Gg;RtUB I famBlesrI nig lMn wg...CMBUkTI18 18-1 Gg;RtUB I famBlesrI nig lMn wg Entropy, Free Energy, and Equilibrium m ETm:UDINamicKWCalkçN³FMeFgehIyBi)akQandl;sMrab;karcUlrYmEbbviTüasaRsþEdl

CMBUkTI18

18-1

GGgg;;RRttUUBBII ffaammBBlleessrr II nniigg llMMnnwwgg EEnnttrrooppyy,, FFrreeee EEnneerrggyy,, aanndd EEqquuiilliibbrriiuumm

ETm:UDINamicKWCalkçN³FMeFgehIyBi)akQandl;sMrab;karcUlrYmEbbviTüasaRsþEdlTak;TgCamYynigGnþrbMElgkMedAnigsNæanepSg²eToténfamBl. ETm:UDINamicCYyeFVI[ eyIgeRbIR)as;B’tmanEdlTTYl)anBIkarBiesaFelIRbBn§½ edIm,IeFVIkarsniñdæanelITidæPaBepSg eToténRbBn§½dUcKñaedaymin)anbegáInkarBiesaF. ]TahrN¾eyIgeXIjkñúgCMBUkTI6 Edlva GaceFVIkarKNnakMedARbtikmμBIkMNGg;tal;sþg;daénm:UelKulRbtikrnigplitpl. CMBUkenH ENnaMBIc,ab;TI2énETm:UDINamic nigGnuKmn¾famBlesrI GIBBS. vak¾BiPakSapg EdrGMBI TMnak;TMngrvag famBlesrI GIBBS nig lMnwgKImI. 1-c,ab;TaMgbIénETm:UDINamic 2-lMnaMekIteLIgÉkÉg nig Gg;RtUBI 3- c,ab;TIBIrénETm:UDINamic 4- famBlesrI GIBBS

5- famBlesrI nig lMnwgKImI 6-ETm:UDINamickñúgRbBn§½énCIvit 1-c,ab;TaMgbIénETm:UDINamic The Three Laws of Thermodynamics

kñúgCMBUkTI6 eyIg)anCYbc,ab;mYykñúgcMeNamc,ab;TaMgbIénETm:UDINamic Edlniyayfa famBlGacRtUv)anbMElgBIsNæanmYyeTAsNæanmYyepSgeTot b:uEnþ vaminGacRtUv)anbegáIt b¤bMpøaj. rgVas;mYyénbERmbRmYlTaMgenHKWCabrimaNkMedApþl;[ b¤ RtUv)anRsUbedayRbBn§½ kñúgkMLúgeBllMnaMsMBaFefr EdlGñkKImIkMNt;faCabERmbRmYlGg;tal;BI (ΔH) . c,ab;TI2énETm:UDINamicBnül;fa ehtuGVIlMnaMKImIeq<aHeTArkeTAedAEtmYy. c,ab;TIbI KWlatRtdagc,ab;TI2ehIyeyIgnwgsegçbkñúgEpñk3enH. 2>lMnaMÉkÉgnigGg;RtUBI Spontaneous Processes and Entropy

eKalbMNgd¾sMxan;mYykñúgkarsikSac,ab;ETm:UKImIEdlGñkKImIcab;GarmμN¾KWGacTayTuk faetImanRbtikm μekIteLIgb¤eT kalNaGgÁFatuRbtikr)anpþl;[KñaeTAvijeTAmkkñúglkçxNÐ

Gg;RtUBI famBlesrI nig lMnwg

18-2

Biess)an[ (cMeNHdwgenHKWmansar³sMxan;fa etImYyKWCakarsMeyaKsmasFatusrIragÁkñúg bnÞb;BiesaFn¾karplitsarFatuKImIkñúgmaRtdæan]sSahkm μ b¤ eFVIkarsakl,gedIm,IEsVgyl; lMnaMd¾saMjaMukñúgekasikaCIv³). RbtikmμEdlekIteLIgeRkamlkçxNÐEdl)an[ehAfa Rbtikmμ ekIteLIgÉkÉg. ebIRbtikmμminekIteLIgeRkamlkçxNÐCak;lak; KWvaminekIteLIgÉkÉg. eyIgGegátlMnaMrUb nig KImIÉkÉgral;éf¶ rab;bBa©ÚlTaMg]TahrN¾dUcxageRkam³ • TwkeRCaHFøak;BIelIcuHeRkam b:uEnþminEdlmanBIeRkameLIgelI ekIteLIgÉkÉg • KMnrsárrlayÉkÉgkñúgEBgkaehV b:uEnþsárEdl)anrlayminekIteLIgÉkÉgkñúgsNæanedIm

rbs;vaeT. • TwkkkekIteLIgTabCag 0oC ehIykarrlayTwkkekIteLIgelI 0oC (enA 1atm) • kMedAqøgkat;BIvtßúekþACageTAvtßúRtCak;Cag b:uEnþminEdlRtLb;mkvij • karBRgIkén]s μ ½nkñúg)aLúgEdlmansuBaaØkas CalMnaMekIteLIgÉkÉg (rUb 1.a). lMnaM

Rcasmkvij KWkarRbmUlénRKb;m:UelKuleTAkñúgGMBUlmUlminekIteLIgÉkÉgeT (rUb 1.b). • dMuelah³sUdüÚmRbtikmμCamYyCamYyTwky:agskm μeTACasUdüÚmGIuRduksIut nig]s μ ½n

GIuRdUEsn. dUecñH]sμ½nGIuRdUEsnminmanRbtikmμCamYysUdüÚmGIuRduksIuteTACaTwk nigsUdüÚm. • Edkdak;[RtUvTwknigGuksIuEsneTACasNæaneRcH b:uEnþeRcHminbþÚrÉkÉgeTACaEdk

]TahrN¾TaMgenHbgðajBIlMnaMekIteLIgÉkÉgkñúgTisedAEtmYyminGaceRkamlkçxNÐ dUc Kña k¾GaccUlrYmÉkÉgkñúgTisedApÞúyKñapgEdr.

ebIeyIgvas;lMnaMekIteLIgÉkÉg eFVIdUecñHedIm,IbnßyfamBlénRbBn§½ eyIgGacBnül; ehtuGVIdMu)al;Føak;cuHBIelIPñM nigehtuGVIniTaXrdUvkñúgnaLikaKμanxül;. Rbhak;RbEhlKñacMnYn d¾eRcInén RbtikmμRsUbkMedAKWekIteLIgÉkÉg. ]TahrN¾ cMehHemtan

kJHlOHgCOgOgCH 4,890)()()(2)( 2224 −=Δ+⎯→⎯+

rUbTI1 (a )lMnaMekIteLIgÉkÉg (b) lMnaMminekIteLIgÉkÉg

CMBUkTI18

18-3

]TahrN¾epSgeTotKWRbtikmμbnSabGasIut-)as kJlOHaqOHaqH 2,56)()()( 2 −=ΔΗ→+ −+

b:uEnþkarKitBIPaBqøgBIpasrwgeTApasravdUcCa ³ )()( 22 lOHsOH → kñúgkrNIenH ]bmafalMnaMekIteLIgÉkÉg EtgEtbnßynUvRbBn§½famBlqøak;cuH. BiesaFn¾ R)ab;eyIgfaTwkkkrlayÉkÉgxagelI 0oC eTaHbIlMnaMKWCalMnaMRsUbkMedA. ]TahrN¾epSgeTot EdlCMTas;kar]bmarbs;eyIgKWCakarrMlayGam:UjÚmnIRtatkñúgTwk³ )()()( 3434

2 aqNOaqNHsNONH OH −+ +⎯⎯→⎯ kJ25=ΔΗ lMnaMenHKWekIteLIgÉkÉg ehIyenAminTan; lMnaMRsUbkMedApgEdr. kareRbIR)as;én)art (II) GuksIut KWCaRbtikm μRsUbkMedAEdlekIteLIgÉkÉgenAsItuNðPaBbnÞb; b:uEnþ vakøayeTACa ekIteLIgÉkÉgkalNasItuNðPaB)anbegáIn. )()(2)(2 2 gOlHgsHgO +→ kJo 7,90=ΔΗ BIkarsikSanig]TahrN¾)ancMNab;Garm μN¾ehIynigkrNICaeRcIn eyIgGacsnñidæan dUcteTA³ karbeBa©jkMedAcUlcitþekIteLIgÉkÉgBIRbtikmμ b:uEnþ vaminFanaeT. vaRKan;EtGac mansMrab;RbtikmμbRsUbkMedAEdl)anekIteLIgÉkÉg vaGacman sMrab;Rbtikm μbeBa©jkMedA EdlminEmnekIteLIgÉkÉg. b¤müa:geToteyIgminGacsMercfa RbtikmμKImInwgekIteLIgÉkÉg EtÉgelImUldæanbNþÚrfamBlkñúgRbBn§½. edIm,IdMeNIrkarnUv karTayTukva eyIgRtUvkarbrimaN ETm:UDINamic epSgeTot EdlbþÚreTACaGg;RtUBI. Gg;RtUBI ENTROPY

kñúgkarTayTukBIlMnaMekIteLIgÉkÉg eyIgRtUvkarsÁalcMNucBIrGMBiRbBn§½enH. cMNuc mYyKWbNþÚr Gg;tal;BI EdlCitesμIeTAnig EΔ sMrab;lMnaMCaeRcIn. cMNucmYyeTotKWGg;RtUBI (S)

EdlCargVas;PaBécdnüb¤ PaB\tsNþab;Fñab;énRbBn§½. RbBn§½énPaB\tsNþab;Fñab;FMCag KW Gg;RtUBIrbs;vakan;EtFMCag. pÞúymkvij RbBn§½)anteRmobRtwmRtUveRcIn KW Gg;RtUBIrbs;va kan;EttUc. viFImYyeTotedIm,IbgðajkarteRmobehIynig\tsNþab;Fñab; KwCakarelgeborh‘U. eborkñúgh‘Ufμ IKW)anteRmobCalMdab;lMedayy:ags¥at (eborKW)anerobBIGat;eTAesþcehIysVItkñúg lMdab;lMedayBIbiuceTAkWBIkar:UeTACYg). Caf μ IeLIgvijh‘URtUv)ansab;eboKWminGacsßittamlMdab; lMedayeToteT. eyIgmanlT§PaBtictYc Edlkarsab;eboGacrkSaPaBedImtamlMdabeLIg


18-4

vij;. manrebobCaeRcInsMrab;eFVI[eboxusBIlMdab;lMeday b:uEnþmanviFIEtmYyKt;sMrab;eFVI[eTA Camandab;lMedaytamniymn½yrbs;eyIg. cMeBaHsarFatunImYy²PaKl¥itenAkñúgPaBénGgÁFaturwg)anteRmobRtwmRtUvCagkñúgPaB énGgÁFaturav EdlPaBrwg nigrav)anteRmobRtwmRtUvCagPaB]s μ ½n. dUecñH sMrab;cMnYnm:UldUcKña énsarFatueyIgGacsresr³ Ssolid < Sliquid << Sgas

müa:geTotGg;RtUBIGFib,ayBIvisalPaBEdlGatUm m:UelKul b¤GIuy:ug)anbric©akkñúg rebob \tsNþab;Fñab;kñúgdMbn;)an[kñúglMh. viFImYyedIm,IKitBIlMdab;lMedaynig\tsNþab;Fñab;KWenAkñúgBaküRbU)ab‘ÍlIet. RBwtþikarN¾ EdlmanRbU)ab‘ÍlIeteRcIn KWCaRbwtþikarN¾mYyEdlelIkmaneLIgenAkñúgviFICaeRcIn ehIy RBwtþikarN¾EdlmanRbU)ab‘ÍlIettictYcKWCaRBwtþikarN¾mYYyEdlGacekIteLIgkñúgviFIFIEtmYy b¤kñúg viFIBIrbIbu:eNÑaH. ]TahrN¾ eyagtamrUb 1a ]bmafa manm:UelKulEtmYyKt;enAkñúgdbxag eqVgenAPaBedIm. Edayehtufa dbBIrmanmaDes μ IKñaRbU)ab‘ÍlIetEnrkeXIjm:UelKulenaHkñúgdb NamYybnÞab;BIr:Ub‘Íen)anebIkKW1/2. ebImanm:UelKulBIrvtþmanenAdMbUgRbU)ab‘ÍetEnrkeXIj m:UelKulTaMgBIrCamYyKñakñúgkUndbEtmYybnÞab;BIebIkr:Ub‘Íen KW

21

21× =

41 . \LÚvenH

41 KWCa

pleFobx<s; ehtuenHvaminKYrmanGVIPJak;ep¥IledIm,Irkm:UelKulTaMgBIrenAkñúgkUndbdUcmYy bnÞab; BI)anebIkr:Ub‘Íen. dUecñH minmankarlM)akedIm,IeXIjfa dUcCacMnYnénm:UelKulekIneLIg RbU)ab‘ÍlIet (P) EdlrkeXIjénRKb;m:UelKulenAkñúgkUndbdUcKñaeTACamanPaBeCOnelOntic Cag ³ P = ×⎟

⎠⎞

⎜⎝⎛×⎟

⎠⎞

⎜⎝⎛×⎟

⎠⎞

⎜⎝⎛

21

21

21 …..

