AJnomie ealeulations In wh positive and work 41.3 Heat Capacities "The (moss specific) heat capacity is given by the relationship a, (120) ozs tah het capacity procs which «parameter, 5 Teepe tonatant. Sine van ates, follows from (4.30) that nt (Gr), The squation forthe constantevolume oF Kochoic, heat capacity Te piiten hut (z= 8 = consti) ant) (1.32) (1.23) while for the constant-pressure, oF Hsoberic, heat eMpacity cp (= ip ronstant) we have pacity *(#),- (4), (1.36) 1 i obvious that these equations are vad when the only typeof woth is expansion wont (cae when gb =). But ais oto then pulsing Ey 1.27) we can aco that from (188) follows thats {Bheatelie fea caacty ofa case that ero er given by the following relation: amie In a similar meaner we can Bad the conseot-pressue heat capacity ot buh 8 nylon ot (a), 11 is important to note that whenevor we speak ofthe hest capacity ott system thet performa other work besides work of expansi¢n. we Sit be careful to state which heat capscity Ie meant, Le. wheter tne aro accounting for (027/97),, since to many cases the magnitude A the correction is significant and substantial errors may Be nico fuced it" neglet i Ty analogy with cp and 2, for systoms performing only expansion work, in the following chapters ‘ne. wil be tuteresied in the heat acti af systems tn witch the genctelied force or the gener titted coordinate is constant (heat capacities ey sadies). Atéonding {o'thw genorsl dosnition 32), T(r), ond) The mathematical tools that thermodynamics uses ace quite simple. ate acl sever esi rlaionaie that we wil eed nthe ‘Arne have already noted, all thermodynemle quantities can be duvidad nga two eateporiet: state functions and, frocetstapetlons The moguitudo of 9 state function i determined solely by the pers reters ofthe particular slate, Hlenee, to determine the changes ta 2 state function inthe course of any pracess we ned row only the Toluer of this function ae the begianing and endef the process (1.30) a. (1.29)0° Complex Therredyaamle Sytem Specie volume, entropy, enthalpy are examples of state functions A for quantitie thet are process functions, they are characteristics tthe process. thelr value iva given sate depends not only on the farameters of this state but alaoron the path (Ee. the proces) which Eiesystem followed in ordor to tech the mate. The work done BY 1 system In tunaferrig coun ome sate to anothr a'one example af {provers fonctions Haat lo snotnon” A nated fn See}, the spelal {eltore of a state function f that its dferential is total ‘Wo kuow thar the total eiferental of function of roveral (inde- pendent) voniabes, t=] (yy), 8 doined a (hw. 2etl ar+( {nthe majority af eases we will consi fee hl arn($),04(2), 47 «v0 ‘Tho eubscripts attached to a partial derivative indicate that the derivative is taken assuming thet the quantities in the subscript are Gonctant, For instance, the derivative of presure with respec Co {Smperaiarey @pl0F, aay be calelated. In various conditions: Snitant volume Vat coustant enthalpy 7, at constant entropy Sy ech Pca ae the dered Cpr dnd (opioT}—. WoploT)p. Uplate. ete. and will difler ta value. A. well- Lown Seoul of wahemat ci analysts Te that for a sate fonetion Figg) we can write tot ae (139) ar functio is of two variables, (at i.e. the value of a mised derivative does not depend on the order ‘of aiferentiation. ‘This means that I «differential of some function Eo / Gey) ie written as as Mde+ Nay 2) nd if it ig known that the diferenial of the function ie total, then fhe following relationship is valld 4s) ‘relation that will enable us to obtain Important equations. For ‘xample, we eal tie it to show that the dilerential of = process function’ ie not total. Consider, for example, the expression for the ‘iferential of the amount.of hest supplied to a syotom, Le. the Equation for tho fest law of thermodynamics, when the system per rus some one type of won, Im this coc, taking (213) into account, ovo find from Bg. (8.1) that 0 = aU + bay. 4.44) ‘To represent Q as a function of two variables, T and Y, we write aU using (40) ay, (4s) and find that 40~(22), ar+| (42), +4] a7, (1.48) Lat us see whether (1.43) ig satisfied for this relation. Comparin (0) ana (U8) We Had that pain %) oy from which i follows that We can see that when wo apply (144) to Eg, (1.46), the condition 1.48) doea not hold, since (ON 2a), diflers fromm OMIOg\e by (E197). Hence dQ is not a total diderentia. ‘We can azrive at a similar conclusion for another process Junction, work (149) an = bay. We see that L i a function of hyo variables: the generalized force E tad ‘the. generalized coordinate ¥ Obviously for the dilereatal of Dn y GV) we can write aL = Mab + way, where, understandably, ¢— § snd y= ¥. is condition (13) tatisfed for this fonction? Comparing (19) ant (cdi) we can soe that Af = Dand N=¢ and henee a7) en % (FE) =4 Toi implies that (F).4 (2) ‘wtuch se proof that dl is uot a total dillorentil In Une cose where 2 = constant, from Eq. (140) it follows thet (3). (2). (Eh -# (1.48)22 Complex Themsedssamie Systeme Obviously, a quantity 2 is ¢ function of two variables = and y, i.ot'= (2), we cam also think of = oa a function af one variables Y and 2, 2g (ye 2, and y as 9 function of vatiablee © ands Ley = 9 (a2). Equstion (1.48) vuiquely relates the derivatives of test threo fitilons. Te makes it possible to relate any tine thet Imodynaenic. state fonctions. For fastence, for py oy ad T froin (455) We find that eel for & u, and 7 We can find one more important relation from Ea. (1.40), namely ().