etemedynanive Pofentiols “* the four puetions \ UA, F and 6 pla 0 xole analog ous te that playect by the pefeutialy energy fer a mechanical Splemythe ate called theemodyranuic ‘aes which o min for stable slate . Maxwell Theemodynonue Relation, . The changes in U, FP, H, during an antinilesimal” change art Aven, aU = Tas- fay? -—— @ | ; dH + TdStvdpP = —_@ i F += PaVoSd7 6 da = VdP- Sd7 -—_ @) Nole that variables on aught hand aude f these egialing ane AV, S ont 4 Inleenal Enetoy ot bilinw, Enexgy > let dQ be» the amount of heal cate absorhed by a Ayplent aud dW= PdVbe the: amout G “ork done 4 Aste an gowng ng er ata Alate 40 fal state, then charge Mm jrilewal ener: 4 agstem B guet ey aU: da-dw ; dQ + TdS and dw>PdV dP dhs it eae oe 2 L2),],- Gd ZT [ss hy Ey) ia AJ] - ta 2 hace but ey (2% hy, = GE), grt the variables Vaud 3 ‘ f vif{~ the snlerual energy (v) partially / ‘ U (2 > =P aud (2) at / s asly p All Sice av 0 fetfert digetential , 40 We can anes 2 (uw). 2(%) as(3y) avi as Using egn C7 woe get e (#),-- oy —@ asly lav ‘The os foat Maxwell's themed ynancical peldhon 2- Helmholts Function _¢F) = l Hdmboly fundin ok Henk et eneagy 1 aipredat _ fe U-. —@ DY a BD, we x df» dU- Td8-SdT Bud du> Tds- Pav . df» TaS- fav- Tas- Sar oe dé = -Pdv-Stt ——@® Oy P pardially tort the vattables Voud T we of Bt « (E48 Since df ws 0 perfect cifetenfial » 50 2(#)- 2(# avi at/ aT av Bing ett HY) 4 toe gek 1. . G,-@) —e 4 This & hid Mawel’ thetonedlynemutcal Aalalion cy Sathalby' ): Exthalpy 4 * Aston u Alefenél ae He Ut PV —_@® . Au. eqn Gi) we gd ; . dit> du Pdv + vaP Sob tia et du» Td$ - pdv- bedu = TaS- Pav t Pav t+ Vap ok dH= TaS +VolP —& Bf. Petey wrt. § and Powe get au) = au) ev a), i aud (3), & Since AH & a perfect alitferential 140 a / aH 2(at) > (32) . Using €@n-@ we gt avy ./at — aa ‘ (i). ‘ ® Th ws the pnond Maxevell ls therrmedynavattal relahor 4. Gibb's Puvahon 6% Gibb's En (4) Gibb's funclon ws alefiired! ag G= H-T8 \ G> Ut PV-TS [- H-v+ ey] Dib en) we get f ag~ AU + Pav+ VeP— ToS - Sat But d= Tas - Pay dG = VaP- Set @ @ Taking Partial diferentalion, of Gs vont: Paud T, s0t get aG =) =v and /0G\ = — po) : fa ee @ Since doy a Petfect eliffetential , 50 3 ar( #)> &(%) Using CGN UD), we y (),>-&), — ® Tha & fourth Maxwell's theemodynanvical kelation- ' @ toi L_otgy sith Velumg Comune thal ia (alin mat ay a+ Tds- try — @ Ruvidle, by AV th obfarn ) dg a TH -? — @ THs ean Wek the chouge in enlernal ences fee a subslance dure mnpiriteaimal process Suphse the process acces at constant lenperoture The takes the foem U with velume | egy ele fo tet 2 Usteg the Maxwell relation, (8) wv/7 th at becomes , ou) = 7/98) -p (el ae Tu GN. AWE the variohin of inlacnal energy orth volume Autang an Botheemal preeceys " @ For beiject_ gos: The eqn. q alate fot ene mole Perfect 906 a PV: RT fae 6 iba) 5 7. eal aie 2 Aubslituting tis Asult 1a ega. 69 we oblain OU a Re fe (a 8 Ung eqn. (5) ut becomes Bir 0 Thus she fnleenal energy Af a ferfedl 4% & independent of abs pe ve sai Inlegraling egn. 61) poe oblain load v ut) “— @ Thes eqn. shows that the imlernal enek oy qa perfect qu 8 : | only A incon temperature . Scanned with CamScanner© far Vowdoe eal Gay i+ The eqn. of Alnle fore one mole % ay 1b) * RT (r alev 6) ( 4) eas AL -4 etek @ Aaferentiate this eqn. padlially sort T hecbing volume constant , d TRY gues ™ Gis —@ Substilute ta patutl gq ey (68) to oblate (3), - fp? — a Useng e9n (51) ct takes the fon 24) eee AT. a. ov V8 Vert VR Bue 2 jt (#),- & —e Since 0 & positive » the inteenal enctgy fa Vander Waal Ue. actual ayy Inceeases aluvceng Absthoemal \ exbarsion Inegraling eqn. 9) we shhin Us =t + #1) —@ To) ache F(T) & some featchion of lemperatine Eqn. 0) shows, that the infernal eneegy of cal FS depenels om beth th Volume Guol Raperalure p Yeruation of Cv uath ydlume !