= N

⎟⎠⎞

⎜⎝⎛

21

Edl N CacMnYnsrubénm:UelKulmanvtþman. ebI N =100 eyIg)an ÷ P =

100

21⎟⎠⎞

⎜⎝⎛ = 8 3110−×

ebI N sßitkñúglMdab; 6x1023 cMnYnm:UelKulkñúgmYym:Ulén]sμ ½n RbU)ab‘ÍlIeteTACa 23106

21 ×

⎟⎠⎞

⎜⎝⎛ EdlCacMnYnmYyd¾tUcvaGacRtUv)ankMNt;es μ IsUnü. kñúgmUldæankarBinitüRbU)ab‘ÍlIet

eyIgGacsgÄwmfa]sμ ½nGacbMeBjeTAkñúgkUndbTaMgBIrÉkÉg nigCamYyRBwtþikarN¾ kMBugman. Tamry³PaBdUcKña \LÚvenHeyIgyl;fa sßanPaB)anBN’nakñúgrUb 1b minekIteLIgÉkÉg

CMBUkTI18

18-5

BIeRBaHvamintMNag[RBwtþikarN¾RbU)ab‘ÍlIetx<s;. edIm,IsegçbkarBiPakSarbs;eyIg ³ kñúgPaB lMdab;lMedaymanRbU)ab‘ÍlIetTabénkarkekIteLIg nigGg;RtUBItUc ehIyenAeBlEdlPaB)an r:ay)a:ymanRbU)ab‘ÍlIetx<s;énkarkekIteLIg nig Gg;RtUBIFM. Tarag 1 tMélGg;RtUBIsþg;da (So) sMrab;sarFatu)aneRCIserIs

sarFatu (So) (J/K.mol) H2O(l) 69,9 H2O(g) 188,7 Br2(l) 152,3 Br2(g) 245,3 I2(s) 116,7 I2(g) 260,6

C(eBRC) 3,44

C(RkahVIt) 5,69 He(g) 126,1 Ne(g) 146,2

dUcCaeyInnwgeXIjfa vaGaceFVIkarkMNt; Gg;RtUBIdac;xat énsarFatu bu:EnþeyIgminGac eFVIsMrab;famBl b¤ Gg;tal;BI. Gg;RtUBIsþg;da KWCaGg;RtUBIdac;xaténsaFatuenA 1atm nig 25oC. enHCatMélCaTUeTA)aneRbIkñúgkarKNna. (nwkeXIjfa PaBsþg;dasMedAeTAelI 1atm. KMnitsMrab;eFVIkarkMNt; 25oC KWCalMnaMCaeRcInEdl)anykecjBIsItuNPaBbnÞb;). tarag 1

CabBa¢IGg;RtUBIsþg;daénFatu nigsmasFatumYycMnYn. xñaténGg;RtUBIKW J/K b¤ J/K.mol

énsarFatu. eyIgeRbI s‘Ul RbesIrCag KILÚs‘Ul BIeRBaHtMélGg;RtUBIKWCaRbePTtUcNas;. Gg;RtUBIénFatu nig smasFatu CacMnYnviC¢man ( So > 0). pÞúymkvij Gg;tal;BI kMNrsþg;da ( o

fΔΗ ) sMrab;FatuTaMgLaykñúgTMrg;sßirPaBrbs;eKKWes μ IsUnü nig sMrab;smasFatuvaGac viC¢man b¤ GviC¢man. eyIgtamtarag 1 eyIgGaceFVIkarGegátCaTUeTA. Gg;RtUBIéncMhayTwkKWFMCagGg;RtUBI énTwkrav BIeRBaHmYym:UlénTwkmanmaDticCageRcInenAkñúgPaBravCagkñúgPaBvaCa]sμ½n. müa:g vijeTotm:UelKulTwkmansNþab;Fñab;CagenAkñúgPaBrav BIeRBaHmanlMhtUcCagsMrab;BYkvataMg TI. Rbhak;RbEhlKñacMhayRbUmmantMélGg;RtUBIx<s;CagGIuy:utrwg. cMeBaHsarFatuxusKñakñúg pasdUcKñam:UelKulsaMjaMu nig m:asm:UlkMNt; EdlmYymantMélGg;RtUBIx<s;Cag. eBRC nig RkahVItCaGgÁFaturwgCa]TahrN¾ b:uEnþ eBRCmankartERmoblMdab;lMedayCag (emIl rUb 28

CMBYk11). dUecñH eBRCmantMélGg;RtUBItUcCagRkahVIt. enGug nig eGlüÚmCa]s μ ½nm:UNUGatUm b:uEnþ enGugmantMélGg;RtUBIFM Cag eGlüÚm BIeRBaH m:asm:Ulrbs;vaFMCag.


18-6

PaBRsedogKñaénfamBl Gg;RtUBI nigGg;talBI KWGnuKmn¾PaB. bgðajBIlMnaMCak;Esþg EdlenAkñúgbMErbMrYlRbBn§½BIPaBedImeTAPaBsMerc. bMErbMrYlGg;RtUBIsMrab;lMnaM SΔ KW ³ if SSS −=Δ Edl fS nig iS KWCaGg;RtUBIénRbBn§½kñúgPaBedIm nig PaBsMerc erogKña. RbsinebIlT§pl ERbRbYlkñúgkMeNIn kñúgPaBécdnü b¤ PaB\tsNþab;Fñab; bnÞab;m b¤ k fS >

iS b¤ SΔ > 0 . rUb 2 bgðajBIlMnaMmYycMnYnEdlnaMeTArkkMeNInkñúgGg;RtUBI. kñúgkrNInImYy²eyIg eXIjfa bMErbMrYlRbBn§½BIPaB\tsNþab;Fñab;eRcIneTAPaB\tsNþab;Fñab;tic. rUb 2 lMnaMEdlnaMeTArkkarekIneLIgkñúgGg;RtUBIénRbBn§½ (a) karrMlay³ liquidS > solidS (b) rMhYt³ vaporS > liquidS (c) karrMlay (d) karkMedA ³

2TS > 1TS .

karenHbBaa¢k;fa TaMglMnaMrlay nig lMnaMrMhYtman SΔ > 0. lMnaMsUluysüúgEtgEt naMeTAkMeNIgGg;RtUBI. kalNaRkamsárrMlaykñúgTwk TMrg;)anerobryx<s;bMputénGgÁFaturwg nig EpñkénTMrg;)anerobryénTwk)anbMEbk. ehtudUecñHehIy sUluysüúgKWmanPaB\tsNþab;Fñab; CagkñúgGgÁFaturlaysuT§ nig GgÁFaturMlaysuT§. kalNaGgÁFaturwgGIuy:UnicrlaykñúgTwk KWmankarpþl;[ BIredIm,IeFVI[Gg;RtUBIekIn KWlMnaMsUluysüúg nig karbMEbkénsmasFatu eTACaGIuy:ug. NaCl(s) Na + (aq) + Cl − (aq)

GaRs½yehtuenH eyIgRtUvEtbBaa¢k;BIGIuRdatkmμ EdleFVI[m:UelKulTwkkøayCaerobry CagCMuvijGIuy:ug. enHCalMnaMbnßyGg;RtUBI. sMrab;GIuy:ugtUcEdlmanbnÞúkGIuy:ugx<s;dUcCa

H2O

CMBUkTI18

18-7

+3Al nig +3Fe karfycuHkñúgGg;RtUBIedayGIuRdatkm μGacCasMxan;CagkMeNInkñúgGg;RtUBIeday karlay nigkarbMEbk. dUecñH karERbRbYlGg;RtUBIsMrab;RKb;lMnaMGacCaGviC¢man. karkMedA eFVI[mankMeNInGg;RtUBIénRbBn§½pgEd. CabEnßm m:UelKulGaceFVI[clnaBIcMnucmYyeTAcMnuc mYyeTot ehIyclnabgVil (rUb 3) nig clnalMj½r (rUb 13 CNBYkTi17). sItuNðPaB kan;Etx<s;clnam:UelKulkan;EtFM. mann½yfa kMeNInkñúgPaBécdnüenAkMritm:UelKulEdlTTYl r:ab;rgeTAelIkMeNInGg;RtUBI. ]TahrN¾dUcxageRkamTak;TgnigbMErbMrYlGg;RtUBIénRbBn§½CalT§pl)anmkBIbNþÚrrUb. ]TahrN¾ 1. TayTukfaetIbNþÚrGg;RtUBIKWFMCag b¤ ticCagsUnüsMrab;lMnaMdUcteTA³ a)kMNkeGtaNul b)karrMhYtRbUmravecjBIEkvEb‘EsrenAsItuNðPaBbnÞb; c)karrMlaysak;RkUskñúgTwk d) eFVI[]sμ ½nGasUtcuHRtCak;BI 80oC dl; 20oC cMelIy a) enHCakarbenÞrpasraveTArwg. RbBn§½eTACamanrebobeRcIn dUecñH SΔ < 0

b) enHCakarbenÞrpasrwgeTAcMhay. RbBn§½eTACamanPaB\tsNþab;Fñab;eRcIn SΔ > 0

c) sUluysüúgKWPaB\tsNþab;Fñab;eRcInminERbRbYlCagPaKpSMrbs;va (GgÁFaturlay nig GgÁFatu rMlay) . dUecñH SΔ > 0

d) clnam:UelKulénkarcuHRtCak;ekIneLIg. dUecñH SΔ < 0

lMhat;Gnuvtþn¾ ³ etIRbBn§½bNþÚrGg;tal;BIsMrab;lMnaMnImYy²RbRBwtþeTAdUcemþc ? a) kMNkcMhayTwk b) karkekIteLIgRkams‘ucRkUsBIsUluysüúgEq¥thYs

c) karkMedA]sμ ½nGIuRdUEsnBI 60oC eTA 80 oC

d) karsMgYtTwkkkd¾RbesIrbMput

rUb 3 clnargVilénm:UelKul. m:UelKulTwkCacrgVilkñúgrebobbIy:agGMBIGkS½ x, y, nig z


18-8

c,ab;TIBIrénETm:UDINamic karP¢ab;KñarvagGg;RtUBI nig Rbtikm μÉkÉgKW)anbgðajeday c,ab;TIBIr énETm:UDINamic ³

Gg;RtUBIénsklekIneLIgkñúglMnaMÉkÉg nig enAsl;minERbRbYlkñúglMnaMlMnwg. edayehtufa sklKW)anbegáIteLIgRbBn§½ nig mCÄdæanCMuvij bMErbMrYlGg;RtUBIkñúgslk( univSΔ ) sMrab;lMnaM nImYy²KWCaplbUkénbMErbMrYlGg;RtUBIkñúgRbBn§½ ( sysSΔ ) nigkñúgmCÄdæanCMuvij ( surrSΔ ). eday eRbIKNitviTüa eyIgGacbgðaj c,ab;TIBIr én ETm:UDINamicdUcteTA³

sMrab;lMnaMekIteLIgÉkÉg ³ uniSΔ = surrsys SS Δ+Δ > 0 (1)

sMrab;karRbRBwtþeTAénlMnwg ³ uniSΔ = surrsys SS Δ+Δ = 0 (2)

sMrab;lMnaMÉkÉg c,ab;TIBIrniyayfa univSΔ RtUvEtFMCagsUnü b:uEnþvaminCMnYskardak; kMriteTAelITaMg sysSΔ b¤ surrSΔ . dUecñH KWvaGacmantMélGviC¢mansMrab; sysSΔ b¤ surrSΔ Edl plbUkbrimaNTaMgBIrenHKWFMCagsUnü. sMrab;karRbRBwtþeTAénlMnwg univSΔ . kñúgkrNIenH

sysSΔ nig surrSΔ RtUvEtesμ IeTAnigTMhM b:uEnþ sBaaØpÞúyKña. etImanGVIekIteLIg RbsinebIlMnaMrk eXIjmYycMnYn Edl surrSΔ GviC¢man ?etImann½yy:agdUcemþc KWfalMnaMminekIteLIgÉkÉg kñúgTisedA)anBiBN’na. dUcCa ekIteLIgÉkÉgkñúgTisedApÞúyKña.

bNþÚrGg;RtUBIkñúgRbBn§½ edIm,IKNna sysSΔ eyIgRtUvsÁal;TaMg sysSΔ nig surrSΔ . Tuk[eyIgBinitüCadMbUgeTA

elI sysSΔ . ]bmafa RbBn§½KW)antMNagedayRbtikmμdUcteTA ³ aA + bB cC + dD

dUckñúgkrNIGg;tal;BIénRbtikmμ[ emIlsmIkar (6.8) ] Gg;tal;BIsþg;daénRbtikm μ orxnSΔ pþl;[eday

orxnSΔ = [c oS (C) + d oS (D) ] – [a oS (A) + b oS (B)] (3)

b¤ CaTUeTA kareRbI Σ edIm,I tMNag[ plbUk ehIy m nig n sMrab;emKuNesÞItüÚemRTI kñúgRbtikmμ ³ o

rxnSΔ = Σ onS (plitpl) - Σ omS (GgÁFatuRbtikr) (4)

tMélGg;RtUBIsþg;daéncMnYnd¾eRcInénsmasFatuRtUv)anvas;KitCa J/K.mol. edIm,I KNna o

rxnSΔ ( EdlCaRbBn§½ ) eyIgRkeLkeTAemIltMélkñúgesckþIbEnßm 3 nig eFVIeTAtam ]TahrN¾dUc teTA .

CMBUkTI18

18-9

]TahrN¾ 2

BItMéldac;xatGg;RtUBIkñúgesckþIbEnßm 3 KNnabNþÚrGg;RtUBIsþg;dasMrab;Rbtikm μdUc teTAenA 25oC .

a) )()()( 23 gCOsCaOsCaCO +→ b) )(2)(3)( 22 gNHgHgN g→+ c) )(2)()( 22 gHClgClgH →+

cMelIy ³ eyIgGacKNna oSΔ edaykareRbIsmIkar ( 4)

a) orxnSΔ = [ oS (CaO ) + oS ( 2CO ) ] - [ oS ( 3CaCO )]

= [ (1mol)(39,8J/K.mol) + (1mol)9213,6J/K.mol] - (1mol)(92,9J/k.mol) = 160.5J/K

dUecñH kalNa 1molén 3CaCO bMEbk[Ca 1mol én CaO nig 1mol én]sμ ½n 2CO

mankarekIneLIgkñúgGg;RtUBIes μ IeTAnwg 160,5J/K . b) o

rxnSΔ = [2 oS ( 3NH ) - [ oS ( 2N ) + )](3 2HS o = (2mol)(193J/K.mol) – [(1mol)(192J/K.mol) + (3mol)(131J/K.mol)] = - 199J/K

lT§plenHbgðajfa kalNa 1molén]sμ½nGasUtRbtikmμCamYy 3mol én]s μ ½n GIuRdUEsn[plCa 2mol ]sμ ½nGam:Ujak; mankarfycuHkñúgGg;RtUBI esμ IeTAnwg - 199J/K.

c) orxnSΔ = [2 oS ( HCl ) - [ oS ( 2H ) + )]( 2ClS o

= (2mol)(187J/K.mol) – [(1mol)(131J/K.mol) + (1mol)(223J/K.mol)] = 20J/K

dUecñH karkekIt 2mol én]sμ ½n HCl BI 1mol én]s μ ½n 2H nig 1mol én ]s μ ½n 2Cl CalT§plmankarekIneLIgtictYckñúgGg;RtUBI es μ IeTAnwg 20J/K .

lMhat;Gnuvtþn¾ (a) )(2)()(2 22 gCOgOgCO →+ (b) )(2)(3 32 gOgO → (c) )()()()(2 22323 gCOlOHsCONasNaHCO ++→

tamry³lT§plén]TahrN¾ 2 KWCak;EsþgCamYylT§pl)anGegátsMrab;Rbtikmμ epSg²CaeRcIneTot. yl;RBmCamYyKñaeK begáItc,ab;CaTUeTAdUcteTA ³

-ebIplitplRbtikmμmanm:UelKul]sμ½neRcInEdlvaeRbI []TabrN¾ 2(a)] enaH oSΔ viC¢man - ebIcMnYnsrubénm:UelKul]sμ ½nfy []TahrN¾ 2(b)] enaH oSΔ GviC¢man - ebIK μankarERbRbYlsrubenAkñúgcMnYnsrubénm:UelKul]s μ ½n []TahrN¾ 2(c) ] bnÞab;mk

oSΔ Gac viC¢man b¤ GviC¢man b:uEnþ nigmanTMnak;TMngticCacMnYnelx.


