v Beemodynonwve Potentials > the fouk functions ut +f and G pla a tole Analogous f that playeet by the peteutial cncegy fer a ee A theemedyranic peleutials thich os "nin for stable slate Maxwell Theemoct Manu Relalions Rhone Relations “the. chawges in U,P,H,6, dwang an ambinilesioal” change are Apeven. AU = Tas~ pay @ dH = Tdst Vap — @& al = — Pav—Sar —®6 da = VeP- Sdq —____ @ Note that variables on keght a OVS ona ' Inleenal__tnetqy or bilkensic Eneegy i Let AG be the amount of beat egy snip td A Ayslen aud dw - PdV be. the aman Of “oKk done. b i ae : br'cnilial slate to feral state, then change mM plecal enekpy rf agslem a geoest by AU da-dw but dQ + TAS and dw- PAV d+. Tda> pay hand Aude f these etialions Scanned with CamScanner® Reff- the anternal cneagy (0) pastially tar le the Variables Vard § (2) > =P and (2) > T Sine lb a petfed dppeeential , ho toe CoM aoxile 2 (x2) » a( wu Bslav) © avlas Using eg C) we get (22) z- as/y Ths & foot Maxwell's thewmedyaanuical helahon 2 Helmhelts fundlion cP) vembolls fonalin os Welmbols ee enetgy 1 lifted of f- U-. —@ (2), = ® av DY en GD, swe get dl > AU- TAS -SelT Bul du: Tds- Pav 2 de> TaS- Pdv- Tds- Sat ok df > -Pdv-Stt = ——® oy P havialty tort the vaktables Vaud T, ave. gt ae) LL 36) .-9 —G &), = =P ane (4a) s—-@ ince de & a perfect dut Pd + VAP But du+ TAS - Pav Scanned with CamScanner I:A dlt= Tal Pav + PaV+ VAP Ok dH = TAS + VolP —s6 Ql He Aretially core. @ and P we get HH OB, - r ong) -v —@ Since AH & 4 perfect olipfecential , 40 (3) & (8) era WA. ® we get GG), —~® TS 45 the aeone Maxevell’s theemodynauital /celahoie 4. Gibbs Punahon 6% Gibbs free Eneegy (CG) Gibh's, fanelion i alefeviedl ag G= H-73 G= 0+ PV-TS Cv tev Py) DH en) we gut dg= AU + Poly VelP~ Tols - Slt But av = Tas - Ply Gl dG = VAP= Setr @ @ Taking Patttal adifferentichou off G wort Pand T, 208 get 4G) Lv and /8G\ = 5 (S), ia (3), @ Since dG a a perfect eifterential , so 5(%) : 3. ( 3) oT( ar oP \ aT Using eqn. (i), we get a) . _ [fas — oth (8), Ths a fourth Maxwell's Lheemodynanuial ‘cela tion Scanned with CamScannerWT pblueations of Maxwell Relalious + * Artahion 9 fen y/ cylin. that x 7 ith Volume :- Consider the pest Tas 40 Tds- Ry -— & Ruvicle. by AV to cblacn = ras av” Tav-P — ® ThE can. gues the chauge im enteenal encegy U x0ith volume for ang Subslance luxe infiinilescoral process ~Suphse the process ocewks at constant lemperotuxe — The eqn lakes the foem Bu) 1(3) -e —eo av av Using the Maxwell Aclation (3),7 Gr) at becomes au) = 7 ( a) =P oY) ath — 6 Ths 4. AWE the variation of fnleenal energy swith volume along an Botheemal process @ foe pesfect_ gas The ean q slole. fot one mole q, perfect 4as re PV: RT Pe g — 4 a) .& —_@ (2) Vv Substitute this kesult “a eqn. 6D we oblaun au) = RT-P WH @& (%), v © Usung eqn. (5) at becomes at) 2 P-P=0 ——— @ aVv/t Thus the rnlecnal enexoy Ala perfect aes & independent 4 als volume a‘ Fi Inlegeating eqn G1) soe oblain us uct) “— @ This eqn. shows that the inleenal energy RT P+ &\ , RL Vv] > v-b Pa ATO La vb ve 8 Dien te eatiale this eqn. paeliall ny gues y sort T heching volume. constant (OER Th ® Substitute ghig result om een.(53) tp oblain BU) 2 RT #), vo? a Using gn (SD Lt takes the form eu). TORT Lg sh Vb Vb tye (#),- & —e & positive , the internal emetsy a Vander Waal 4s (ie. actual 44) incxases alivcong isethoemal expansion, Integrating ean. 69) we stain Us ~4 4 #7) 6 " achee £(1) & some function, of lemperctene Since q + Eqn. bd shows that the rnleenal energy of 0 Heal JOS depewels on beth ats Volume ausol Retperaleere Veruatiou Cv with velume i The Apecthic heat at constant Volume is difiixeel ax 2 (26 re (3) Y But aa- Tas %) __@ Thus ow (et) 8 Rufferentale both aides govt: volume Keebing — teruperatire conslawt . this guts (26) 7 alr(%),), 1 (Ss), ter © aveT Scanned with CamScanner —Now consider the Maxwells pclahion (3), > @,— / Pe athe. at prctally wrt i, iat volume conslaut . Ths (1 > 1G (3,)=-Gk], == 8 Substitute unis result ya ega.