- The specibic heat at constant Volume it difineel as «(Hs but Aas Tas : Wey ee Thus Gy (3), Aiferentiale both aides tomt» volume heebong tenuperature conslawt . this guves (3) : alr(%),- a Now contider the Marvels pelaticn (#), - , —o atly fi Puy at fowtally wrt T en volume conslaut . THA ee 5 a a (2 (?). lac 2 [(2) Ml (2) » (2) dTav. at/y Substitute wis result yn eqn. (er) ty chtain acy). 7/8°e i, 4 mh o Ths eqn. quer the variation of Cy 40th volurne. during asstheemal pedcers @ For. perfect gas = The eqn Alle Jor one mole q ferfed a Py> RT Ls P> RI —— © Qif- this eqn. w7t- 7 beefing V conslant - This qe pee Kee . Gy: 4-8 Mi & again worl: T keebun V constant . Ble oblain (2) a d Vat yy @ Substitute 4nis value mm eqn. (6 de cblain acy 9x) 29 (7), ® Thos eqn. shows Lnot Cy does not cha cotth volume during vadiabatic expantiin on Compiesion of perfect @) for 2 Vbnoler pal gas : The ean of slate x one role actual ast te ; (0+) 0-9 = RT ar - &, —— lmao . @ Dit Anis eqn. tote 10 7t tenperatire keeping volume. constant. Ths quis (2) aes Bis 7 oT V-b Scanned with CamScanner _ut) 0 — @ (it the {om Cyn GA) taker : : (xe) oo GW ‘av/t estaba i NT i Ths the a mo change on Cv ea 4 md ; [On Non ay comprersin [ae 9 vandee 4 Yartation heat al comlant AC with Lavsurt = The melon specie bretsue AS alifuntd as Gr») waa BT/p But , above das Tas TM eaN. for) lake the form NOW consider the Morwell selation Gr, ‘ mat) oe ar ll ar, eh, ( poten ee 1% ore Substitute AMS value ap 1. TD 49 oblain (3) (8 ary are ——@ : Tha eqn. FS the varualion { Cp coith pirsure during Uo themal change. ® fa bred. The ey. of Hale $ot one mole of Perfect qu a PY = RT VirahTe mak og Pwrt T keeping prtisuce consfout: Thy Qn. twice athe PP BY\ be () > o Stebililute iy value un €Qn.(al) ty obtain, Or) 24 il 8 Thus Co does not very wotth pranuee for a pangect gm sat constout Terberaticce , : General Relahén beliwecn Cp and Cy + The max specifies heat sal comlont preamure te que ab Co» t ( 4s) — 8 > ; dt us awume that enkeoby San funclion of leruperdlure T and volume V. That a \ | $+ sity © The total aliferential 4 Su | | dSs (3S) ax + (2) QV ee oT, ae ® Theale a8 . (38) ¢- +(8) dy nbc | at oT’/y OWT aT r | * (5) > + @ (ey; He Subsliluke this Value oq an. (70 to oblaim pete 7(4),+ (i), (e) Pe Using eqn: (¢s) 1k becomes Whee Cpe +18), (34), —@ os t/3 (8 ths Morwell Relahin &, ¢ (4), m ean (92) we obbin ae = Cys 7/aP) fav : ice 1a (2), ‘8 mad til. Rigi Pn = etd EGU Be agfaa peje gobs te caret ae | OMAl- pve RT p+ 1 ——® yf tne eg patil wort T hesbieg Se ea ~ at ebowter © ele M4 Thus 47 (43) becomes 6 o-s AT ( a), _—_ vor €qn. dv) at be eanitle a8 va oF Pqt at wrt T hreefumag P constant we sblain av R er eae. ® Substitute this result un egn, (4 do obtain Cpe W> MR , RI Viele Pv G-cyv= RI RT apeg~ 8 === 8) ThA ¢ well hrown xesutt fou -0 perfect en © for Voudes Weal Gass Ths eqn. of slate fore (rmsle of a&luel oe [+ s)o-9 + — e = Al. - 4 -—{q Peel rn uaa Aifeutiste ye ey batlly wort T Reching volume | Conslou . Ts ques (Seen ees od! (3 vo V-b ® Now Aijouutiote eg: (od wrt» ri. keefurg peewure constant, “he oP 3 f a fae) (%), +9[e- 4/2) eR (r+) (a), - 5 09(B), shy bah [reeseey| SeT/p () at), ~ yay ts (02) and (lod sr opt AD 106 oblain -cq - 12&—A—, Cp-Cy = wee [ret (r- $9 4) —G vi aT —G O-ty = Wal e-% + 288) Using eqn. (Ie) at takes the fotm eee ie es Ore = ay Ri 2 +8) tv en fet V3) give the gunval exbreiaidn fre Cp-Cy fpr deal gate Shecral Cases: Cate + The Vander Waal a becomes tdailical with A perfect gas ga fpr 4 —+0, b—e. Thus hi the Limit ¢ Aight hand ncle twohen both a and b tne ae soe obtain RT 7 iBall. Ths null 1 relertical with ean. Ad. Case 2! Since a ond b ake amall qyiardiles 5 the teem 2a ects neglected un combakussn to othe “Leems. Thus ean. (Jo) Laker -Lhe ee ee cece &-v/, -0( E78 - 2 Vv NE ed. RIV 2a(V-b) RIV=2aV42ab C Negledling teem rab it become. * Ce-Cy = Rete, etry RIV? -22V avi hey ) Cp -Cy = “ teen *) @® ee by Binomcal oul fins fost onder team’ it Cp- ly 5 a chee: Scanned with CamScanner