18-10

karsnñidæanTaMgenHeFVI[mann½ybBaa¢k;fa ]s μ ½nminERbRbYlmanGg;RtUBIFMCagGgÁFaturav nig GgÁFaturwg. cMeBaHRbtikm μEdlTak;TgEteTAnigGgÁFaturav nigrwg karTayTuksBaaØén oSΔ KWmankarlM)akeRcIn b:uEnþ kñúgkrNICaeRcIndUcCakMeNInkñúgcMnYnCasrubénm:UelKul b¤ GIuy:ug Edl Cab;eTACamYyekIneLIgkñúgGg;RtUBI. ]TahrN¾ 3

TayTukfaetIbMErbMrYlGg;RtUBIénRbBn§½kñúgRbtikm μdUcteTAenHmansBaaØ viC¢man b¤ GviC¢man. (a) )(2)()(2 222 lOHgOgH →+ (b) )()()( 34 gHClgNHsClNH +→ (c) )(2)()( 22 gHBrgBrgH →+

cMelIy (a) ]sμ ½nBIrcUlRbtikmμeTACasNæanGgÁFaturav. dUecñH SΔ KWGviC¢man (b) edayehtufa GgÁFaturwg)anbMElgeTACaplitpl]sμ ½nBIr . dUecñH SΔ KWviC¢man (c) eyIgeXIjfacMnYnm:UldUcKñaén]sμ ½nKW)anTak;TgKñakñúgGgÁFatuRbtikrk¾dUcKñakñúgplit pl. dUecñH eyIgminGacTayTukBIsBaaØén SΔ b:uEnþ eyIgdwgBIkarERbRbYlKWtUcNas; lMhat;Gnuvtþn¾ BiPakSaCalkçN³KuNPaBsBaaØénbMErbMrYlGg;RtUBI)ancUlrYmsMrab;lMnaMdUcteTA ÷ (a) )(2)(2 gIgI → (b) )(2)()(2 2 sZnOgOsZn →+ (c) )(2)()( 22 gNOgOgN →+

bMErbMrYlGg;RtUBIkñúgmCÄdæanCMuvij bnÞab;mkeyIgnwgeXIj surrSΔ RtUv)anKNnay:agdUemþc. enAeBlmanlMnaMbeBa©jkMedA

cUlrYmkñúgRbBn§½. kMedAEdl)anbBa¢ÚneTAmCÄdæanCMuvijbegáInclnaénm:UelKulkñúgmCÄdæanCMuvij. ehtudUecñHehIy mankarekIneLIgkñúgPaB\tsNþab;Fñab;enAÉkMritm:UelKul nig Gg;RtUBIén mCÄdæanCMuvijekIn. pÞúymkvijlMnaMRsUbkMedAkñúgRbBn§½RsUbkMedA nig eFVI[fycuHGg;RtUBI énmCÄdæanCMuvij BIeRBaHclnam:UelKulfycuH (rUb4). cMeBaHlMnaMsMBaFefr bMErbMrYlkMedA KWes μ IeTAnigbMErbMrYlGg;tal;BIénRbBn§½ sysHΔ . dUecñH bMErbMrYlGg;RtUBIénmCÄdæanCMuvij surrSΔ KWsmamaRteTAnig sysHΔ

surrSΔ ∝ sysHΔ

CMBUkTI18

18-11

sBaaØdkKW)aneRb IBIeRBaHebIlMnaMCakarbeBa©jkMedA sysHΔ KWmantMélGviC¢man nig surrSΔ KWCabrmaNviC¢man EdlbgðajBIkarekIneLIgkñúgGg;RtUBI. müa:gvijeTotsMrab;lMnaM

RsUbkMedA sysHΔ KWviC¢man nig sBaaØGviC¢manR)akdfaGg;RtUBIénmCÄdæanfycuH. bMErbMrYlGg;RtUBIsMrab;brimaN)an[énkMedAk¾GaRs½ypgEdreTAelIsItuNðPaB. ebI

sItuNðPaBénmCÄdæanx<s; m:UelKulKWeBareBjeTAedayfamBlrYcCaeRsc. dUecñH karRsUb kMedABIlMnaMbeBa©jkMedAkñúgRbBn§½nigmanTMnak;TMng\T§iBlbnþicbnÞÜcelIclnam:UelKul nig CalT§plekIneLIgkñúgGg;tUBIniwgmantMéltUc. dUcecñH ebIsItuNðPaBénmCÄdæanTab bnÞab;mk karbEnßmbrimaNdUcKñaénkMedA nwgeFVI[mankarekIneLIgKYr[kt;sMKal;kñúgclnam:UelKul ehtuenHkMeNIneLIgFMCagkñúgGg;;RtUBI. edayPaBRsedogKñaGñkNamñak;kMBugk¥kkñúg ePaC-nIydæan EdlmanmnusSkkkuj niwgnaM[rMxandl;GtifiCnCaeRcIn b:uEnþ GñkNamñak;kMBugEtk¥k kñúgbNÑal½yKWnwgBitCamankarxMxandUcKña. BITMnak;TMngRcasKñarvag surrSΔ nig sItuNðPaB

¬KitCaEklvin¦ KWfa sItuNðPaBx<s;Cag surrSΔ tUcCag nig Rcasmkvij eyIgGacsresrTMnak;TMngxagelICa³

sorrSΔ = TH sysΔ− ( 5)

rUb 4 (a) CalMnaMbeBa©jkMedAepÞrkMedABIRbBn§½eTAmCÄdæanCMuvijnigCalT§plkñúgkarekIneLIgkñúg Gg;RtUBIénmCÄdæanCMuvij. (b) lMnaMRsUbkMedARsUbkMedABImCÄdæanCMuvijnig dUecñH fycuHGg;RtUBI énmCÄdæanCMuvij.

\LÚvenHTuk[eyIgGnuvtþn¾lMnaMsMrab;karKNna sysSΔ nig surrSΔ edIm,IsMeyaKGam:Ujak; nigsYrfa etI RbtikmμekIteLIgÉkÉgenA 25oC ³

)(2)(3)( 22 gNHgHgN g→+ oHΔ = -92,6kJ

BI ]TahrN¾ 2b eyIgman sysSΔ = -199J/K nigeFVIkarCMnYs sysHΔ (-92,6kJ) kñúg smIkar ( 5) eyIg)an³


18-12

sorrSΔ =K

J298

)10006,92( ×−− = 311J/K

bNþÚrkñúgGg;tal;BIénsklKW ³ univSΔ = sysSΔ + sorrSΔ

= -199J/K + 311J/K = 112 J/K

edaysarEt univSΔ viC¢maneyIgTayTukfa RbtikmμnwgekIteLIgÉkÉgenA 25oC. vamanlkçN³sMxan;edIm,IrkSaKMnitfa RKan;EtRbtikmμKWekIteLIgÉkÉgminmann½yfa vanwgekIt eLIgenAel,OnEdlGacGegát)an. sMeyaKGam:Ujak;KW CakarBitmanlkçN³yWtNas;enA sItuNðPaBbnÞb;. ETm:UDINamicGacR)ab;eyIgfa RbtikmμnwgekIteLIgeRkamlkçxNÐCak;lak; b:uEnþ minGacdwg c,as;las;BIel,OnnwgekIteLIg. RbtikmμKWCavtßúbMNgénKImIsIuenTic. c,ab;TIbIénETm:UDINamic nig Gg;RtUBIdac;xat

CacugbBa©b;KWvamanlkçN³smrmüedIm,IbBaa¢k;BIc,ab;TIbIénETm:UDINamic edaysegçb kñúgTMnak;TMngCamYykarkMNt;éntMélGg;RtUBI. dUecñH eyIg)anTMnak;TMngGg;RtUBInwg PaB\t-sNþab;Fñab;énm:UelKul-PaB\tsNþab;Fñab;kan;EtFM b¤ PaBesrIénclnarbs;GatUm b¤m:UelKul kñúgRbBn§½ PaBFMCagGg;RtUBIénRbBn§½. kartMerobd¾mansNþab;Fñab;énRKb;sarFatuCamYynig PaBesrIticénclnaGatUmnigm:UelKulKWBitCaRkamsarFatuenAtMéldac;xatsUnü (0K) . dUecñH KWGg;RtUBITabbMputénral;sarFatuGacrkSaKWfaBitCaRkamenAtMéldac;xatsUnü. eTAtamc,ab; TIbIénETm:UNamic Gg;RtUBIénRkamsarFatuKWBitCasUnüenAtMélsItuNðPaBdac;xatsUnü. enA sItuNðPaBekInclnaesrI k¾ekIneLIgEdr. dUecñH Gg;RtUBIénral;sarFatuenAsItuNðPaBxagelI 0K KWFMCag. Kt;sMKal;pgEdrfa ebIRkamKWminsuT§ b¤ ebIva)anxVHcenøaH bnÞab;mk Gg;RtUBI rbs;vaKWFMCagsUnü sUm,IEtenA 0K dUecñH vaminKYr)antMerob\tex©aH. cMnucsMxan;GMBIc,ab;TIbIénETm:UKImI KWGnuBaaØti[eyIgeFVIkarkMNt;Gg;RtUBIdac;xatén sarFatu. karcab;epþImCamYycMeNHdwgsMrab;Gg;RtUBIénRkamsarFatusuT§KWes μ IsUnüenA 0K . eyIgGacvas;kMeNInkñúgGg;RtUBIénsarFatukalNa)andutkMedAdl; 298K. bNþÚrGg;RtUBI SΔ )anbgðajdUcxageRkam³ if SSS −=Δ = fS (eday 0=iS )

CMBUkTI18

18-13

Gg;RtUBIénsarFatuenA 298K bnÞab;mk)an[eday SΔ b¤ fS EdlehAfa Gg;RtUBIdac;xat BIeRBaHenHKWCatMélBitnigminmantMélNa)anmkedayeRbIeyagminsmRsb. dUecñH tMél Gg;RtUBI)anmkBIRbPBNamYy EdlCaRKb;tMéldac;xaténGg;RtUBI. pÞúymkvij eyIgminGac mantMéldac;xaténfamBl b¤ Gg;tal;BIénsarFatu BIeRBaHtMélsUnüénfamBl b¤ Gg;tal;Bi minkMNt;. rUb 5 bgðajBIbMErbMrYl(ekIn)kñúgGg;RtUBIénsarFatuCamYysItuNðPaB. enAtMél dac;xatsUnü (]bmafa enHBitCaRkaménsarFatu). dUcEdl)ankMedA Gg;RtUBIrbs;vaekIneLIg bnþicmþg²edaysarEtclnam:UelKulFMCag. enAcMnucrlayTMhMGacekInkñúgGg;RtUBIdUcCa PaBravécdnüeRcInKWRtUv)anekIteLIg. kan;EtbegáInkMedAGg;tal;BIénGgÁFaturavCafμ IeLIgvij k¾begáInclnam:UelKul. enAcMnucrMBuHmanman karekIneLIgxøaMgkñúgGg;RtUBIEdlCalT§plén GgÁFaturaveTACaPaBqøgén]sμ ½n. putBIsItuNðPaBenH Gg;RtUBIén]s μ½nbnþkarekIneLIgCamYy nigkMeNInsItuNðPaB.

rUb 5 kMeNInGg;RtUBIénsarFatuenAeBlEdlsItuNðPaBekInBItMéldac;xarsUnü

KImIGnuvtþn_ RbsiT§PaBéneRKOgynþkMedA

eRKOgynþKWCam:asIun EdlbMElgfamBleTACakm μnþ kMedAeRKOgynþKWCaKWCam:asuInEdl bMElgkMeDAm:asIuneTACakmμnþ. kMedAm:asIunedIrtYCac,ab;sMxan;kñúgbec©kviTüasgÁmrbs;eyIg eKerobcMBIm:asIunrfynþeTAcMhayTYb‘ÍnEdleFVI[m:asIunePøIgedIredIm,IbegáItGKÁIsnI. Edaymin Kitdl;RbePTkMedAm:asIunkMritRbsiT§PaBrbs;vaKWmanlkçN³sMxan;. KWfasMrab;brimaN)an


18-14

bBa©ÚletIkmμnþmanGtßRbeyaCn¾b:un μan EdleyIgGacTTYl)anBIm:asIun? c,ab;TIBIrénETm:U DINamicCYyeyIg[cMelIysMrab;sMnYrenH. rUbxageRkambgðajBIsNæangayénkMedAm:asIun. sIuLaMgRtUv)anbMeBjedayBIsþúgK μan TMgn; KWenAsItuNðPaBedIm 1T . bnÞab;mksIuLaMgRtUv)andut kMedAenAsItuNðPabx<s;Cag 2T . ]sμ ½nkñúgsuILaMgrIk nigRcanBIsþúgeLIgelI. cugbBa©b;KWRtUv)an [RtCak;mksItuNðPaB 1T nig]bkrN¾Rtlb;eTAPaBedImrbs;va. edaykareFVIsarcuHeLIgeTA vijeTAmkclnaeTAelI-cuHeRkaménBIsþúgGacRtUv )aneFVI[BIsþúgRtUv)anbegáIteLIgeFVI[man kmμnþemkanic.

lkçN³dUcKñaénkMedAm:asIun KWkMedAmYycMnYnRtUv)anbeBa©jeTAmCÄdæanCMuvijkalNaeK eFVIkmμnþ. CamYyBIsþúgkñúgTItaMgxagelIminCYy[km μnþGacdMeNIrkar)an RbsinebIeyIgminTuk [RtCak;sIuLaMgRtLb;eTA 1T .