= GE), + G5) GE)» 49) ‘which makes Jt possible to establish a relationship between the Barta ervativoe of the seme. quontities celeulated with various Derameters kept eonstent, 1 the system consste of e pure substance? and performs a single type of work (ee expansion work), the stete of the aubatasce will bevniquely determined Wf two poramoters sre given. Any other parameter fs » uniguo function othe evo givon parameters, Aenea, erstch‘a system any three paremetersof State (ees Py vv and 7) of agar subnange az niguey elated to fact offer, The equation {il Connet the hee poremeters eld the ngvation of se fa eystem performs two types of work, then, obviously, the state ‘of pure substance in such a ayetetn Is determined not by two parse ineters but by three (the equation of state will contain eonrcopou ingly four parameters) Wor can go further It «system with & pure substance. performe m types of work, then the state of the substance 4 "dotermlned hy." 4 paramelers and the respective equation Gt state haa +2 variable, Aa'n rule fn what folows we will be interested systems that perform not more than two types of work (one is expansion work done By'the syuem gent extorvel prosure) ee sas bok we wil del onby with spt tata composed of » pe 2 Equilibrium in ‘Thermodynamic Systems Performing Other Work Besides Work of Expansion 2A Criteria for Equilibrium in Thermodynamic Systems ‘the secon law of thermos omicy establishes on important criterion for equilibrium. in isolated. thermodynamic systems, system is fated olated if ft doos not exchange heat ar work with the surround- figs, Honce’ in such a aystem the taternal energy U, the volume ¥, ne the genertlized coordinate X (the latter corresponds to 1 type af work Sther than expansion Work) are constant. Jn secordance wth the second law of thermodyaamics the entropy of en olated systors tends to bo maximal. Ie has the greatest pos ‘Slate vate for auch a system in eqitbriuin: n other words, i aa iSoluced systoro tn equilibelum a= 0. Tadeed, for such a system dg 0, B= 0, and dX =O; hence from Bq. (128) T aS pau + padv 4 Bax we find that as >0, en {condition that determines the evolution of am iolaed system, The inequality corresponds to's nonequilibrium state of the system, when the‘ystem is sll con the way” to equilibrium state (nonsquilibriom procues azo irayorsible), sad the equality corresponds to 4 system iy ia equiliorors. "Phu for aa isolated system in an e aso, ey But if the system is aot isolated from the surrounding medinm ‘ail can interact with it in some way (coupled with the medium, as fs tsuelly said)y the criteria for equitbelum wil difer from (22), ‘Tey mill dopead on the conditions in which the system interacts ‘vith the serroundings For a system performing only work of expansion (for the sake of brevity, we wil call such systems "simple? the following Tour {ypes of interaction (or coupliog conditions) between tho system ond the surrounding medium are of the most ioterest. (‘The systetn’s volume fs xed, but the system can exchange beat wilt) tho surroundings te such sway thot the system's entropy vilibeium stateV = constant, 5 = constent. (2) The system can exchange both kext aud work of expansion with} the surroundings, but in such a way that the systers's presse an entropy remain constant {@) The system's volume remains constant, but the system cea exshonge heat with te surroundings in such nay the fe tem erature remaing constant. (an fnchorickathermal spelen T= constant. (4) The system can exchange both heat and work with the sure soundings, but tho system's Pressure and teiaperelure remain col Stant (am isobarie-eethermal system) T = constant V = constant, P= constant, ‘The criteria for equilibrium foreach ofthe four cases of interaction ve a fli (G) Interaction conditions V = constant and S— constant. If we rewrite Eq. (123) inthe fore ay

= 0). aaa Rettrring to G16) we Gan wale @ 4 8X a8 OE AU ph PS he oT TS 4 ax. 47 Since scoring t (239) Meer wwe have ae O47. e. By analogy with (2.39) we introduce the notation t orale 7S, 249) where * can bo regarded a8 the isobari-istheraal potential for Such systems. This new quantity is releted to the “old” isobaeie= Isothermal "potentiel by" ° =O 4 EK, 250) Wo can now write (2.40) im the form ab" = 0. est) In this form the equilibrivm condition is similar Lo that of a “senp Golem iyi id 7 ay constant (40 0 he Sern ang that Eq.(@.51) contains @ instead of the “old® lnoberieiwothermal potential = ‘These are the ccterla of equilibrium for thermodynamic systems ‘that perform other work tesides work of expansion aid’ whace con ditions of interaction with the surroundings are such that, in addition to the usual interaction conditions, either £ or X in kept constant. ‘The volution conditions we hive obtained ebove or seriosa conan iniosed om the atgaction between 2 portale tm fra its surroundings and for the various types of work performed Uy the system are presented in Table 2.1. " U,V constant aso as >Eax z rn # te BR con wee apes ee wee BE ee Ee z Be, £2 Eqalibsium in Thermodyuemte Systeme 31 2.2 The Chemical Potential ‘The chetical potential concept plays. signficant role Inthe analysis UT ihe various processes that take plsce in thermodynamic systems feg. in the audlysis of phase tronstions). (“Fie chemical potential of the substance in a "simple" system (se sec 2.1} fe the mage specific isobarie-aothermal potential vot fe @52 ‘where {and s ane the macs specif enthalpy end entropy, or syeteuts that perform other work besides work of expansion swe must define tho Ghemice! potential in the following way gait bea Te 253) wwhese = isthe mss specific generalized X coordinate and where we TiNe included @238)""We cau rewrite the above formule os gratis es with = it te "The chemicel potential occupies « special position with respact to other mass apacibe thersuodynamic potentials, such ae the inter hol energy. enthalpy, and Sree energy. What sve the reasons for this? ‘Won we considered the equilibrium criteria for thermodynamic systiny that interact with the surrounding medium, we tacity a=- tmed that the amount of substance @ nthe system doos not chase However. in'a number of protiems (eg. io the analysis of phaco Soult confit) fe beipfal to etblish how the thin ‘Banale potentials af the systens change when a coetain amount 9 ‘Motence’ dG, iv taken from or added te the systom. (Naturally, the Eubstonce'talien away or adéed has the same slate parameters a3 ife'main substance) Hence we must find the quantities ( (BD aey oF a eostem wish Sy p, and E constant, (Sane (2B a,j for a system wie 7, py and & const BL), gf @ system with §, V, and X constant, for a systom with 2, ¥, and X constant, We stort with the system in which S, V, and X ave kept constant, ‘Tho intornal energy of such a system ‘ah evidently be written 83 U= Ge, (255)32 Complex Thermadynamie Spetame where @ is the mass af the substaace in the system, and iis the mass Specie Internal energy.” This, yuelis aU = Cau + wae. @s8) Since = Tas pdo— tae (ove (1.286)), we con teaneform Bq. (2.56) into aU = TG ds ~ pode ~ iG de + a6. es Applying the Legendre transformations Gas =a (Gs) — 206, 2.38) 6 do = 4 (@) ~ vas, 2.59) Gade ~ 4 (G2) ~ 200 2.0) and bearing im mind that Gr=S, Go=V, Gr=X, @6n) ve flad that (2.57) yields aU — (a+ pot te HAG 4 TAS pav— tax. 62) ‘Since S, ¥, and X are kept constant in the system, using te ut pe 7a) and (2.53), we Bad that ” a) au = 9° ae 263) ‘and consequently (He dara™ (2.830) Lot rath yan tk fa be opt constant, ‘The’ obvious relation for the system's anthalpy. T= Ge es is tho mass specie enthalpy, yields ar = Gee + 1 a6. 