(¢7) ty cblain (4), ~ rely ra ® Ths eqn gives the variation of Cy south volume duking asstheemal peoceys @ foe & perfect gos ‘+ The eg Shale Jor one mele. of fetfect a PV RT et Tg Adf- Anis eqn. wrt T keeping V conslant . Ths gudee foe) 2 R &),-4—e Au. uk egeu vorl. T keeping V conlaut . We oblain fir) 9 “6 oTy Substitute ‘this value om eqn. (6) do cblain acy Ov) 29 (1), ® Thos eqn. Ahows thot Cy does not change wotth volume dung adiabatic expansion of Comptession of perfect gas O Foe A Vande Weal gas: The ett of slate Jot one mole of actual & r (P+) Oo = et p= &L- 4,—O V-b Dulf this egn. taice tort tenperatere Keeping volume conslaut: me que li), > vr Scanned with CamScanner —wt) __§ ory €en. (taker the {oem (g) -. —e ov/t TUS theta ome chan im Co with volume desing ‘lhe exponsy 9M ak combtersion, tot. Vander Waal gr tho Variation Co with Pressure s- The rma specific heat ot covtlent resstere aS Alefercedt as q - (2a Aang ° oh But A abeve da = tas AO". Ge) fake the form - as o-1(8), —@ DM. both sides wort P hecbing leuperature censlout Ths fe = B[r(% es wr), Bl ah], fi, 1, —o araT Now consider the Maxevell sea, vi! GW, - -@, —@ Delf. both icles tort. 7. heaping P constaut This quoes IGA] = 20-03] oT th arble = arl-( Sp) ip 24 _ (--2, —e Substitute kis value yn latin, eqn. 1 do oblain (20). -1( | ath rh 8 The eqn ee the vantalion of Cp coith ptesure dung U6 theemal change @ Pot perfect ans The eqn of Alate foe one mole of perfect qe ws PV = RT v= RT _ eg P ~~ Scanned with CamScanneree | OH. this i Leon fee “ie en T Keebing brtisuke constant Tha nm), 8 By ao ; 1 ® eblilute tig value ein eqn. (al) to obtain (2 26 art = —— & Thes Co does net ory wil prenure fox ot sat constout leniberative , d moe " General Relahin helween Cp avel Cv The rmolax specipe heat val constant peesuce i gwen var = as) ce=t ( x) 6 Jet us arstume that enkkoby Swan functidu, of leruperature T and volume V. That is S= sit,v) © The tolal luphereutial 4 sSu as (38). at +(%) av ® Therefore as = (2 28) a a 8) dv 6 at or awr ato * (5), - @),+ ig, +e Subslilute this value um fan J fo oblaim = 1/as) 4 (™ a 7(48), rt (3), Osing eqn (65) ck becomes as) [al Cp > a 35) as ® GWT (3), (%, ® at Using Maxwell tlie sy _ ae. [si . (%), mM eqn. (42) we oblwa Cr eye 1/20) (2), —® Scanned with CamScanner@) for a _berfect Gar : the eqm-of ‘lite for one mole perfect pve RT Pe a — ® Qf. this eqn. fay worl T keeping Volume constant TiN a ae). & (3), - v 6 Thus €¢7-(93) becomes, -G= RT/ av Cp- vy Sf €qn. Ay) may be coxitler as ~ RI v- @ Dey at rl T hecfimg P constant we oblain 2° Ree (3), OP - Substitute this Aesult un eqn. 0 ty cblain cpe- v= STR , gtr v Pe pv ® © foe Vande teal Ges: Ths egm of state fpr (role of aatual ye Be B)eve =e — ® RE_- @ ——g¢ i rete SG Diferntote us can fewlily cor T heching volume couslost - Ths gues ee —e Now aiffercutiale <¢n ae wrl T keafung prewseuce constant hes awe (e+) (2%), + (vi [o- 2% 2] =R ey (2), ee av woh ere) es ) [roe at + 28h] R anned with CamScanneray ($i), (Sa 2). R (%) . R ot), (P= 4 288) — v SF e412) and (10) wr eg 9) wwe oblain Co-cy 2 TR R v-b - Ab ore) -w R aed Wafr-gviay —S at Using gn. (Ish) ct taker the fotm Co- Cy = RT — ON Cre RE 28, + 22h) eS v-b Vv ¥ gee the gencral exprcersicn fore Cp-Gy for Aeal gates Special Cases: Cased 1 The Venclet Waal gat becomes tdeilical with a petfect gas foe &@ —+0, b—+0. Thusclaking the Leuit Aight hand avole wohen both a aud b approach geo, L0e obtain oly = Thes nesult & selentical with eqn. QD Case 2'* Since a and b ake small quaudiles , the toon 2ab anys] meglecled un combarescu to othe “Lees. Thus ean. (lo) lakes ~Lhe fem Cp-ly = we mal - 3) Cp-Cy = RUT . RUTV™ . RTV*- 2aC V-b) RIVv*- 2aV tab S Neglecling tem dab it becomes Cp-Cy = _R*TV™_ 4. Rts RIV? -2aV arv(t =e) Ce -Cy = R(1 - 20)" @ RIV. Exhavteng by Binonwal andl selaining forst ordet fem xb becomes ® () Scanned with CamScanner Coty s RI a)