kMedAm:asIungay (a) m:asIunKWcab;epþImenA 1T (b) kalNa)ankMedAdl; 2T BIsþúg)anRcaneLIg elIrhUtdl;]sμ ½nrIkmaD. (c) kalNaTuk[RtCak;dl; 1T BIsþúgRtLb;eTATItaMgPaBedImvavij.

lMnaMeFVI[RtCak;bnßykMedABIm:asIun EdlKYrEttamviFIepSgeTot)anbMElgeTACakmμnþ ehIyedayehtuenH kEnøgkMNt;elIRbsiT§PaBénkMedAm:asIun. rUbenATMB½rbnÞab;bgðajBIlMnaM benÞrkMedAkñúgkMedAm:asIun. enAPaBedImbrimaNCak;lak;énkMedApøas;TIBIkMedAbMrug (enAsItuNð-PaB hT ) eTAkñúgm:asIun. dUcCam:asIuneFVIkm μnþ kMedAmYycMnYnKW)anbeBa©jeTAmCÄdæanCMuvij b¤ kMedA)at;bg; (enA sItuNðPa cT ) . tamniymn½y RbsiT§énkMedAm:asIunKW ³

Tinñplkm μnþmanRbeyaCn¾ 100×

viPaKEp¥kelIc,ab;TIBIrbgðajfa RbsiT§PaBk¾GacbgðajtamkenSambUcxageRkam³ RbsiT§PaB = %1001 ×⎟⎟

⎠

⎞⎜⎜⎝

⎛−

h

c

TT

RbsiT§PaB = famBlbBa©l

CMBUkTI18

18-15

= %100×−

h

ch

TTT

dUecñH RbsiT§PaBénkMedAm:asIunKW)anpþl;[edayPaBxusKñakñúgsItuNðPaBrvag kMedAbMrug nig kMedA)at;bg; (kMedATaMgBIrKitCaEklvin) edk[sItuNðPaBénkMedAbMrug. kñúgkarGnuvtþ eyIg GacbegáIt)an ( ch TT − ) kan;EtFMRbsinebIGaceFVIeTA)an b:uEnþ edayehtufa cT minGacesμ IsUnü nig cT minGacminkMNt; enaHRbsiT§PaBkMedAm:asIunGacminTTYl)an 100%. enAeragcRkfamBlkMedAcMhayhYsehtuenARbmaN Co560 ( K833 ) KW)aneRbIedIm,I eFVI[dMeNIrkarTYb‘ÍnsMrab;karbegáItGKÁIsnI. sItuNðPaBrbs;kMedAEdl)at;bg;KWRbmaNCa

Co38 (311K) . RbsiT§PaBKW ÷ RbsiT§PaB = %100

8833311833

×−

KKK = %63

kmμnþ karepÞrkMedAenAeBlEdlkareRbIR)as;kMedAm:asIun kñúgkarGnuvtþn¾RbsiT§iPaBGtibrmaNKWEt40PaKryeRBaHmankkit nigkar)at;bgkMedA.

dUecñH kñúgmYyetanFüúÚgfμmanEt0,4etanEdlplitGKÁisnI ehIy0,6etanx¢Hx¢ayedaykar)at; bgkMedA.

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

famBlesrI GIBBS

c,ab;TIBIrénETm:UDINamicR)ab;eyIgfa Rbtikm μÉkÉgekIneLIgGg;RtUBIskl KWfa univSΔ >0. müa:geTotedIm,IkMNt;sBaaØ univSΔ sMrab;Rbtikm μ dUecñH eyIgRtUvkarKNnaTaMg sysSΔ nig surrSΔ . Gars½yehtuenH eyIgEtgEtykcitþTukdak;EteTAelImanGVIekIteLIgkñúg

EpñkRbBn§½ ehIyeFVIkarKNna surrSΔ EdlGacmanPaBlM)ak. dUecñH CaTUeTAeyIgeCOCak;elI

kMedAbMrug hT

kMedAm:asIun

kMedA)at;bg; cT


18-16

GnuKmn¾ETm:UDINamicepSgeTot edIm,ICYy[eyIgkMNt;fa etIRbtikm μniwgekIteLIgÉkÉg RbsinebIeyIgKitEtBIRbBn§½ xøÜnvaKt;. BIsmIkae 1 eyIgdwgfa sMrab;lMnaMekIteLIgÉkÉg eyIg)an³ surrsysuniv SSS Δ+Δ=Δ > 0

CMnYs T

sysΔΗ− sMrab; surrSΔ eyIgGacsresr

univSΔ = sysSΔT

sysΔΗ− > 0

KuNGgÁTaMgBIrénsmIkarCamYynig T eyIg)an ÷ syssysuniv STST Δ+ΔΗ−=Δ > 0

\LÚvenH eyIgmanlkçxNçRbtikmμÉkÉg EdlCasresredayEtlkçN³rbs;RbBn§½ ( sysΔΗ nig sysSΔ ) ehIyeyIgGacminKitdl;mCÄdæanCMuvij. edIm,I[manPaBgayRsYl eyIg GacbþÚrsmIkarxagelI edaykarKuNvaTaMgmUlnig –1 ehIyCMnYssBaaØ > edaysBaaØ < :

syssysuniv STSST Δ+ΔΗ−=Δ− < 0

smIkarenHbgðajfa cMeBaHlMnaMbBa©úHsItuNðPaB T RbsinebIbMErbMrYlkñúgGg;talBI nig Gg; RtUBIénRbBn§½dUcCa syssys STΔ+ΔΗ KWticCagsUnü enaHlMnaMRtUvEtekIteLIgÉkÉg.

kñúgkarteRmobedIm,IbgðajBIkarekIteLIgÉkÉgénRbtikmμedaypÞal;eRcIn eyIgGac eRbInaTI ETm:UDINamicepSgeTotehAfa famBlesrI Gibbs (G) b¤[kan;Etgay famBlesrI ³

TSHG −= ( 6)

RKb;brimaNkñúgsmIkar (6) Cab;Tak;TgeTAnigRbBn§½ nig T CasituNðPaBénRbBn§½. Gñk GaceXIjfa G manxñatCafamBl (TaMg H nig TS KWmanxñatCafamBl). dUcCa H nig G,S

KWCa PaBénGnuKmn¾. bNþÚrkñúgfamBlesrI ( GΔ ) énRbBn§½sMrab;lMnaMsItuNðPaBefrKW ³ STG Δ−ΔΗ=Δ (7)

kñúgbribTenH famBlesrIKWCafamBlEdlGaceFVIkm μnþ. dUecñH RbsinebIRbtikm μeday Epñk KWtamCab;CamYyedaybeBa©jfamBleRbIkar)an (KWfa ebI GΔ GviC¢man). enHCakarBitEt mYyKt;FanafavaekIteLIgÉkÉg ehIyminRtUvkar)armÖGMBIGVIEdlnwgekIteLIgeTAelIEpñkenA sl;énskl.

Kt;sMKal;fa eyIgkMr)anerobcMkenSamsMrab;bNþÚrGg;RtUBIsklkarbM)at; univSΔ nig eFVI[es μ IeTAnigbNþÚrfamBlesrIénRbBn§½ ( GΔ ) CamYy univSTΔ− eFVIdUecñH eyIgGacBinitüeTA

CMBUkTI18

18-17

elIbNþÚrkñúgRbBn§½. \LÚvenH eyIgGaceFVIkarsegçblkçxNÐsMrab;karekIteLIgÉkÉg niglMnwg enAsItuNðPaB nig sMBaFefrkñúglkçN³dUcteTA³ GΔ < 0 RbtikmμekIteLIgÉkÉgkñúgTisedARsb

GΔ > 0 Rbtikm μKWminekIteLIgÉkÉg. RbtikmμKWekIteLIgkñúgTisedApÞúyKña. GΔ = 0 RbBn§½sßitkñúgPaBlMnwg. KμankarERbRbYl

bMErbMrYlfamBlesrIsþg;da Standard Free-Energy Changes

famBlesrIsþg;daénRbtikmμ ( orxnGΔ ) KWCabMErbMrYlfamBlesrIsMrab;RbtikmμkalNa

vaekIteLIgeRkamlkçxNÐPaBsþg;da. enAeBlRbtikmμkñúgPaBsþg;darbs;eK)anbMElgeTACa plitplkñúgPaBsþg;darbs;eK. tarag 2 segçbBIkarsnμt)aneRbIedayKImIviTUedIm,IkMNt; PaBsþg;da énsarFatusuT§)any:agl¥dUckñúgsUluysüúg. tarag 2 karsnμtsMrab;PaBsþg;da

PaBénrUbFatu PaBsþg;da ]sμ ½n sMBaF 1 atm

GgÁFaturav GgÁFaturavsuT§ GgÁFaturwg GgÁFaturwgsuT§ Fatu * o

fGΔ (Fatu) = 0

sUluysüúg kMhab; 1 m:Ul

* sNæansMelah³KWsßirPaBbMputenA 25oC nig 1atm

edIm,IKNna o

rxnGΔ eyIgcab;epþImCamYYy smIkar ³ aA + bB cC + dD

bMErbMrYlfamBlesrIsþg;dasMrab;Rbtikm μenH )an[eday ³ )]()([)]()([ BGbAGaDGdCGcG o

fof

of

of

orxn Δ+Δ−Δ+Δ=Δ

b¤CaTUeTA )tan()( tsreacGmproductsGnG of

of

orxn ∑∑ Δ−Δ=Δ ( 8)

Edl m nig n CaemKuNesÞItüÚemRTI. ofGΔ KWCa famBlesrIsþg;daénkMNr

rbs;smasFatumYy. enHKWCabNþÚrfamBlesrIEdlekIteLIg kalNamYym:UlénsmasFatu RtUv)ansMeyaKBIFaturbs;va enAkñúgPaBsþg;darbs;BYkeK. sMrab;cMehHénRkahVItKW ³ C(RkahVIt) + )(22 gCOO →


18-18

bNþÚrfamBlesrIsþg;da [BIsmIkar 8] KW ³ )](),([)( 22 OGgraphiteCGCOGG o

fof

of

orxn Δ+Δ−Δ=Δ

dUckñúgkrNIkMNrGg;tal;BIsþg;da eyIgkMNt;kMNrfamBlesrIsþg;daénFatunImYy²kñúg sNæansßirPaBrbs;vaKWesμIsUnü. dUecñH 0),( =Δ graphiteCGo

f nig 0)( 2 =Δ OGof

dUecñH bNþÚrfamBlesrIsþg;dasMrab;RbtikmμkñúgkrNIenHKWKitCaelxesñIeTAnig famBl esrIsþg;daénkMNr rbs; 2CO ³ )( 2COGG o

forxn Δ=Δ

kt;sMKal;fa orxnGΔ KitCas‘Ul (J) b:uEnþ o

fGΔ KitCa KJ/mol. smIkarenHTTYlyk)an BIeRBaHemKuNenABIxagmux o

fGΔ (1 kñúgkrNIenH)

manxñatKitCam:Ul. KNnabNþÚrfamBlesrIsþg;daEdl)aneRbIdUc)anbgðajkñúg]TahrN¾dUcteTA. ]TahrN¾ 4 KNnabNþÚrfamBlesrIsþg;dasMrab;Rbtikm μdUcteTAenA Co25 ³ (a) )(2)()(2)( 2224 lHOgCOgOgCH +→+ (b) )()(2)(2 2 gOsMgsMgO +→

cMelIy (a) tamsmIkar ( 8) eyIgGacsresr

)](2)([)(2)([ 2422 OGCHGOHGCOGG of

of

of

of

orxn Δ+Δ−Δ+Δ=Δ

CMnYstMélsmrmükñúgesckþIbEnßmEpñkxageRkayelx 3 ³

kJmolkJmolmolkJmolmolkJmolmolkJmolGo

rxn

0,808)]/0)(2()/8,50)(1[(]/2,237)(2()/4,394)(1[(

−=+−−−+−=Δ

(b) smIkarKW ³ )](2[)()(2[ 2 MgOGOGMgGG o

fof

of

orxn Δ−Δ+Δ=Δ

CMnYstMélsmrmükñúgesckþIbEnßmEpñkxageRkayelx 3 ³ ]/6,569)(2[()/0)(1()/0)(2[( molkJmolmolkJmolmolkJmolGo

rxn −−+=Δ = 1139kJ

lMhat;Gnuvtþn¾ KNnabNþÚrfamBlesrIsþg;dasMrab;Rbtikm μdUcteTAenAsItuNðPaB Co25 ³ (a) )(2)()( 22 gHBrgBrgH →+ (b) )(6)(4)(7)(2 22262 lOHgCOgOgHC +→+

CMBUkTI18

18-19

kñúg]TahrN¾muntMélGviC¢mankan;EtFMén o

rxnGΔ sMrab;cMehHemtankñúg (a) mann½yfa KWCalMnaMekIteLIgÉkÉgeRkamlkçxNçPaBsþg;da cMENkÉkarbMEbkén MgO kñúg (b) KWmin ekIteLIgÉkÉgeRBaH o

rxnGΔ KWmantMélFMCabrimaNviC¢man. cMNaMeTaHbIfatMélFMén orxnGΔ

GviC¢man minR)ab;eyIgGVITaMgGs;GMBIel,OnBitR)akdénlMnaMekIteLIgÉkÉg. l,ayén 4CH nig 2O enA Co25 KYrEtrkSaminERbRbYlsMrab;ry³eBleBjeljmYycMnYnkñúgcMeBaHmuxén páaePøIg b¤ GNþatePøIg. karGnuvtþénsmIkar ( 7)

kñúglMdab;edIm,ITayTukBIsBaaØ GΔ tamry³smIkar ( 7) eyIgRtUvkarsÁal;TaMg ΔΗ nig SΔ . tMélΔΗGviC¢man (RbtikmμbeBa©jkMedA) nigtMél SΔ viC¢man (CaRbtikmμEdlCa lT§plkñúgkMeNInkñúgPaB\tsNþab;Fñab;énRbBn§½) manTMenaredIm,IbegáIt GΔ GviC¢mansUm,IEt sItuNðPaB GacCH\T§iBleTAelITisedAénRbtikm μekIteLIgÉkÉg. lT§plTaMgbYn EdlGac ekItmanelITMnak;TMngenHKW ÷

ebI ΔΗ nig SΔ viC¢man bnÞab;mk GΔ nwgeTACamantMélGviC¢man kalNa lkçNç STΔ KWFMCagkñúgTMhMCag ΔΗ. lkçxNçenHKW)anCYbRbTH kalNa T FM.

ebIΔΗ viC¢man nig SΔ GviC¢man enaH GΔ nwgCanic©kalviC¢man minKitdl;sItuNðPaB.

ebI ΔΗGviC¢man nig SΔ viC¢man enaH GΔ nwgCanic©kalGviC¢man minKitdl;sItuNðPaB.

ebI ΔΗGviC¢man nig SΔ GviC¢man enaH GΔ nwgGviC¢man kalNa STΔ tUcCagkñúgTMhMCag ΔΗ. enHCalkçxNçEdl)anCYbRbTH kalNa T mantMéltUc. tarag 3 ktþaCH\T§iBlelIsBaaØén GΔ kñúgTMnak;TMng STG Δ−ΔΗ=Δ

ΔΗ SΔ GΔ ]TahrN¾ +

+

lMnaMRbtikmμekIteLIgÉkÉgenAsItu>x<s;.enAsItu>Tab Rbtikm μKWekIteLIgkñúgTisedApÞúyKña.

