FFor an exothermic reaction, the slope for the Gibbs-Helmboltz equation given in Eq. (10) is negative, as illustrated in Figure 2. Exothermic case AGT slope = AH? <0 Thigh Thow WT Figure 2. Typical Gibbs-Helmbolz plot for an exothermic reaction ‘From Figure 2, we see that a the temperature increases (from right to left along the x-axis) the Gibbs free energy Chante also increases (as long as the Final and inital temperatures are not too different from one another); thats, Bor Tyas >Tiniiat > SGpmat > AG aay ‘Note in this case that if the Gibbs free energy change ut the initial temperature is negative (indicating a spontaneous process), then increasing the temperature increases the Gibbs free energy change (in olher words, the value becomes less negative). Example Gibbs-Helmholtz Calculation Determine the standard molar Gibbs free energy change at 500 K for the reaction, 2H (eg) + O2(8) + 2H.0(8 - 03) ‘The standard molar Gibbs free energy change at 500 K may be estimated from the available values at 298 K using Pe Gaeta can ac (| - a: a aur) 1 we approximate the partials by finite changes (as when estimating the slope ofa Hine) the Gibbs-Helmhol, ‘equation becomes as)‘The changes are defined as the differences in the higher temperature (500 K in this case) and 298 K, (16) Inserting these elation (iy) Sobtimtng the temperatres, aa;(r, ql ) AGT) gy ef T 7, 7,” 7, Gig Ain 1 ot ft) SOOK 298K 21 500K ~ 298K, Here, it has been assumed that the standard molar enthalpy of resetion is constant and the value at 298 K (available in tables) has been used. Solving for the unknown standard molar Gibbs free energy change at 500 K,, we have a(t 1 AH g(t - 19) ela an] ey In order to complete the determination of the Gibbs free energy change at 500K, the values of the Gibbs free energy ‘and the enthalpy of reaction at 298 K are required. These values may be obtained from the tables in the appendix. ‘The standard molar enthalpies and Gibbs free energies of formation at 25°C of the reactants and products are: Compound any AG; (y/o!) (kno) Hie) o 0 Oe) o 0 H,0 (g) =285.83 237.18 ‘The standard molar enthalpy of section at 25°C is. AH ns 2 AH;(H,0) - 2.AH;(H,) ~ AH7()2) 2(-285.83kd/mol) ~ 2 (0 kitmol) ~ (0 ki/mo!) 571.66 Kimo. 20) AH i‘The standard molar Gibbs free energy of reaction at 25°C is AGigg = 24G;(H;0) ~ 28G;(H.) ~ 46)(02) = 2(-287.18k/mol) ~ 2 (0 k¥lmol) ~ (0 K5imol) AGigg = 474.36 Koi en ‘Now we can subsite these values into the expression above to get the standard rmolar Gibbs free enerzy of reaction at 500K, AGio ~ (sx SS + att so - all 500K = (soon) 2UAS8HML 4 (571.6644 moI) _t - 78K Wok ” 28K Gin = 49.9 Wo. a ere we observe that inthis case, a8 aresult ofthe exothermic enthalpy of eatin, the standard molar Gibbs free energy change at 500 K is larger (les negative) than the value at 298 K.Culula £ a a BS oF op st Sgle ae a pati de hes Calves g fuse eclaue dor 3 eedfeapior “di le) pecTascen popeuucstel dsua le OHs CQH (2) + 2% 2 2 CO, fg) t 2 no ‘ane & Re esponosr a c2Ta Zh Ge pate 2.(9) 9 eataute 9 ae CHs Cony (t) + 220)—7 260yo) + ate) 2 (309) + +e — *) afi, bB. ~ 4845 ie (0), —— 41845 7 92996 dH = Mh EM, fa. 44) as j2996 — (7 , cae 5 By )4 4p ht) DO eff COHN CE) t Pen eM 2 20) 2 - o 4 eet te ae s° ee an wo B2572= As? = PIG - 555 2 joe~ 5902 = OF B= a 235 key e) 06° 2 288 (28) L6°2 OH. 7 AF 0407) me Wy. /a pene on 4250La dV dob. yereuto Kiuutbo o7 0,199 bay 2 160TC Aon bev XC Dsvmialo 1 fap] dd tt ey a precer eompaeatil {24 Jf. fer febfea 2atat luie al A “taal iz sn at patil ae dhe “yele? dl Vapor 20 a Slee jpibeo LV Dela ce. de Clavitef= clap fone on — bu fe je Yn ae - 5 (£)-4 hl -% — p(y) _ ne CP) . 3020 Tied [aan G03 / SE Uv = 5303 hl pha hi « 25, 46, Mn - TOSip he lace. te clase cpr (Pe RT. ra Jaa he 0,122 69, T ZL ba)? swe ae y/o) fco 7 533, /9 BB = panes ig _posy pf 672) = 2bor te IF i * 0 @2tc, ter 2 ile (20%, by = ee pe ene! 7Lac pass t laper eet husceuo beptto oheice Ceca - SEIZE fa P = 24,4 ~ ands la un fate Tr 2 A Tape i Calule la utebpa pele; Ve” tia Che [cent norndl Levin - ad beuauo yg & 77 Seluseai 7 Le ceuaeny’ dade, wmegite £27 trust la ms clapeyoe Alece, de Chel Libs +6 pl thy 2 5ams 7 st) z antes di = 3,9 iC gyothh Sy = 470007 ie : de ebatleant poral” P= ai bu P = 204U- + = 58493,5 = Fp 24 | a7 ie” o58,9k (147 OQ T= " ke yoo )- 2801ts aypesfen I aay angete’ (a fase, ‘222 sa (22°C Al canbe 04 de fuser) dk wee auun yarn ce la Vanaom a Yume J 32Q00 A. 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A get frceegt herein! cheque eons A Facfeater a fea (ROC “4 Gor a, 4 Lato: «) Uhh = 40lYig = 406003, 7, 2 ot (3 H SR = dake ae aie [ 23e he be ip on hep ( a) 7) r Ae ba My + te (= Ht’ 4 ¥ a (i)+ als, ( eR 3 | a ° we fie 4 93ah Te we (seat) ayy { T-T uh = M+ a eo if deh. fale) + LORS | 288= 39 ) BM 39343 Jub. —0,3606 Pr = 060? ad, ( 532° ray)Cabucler ef paw to nibs ded hub qusa “7 WSO gu la Tew cihten aa Pum Le dumbed dent a fear 4 ate iq dewudad del @ pea Wguade A fo00 Yau» ay 1 ll a Gee bork « / beaten ynater ak fetvinr Selusctert cienee armen al elequibhc O¢Ke deat a aP. AH paper a Fe On AP. Dijoe en wt Ty. V— Jurhh yet 3 AP. Duy qual noel ciyynte AT" Hig 6 Te-TNh= Tau: (fs) he th tenth) Mf tb aN oust Vie \s . (5 ooowL . ( 4 ~) )\{ooow WF m re Ha) Seeger Lin , Vi a 0,0 1807" bf! _4 bo) Ona depee Kaas 7 18,080 C ae i 7 ,009-m! a ee To = 293156 + = 2931S qoanee o a - 03S Sw = Tr = 292, 80%