285) As to 1, fis obvious from (2.98) aad (2.30) that mut webeitts 208) Employing this regult and beating in mind that 4 Pde = d (pr) — vdp een ™ Baza (te) — ret, ees) sve find from (1.28b) that ae = Pde odp + 2a. 2.09) 2 gulibeinm in Thermodynamic Sy 1 wo now use this rel ster tothe form al" = 7G de + eG dp Combining this with @.88) and @.61), we obtain alt = (% = To) dG + aS + V dp +X at, Sinco S, p, and ¥ are hopt constant in the system ation, combining 54) with G71) wo find thet on la By. (2.65), we can transform the ade + «ac 2.70) ert) indor consider at = gt er and consequently (Hance (7%) We take up the systom fovo energy of the system fs whieh 7 V, and ¥ ato constant, The Fact, 278) where J Is the moss specific free energy: jaunts em This means that OF = 6a +466 (2.35) and, a a consequence of (2.74), OY du Td 0a 76) ory using (1.281), of = =p de — bade — sar, em I wo substitute the last relation into (2.75), we obtain aP = —pG do — 2G de — a6 dT + J a6, 78) Combining (2.59), (2.00), and (2.01), we obtain a (f + pot be) do — pV — FAX — SAP. (2.79) Also, 08 we see from (2.52), (2.54), (2.7), and (2.74), ae omni et ut pte Tem st pote 2.80) Since wo have 7, V, and X constant in the system, combining (278) with C0} we nd that aF = 9° 66 est) and consequently em ewe est2. Eqlinion im Thermodynamic Systems ‘Complex Tharmedynante Systema tvious relationship inaty wo consider sytem in which 7p, and fave kept cost sea es From te obvious elation forthe obane boon patenal oa sede fue a , a5 = Gds + 206 0 {follows that i. OE ing (1.280), we Ona that a0" = Cdot + oF 66 e a8 4 (Gant pode + ¥6da) +046, eas From Eq. (2.80) if +e aa een mutter Aprlying tronslormetions (2.59), (2.60), and ve nd that, G du ~ d (Gs) — uae es) det = du pau + vdp + Ede + 248 — T de ~ 047. 28M sua wsing (2.61) and tho obvious relationship Using Ba. (4.280) v= tu, 233) Ta du + padvt bes, wwe obtain, combining it with (2.84), gt = vdp + adh — eT. a Il-we subutitate the lat relation into (83) and combine the ren with (2.61), we find that ee 7 wwe can transform (2.08) into a8 =f (00 + pa¥ +80%)— 2 wt 4 e—THdG, 2.84) fn iow of 2.86), aS —-4 U4 nav $3ax)— $a 29%) dO = ape Xa— sary a. Qs Come ee Since inn slat stom aU — 0, ~ 0, and oor ae on as—— $20 2.0) and consequently snd consoquently 200 : 28 - Q Pr oane 5 ova" —F es Comparing (2.882), (2.728), (2.818), snd (2.874), we can Equation (2.95) can algo be written as Tas = dU 4 pav + bax —g* ae. (2.084) Obsiously, this relationship is the combined equation of the frst and ‘second laws of thermodynamics for systems with & variable Stout of substance Tn conclusion let us formulate certain relationships that we will 1a in the future. From Eq. (2.80). ayt = dp + eat — ser, G (called, a8 we know, the chemicel potential) ocespies # speci Position among te mats specif characteristic functions: ustog Ie can caleolnte the change in the characteristic fonctions of So system produced by the change in mse of eubstance in the eystety ‘This is the reason why 9 is called the chemical potent ‘One’ more remark is in ender. Aw nated eacliny the quoatity tha wwe obtain ae choracterizes tho equilibrium stato of ah isolated spstem 1, Ps goa a (2.98) Sonstout) is entropy (inthe quilibelum state the entropy is asim). Cy ‘The entcopy, as we know, fe nota chardcteistichanctie. [Ls inte oe) as 2.90 {ng to note, however, that the darivative ofthe entropy ofan feeltedl I C2 system ‘With respect to Gis so closely vl Tees, the}3 Complex Thenodynanle Systems Eye OF tie various thermodynamic systems that differ in their interact uth the Semounine mdm, the sty ofthe eur contin for au isolated theemodynaieic apstem has the greatest practical importance, We wow tua Yo the study of auch a system, sshematicaly| Weplcted in Fig. 2-1. Let us wieutaly dri Ue system into to pars (ve may call tesa y, pasts subsystems) 1 aS, Our goal it (lind. the equilibriana conditions beincen irium la an Isolated Homogeneous System Y/*"Since tie system a2 a whole is isolated Cage = constant, —Vaye — constant, Neve = constant. (2100) But we can alen imagine a infinitesimal ppracese in the iolated systeny thelial Gack of the subystems ona tf these yuan Luties or any pur or even al of then change Let te voliune ofthe ret subsystem Vy change by aa amount dVy. the %, coordinate by” om niount dX, "and tie interuel energy C's a0 amount Up: for Ue! second subsjstem the quantities ove yy diy amd dy i fae evident that Van Vat Ve e109) ond Us =O + Ue (2.402), We will assume, by analogy with @.401), that? nse = My + Xp (2.103) Combining the Last thee relations with (2100), we hav AV54 = dV, + dV, = 0, e204 OXyye = aX, ob aX, = 0, 2105) Aiyyy = aU, + aU, = 0, (2.106) av, = av, e107) aX, = ax, (2.108) a, = aU, @.109) In other words, a decrease in tha volume (or X or 1} of the fest rubsystem is compensated Ly a matching increase in' the ‘volume (oe or U) of the second, TAT The range of applicability of 2409, se p 2 Earlion we established an important eriterion for the equllidsium of an isolated eystern, namely, that in thermodynamic equilibeiuan the entropy uf a isolated syatem rematas constant (and is maxtnal, ve. in equlliprium eye =O. 2.110) Since entropy is additive, itis obvious that in our esse Son Sy + Sy em svhere S) and Sore the enteopics of the est and cocond subsystems rapectively. This fact togethor with (2-10) yields WS py = AS, + AS, 0. e212) From (1.28) we find that as—havs$aredux. etsy CConsagentiy, for the Art subsystem AS of dit FE aye Hedky, e144) AS pm fea fe ay HLA ets) Suhstitnting dS, and iy from (2.114) oul @15) into Bq. 2.112) and esing @107)42. 108), obtain (e—B) ie (BB) ore (EE) ax 0. 