)(2)()(2 gHIgIgH →+

+

-

GΔ KWmantMélviC¢man. Rbtikm μekIteLIgÉkÉgkñúg TisedApÞúyKña enARKb;sItuNðPaB.

)(2)(3 32 gOgO →

-

+

GΔ KWmantMélGviC¢man.lMnaMRbtikm μekIteLIg ÉkÉgenARKb;sItuNðPaB.

)()(2)(2 2222 gOlOHlOH +→

-

-

lMnaMRbtikmμekIteLIgÉkÉgenAsItuNðPaBTab. enAsItu>x<s; RbtikmμRcas eTACaekIteLIgÉkÉg.

)()()( 43 sClNHlHClgNH →+


18-20

sItuNðPaBnwgeFVI[ GΔ GviC¢mansMrab;krNIdMbUg nigkrNIcugeRkayGaRs½yeTAelI tMélBiténΔΗ nig SΔ rbs;RbBn§½. tarag 3 segçbBI\T§iBlénPaB EdlGaceFVIeTA)aneTIb )anBN’na. sItuNðPaB nig Rbtikm μKImI

kal;süÚmGuksIut (CaO ) RtUv)aneKehA kMe)ar KWsarFatuEr:d¾mantMél)aneRbIkñúg karplit EdkEfb plitkmμénelah³kal;süÚm ]sSahkm μRkdas RbRBwtþikmμTwk nig RtYtBinitükarbMBul. KW)anerobcMeLIgedaykarbMEbkfμkMe)ar ( 3CaCO ) kñúgLenAsItuNðPaB x<s; (rUb 6) : )()()( 23 gCOsCaOsCaCO +⇔

RbtikmμKWeTAmk nigkal;süÚmGuksIutcUlpSMCaeRscCamYy 2CO eTACa 3CaCO . sMBaF 2CO kñúglMnwgCamYy 3CaCO ekIneLIgCamYysItuNðPaB. kñúg]sSahkm μ karerobcM kMe)arRbBn§½KWminEdlRtUv)anEfTaMenAPaBlMnwg dUcCa 2CO RtUv)anykecjy:ageTogTat;BIL edIm,IeFVI[lMnwg Rtlb;BIeqVgeTAsþaM eFVI[karkekItkal;süÚmGuksIutmanlkçN³RbesIreLIg. Bt’mand¾sMxan;sMrab;GñkKImIGnuvtþn¾ KWsItuNðPaBNamYyEdlkarbMEbkén 3CaCO

TTYl)aneRcInbgÁÜr(KWfasItuNðPaBEdlRbtikmμeTACaekIteLIgÉkÉg). eyIgGaceFVIkarRbmaN Cak;lak;énsItuNðPaBdUcteTA. TImYyeyIgKNna oΔΗ nig oSΔ sMrab;RbtikmμenA Co25 edayeRbI Tinñn½ykñúgesckþIbEnßm 3 . edIm,IkMNt; oΔΗ eyIgGnuvtþn¾smIkar (6.8) :

oΔΗ = [ )]([)]()( 32 CaCOCOCaO of

of

of ΔΗ−ΔΗ+ΔΗ

=[ )]/9,1206)(1[()]/5,393)(1()/6,635)(1( molkJmolmolkJmolmolkJmol −−−+− = 177,8kJ

bnÞab;mkeyIgGnuvtþn¾smIkar ( 4) edIm,Irk oSΔ oSΔ = )]([)]()([ 32 CaCOSCOSCaOS ooo −+

= )]./2,92)(1[()]./6,213)(1()./8,39)(1[( molkJmolmolKJmolmolKJmol −+ = 160,5J/K

sMrab;RbtikmμEdl)anykecjeRkamlkçxNÐPaBsþg;da smIkar( 7) eTACasNæan³ ooo STG Δ−ΔΗ=Δ dUecñH eyIg)an³

JkJKJKkJG

10001)/5,160)(298(8,177 −=Δ

= 130,0kJ

CMBUkTI18

18-21

edayehtufa oGΔ CabrimaNviC¢manFM eyIgsnñidæanfa Rbtikm μKWminGnueRKaHenA 25oC

b¤ (298K).müa:geTotedIm,IeFVI[ oGΔ GviC¢man CadMbUgeyIgRtUvkMNt;sItuNðPaBsMrab; oGΔ KWsUnü dUecñHKW³ =0 oo STΔ−ΔΗ o

o

ST

ΔΔΗ

= =KJ

kJJkJ/5,160

)1/1000)(8,177(

= 1108K b¤ 835oC

enAsItuNðPaBx<s;Cag 835oC oGΔ eTACaGviC¢manbgðajfa karbMEbkKWekIteLIg ÉkÉg. ]TahrN¾ enA Co840 b¤ K1113 ooo STG Δ−ΔΗ=Δ =

JkJKJKkJ

10001)/5,160)(1113(8,117 −

= kJ8,0−

cMnucBIrKW[mantMélsMrab;karKNna. CadMbUgeyIgeRbItMél oΔΗ nig oSΔ enA 25oC edIm,IKNnabNþÚrEdlekIteLIgCamYysItuNðPaBenAsItuNðPaBx<s;CageRcIn. edayehtufaTaMg

oΔΗ nig oSΔ ERbRbYlCamYysItuNðPaB. karxitCitdl;enHmineFVI[eyIgnUvtMélCak;lak;én oGΔ b:uEnþ vamanlkçN³RKb;RKan;l¥sMrab;kar)a:n;sμan. TIBIreyIgminKYrPan;RcLMkñúgkarKit

EdlfaKμanGVIekIteLIgeRkam Co835 minmann½yfa K μan 2CO )anekIteLIg. b:uEnþ KYrKitfa sMBaF]sμ ½nkabUnic)anekIteLIgenAsItuNðPaBenHnwgTabCag 1atm (tMélPaBsþg;darbs;va emIltarag2).

rUb 7 sMBaFlMnwgél]sμ ½n 2CO BI karbMEbkén 3CaCO CaGnuKmn¾én sItuNðPaB. ExSekagenH)anKNna eday]bmafa ΔΗ nig SΔ énRbtikmμ minERbRbYlCamYysItuNðPaB.


18-22

rUb 7 bgðajfa sMBaFén]sμ ½nkabUnicCadMbUgekIneLIgy:agyWtCamYysItu>vakøayCa gayRsYlkñúgkarvas;xagelI Co700 . lkçN³sMxan;én Co835 enHKWCasItuNðPaB EdlsMBaF lMnwgén 2CO Qandl; 1atm. xagelI Co835 sMBaFén]sμ½nkabUnicelIsBI 1atm. kñúgEpñk 5

eyIgnwgeXIjfaetI oGΔ KW)anTak;TgeTAnigefrlMnwgénRbtikm μ)an[y:agdUemþc. ebIRbBn§½enAPaBlMnwg bnÞab;mkK μandMeNIreq<aHeTArkbNþÚrÉkÉgkñúgTisedANamYYy. lkçxNÐ GΔ = 0 Gnuvtþn¾eTAelIral;pasqøg. karqøgpas Phase Transitions

enAsItuNðPaBEdlpasqøgekIteLIg (cMnucrMBuH b¤ cMnucrlay) RbBn§½KWenAPaBlMnwg ( GΔ = 0) . dUecñH smIkar 7 eTACa ³ STΔ−ΔΗ=0

T

S ΔΗ=Δ

dMbUgTuk[eyIgbgðajBIrbs;TwkkkeTAlMnwg. sMrab;BIBITwkkk→PaBqøgénTwk ΔΗ KWCakMedACam:Ulénkarrlay (emIltarag 11.8) ehIy T KWCacMnucrlay. dUecñH bNþÚrGg;RtUBIKW

KmolJS waterice 273

/6010=Δ →

= 22,0J/K.mol

dUecñH kalNa 1 m:UlTwkkkrlayenA Co0 mankarekIneLIgkñúgGg;RtUBI 22,0J/K. kMeNInkñúgGg;RtUBIKWminERbRbYlCamYynigkarekIneLIgkñúgPaB\tsNþab;Fñab;BI GgÁFaturwgeTArav. pÞÚymkvij sMrab;PaBqøgBITwk→TWkkk kMeNInkñúgGg;RtUBI)an[ ³

KmolJS icewater 273

/6010−=Δ →

= − 22,0J/K.mol

kñúgTIBiesaFn¾ CaTUeTAeyIgykecjbNþÚrTisEtmYy KWfaTaMgTwkkkeTATwk b¤ TwkeTA Twkkk. eyIgGacKNnabNþÚrGg;RtUBIkñúgkrNInImYy²edayeRbIsmIkar

TS ΔΗ=Δ enAeBl

EdlsItuNðPaBenAEt Co0 . dUcKñanigkarRbRBwtþeTAGacRtUv)anGnuvtþn¾BIPaBqøgTwkeTAcMhay Twk. kñúgkrNIenH ΔΗ KWCakMedArMhYt nig T KWCacMnucrMBuHénTwk. ]TahrN¾ 5 begðIj karqøgpasrbs;bg;Esn.

CMBUkTI18

18-23

]TahrN¾ 5 ³ kMedACam:UlénkarrMlaynigrMhYténbg;EsnKW molkJ /9,10 nig molkJ /0,31 erogKña. KNnabNþÚrGg;RtUBIBIGgÁFaturwg→ rav nig BIPaBqøgGgÁFaturav →cMhaysMrab;bg;Esn. enAsMBaF 1atm bg;EsnrlayenA Co5,5 nig BuHenA Co1,80 . cMelIy enAcMnucrMBuH RbBn§½KWsßitkñúgPaBlMnwg. dUecñH GΔ = 0 nig Gg;RtUBIénkarrlayKW ³ fusffus ST Δ−ΔΗ=0

f

fusfus T

SΔΗ

=Δ

= K

kJJmolkJ)2735,5(

)1/1000)(/9,10(+

= molKJ ./1,39 Rbhak;RbEhlKña enAcMnucrMBuH 0=ΔG eyIg)an ³

bp

vapvap T

SΔΗ

=Δ

K

molJmolkJ)2731,80(

)1/1000)(/0,31(+

= = molKJ ./8,87

cMNab;Garm μN¾ ³ edayehtufakarrMhYtbegáIteLIgPaB\tsNþab;Fñab;eRcInCaglMnaMrMlay enaH vapSΔ > fusSΔ .

lMhat;Gnuvtþn¾ ³ kMedACam:UlénkarrMlay nig rMhYténGakugKW 1,3kJ/mol nig 6,3kJ/mol ehIy cMnucrlay nig cMnucrMBuHénGakugKW Co190− nig Co186− erogKña. KNnabnþÚrGg;RtUBIsMrab; karrlay nig karrMhYt. famBlesrIniglMnwgKImI Free Energy and Chemical Equilibrium

]bmaeyIgcab;epþImRbtikmμkñúgsUluysüúgCamYyRKb;GgÁFatuRbtikr kñúgPaBsþg;da rbs;eK(kMhab;TaMgGs;kñúg 1M). rMeBcenaHRbtikm μcab;epþImkMhab;PaBsþg;daminmansßit esßryUrsMrab;RKb;GgÁFatuRbtikr b¤ plitpl edayehtufa kMhab;rbs;eKxusBI 1M). RKb;lkçxNÐ EdlminEmnPaBsþg;daeyIgRtUvEteRbI GΔ RbesIrCag oGΔ edIm,ITayTukBITis edAénRbtikmμ. TMnak;TMngrvag GΔ nig oGΔ KW ÷ QRTGG o ln+Δ=Δ (9)

Edl R Caefr]sμ ½n (8,314J/K.mol) T CasItuNðPaBdac;xaténRbtikmμ nig Q KWCa plEckénRbtikmμ. eyIgeXIjfa GΔ GaRs½yeTAelIbrimaNBIr ³ oGΔ nig QRT ln . cMeBaH


18-24

Rbtikmμ)an[enAsItuNðPaB T tMélén oGΔ KW)ankMNt; b:uEnþ QRT ln KWminkMNt;BIeRBaH Q xusKñaGaRs½yeTAelIsmasFatuénl,ayRbtikr. xageRkamenHkrNIsMxan;BIr ÷ krNITI1 ³ ebI oGΔ mantMélGviC¢man enaH QRT ln minGacmantMélviC¢manRKb;RKan;edIm,I TayBI oGΔ rhUtdl;brimaNCak;lak;énplipl)anekIteLIg. krNITI2³ ebI oGΔ mantMélviC¢man enaH QRT ln nigmantMélGviC¢maneRcIn. cMENk oGΔ Ca tMélviC¢manEtmYyKt;EdleFVI[plitpl)ankrekIteLIgtictYcehIykMhab;énGgÁFatuRbtikrKWmanTMnak;TMngx<s;eTAnigplitpl. enAPaBlMnwg tamniymn½y 0=ΔG nig KQ = Edl K CaefrlMnwg. dUecñHeyIg)an KRTGo ln0 +Δ= b¤ KRTGo ln−=Δ ( 10)

kñúgsmIkarenH pK KW)anebIsMrab;]sμ ½n nig cK sMrab;RbtikmμkñúgsUluysüúg. kt;sMKal fa K kan;EtFMKW oGΔ kan;EtmantMélGviC¢maneRcIn. sMrab;GñkKImI smIkar ( 10) KWCasmIkar mYyd¾mansar³sMxan;kñúgETm:UDINamic BIeRBaHvaGnuBaaØti[eyIgrkefrlMnwgénRbtikmμ RbsinebI eyIgsÁal;bMErbMrYlesrIfamBlsþg;da nig pÞúymkvij. rUb 8(a) o

productsG < otsrecG tan dUecñH oGΔ < 0. enAlMnwg mankarERbRbYlCasMxan;énGgÁFatu

Rbtikr nig plitpl. (b) oproductsG > o

tsrecG tan dUecñH oGΔ > 0 . enAPaBlMnwgGgÁFatuRbtikr )anGnueRKaHelIplitpl.