2.110) ‘ve hase alrvady noted that senna energy C, volume, and sgonvraized coraitate X can be varied ldepradenily of eel thee, fete ca smogine proces im which the vahome of each nokastem titnges hile the internal enorgi hd generslized. coordinates femain ized emir. we can imagine processes ih which t change In" does not imply changes in Vana ors change in & Joes net inp changes in'U and). In other words, the dillereatias dy, yan ah, ove independent iy principle, It this ds sy then (or th lefts nae in (2146) to be Weaically zero, the cotbelents Ful dierentini im his equation must be sore independently of ach other e417 2.118) e119)8 Complex Themedynamie Sytena It follows from @.487) that r= e.120)] ‘and combining (2.118) with 2.120) and thea (2.489) with (2.120) ‘we find that map e134) and bak 2.122) Obviously, we will arrive at the same susult ierespective of how we mentally’ divide the system inte two sebsjstems: We ean thus onciude that im an isolated system that perforss work agetast 9 certain force & in adeition to expansion work, it the equilibria state the temperature, pressure and fore fave the same ia all pants ‘We clearly see that for an “ordinary” isolated system, which per. forms only work of expansion, the aqulitzfum state is charactorired by @.120) and (2-121). But are our conclusions valid forall iolated sYstems or have we made some asrumptions that lat their scope? Indeed, 2 gumber of limitations were tacitly introduced in out Aecivation. Fiesty the derivation ts ani) valid for generailued coor: dinotes that are extensive aud for which, cousoquently, the additicity ‘condition 2-403) is satished (as for volume. V). Bot for quite 2 Inutaber of generalized coordinates this is not 2s. For exowple, & system located in a gravitational fold docs pot ebey (2.108), which ‘in ths case is meaningions, Here the height his the generalized coor: dinate, and obviously the height of the centre of macs ofthe systors is not the nam of the heights ef the centees af mss of the subsystems, Fience (2.121) fs not satished for Nuide in a gravitational Geld: the pressure inthe gee (or guia) column increuses with decreasing height boce Chap. 7) In eating various systems we will, always state whether the aaditivity condition for the generalise? coordinates characterieing the properties of the particular system is seis. Second, in our derivation we have assumed all slong that the sueystems has no special festure tl tem thin ie t phos, ther, f a Fort But when the substance of the subaystema if strictly speaking, itis aecessory to necount for suf Have « number B the energy of the surface Inger, to the right-hand side of eq. (2.102). We note thet wien the ‘sollace thal separates the subsystems is plane, oll three equilibrium conditions, Le. @.120),, 2121), and. @.122), IPthis surfaca ia Sot pline, the fressure In the phases which ate i i} equilibeium, will bo diferent, fact that will be extnutined in'Ghap. 2. Egullttum ta Thermodynamle Syteas 38 Finally, wo mist sgeas that gs, (@2.420)(2.422) were obtained spelt" HG iain af cies comer ok the neflgn of an lalatod sytem fay so" practenl mosuing, Hileed, tach; for example, we kogw of ne wey =X peesens fo ehich te ca shied things frm gravitation, there iano sense im apOnkng ‘isoatingsystoms fom a gravitational fel Although system ca Se laistel rom a magootie teld' by aurroundiag 3 with a super: Couducting siold innperaeatle to s magnetic Sela, in most prac [xTeass sich Isolation is not applicable: Other examples cam aise fe cite, 2.4 Phate Equititeiura {a Gelprovious stig wo examined tho conditions for phase equilib ‘Hom ian aolstd. Homogeneous system and ound that the te perature, pressure, and force £ are the sume tn all parts of the system Ewithin cevato Hinittions). We will now consider isolated systems {hat consist of two or move phases! and find the general conditions {or phase egullibism, talon 4 iolted, thermodynamic asta hat conta of two subsystems, 7 and’. The method we use isthe some a {he provious section, The diderence i thet now the substance ofthe fubsbrims isn two diferent pisses: subsyetem 7 conse of one hase, subayatem 2 of the other, nnd the amount of substance in {be htatea can gr (hasan can psn hos one alates {o"the other). Thus tn our nytam Vagus Raves ryan Gag a0 Shastant (here dary isthe total mmouat st susiance in the sytem) itis obvious, Tou the reasoning of the previous section, that Vore = Va + Vas 2.128) Gis — G+ Gye es Un = Us + Ue e251 We elso serume that Xan = Xt Xe 2.126) (here the Inbels { and 2 refer to the first and second phases, respec- Seely) ‘The’ relationships (2.123), (2.425), and (2.428) are similar, re- (9 (2.401), (2.102), 4nd (2103), tho diflerence being ‘dat t hand the dierent subsjatcms correspond to diferent the transfer of subetenee from obe subsystem tothe other fecurg vin'a phase transition. We also uote that 18 this cng, 89 pro= Viousiy, we da not take into aecount the energy of the surface layer in general, Uis layer has Vy piss we meen bomogsccous gins ia etrogeoeoes spetem,40 Complex Thersiynamte Systeme certain amount of additional (ourfuco) energy. However, 2s, noted farlist, for plaue foterfoces this fact dows not afiect the validity of tig pliose equilitetum conditions, which il be obtsined. below. ‘and Gaye ate coutant, the Testiouships av, = ~a¥,, e127 2G, = a6, 2.128) aU, = —a, 2.129) ax, — aX, (2.190) Wo know that the entropy of sn isl stato vemeiae constant (ond ie auxime tot system in equilibsiom Sq = 0. 2.410) We also know that entropy ia additive: Sipe = 5: + Se e431) ‘This together with (2.410) yields dSvyu = Sy + dy 2.132) Let vs now turn to the study of the entropy differeutial for each of the subsystems. Obviously, in contrast to the case of Sec. 2.3 ‘where the simout of substance in each sulnystem remeined cossiant ‘einiust now vegard the eutropy af the Hest subsystem, forex ‘ss a function of 6 im edditton to bolug a fanelion of Uy, Vy, an Sy =F Wa Vay Xu OD: 2.133) ‘Tho camo ie the cage with the second subsystem. In accordance with Ba. (2.85) we And that for the Best subsystem a5, ate fava aK, 2.1% fn similarly for the second. subsystem Wy dU fe dat aN, —$hadGy, (2.135) Spacing thse relationships into (2192) and applying @2.127> (2.180) "yield (F-t)er (R-Rdar +(e Ben-(E-Hyan—o ess Since dU dViy AX, and dig are completely independent (accord ing. tothe Feesdhing developed. in Sec."23 when dealing with tho {nkependsnee of dU,,d¥,, ond dX), the left-hend side af Ba, (2130) is identically zero only ifthe cooficients of dU, AV, AXy, and dy tre lndepeutently equal to vere 2.137 (2.125) 129) (2.40) Tho feet theee relationships give ue the conditions which we already know: ner @.120) Be ety a e122) and from Eq. (2140) we find new condition: Riley ea Hace i ewe pha ar ia olivine he, eerat, esure, fore fan chemical potential g* of these phieses must be Equal, The sane result cam he obtaiaed ina similor manner Tor Se hs Bh hen ihe oes As to the rogion of applicalty of these results we met make tua sum seseratione ati thee of the preven section. For ate: swe must sree that our deivation hos not Conaiered cesta specs] Properites of the taerlace between the cocnisting nhazes, We wil ribs question bn detail in Se. 655. 2.5 The Maxwell Equations Wo write Ea, (1.288) as ae Which for the case where a= Ta bar 14s) Since the internal energy w is a state function end therefore i “iffereatial is total, in aeenrdance wath (42) wo obtain from 2.148) FS 4a Similoely, for £ constant we obtain (4),.=-(S)he ey62 Complon Therodyaaiie Systems Equation (2.69) ae = de + wap + edb for the caso where p is constant becomes am Tet eat 2.446) Since the enthalpy 1 is a state function, in accordance with (1.43) wwe obtain (eh, Similarly, for & constant we obtain Eeuation @.77) 0 of —pdo~ kde — sar Yor the case where » i constant becomes Y= Rae m sar. 2.140) Since the trop eneray J ig « state fonction, in accondaues with (033) se eotain row tts} $) 47 (2.448) eet (B ae (250) Similarly, for constant we obsin Bae) G51) Floally, Bg, (2.85) dg = vdp +edt— edt for the case where p i constant becomes age = xa — sar. 2.152) Since the chemical potential g* ie state function, in accordance vwith G4) Sve obtain ah (Ene es) Similarly, for & constent we obtain yam ne e159 ‘ho dierontial equations (2.444), (2-445), (2.447), (2.448), (2450), 2.151), 2-453), and @-154), whieh relate the thermal (P and 5) pare ‘lors with the nonthermal (E and Zor p and vy ae colod the Base ‘tell equations. We obtained these exuations for mass specific quan- Utley and 2, but the same can be devived forthe total quauitie, sve and %: (2.4460 (2.4450) A470) as ) (2.1508) sts) (2.4583) Jae Gas @ad4a) Wo will use those importaat equations many times in the future. For one, the Maxwell equations enable us to ealeulate the diderence between the heat capacities at eonstent generalized force and at constant generalized coordinte. tn accordance with Eq. (LA) we waite (em (ade (2)s GF) 85) Using the Maxwell equstion (2.450) to replace (282) x: F)e= Fas and combining the result with (17) and (1.98), we obtain ace t F)F), (2.156) imple” systems. in which & = p and z=, we arrive at oe), (GF), (east3 Magnetic Substances 3.1 A General Survey pa nen. an ine crsaied y he mgt Ei mngucinaton vector? substance: * - 33 ea AREER Smug oe net no tae CHE Ponies ie age! SS hat, Caleta Sate "Berge ieee! Onin iaear ne ewodememice 4 MagutieSotstances 48 gree Sj ls the vector stm of the mnagaetie moments fy of 1he Hae ealy dis an extensive quantity. We will now show that J soi are uniquely elated. 7 HY ae oni external magnetic field (/7) the stronger, the cnet antfes are signe to the feld sn the greater the magne ere emce J depends on A Physics tel ws that magnetiat- eheh gelated to mognetie field strength as Int, ea eiere % in the magnetic susceptibility, ox simply eugceptibility eee eemetiliey is an individval property of cach ag EuiMebisance ne varies wath temporatwre, Fes instance, oe higher the temperature the lower the ssc iil Ferman Meaaperatureiperowse the candor thermal mauion fs fy ne othe wrveata the magnetic Jipole moment fom Signing neste verdad magnetic field, As to the dependence of % o8 Hy Thine forsome subttances but does not for athe Foie ee jem sear tht the aduitiowal held crete by, the 2 neta he presence of ail external magnet Held BeEMsely’ connected withthe magnetiaation J iuiguety, Pom physics that the dependence of 2" on J hos the following form : Ww bal. a4 Combining this with QA), we obtein Beat + bd, os) which together with (3) yields Bat dont, 6s) Baw, an where pate daw 68) is called the permexbiity of the sedium Fee MEETS the above ention isthe magnetization vector pera vettine af the magutic substance (see (3.2)), Coresponding Ber unit nignetic sasepubality x dened hy Ba. @.t) refers fo 2 unit 1 the ee pntange, too. Obviously, the ass speci: magnet fom fis elated to F by 6s) jase,Complex Thermodyname Systeme where vs the specific volume of the magnetic substance, For jne ea trite Bg. (3) in the form Potanse, Fors a, a where x is the mats specific magnetic susceptibility "From (3). (83}s and (8-10) Ie follows that xa. ety The total agnelic moment of the magnetic substance ly be weltten a a substance can obviow == 16, on where Vand Gare the volume and mas of thesubstane, epectiv Tesh iollows we iltginy ate he mace spose lee) and Both 7 and x can have either positive or negative valves. If y = Of the diretion of vector J coincides with that of the externa Bel Secior fe theta magnets eld othe aligaed magnetic Spel ints the some direction asi external magoetle held Non Bey sceordnce with (hl). Bus Hy -< , te teiats J and aint oppniteSetions othe hal Geld af the ape Eile ig buried rom Wf; ty thie ase A JF in accion windy ‘Depeiig om the sign of and om how x depends on 27, magnetic substances da be divided isto two isin incre, diemagnell ‘epeandPitagce eis Gomstine ll Sa “hulognate ivan tone&negtive magnetic seni SO eprom a ha entra mage el sent field (8 & iy Exomples of iomagnetie rutctentes are exons esc. ely avr copper sn plrpbon ation Dama End mais cheealcompoutie Gicudlng aise! ll sani com Sitnett gases watery petolesm’ woods meri, and gles corditg to Langtvits theory, Samagoetnn artes itm the pevesion St the ahcigonic site inthe stone shou tho Sects oF Eoetortal magnetic eld Ae veal theses ofthe diamagoete imneraie Suid Hence the mognetanson sector of te Subsanee 3b tlle’ ected opposite te the el: (ere, te phessecnon of otamagetism cannot he esplaned onthe bai f the ideas about Sementnty tags given al the toponing ef i section) eect cegure in l substoces including paocegnti ituetnnces iorannl below: owense im re substance the eee ott forthe majority a moet unaney e magete eA RaT Ges esp ls smote independent of trperat ur. exept LE eagats we can take (OUT) x caval 0 200, etc hn orton ncependent of tempat va eee es pet anat the fntesety of the thermet motion de slain oe cecsion of the electronic orbits fn 8 magaetic la Bele rked Wemperture dependence of 7 occurs only for a small TA emer sufataneee that have, anomalously srgo amber st iomSineade for exemple, Diswuth aed halliom. To TE ELE ese prontmstely 20 porcent higher 30 14 7 thon at ‘om temperature (00 K)+ om temp eraterseares (ol the onder of several kelvine), varies ni ded tee tome etal: Tres pctode nc, in, and Diet nighly with Mag we nave already mated for the majority of (anal eres), Mmugnetic suceeptbity oes not, depend on the Slamagnets Trou strength within. broad temperate range srr amc mbsances ave n postive magnetic sueceptibty Permagnee tine povomngnet strengibens the exter > OF esas Py in a uummber of peramagnets xi independent Seat le oe ai the external maghetic held HY. These include of fae nea tina, ware earths, io-growp ith, 09 ike metals, ee nor molecule a» pgamgnaiculsanc som sce etch Sam cic moment