enHmanlkçN³sMxan;KWsmIkar ( 10) Tak;TgeTAnigefrlMnwgeTAnigbMErbMrYlesrIsþg;da

oGΔ dUcCaeTAnigbMErbMrYlfamBlesrIBit GΔ . famBlesrIBiténRbBn§½ nWgbMErbMrYlenAeBl manRbtikmμ nigkaøyCasUnüenAPaBlMnwg. müa:gvijeTotTaMg oGΔ nig K rbs;RbtikmμmYy

CMBUkTI18

18-25

enAsItuNðPaBeK)an[ KWminERbRbYleT. rUb 8 bgðajBIExSekagénfamBlesrIrbs;RbBn§½ Rbtikmμkñúgry³eBlmanRbtikmμ sMrab;RbePTénRbtikm μBIr. dUcCaeyIg)aneXIj ebI oGΔ < 0

enaHplitplKW)anGnueRKaHeRcInsMrab;GgÁFatuRbtikrenAPaBlMnwg. pÞúymkvij ebI oGΔ > 0

enaHnwgmanGgÁFatu RbtikreRcInCagplitplenAPaBlMnwg. tarag 4 segçbBITMnak;TMngTaMgbI EdlGacmanrvag oGΔ nig K dUc)anTayTukedaysmIkar (10) . cMeBaHRbtikmμEdlmanefrlMnwgFMxøaMgb¤tUcxøaMg KWCaTUeTAmankarlM)akNas;ebIminGac RbRBwtþwTA)an. edIm,Ivas;tMél K edaykareRbIR)as;kMhab;énRKb;RbePTRbtikmμ. ]TahrN¾ bBaa¢k;BIkarkrekItGuksIutnIRDicBIm:UelKulGasUt nig m:UelKulGuksIuEsn ÷ )()( 22 gOgN + )(2 gNO

enA Co25 efrlMnwg cK KW ÷ 31

22

2

100,4]][[

][ −×==ON

NOKc

cK mantMéltUcNas;mann½yfa kMhab;én ][NO enAPaBlMnwg nigmantMéltUc. kñúgkrNIenH eyIgGacTTYl)anefrlMnwgBI oGΔ RsYlCag. (dUcCaeyIg)aneXIj oGΔ Gac RtUv)anKNnaBI oΔΗ nig oSΔ ). müa:gvijeTot efrlMnwgsMrab;karkrekIténGIuRdUEsnGIuy:UdY BIm:UelKulGIuRdUEsn nig m:UelKulGIuy:Ut KWEk,r1enAsItuNðPaBbnÞb; ÷ )()( 22 gIgH + � )(2 gHI

sMrab;RbtikmμenH KWgayRsYlCagedIm,Ivas; K ehIybnÞab;mkKNna oGΔ edayeRbI smIkar (10) bnÞab;mkeFVIkarvas; oΔΗ nig oSΔ . tarag 4 TMnak;TMngrvag oGΔ nig K RtUv)anTayTukedaysmIkar KRTGo ln−=Δ

K ln K karBnül; > 1 viC¢man plitplKWeRcInCagGgÁFatuRbtikrenAPaBlMnwg

1= 0 plitplnigRbtikrKWesμ IKñaenAPaBlMnwg < 1 GviC¢man RbtikrKWticCagplitplenAPaBlMnwg

lkçN³enHmansar³sMxan;Nas;kñúgkarcgcaMenAeBledaHRsaysmIkar (10)Edl oGΔ manxñatCa J b¤ kJ rIÉ KRT ln KWKitCa J/mol. ehtuplénPaBxusKñaenHKW)anmkBIsmIkar (10)EdlmanxñatCa " m:Ul " RtUv)aneFVI[eTACaelakarIt (ln K) . dUecñH kñúgkareRbIsmIkar eyIgnwgbEnßm (1mol) eTAelI KRT ln edIm,IeFVI[xñatminERbRbYlelIGgÁTaMgBIrénsmIkar. ]TahrN¾dUcteTAenHbgðajBIkareRbIsmIkar (9) nig (10) .


18-26

]TahrN¾ 6

edayeRbITinñn½ykñúgtaragkñúgesckþIbEnßm 3 . KNnaefrlMnwg )( pK sMrab;Rbtikm μdUc teTA enA Co25 : )(2 2 lOH )()(2 22 gOgH +

cMelIy³ tamsmIkar ( 8) eyIg)an ³ )](2[)]()(2[ 222 OHGOGHGG o

fof

of

orxn Δ−Δ+Δ=Δ

= [(2mol)(0kJ/mol) + (1mol)(0kJ/mol)]- [(2mol)(237,2) kJ/mol)] = 474,4kJ

edayeRbIsmIkar (10)

porxn kRTG ln−=Δ

474,4kJ pKKmolKJmolkJ

J ln)298)(./314,8)(1(1

1000−=×

5,191ln −=pK

845,191 100,7 −− ×== eK p

karBnül; ³ efrlMnwgtUcNas;KWminpøas;bþÚrCamYynigkarBitEdlTwkminGacbMEbkeTACa]sμ ½n GIuRdUEsn nigGuksIuEsn enAsItuNðPaB Co25 . dUecñH tMélviC¢manén oGΔ GnueRKaH[GgÁFatu RbtikreRcInCagGgÁFatuplitplenAPaBlMnwg. kt;sMKal;fa eyIg)anbEnßmBakü (1mol) eTA elIGgÁxag0sþaMénsmIkar (10) TIenH edIm,IeFVI[xñatminERbRbYl. lMhat;Gnuvtþn¾ ³ KNnaefrlMnwg )( pK sMrab;RbtikmμenA Co25 )(3)(2 23 gOgO → ]TahrN¾ 7 ³ kñúgCMBUkTI 16 eyIg)anBiPakSaBIplKuNkMritrlayénsarFatuEdlrlaytic. edayeRbIplKuNkMritrlayénR)ak;kørYenA Co25 ( 10106,1 −× ) . KNna oGΔ sMrab;lMnaMenH. )(sAgCl )()( aqClaqAg −+ +

cMelIy edaysarenHCalMnwgeGetr:UEsn plKuNkMritrlayKWefr. 10106,1]][[ −−+ ×== ClAgKsp eRbIsmIkar 10 eyIg)an³ 10106,1ln)./314,8)(1( −×−=Δ molKJmolGo J4106,5 ×= kJ56=

CMBUkTI18

18-27

karBnül; ³ oGΔ viC¢manFM bgðajfa AgCl KWrlaytictYc ehIylMnwgPaKeRcInrMkileTA xageqVg. lMhat;Gnuvtþn¾ KNna oGΔ énlMnaMdUcteTAenA 25oC . )(2 sBaF )(2)(2 aqFaqBa −+ +

spK én 62 107,1 −×=BaF

]TahrN¾ 8 bNþÚrfamBlesrIsþg;dasMrab;Rbtikmμ ³ )(3)( 22 gHgN + )(2 3 gNH

KW kJ2,33− nig efrlMnwg pK KW 6,59 510× enA 25oC . kñúgBiesaFn¾BitR)akd sMBaFedIm atmPatmP NH 870,0,250,0

22== nig atmPNH 9,12

3= . KNna GΔ sMrab

RbtikmμenAsMBaF TaMgenH nigTayTukBITisedAénRbtikmμ. cMelIy smIkar 9 eyIgGacsresr ³ p

o QRTGG ln+Δ=Δ

22

3

3lnNH

NHo

PPP

RTG +Δ=

)870,0()250,0(

)9,12()298)(./314,8)(1(102,33 3

23 ×+×−= KmolKJmolJ

JJ 33 103,23102,33 ×+×−= kJJ 9,9109,9 3 −=×−= edayehtufa GΔ GviC¢man lMnaMRbtikmμsrubBIeqVgeTAsþaM. karBnül; ³ dUcbgðajkñúglMhat; bBaa¢k;BIkarTayTukenHedaykarKNnaplEckRbtikmμ pQ nig eFVIkareRbobeFobvaCamYyefrlMnwg pK . lMhat;Gnuvtþn¾ ³ oGΔ sMrab;Rbtikmμ ³ )()( 22 gIgH + )(2 gHI

KW 2,60kJ enA 25oC . kñúgBiesaFn¾mYy sMBaFedImKW atmPatmP IH 024,0,25,422==

nig atmPHI 23,0= . KNna GΔ sMrab;Rbtikmμ n ig TayTukBITisedAénRbtikmμ. 6 ETm:UDINamickñúgRbBn§½énPavrs;


18-28

RbtikmμKImICIv³CaeRcIn KWminekIteLIgÉkÉgeT (KWfa oGΔ mantMélviC¢man) b:Enþ BYkeK mansar³sMxan;sMrab;EfTaMCIvit. kñúgRbBn§½énPavrs;RbtikmμTaMgenHKWrYmKñaCamYylMnaMfamBl mYyeTotEdlmantMél oGΔ GviC¢man. eKalkarN¾énRbtikmμCaKUdUcenH KWEp¥kelIbBaaØtigay fa³ eyIgGaceRbIRbtikm μEdlman oGΔ GviC¢man edIm,ICYyRbtikmμEdlman oGΔ viC¢man. BicarNalMnaMkñúg]sSahkm μ. ]bmaeyIgcg;Tajyksgá½sIBIEr: ZnS (sphalerite). Rbtikmμ dUcteTAmindMeNIrkar)an edayehtufa vaminekIteLIgÉkÉg³ )()()( sSsZnsZnS +→ kJG o 3,198=Δ müa:geTot cMehHs<an;F½reTACas<an;F½rDIGuksIut KWekIt)aneRBaHtMél oGΔ GviC¢manFM³ )()()( 22 gSOgOsS →+ oGΔ = kJ1,300−

edayrYmKñaCaKUénlMnaMTaMgBIr eyIgGacbegáItGMBIkarEjkénsgá½sIecjBIsgá½sIs‘ulp. kñúgkarGnuvtþn¾ edayeRbImeFüa)aykardutkMedA ZnS kñúgxül; dUecñH S manTMenareTACa

2SO nwgeFVI [RbesIreLIgkarbMEbkén ZnS ³ )()()( sSsZnsZnS +→ kJG o 3,198=Δ )()()( 22 gSOgOsS →+ oGΔ = kJ1,300− )()()()( 22 gSOsZngOsZnS +→+ oGΔ kJ8,101−= RbtikmμeTVedIrtYCasMxan;kñúgCIvitrbs;eyIg. kñúgRbBn§½CIv³ Gg;sIumeFVI[gayRsYlrIkral daly:agTUlMTUlayxus²KñaénRbtikm μminekIteLIgÉkÉg. ]TahrN¾ kñúgsarBagÁkaymnusS m:UelKulGahar tMNagedayKøúykUs )( 6126 OHC KWRtUv)anbMElgeTACakabUnDIGuksIut nig Twk kMLúgeBlemtabUlIs CamYynigbeBa©jfamBlesrIeRcIn. )(6)(6)(6)( 226126 lOHgCOgOsOHC +→+ kJG o 2880−=Δ Kñúgekasikars;enARbtikmμenHmin)aneFIVkñúgCMhanEtmYy (dUccMehHKøúykUskñúgGNþat ePøIg) CaCagm:UelKulKøúykUsbMEbkCamYycMnYyGg;sIumes‘rIéndMNak;kal. famBlesrICaeRcIn RtUv)anbeBa©jtamCamYyrebobEdl)aneRbIedIm,IsMeyaK adenosine triposphate (ATP) BI adenosine diposphate (ADP) nig GasIutpUsV½ric (rUb 9) . ADP + OHATPPOH 243 +→ kJG o 31+=Δ

naTI ATP KWedIm,IrkSafamBlrhUtdl;va)anRtUvkaredayekasika. eRkamlkçxNÐ smrmü ATP rgGIuRdUlIs[Ca ADP nig GasIutpusV½ric RBmCamYykarbeBa©jfamBlesrI 31kJ EdlGac RtUv)aneRbIedIm,ITayykfamBlBIRbtikmμminGnueRKaH.

CMBUkTI18

18-29

rUb 9 TMrg;én ATP ADP kñúgsNæanCaGIuy:ug.

RbUetGIunKWCab:UlIEm)anbegáIteLIgBIGasIutGamIen. dMNak;kalsMeyaKnImYy²én m:UelKulRbUetGIunTak;TgeTAnigkartP¢ab;énGasIutGamIennImYy². bgðajBIkarkekIteLIgén DIbiubTIt (BIrÉktaénGasIutGamIen) GaLanIlKøIsIun BI GaLanIn nig KøIsIun. RbtikmμenHtMNag edaydMNak;kalTImYykñúgkarsMeyaKénm:UelKulRbUetGIun³ GaLanIn + KøIsIun →GaLanIlKøIsIun kJG o 29+=Δ

dUcCaGñkGaceXIjRbtikmμenHKWminekIteLIgÉkÉg ehIydUecñHKWmanEtbrimaNEtbnþic bnÞÜcénDIbiubTItEdlnigKYr)anekIteLIgenAPaBlMnwg. dUecñH CamYycMnYnBIGg;sIumRbtikm μKWman lkçN³eTVedIm,IGIuRdUlIs ATP dUcteTA÷ lycineAlanyPOHADPGlycineeAlaOHATP lgmin 432 ++→+++ bNþÚrfamBlesrICasrubKW)anpþl;[eday kJkJkJG o 22931 −=+−=Δ Edlman n½yfaRbtikmμeTVKWekIteLIgÉkÉgnigbrimaNsmrmüén alanylglycine nwgRtUv)anekIteLIg eRkamlkçxNÐenH. rUb 10 bgðajBIGnþrbMElg ATP-ADP Edlskm μPaBdUcCarkSafamBl (BIemta-bUlIs) nig beBa©jfamBlesrI (BIGIuRdUlIs ATP) edIm,I)anmknUvRbtikm μCasMxan; ÷


18-30

rUb 10eRKagtMNag[RbBn§½karsMeyaK ATP nigKURbtikmμénRbBn§½CIvit. karbMElgBIKøúykUs eTACakabUnDIGuksIut nigTwkkMLúgeBlemtabUlIsbeBa©jfamBlesrI. karbeBa©jfamBlenH KW)aneRbIedIm,IbMElg ADP eTACa ATP. m:UelKul ATP bnÞab;mk)aneRbICaRbPBfamBl sMrab;Rbtikm μminekIteLIgÉkÉg dUcCasMeyaKénRbUetGIuneTACaGasIutGamIen.