ead. therclore behaver 29 moguetc Berea ee nc the beginning of tris section in the absence of pele Ae eegatic held eos Soles ave oriented randomly, 20d {he external mere omen fe zero, When an external magootic Sela oN dhl’ ie rtnitin of te magnetic dipoles smprove ef ig etches orgeld strength rows. As a result there 2ppeare » Bom fhe mage Fel tomcat whose vector lis along the held... Hee aaaee eer temperature disorders this ovieatation Sve Fe Mensa Ta the intensity of tho thermal motion (7, drops as ther temperatore terest) he tempera vemugnote lie maguetic susceptibility varies grey Ae a ire Se not too low temperatures the temperate ye amnesic oat pertmagnets is well described. by the re aw x4 eas) where A isthe so-called Curle constant, which is diferent for diferent Iibetances. Tbe mnvore of tbe dleannstem in neck metals (8 somewhat dierent trom ie hae dena aboveThi his low was experimentally established in 1006 by Pigere Car su ilon given 2 Yhooredtenl basis hy Pout Langevin 1 seed Salil saty for Timited. number of poramepiste[eettaia pu platinum. palladium, rare ears and their sate Tho great maforiy S"pacomagnetie substances obey the Cune-Weiss log " wake .14 where isa constant and is chacacteristic ofthe substance (it Sithes ‘postive ar aegative) Sebstense (can AT emperatnres close fy sol in edaperators lise tsa ser th Cale law breaks down, Ba ( as) shish when combined with @.40) yields 2g. (H#).=6 6.10) atkaline-earth metals) whose piramagnotism is due to the spia itngnetic moments of the condrctinn electrons: te mente eee ceptibility 7 depends very little un temperature * ~ faut TuctherTnernse in It produces to sncrene in he maga "special class of poramaguetic substances ace ferromagnets he miagaetic suscepuility of ferromagnetic substances, es 8) aries gretly with MH. Since 7s postite, Temomogne increasey {Be magnetic Geld. Pxampes ace tron, alekel, no cobalt. The chet ileonce between forromagnets and other pstnmagnante sabetsrees shat inthe me the addtional tld Fw many ontere of magn vlestronger than in ordinary pasatagncte (in other words, the Imignetie sacepibity of etromagneto aey tone aes tee that of an ordinary paramagnetic substance). The explaantinn isthe Following. “Instead of individuat magoetic dipoles, molecves; te fesromagtels here re considerably Tanger clumentiry groups, the so-called ‘domains (regions of spontantous. magneliention, which consist of associations of magnetic dipoles) The dornains cagily come orivutad along the Held sd, fmportantly. resin like that attr the external magnatie fel i witehed off Hence a fercermagot femaine maguetized even after the externa Bold Ie tomoveds Mii swvdiainagnete and paremagusts the magoetaation vanwhes wile Uhe'exteral mognstle held 3: Magnetic Sabatncer 2 aa cn ith “H and reaches saturation (j — j,) for Sonata acm hn eee een eats age Sahn cere es cuca | For iron the Caria point is, 770°C, for Eobait 130°C, and for nickel 300°C, As fhe temperatere approsehos the. Curle DPotats the residual mogastizetion i fer- 4 Pemagnet decreases md. become oro at . ihe Curie poiut: Here the ferromagnet un tlergocs sl second-order phase. traustion Heoet fe ferromagnetic te the paramagnetic state. When the tempor ture ts bigher than the Gus point, the predominant orientation Sf the domains’ magnetic fede Vanishes and the substance behaves Gs am ondinnry parainngpet dependence of for a fereo- ee asa the teopersace dependence of the ponmeablity 7 Sn Ne Leger iow i shown af =O. We can tro eh graph that he ngetie suscep bility of « femagaet SLANE fe feaporture approsces the Carle poset Gath A= teeeaea) bu in he iumetiaceneigboutiowd of te Curio point Tam Rocrtses (the Hophingon ett, whieh i observed oy 10 sere cic elds ‘The mosimum appears because of «substan See area tte magnets magnette apiatropy near the Eel deerme ho" ‘Shieh the frromagant becomes nar” (0 sede deus w Sh emomstarecominus te eprrch the Samomigact vanisies. At 7 greater than © we have a still further remagrt arhe tompecute Suen The relation botween y and 7 scree ad goveene by the Cule-etas iw (yi thie case Boa Bye ea ie wurst once more that the magnetic suscoptibility of perviaddle Wereses ae the temperature "eet, i (107) a <0 sence aT D. Tuis law aot vald dor Jrromegnel, 2s eer ke Peron where the Hophinoon eect rnaniets isl Teagan dace OST) os postive tothe let ofthe maxima Sn he peenus T cvs 1 aigonttal mageatie surcepubilty BART BR 2SG. Cr seabnits $2 sin atiad oy a dood‘3. Magotle Substances wale “0 ase} i 7 | Fas rapa oa A Ini C zly ae tir 7 Peon Firwe 32 Pie 3 | To finish thelist of basic types of magnetic substances, we must camp sention ontiferomagnets. These constitite 0 special cae of paren 7 sispnst; thett manuel saseopUilies re pesitive but ipetease —- ~ ‘Cid erperatare, in contrast to ordinary poeomognets. This in e esta ‘continnas ip ta a certain temperature called the aniero. i. SEagoctie Corie point, By At thi pat the aptiferrmmagnat winder | poset feet 9 secon order phate tramilon, unl above ithe magneto f ae Riscputiity varln according” to the ‘Cure'Wla law for para Cy Awe smognetesulane 3 G49) Flgue'3 | ive the temper eromognetie suv ca ance Ws miu sgn nate tht at Oy the olve a Nonea ¥ fc a Solptaataly wit — Example of antiferomagrets area number of tragsivon elements a anit thetr compounds aod slioys uch 43 Cr, a0, Mats, nee, Feey Feds Clg | 2 rd (8) we ca so tha sn dlamgaets (x < 0) the permeability | HL |e is Toco then waity while ia paramaguets (z= 0}, including ferro. Iaguets, the permeability Ip greater than ‘nity ‘The behaviour ofj, 8, andy with espect to PT and the temperature dependence of y fof the didérent type of magnetic substances are town in Fig. 3.5 ‘One moze remark is in order. The magnetic field strength inside f moguetic substance will equal the external noiform magnetic eh Surength only i the substance is in the form af a long cylinder nd {placed n'a longitudinal magnetic field” In all ather eases the pretence of a magnetic substance distorts the external held, and the corresponding relationships (eq. @.) and others) must contain the Value of the meguette eld inside the subctenee. My, whlch Alters from 7. For peramagnots and ferromaguets Hq) 2H, a for diomagnets’ jy, 21. The two a0 connestod vie the formula Mig =H — San, ‘wees 58 the demagnetization, or demagnetizing, factor. Using (3.8) |Complex Teemodynanle Systeme wwe Bod that A ‘This shows that for magastic sustance of arbitrary shope the ctlct can be neglected only if is small compared t0 uaity (parte ognels and ‘dlamagnel}; we eannot do this when dealing With ‘The value of m is 4/3 for a sphere, Lends to 4 for a at dise in a transverse field, ta U2 for a long eplinder ia'a transverse Sey sad 4s tro for a log cylinder in longitudinal Bold. In Gap.