KImIGnuvtþn_ ETm:UKImIénExSekAs‘U

etIeyIgRKb;KñadwgdUemþcBIGtßRbeyaCn¾énExSekAs‘U. b:uEnþminEmnmnusSRKb;rUbKW)andwg faExSekAs‘Umankarcab;Garm μN¾xøaMgmYycMnYneTAelIlkçN³ETm:UDINamicedayEp¥kelITMrg;. GñkGacbgðajPaBgayRsYlénBiesaFn¾dUcteTACamYynigExSekAs‘UEdlmanTMhMy:agtic bMput 0,5cm TajExSekAs‘Uy:agrh½sehIybnÞab;mksgát;vaTb;Tl;nigbbUrmat;rbs;Gñk. GñknigmanGarmμN¾ekþAtic². bnÞab;mkeFVItamlMnaMbRBa©as. TajekAs‘UyWtnigTb;va[nwgry³ eBl2-3naTI. bnÞab;mkRBElgPaBtwgvaPøamnigsgát;ExSekAs‘UTb;vaCamYybbUrmat;rbs;Gñk. eBlenHGñknwgmanGarm μN¾RtCak;tic². viPaKETm:UDINamicénkarBiesaFn¾TaMgBIrenHGacR)ab; eyIgmYycMnYnGMBITMrg;m:UelKulénekAs‘U. teRmobsmIkar ( 7)eLIgvij ( STG Δ−ΔΗ=Δ ) eyIg)an ³ GST Δ−ΔΗ=Δ \T§iBlénkMedA]Nð² (lMnaMbeBa©jkMedA) rhUtdl;eFVI[yWtmann½yfa ΔΗ< 0 ehIy edayehtufa kareFVI[yWtminekIteLIgÉkÉg(KWfa GΔ <0 nig - GΔ <0) STΔ RtUvEtGviC¢man. edayehtufa T CasItuNðPaBdac;xat EdlCanic©kalviC¢maneyIgsnñidæanfa SΔ enAeBl EdleFVI karTajRtUvEtGviC¢mannig dUecñHekAs‘UkñúgPaBFm μCatirbs;vaKWmanPaB\tsNþab;Fñab;CagenA eBlEdlvargnUvkartwg. enAeBlPaBtwgRtUvdac; exSekAs‘UyWtekIteLIgÉkÉgdac;RtLb;eTAPaBedImrbs;va KWfa

GΔ GviC¢man nig GΔ− KWviC¢man. \T§iBlénPaBRtCak;mann½yfa KWCalMnaMRsUbkMedA (ΔΗ>0)

dUecñH STΔ KWviC¢man. dUecñHGg;RtUBIénExSekAs‘UekIneLIgkalNavabþÚrBIPaByWteTAPaBFm μCati.

CMBUkTI18

18-31

rUbelI (a) m:UelKulekAs‘UkñúgPaBFm μtarbs;eK. kt;sMKal;fa kMritx<s;énPaB\tsNþab;Fñab; (Gg;RtUBIx<s;). (b) eRkamPaBtwg m:UelKulbegáItCaCYr nigeFVIkarteRmobeTACamanrebobeRcIn (Gg;RtUBITab)

smIkarKnøwH

surrsysuniv SSS Δ+Δ=Δ >0 (1) c,ab;TIBIrénETm:UDINamic (lMnaMekIteLIgedayÉkÉg)

surrsysuniv SSS Δ+Δ=Δ = 0 (2) c,ab;TIBIrénETm:UDINamic (lMnaMekIteLIgenAPaBlMnwg)

∑ ∑−=Δ )tan()( tsreacmSproductsnSS oo (4) bERmbRmYlGg;RtUBIsþg;daénRbtikm μ STG Δ−ΔΗ=Δ (7) bERmbRmYlfamBlesrIenAsItuNðPaBefr

∑∑ Δ−Δ=Δ )tan()( tsreacGmproductsGnG of

of

(8) bERmbRmYlfamBlesrIsþg;da énRbtikmμ QRTGG o ln+Δ=Δ (9) TMnak;TMngrvagbERmbRmYlfamBlesrI nigbERmbRmYl

famBl esrIsþg;da nigplEckkñúgRbtikmμ KRTG o ln−=Δ (10) TMnak;TMngrvagbERmbRmYlfamBlesrIsþg;da nigefrlMnwg.

segçbxøwmsarsMxan;²

1. Gg;RtUBIKWCargVas;énPaB\tsNþab;Fñab;rbs;RbBn§½mYy. lMnaMekIteLIgedayÉkÉgnImYy² RtUvEteq<aHeTArkkMeNInsrubKitCaGg;RtUBIkñúgskl (c,ab;TIBIrénETm:UDINamic) .

2. Gg;RtUBIsþg;daénRbtikmμKImImYy GacRtUv)anKNnaBIGg;RtUBIdac;xatrbs;GgÁFatuRbtikr nig plitpl.

3. c,ab;TIbIénETm:UDINamicEcgfa Gg;RtUBIénsarFatuRkam EdlmanTMrg;minsμ úRKs μajKWes μInwg sUnüenA K0 . c,ab;enHGac[eyIg eRbIedIm,IkMNt;Gg;RtUBIdac;xaténsarFatu.

4. eRkamlkçxNÐsItuNðPaB nigsMBaFefr bNþÚrfamBlesrI GΔ KWtUcCagsUnüsMrab;lMnaMekIt eLIgedayÉkÉg nigFMCagsUnüsMrab;lMnaMEdlminekIteLIgedayÉkÉg. sMrab;lMnaMekIt eLIgenAPaBlMnwg GΔ =0 .


18-32

5. cMeBaHlMnaMKImI b¤lMnaMrUbenAsItuNðPaB nigsMBaFefr STG Δ−ΔΗ=Δ . smIkarenHGac RtUv)aneRbIedIm,ITayTukBIlMnaMEdlGacekIteLIgedayÉkÉg.

6. bNþÚrfamBlesrIsþg;dasMrab;Rbtikmμ oGΔ GacRtUv)anrkeXIjBIfamBlesrIsþg;daénkMNr GgÁFatuRbtikr nigplitpl.

7. efrlMnwgénRbtikmμ nigbNþÚrfamBlesrIsþg;daénRbtikmμ KWRtUv)ankMNt;edaysmIkar KRTG o ln−=Δ .

8. RbtikmμCIv³PaKeRcIn KWminekIteLIgedayÉkÉgeT. RbtikmμTaMgenHGacbNþaleGayekIt maneLIgedaysarGIuRdUlIsén ATP EdlkñúgkrNIenHvaman oGΔ GviC¢man.

BaküKnøwH Gg;RtUBI Entropy 18-3

c,ab;TIBIrénETm:UDINamic Second Law of Thermodynamics 18-8

Gg;tal;BIsþg;daénRbtikm μ orxnSΔ Standard Entropy of reaction 18-8

c,ab;TIbIénETm:UNamic Third Law of Thermodynamics 18-12

famBlesrI Gibbs (G) Gibbs free energy 18-16

famBlesrI Free energy 18-16

famBlesrIsþg;daénRbtikmμ( orxnGΔ ) Standard free energy of reaction 18-17

famBlesrIsþg;daénkMNr Standard energy of formation 18-17

sMnYrnigbBaað 1 cUrBnül;etIGVICameFüa)ayCalMnaMekIteLIgÉkÉg. []TahrN¾nImYy²cMnYnBIrsMrab;lMnaM ekIteLIgekIteLIgÉkÉg nig lMnaMminekIteLIgÉkÉg. 2 etIlMnaMdUcxageRkamenH NaxøHCalMnaM eLIgekIteLIgÉkÉg nig lMnaMminekIteLIgÉkÉg ³

(a) karrMlayGMbilsML (NaCl)kñúgs‘ubekþA (b) kareLIgPñM Everest

(c) karsayPayénkøinTwkGb;kñúgbnÞb;edaykarebIkKMrbdbTwkGb; (d) karEjkeGlüÚm nig eNGugecjBIl,ay]sμ ½n

CMBUkTI18

18-33

3. etIlMnaMdUcteTACalMnaMeLIgekIteLIgÉkÉg nig lMnaMminekIteLIgÉkÉgenAsItuNðPaB )an[÷ (a) )()( 33

2 aqNaNOsNaNO OH⎯⎯→⎯ sUluysüúgEq¥t (b) )()( 33

2 aqNaNOsNaNO OH⎯⎯→⎯ sUluysüúgminEq¥t (c) )()( 33

2 aqNaNOsNaNO OH⎯⎯→⎯ sUluysüúgEq¥thYs 4. cUr[niymn½yGg;RtUBI. etIGVICaxñatsMrab;Gg;RtUBI ? 5. etIGg;RtUBIénbNþÚrRbBn§½sMrab;lMnaMdUcteTAenHdMeNIrkareTAdUemþc ?

(a) rMlayGgÁFaturwg (b) kMNkGgÁFaturav (c) rMBuHGgÁFaturav (d) cMhayKW)anbMElgeTACaGgÁFaturwg (e) cMhaykkeTACaGgÁFaturav (f) GgÁFaturwg)anrMehIr (sublime) (g) G‘uyer:rlaykñúgTwk

cMeNaT 6. eyageTAelIrUb 1a KNnaRbU)ab‘ÍlIeténRKb;m:UelKul bBaÄb;kñúgkUndb RbsinebIcMnYnKW (a)

6 (b) 60 (c) 600 . c,ab;TIBIrénETm:UDINamic 7. beBa©jc,ab;TIBIrénETm:UDINamicCaGkSr nig kenSamvaCalkçN³KNitviTüa. 8. beBa©jc,ab;TIbIénETm:UDINamic nig Bnül;PaBmanRbeyaCn¾bMputrbs;vakñúgkarKNnatMél

Gg;RtUBI. cMeNaT 9. sMrab;KUrénsarFatunImYy²kñúgtaragTIenHcUreRCIserIsmYyEdlmantMélGg;RtUBIsþg;daFMCag

eKenA25oC.dUcbrimaNCam:UlKW)aneRbIkñúgkareRbobeFob. cUrBnül;edayEp¥kelICMerIs rbs;Gñk(a) Li(s) b¤ )(lLi ; )(52 lOHHC b¤ )(33 lOCHCH (karENnaM ³ etIm:UelKul mYyNaEdlGaccgsm<n§½GIuRdUEsn ? ) (c) Gr(g) b¤ Xe(g) ; (d) CO(g) b¤ CO2(g) ; (e)

)(2 gO b¤ )(3 gO ; (f) )(2 gNO b¤ )(42 gON 10. teRmobsarFatudUcteTA (nImYy² 1m:Ul) tamlMdab;Gg;RtUBIekIn enA 25oC ÷

(a) Ne(g)


18-34

(b) SO2(g) (c) Na(s) (d) NaCl(s) (e) NH3(g)

cUrbgðajehtuplBIkarteRmobrbs;Gñk. 11. kareRbITinñn½ykñúgtaragsegçb3KNnabNþÚrGg;talBIsþg;dasMrab;RbtikmμdUcteTAenA25oC

(a) )()()( 22 gSOgOsS →+ (b) )()()( 23 gCOsMgOsMgCO +→

12. kareRbITinñn½ykñúgtaragsegçb3KNnabNþÚrGg;talBIsþg;dasMrab;RbtikmμdUcteTAenA 25oC (a) )()()()( 22 lOHsCuSCuOgH +→+ (b) )(3)()(3)(2

23 sZnsAlOsZnOsAl +→+ (c) )(2)()(2)( 2224 gOHgCOgOgCH +→+

13. edayK μankarBieRKaHCamYyesckþIbEnßm 3 cUrTayTukfaetIbNþÚrGg;tal;BImantMélviC¢man b¤ GviC¢mansMrab;Rbtikm μdUcteTA. cUr[ehtuplsMrab;karTayTukrbs;Gñk.

(a) )()()(2 234 gOsKClOsKClO +→ (b) )()( 22 lOHgOH → (c) )()(2)(2)(2 22 gHaqNaOHlOHsNa +→+ (d) )(2)(2 gNgN →

14. bgðajfaetIsBaaØénbNþÚrGg;RtUBI)ancUlrYmsMrab;lMnaMnImYy²dUcteTAnwgmansBaaØviC¢man b¤ GviC¢man ehIycUrBnül;BIkatTayTukrbs;Gñk.

(a) )()()( 523 gPClgClgPCl →+ (b) )()(2)(2 2 gOlHgsHgO +→ (c) )(2)(2 gHgH → (d) )()(3)( 62 sUFgFsU →+

famBlesrI GIBBS

sMNYrrMlwk 15. [niymn½yfamBlesrI. etIvamanxñatCaGVI ? 16. ehtuGVI)anCavamanPaBgayRsYledIm,ITayTukBITisedAénRbtikm μkñúgBakü sysGΔ CMnYs

univSΔ ? eRkamlkçxNÐGVIGac sysGΔ RtUv)aneRbIedIm,ITayTukBIRbtikm μekIteLIgÉkÉg ? cMeNaT 17. KNna oGΔ sMrab;RbtikmμdUcteTA enA 25oC ÷

(a) )(2)()( 22 gNOgOgN →+ (b) )()( 22 gOHlOH → (c) )(2)(4)(5)(2 22222 lOHgCOgOgHC +→+

CMBUkTI18

18-35

(karENnaM³ emIleTAfamBlesrIsþg;daénkarkekItrbs;GgÁFatuRbtikr nigplitplkñúgesckþI bEnßm 3) . 18. KNna oGΔ sMrab;RbtikmμdUcteTA enA 25oC ÷

(a) )(2)()(2 2 sMgOgOsMg →+ (b) )(2)()(2 322 gSOgOgSO →+ (c) )(6)(4)(7)(2 22262 lOHgCOgOgHC +→+

(emIlesckþIbEnßm 3 sMrab;Tinñn½yETm:UDINamic)

19. BItMél ΔΗ nig SΔ TayTukRbtikmμdUcteTAenHNaxøHKYrEtekIteLIgÉkÉgenA 25oC ÷

Rbtikmμ A: KJSkJ /30,6,10 =Δ=ΔΗ

Rbtikmμ B: KJSkJ /113,8,1 −=Δ=ΔΗ . ebIRbtikm μNamYyKWminekIteLIgeday ÉkÉgenA 25oC etIsItuNðPaBNaEdlvaGacekIteLIgedayÉgÉg ?