“ wo will obtoin similar relations for the cose of» Tong. cylindrical dietectrie (a's longitudinal electric fel Tn ail othe tone ve must introduce into thasy relations a factor that is the Aivlectzic "analog" of the demagastisation factor, 3.2 The Basle ‘Thermodynamic Relations for fagnetie Substances We kaow from physics that the elementary work performed by a ac Geldof strength Mtn incresing the masectcaton of 6 magnetic substance from J to'J df tof ate = Has, oF per unit mast of the substance ane, a Cd peo renee auras re deta net apne stene rom Lo ean Hal a aH. @.7—) Adyuem ea (19) Goneawenty, to crate a meget eld 17 inside » given votune Y ine absene cfs magnets sabstonce wo must pte work etal te fe daaeh Hand J are rector quaatte, we ust tear ip mid Yat as inate pele orcjck oe st ada ibe wot, te pc a. Mgnt Substances 99 fate aT il Soren mene aE tietie held im vacuum and the Wot en agnell {per unit volume): mus 20d 2h sles that Lae x the energy of the magnetic field #9 vacua ah etpagnetic substance Bdygat= ic mbataces ve nme sltions fp magni muta 2 ner shoe Ze APE rman ‘Siete gee prone el Stace sabe ah fign ni i2 the generalizod force, End Fs are ance ie uson OTR Bae een SR oct et = “allows dsm du tp doa 22) for mats specific values eve and yelow all relationships ate given 7 ora vith 2.66) the enthelDy eeu t pe Hh {for such « system is rs which 6 he SABE sing (2) with Ba 2), 08 8 . osuaog pds = dit — vdp +5 aH. @ y oe ta tema) pee Ee tae tential) go of ruch & system = coe Bee: pte oF ek sen _ . 1 2 “ grates and. 159, we com GO sage bold accordance vith 2.14), G07), ws ieee ne equations for 8575 (H.-G Bae 28) 29 ee@. ey ‘Maxwell aguations it (a u.e™ (ee. By combining (3.22) and @25) with th sag) tnd the eating Heteen the tal netic subs a ieee ei Sore ery sph aan aioe ch (Fe. 4-8), where we have used (3.30). “ Skat how teh if mist ’be ined ith arening meee slready noted, changes the maget Fore stitute ao we find that mae respectively, fr “ord Deve Jeet 3.3% (3.33) i etapa, ech sme hy '38), thea, in accordance with (3.10), Sn E+E), ] wifes Slamagny in which, a noted bor, = —— temperature independent, this equation wekes the fees (Bland a9 ee . 4 relution which allows us to d ouch the internal energy of dinmagnet changes ests mayaotion, Hom inereare run Dor * SURAFDEEchaners a6 magnotea: 40 T—m=0, om f, Shhh isthe same, as the magsetic 6.35) field strength changes from MU, T,) uy (H~0, P, ype ; or, finaly, hE 6.37 4,7, 9) 14 Ut =0, 7, vp Bt (0,7, vpn Ht 0, 2, vm ice for diamagnetic substances x <0, from (3.37) it follows os the Gatsrnal tuorgy of 2 dlamagost decreases (with T and & tat Bsatant according to 9 parabolic law as held strength HT grow ser nso not dopent on temperature for ciamagnets, for # given, Stine OL 7 the internal energy, as we see from (9.37), decreases TUfald strength #7 grows by te sate amount for diferent others. se for porsmagnets and fervomagnets, they havea negative deriv sine GalaT) as uated above, which means thot their magnetic seerspuiicy decreases, se the vemperataro grows.» Because of this $llows froma. Ged that (dula))y, can De elther posit Betige, for these types of magnetic “substances, “Obviously, it TEP yal salts them (Ould. » <0. and Hf 1xl7P),. «|< ir Mien ule,» > 9 Poe aan scone Feucular kind of paramagnet, It follows from, {@.i0) and (8.13) that for paramagoats that obey the Gor y ate n 0.9 (),.-F (3.4) re teen with (29) le (Fan en i.e, the interaal energy of paramagnets that obey the Curle Inv does Adc Ggpent'’on the sagoetigation, Such paramagnetic substances Ure called ideal pargmagnete” ‘Plo (diy and G10} we also see that for ideal paramagoets (35),,.2% 6.2) From (@.25) we find the enthalpy of a magnetic substance (Bre, = 7 (Gr bee 643) whence nsing (2.34) we find (Fey? (ne ea of Ee Hep logy Between the nation of an ides! paramagnel of tea gat inte ftir tp, the ner) ergy esha ielx Thermodyaaaie Systems We con transtorm Bq. (@.48) by using (8.10) thus: Sao 8? (Fn HD: (3.439 For dismagnets tho magnetic susceptibility does not depend 1 tomperature and hence (ar). After integrating this equation (aud wring the fect that for dis ssegnets 7 does B08 change with H) 8 fad that 28, aan a G48) HT, ple =0, Py 9) ‘This oquation shows how moch the enthalpy ofa dismnagnat grows (oeenuse's 20} an tho magnetic ld strength Ineeoves from 00 I ‘Another way tp obtain Eq, (ft) isto subettate tate Ba. (9.28) tha values oft fro By, (239) aun tne Ee, G0). Shave fis tee ‘eratre independent for dianaqe ete for a given vale ofp the fnthalpy TnGremes as" the ‘eld Stength "grows snd ths ine fens fe the smo for dle ones (L.2) it follewe thot 08 tue bl Stsngth 2! increase, tho htialpy tf dlemopnetipscases Becordlag to ¢ pivabelte law Ae know the ateroal energy af Soiamognet decrnses sceottiog tothe some law. hore is nothing semethable in thie sell ietesses, {he Hoterza energy wot diamognee drerewas hy Hy bot since In accondaucr wth (323), to ealentate the enthalpy we must ald the Guantlty mej = po — 301 to'm, doxpite the Geerense int the enthalpy Incense by ak tmeant yb Figuce 39 illustrate the various changes inthe cathalpy ad inter- nal energy of 9 Uiemognet profuced My n chasging mepnetie tela Romi Anam G48} We cam tov that for thew Wopes of higdlie substances te) (p< 6.9 fe, under isothermal conditions the enthalpy of such substances decreases ag the external magactie find strength grows, « fact that. is closoly rotateu to the magnetocalorie elect dactrend In Sec. 3.5 For ideal paramagnets (which obey the Curie law) (8.48) yields (3), .--# 6.49) Substituting this value of the derivative into Eq. (2.45), we find that ( (05) In contrast to the internal energy, which in gecordanco with Eq. 8.42) dose not depend on Z1, the entaaipy of an ideal paremagnet decrectey S84 grows in proportion (a ‘We can algo easily show thet for {desl paramagnets (B)..7 aan a 14 follows that the enthalpy * difiers from the enthalpy of the same Sulgtance without ¢ feld (H =O) by if} meet fe the enthalpy StH <0, However this is not co. The quantity # =u po changes ‘with 7 becavee the interoa] energy of s magnetic subsiance changes il, 2, as we have shown above: from Eq. (3.38) tt fellows that (ula ond \ouloH1), am general do not vans ‘We dan write Bq, (8.28) n the foro. = uyay + Ste + pe HT (5) where wary is the internal energy, of « magastic substance ia the Thence Of the magnetic field, and Guy is the change in the internal hergy’ produced fy the increase in the magnetic eld strength from sero to! H, Obviously unm | (Ee), 2th 59) Equation (9.52) can also be weltten as 1 = tye + Btw — Hh ash where tae = Usneo + pv 36 tho past of the total enthalpy of the Tnagnotic substance aot depentiag on J fictly speaking, su tho iuguetic held strongth H changes, not ‘only the internal eacrgy of the sulstonce changes but also its spe~ le volume: this is the so-called magnetostrictive oct (cee Sec. 3-8). it this etect is taken foto accounts ws see that the os Eq. (22) ig the specific volume of the magnetic substance in » fold of sicength di, whieh difer somewhat from thet outside tho held. This hap58° Complex Thermodyamie Spates that we can write Eq. @.52) a8 buy + penne + Paen— Hh, 8.522) ta veo hie we can wots Bg. 6.58 a8 f= tae + Atte + POD — HI ~ tammy + Me = Hi 548) For {deal poremagnets, ia which the interne] onergy in accordance ‘with (42) one not depend on Hand consequently Aug is zero, ‘We fad fom (8.54) together with (8-10) that 0H 55) 43.3 The Heat Capacitin of Magnetic Substances waslogy with the coastant-pressure and constant-volume beat i ie ‘magnetic fi iy it the presure of the ‘Eurrounding modiom is constant, thon the two heat capacities Are ‘enoted, respectively, egy and cy, ye Here 6.58) esp vusing the fact that (Feet dea aH ind the Maxwell equation (@.31), ve find that cme t (Hn (Ben 8) between ep and cn, onan 1H) (HA (GGD.=- ean (8.60) 2. Magetie Substances 52 Replacing the partial desivatives én Bq. (@.59) with the help of this equation, we Bod that carmen (Pele O89 (ae) at Since ia accordance with (8:10) f= at, the parti derivatives in Eqs. (3.59), (882), and (68) moy be feprmented 9 and Dace es (3) no (Fo sy Fir) EERIE 85) wa (37),.2- FG). G8) {ith thes relationships at hand can mow enablioh the vans ot ee far detent types of magnetic substances. ‘Mhhagnati : 2<0 (a= (F)-% E),=0. (sn Hexce (#)a- 59 From 6.59), (82), 0° (LOB) we tho find that en = 9 = 8, 80) du, for dtamagoeis the two hen capacities ure the same ‘aruangust nd feromagnes apo and ($), <2 6.1 ‘st the magnitude of (Hy, for paramopoets (4). em Taye equation for cgay — up ean be found a anotber way By as eq. ts0 Compler Thermody sume Systens ‘while for ferromngoots gO 0.73) so that in accorénco with (65) for paramagnets e79) while for ferromagnets ( am ots FARCE thle OBI). ence or pevmagbets and (Faso mt (Ge), .>° (5) If we combine (3.62) with all Yhese rolationships, we see that for ‘these two mapnetie eubstances alweys ema > che 6.78) For ideal paramagnets ey, » — ¢j,» com be caleulated explicitly. Using the Curie law (3.13), We Gnd that (Hie (HE), geo 14 (Ges, 87D Then fom (2.64)48.6) we obtain (aa. 6.78) (a), (79) ah), 6.40) Substituting these values ofthe partial derivatives into Bas. (3.59), (@.82), and (8.53), We find that for ideal paramagnets or ntnen de coment esp ‘There is a certain analogy between the relation connecting ey.» snl sj p of a ideal paremegnet and the wel kaown relation Wisk ‘conneti® 6 and cy of An idea! ens, aR 382 3: Magntle Substances 61 wich when combined with the ideal gas law becomes aa 69) to see that the righthand sides of Ege. (81) and (@.83) have the some structure, tho product of the ganerelized force and the geascalied coordinate divided by the temperature. ‘ye now turn to the relations betwean ey, » end Hand between cy p and), They ean be obtained tn the folowing way. ‘From Bq. (3.06) cnn? (Su. » wo Smmediatoly Gnd that de oot air (Gm ele ey ‘Since ig calculating mixed derivatives tho result does not depend fon the order of difersatiation, we can write (@.64) 08 an eT Lae (dire bie oo eich when combined with @.9) yilas Hea T (item e 8 ‘uinlty the hang in he best capsty em lone a sotherm, Drougnton by 2 change in the magnate Sold strength, and the derive. tive HOT a "Aster integesGing (8.88) wo Hind that smalls aorta 0=7 | (Sey 80 where the integral is calculated along tho isotherm Ta fs een ine eon eae Soo eugtthT pm eKt APS Hh)y A — 080 hich shows how msch th cotant-pressare hatte of ¢ BROT S See aie#2 Complex Thermadynanie Systeme ae a Ht we combine the last equation with ¢ 4 oUt Te Penis PITY Prom this equation we can see that for di (ir loP)y, p= O40 accordance with (3.57), $9 which 69 se, the heat capaity of a diamagnet does not depend on the mag- hale eld stredgth. Thus also claribes the statement mate above thet for dinouneto the beat capacities cy, » and,» tr0 indie ite ce Ba (888). at paramagasts 1 feilows from (8.77) tat 2) Sutatiating this vale ato Bq, (2.90), we obtain noth. pment, = AE, (asm) or, combining tis with (242), pete esp {Ving @.10, we can welts this equation 4s follow: easement 25) A. comparison of this relation with (81) shows that idea! paren ‘nets have equal cy, » and cp. a fea - In speaking of hest capacities of magnetic substances we must aid Eaton te fect that ey,» of = feromagnet experiences» bap Tee Ne cmperature appidaches the Curie point (we Fig. 3.6, Pe Bich une teenperatuce dependence of the Hect capacity cy. Mieke! is given) The heat capacity ey, » of an antiferromagnet Slances similarly ae the temperstire approaches the antiferroméa- TENE Cnsie point (ove Fig. 2,7 which shows the temperature depend ite of cm, pot amhydeots NinCly) nie Processes in Magnetic Let us consider the characteristics of the matn roverstble thermody- tile processes in magnetic substances, Tighe isothermal process. 1 the magnetic field stiength (and hetce' the maguetivasien f) varie lothermically, ‘re. when the hence, the mae the maprese cwnwtance is kept constant (eg. the SunRSnce tp placed ins heat bath}; then, ay we see from the Maxwell enation @ 4, (aie) GPIne Hence, it the derivative (2/07) x,» Is negative Uhe magastization Fence i tie temperouire Het’ the entropy ¢ of the magnetic ibstance decrases ne the magnetic Held strength grows: 6.06) ‘The evlo holds for yaremagasty ond ferromagnets, Since for die magnate the derivative (aj OF} is ero, in aceordance with (9.68), ‘RaFentropy in this case done not depend on the fed strength Tene iectute the cheage that the entropy of, magnetic sub- ston anaes upder Ingthermal conditions (and with p = con Sant) using the following formula 55h ee D> SE A eal 97) Using Bg. @.31) we con write the above equation as slit, Pye T= |p, 9H (2.98) {Gs In view of (3:78) S hecomes obvions that for paremagnets and fetedttG uve entropy decresses along an isotherm when H in-