20. kMNt;sItuNðPaBEdlRbtikmμCamYynigtMél ΔΗ nig SΔ KYrEtkøayCaekIteLIgÉkÉg ÷ (a) KJSkJ /84,126 =Δ−=ΔΗ (b) KJSkJ /105,7,11 −=Δ−=ΔΗ

famBlesrI nig lMnwgKImI sMnYrrMlwk 21. cUrBnül;BIPaBxusKñarvag GΔ nig oGΔ 22. cUrBnül;ehtuGVIsmIkar 10 KWmansar³sMxan;y:agFMeFgkñúgKImI cMeNaT 23. KNna pK sMrab;RbtikmμdUcteTAenA 25oC ÷

)(2)()( 22 gHIgIgH →+ kJGo 60,2=Δ

24. sMrab;sV½yGIuy:ugkm μénTwkenA 25oC ÷

)(2 lOH )()( aqOHaqH −+ + Edl 14100,1 −×=wK etI oGΔ sMrab;lMnaMenHesμ Ib:unμan ?

25. cUrbgðajBIRbtikmμdUcteTAenA 25oC ÷

)()( 2 sOHFe )(2)(2 aqOHaqFe −+ +

KNna oGΔ sMrab;RbtikmμenH. spK sMrab; 2)(OHFe esμ I 14106,1 −× 26. KNna oGΔ nig pK sMrab;Rbtikm μenAPaBlMnwgdUcteTA 25oC ÷

)(2 2 gOH )()(2 22 gOgH +


18-36

27. (a) KNna oGΔ nig pK sMrab;Rbtikm μenAPaBlMnwgdUcteTA 25oC . tMél ofGΔ KWsUnü

sMrab; )(2 gCl , molkJ /286− sMrab; )(3 gPCl nig molkJ /325− sMrab; )(5 gPCl . )(5 gPCl )(3 gPCl + )(2 gCl

(b)KNna GΔ sMrab;Rbtikm μRbsinebIsMBaFedayEpñkénl,ayRbtikmμedImKW ÷ atmPatmP PClPCl 27,0,0029,0

35== nig atmPCl 40,0

2= .

28. efrlMnwg 40.4=pK enA 2000K sMrab;Rbtikm μ ÷ )()( 22 gCOgH + )()(2 gCOlOH +

(a)KNna oGΔ sMrab;Rbtikm μkalNasMBaFedayEpñkatmPatmP COH 78,0,25,0

22== , atmP OH 66,0

2= nig atmPCO 20,1= .

29. cUrbBaa¢k;BIkarbMEbkénkal;süÚmkabUNat ³ )(3 sCaCO )()( 2 gCOsCaO +

KNnasMBaFKitCaGat;m:UEsVrén]s μ½nkabUnickñúglMnaMPaBlMnwg (a) enA 25oC nig (b)

enA 800oC . ]bmafa kJo 8,177=ΔΗ nig KJS o /5,160=Δ sMrab;sItuNðPaB teRmobxag elI.

30. efrlMnwg 351062,5 ×=pK enA 25oC sMrab;Rbtikmμ ³ )()( 2 gClgCO + )(2 gCOCl

KNna ofGΔ sMrab; )(2 gCOCl enA 25oC ?

31. enA 25oC oGΔ sMrab;lMnaM ³ )(2 lOH )(2 gOH KW kJ6,8 . KNnaefrlMnwgsMrab;lMnaM. 32. KNna oGΔ sMrab;lMnaM³

)()( graphiteCdiamondC → etIKWCaRbtikm μekIteLIgÉkÉgenA25oC? RbsinebIEmn ehtuGVI)anCaeBRCminCMnYsRkahVIt? Etm:UDINamickñúgRbBn§½énkarrs;enA sMnYrrMlwk 33. etIRbtikmμCaKU CaGVI (coupled reaction) ? GVIeTACasar³sMxan;rbs;;RbtikmμenaHkñúgCIv³ ? 34. GVIeTACatYnaTIrbs; ATP kñúgRbtikm μCIv³ ? cMeNaT 35. eyageTAelIlMnaMemtabUlIsEdlTak;TgnigKøúykUs. cUrKNnacMnYnGtibrmaCam:Ulén

ATP EdlGacRtUv)ansMeyaKBI ADP BIkarbMEbkénmYym:Ulrbs;KøúykUs. 36. kñúgemtabUlIsénKøúykUs CMhanTImYyKWkarbMElgénKøúykUseTACaKøúykUs-6-pUsVat ³

CMBUkTI18

18-37

OHphosphateegluPOHeglu 243 6coscos +−→+ kJGo 4,13=Δ

edayehtufa oGΔ viC¢manRbtikm μenHminekIteLIgÉkÉg. cUrbgðajeFVIdUemþc[RbtikmμenHGac RbRBwtþeTA)anedIm,IbnþCalkçN³KUvaCamYyGIuRdUlIsénATP. sresrsmIkarsMrab;RbtikmμKU nigeFVIkar)a:n;s μanefrlMnwgsMrab;lMnaMCaKU. cMeNaTbEnßm

37. 38. KNna GΔ sMrab;Rbtikmμ ÷

)(2 lOH )()( aqOHaqH −+ +

enA 25oC sMrab;lkçxNÐdUcteTA ÷ (a) MOHMH 77 100,1][,100,1][ −−−+ ×=×= (b) MOHMH 43 100,1][,100,1][ −−−+ ×=×= (c) MOHMH 812 100,2][,100,1][ −−−+ ×=×= (d) MOHMH 4108,4][,5,3][ −−+ ×==

39. etIGnuKmn¾ETm:UDINamicdUcteTAenHNamYyEdlCab;Tak;TgEtmYyKt;CamYynigc,ab;TImYy énETm:UDINamic ³ S,E,G nig H .

40. nisSit)andak;cUlnImYy² 1g énsmasFatubI A ,B nig C kñúgvtßúpÞúk nig)anrkeXIjfa bnÞab;BImYys)þaN¾mkminmankarERbRbYl)anekIteLIg. cUrpþl;[nUvkarBnül;epSg²sm Rsbfa ehtuGVI)anCaK μanRbtikmμ. sμanCamun A, B nig C CavtßúravGacrlaycUlKña)an.

41. cur[]TahrN¾lMGitnImYy²dUcteTA CamYynigkarBnül;³ (a) ETm:UDINamicCalMnaMekIteLIgÉkÉg (b) lMnaMEdlmanlkçN³xøaMgKWCac,ab;TImYyénETm:UDINamic (c) lMnaMEdlmanlkçN³xøaMgKWCac,ab;TIBIrénETm:UDINamic (d) lMnaMminGacRtLb;eRkay)an (e) lMnaMenAPaBlMnwg

42. cUrTayTukBIsBaaØ SΔΔΗ, nig GΔ énRbBn§½sMrab;lMnaMdUcteTAenAsMBaF 1atm :

(a) Gam:Ujak;rlayenA Co60− (b) Gam:Ujak;rlayenA Co7,77− (c) Gam:Ujak;rlayenA Co100− . (CaTUeTAcMnucrlayénGam:Ujak;KW Co7,77− )


18-38

43. cUrbgðajBIkarBitdUcteTA÷TwkkkekIteLIgÉkÉgenA Co5− nig 1atm nig Twkkk)anerobcM sNþab;Fñab;CagTwkenAPaBrav. cUrBnül;ehtuGVIlMnaMekIteLIgÉkÉgnaMeTArkkMeNInkñúg Gg;RtUBI.

44. Gam:UjÚmnIRtat ( 34 NONH )rlayÉkÉg nigRsUbTwk. GVIeTAEdlGñkGaceFVIkarRsavRCav GMBIsBaaØén SΔ sMrab;lMnaMsUluysüúg ?

45. KNnasMBaFlMnwgén 2CO rhUteTAdl;karbMEbkén 3BaCO enA 25oC . 46. (a) c,ab; Trouton's bgðajfapleFobCam:UlénkMedArhYtrbs;GgÁFaturav )( vapΔΗ eTAnig

cMnucrMBuHrbs;vaKitCaEklvinKWRbEhlCa molKJ ./90 . eRbITinñn½ydUcteTAenHedIm,Ibgðaj faenHCakrNI nigBnül;faehtuGVIc,ab;Trouton's bBaa¢k;faRtwmRtUv³

)( Ct obp )/( molkJvapΔΗ

Benzene 80,1 31,0 Hexane 68,7 30,8 Mercury 357 59,0 Toluene 110,6 35,2

(b)eRbItMélkñúgtarag6CMBYkTI11 edIm,IKNnapleFobdUcKñasMrab;eGtaNulnigTwk. cUrBnül; ehtuGVIc,ab; Trouton's minGnuvtþn¾eTAelIsarFatuTaMgBIrenH[)anl¥dUceTAnigGgÁFaturavdéT eTot. 47. eyageTAelIbBaaðxagelI cUrBnül; ehtuGVI)anCapleFobKW)anbBaa¢k;tUcCag molKJ ./90

sMrab;GgÁFaturav HF . 48. kabUnGuksIut (CO) nig GuksIutnIRTic (NO) Ca]sμ ½nbMBulpÞúkkñúgEpSgrfynþ. eRkam

lkçxNÐsmRsb ]sμ½nTaMgenHGacRbtikmμeTACasNæanGasUt (N2) nigeRKaHfñak;ticCag kabUnDIGuksIut (CO2) .

(a) sresrsmIkarsMrab;RbtikmμenH (b) sMKal;Pñak;garGuksIutkmμnigerdukm μ (c) KNna pK sMrab;RbtikmμenA 25oC

(d) eRkamlkçxNÐsMBaFFmμtasMBaFedayEpñkKW³ atmPatmPatmP COCON

54 100,5,100,3,80,022

−− ×=×== nig atmPNO

7100,5 −×=

KNna pQ nigTayTukBITisedAeTAmuxEdlRbtikmμnwgRbRbwtþeTA. (e) nwgmankarekIneLIgsItuNðPaBsMrab;karkekItén 2N nig 2CO ?

CMBUkTI18

18-39

49. sMrab;RbtikmμEdl)anykecj eRkamlkçxNÐPaBsþg;da smIkar ( 7) ykmkBIsNæan ooo STG Δ−ΔΗ=Δ .

(a) eFVIkar]bma oΔΗ nig oSΔ KWminGaRs½yelIsItuNðPaB Taj ecjsmIkar ³ ⎟⎟

⎠

⎞⎜⎜⎝

⎛ −ΔΗ=

21

12

1

2lnTT

TTRK

K o

Edl K1 nig K2 CaefrlMnwg enA T1 nig T2 erogKña. (b) R)ab;fa enA 25oC Kc KW 31063,4 −× sMrab;Rbtikm μ ³

)(42 gON )(2 2 gNO kJo 0,58=ΔΗ

KNnaefrlMnwgenA 65oC ?

50. spK énR)ak;kørY (AgCl) )an[ 1,6x10-10. etItMélrbs;vaenA 60oC esμ Ib:un μan?[karENnaM³ GñkRtUvkarlT§plBIcMeNaT 49(a) nig Tinñn½ykñúgesckþIsegçb3edIm,IKNna oΔΗ ]

51. eRkamlkçxNÐGVIeFVI[sarFatumanGg;RtUBIsþg;daesμ IsUnü ? etIsarFatuEdlFøab;manGg;RtUBI sþg;daGviC¢manEdrb¤eT ?

52. ]sμ ½nTwkCal,ayén 2H nigCO KWCa\nÞn³)anbegáIteLIgedayRbtikmμrvagcMhayCamYy FüÚgekþARkhm (GnuplénbMNitFüÚgfμ)

)()(2 sCgOH + )()( 2 gHgCO +

BITinñn½ykñúgesckþIsegçbTI 3 eFVIkarTsSn¾TayBIsItuNðPaBEdlRbtikmμGacekItman. 53. bBaa¢k;BIRbtikm μGasIut-)as Bronsted enA 25oC ³ )()( aqClaqHF −+ )()( aqFaqHCl −+

(a) TayTukfaetI K nwgtUcCagb¤FMCagÉkta. (b) etI oSΔ b¤ oΔΗ )aneFVI[karpþl;[eTAelI oGΔ FMCag ? (c) etI oΔΗ GacmantMélviC¢man b¤ GviC¢man ?

54. kMNkCaRkaménsUdüÚmGaestatBIsUluysüúgEq¥thYsekIteLIgÉkÉg. etIGVIeTAEdlGñk GacRsavRCavrkGMBIsBaaØén SΔ nig ΔΗ ?

55. bBaa¢k;BIkarbMEbkedaykMedAén 3CaCO ³ 3CaCO (s) )()( 2 gCOsCaO +

lMnwgsMBaFcMhayén]sμ ½nkabUnicKW 22,6mmHg enA 700oC nig 1829mmHg enA950oC. KNnaGg;tal;BIsþg;daénRbtikmμ [karENnaM³ emIl 49a]


18-40

56. RbtikmμCak;EsþgmYyKWekIteLIgÉkÉgenA72oC. ebIbNþÚrGg;RtUBIsMrab;Rbtikm μKW19kJ. etI tMélGb,brimaén SΔ Rbtikmμesμ Ib:unμan (KitCas‘UlkñúgmYyEklvin) ?

57. TayTukfaetIbNþÚrGg;RtUBImantMélviC¢man b¤ GviC¢mancMeBaHRbtikmμdUcteTA ÷ (a) )(2)( aqHClsZn + )()( 22 gHaqZnCl + (b) )()( gOgO + )(2 gO (c) )(34 sNONH )(2)( 22 aqOHgON + (d) )(2 22 aqOH )()(2 22 gOaqOH +

58. Rbtikmμ )()()( 43 sClNHgHClgNH →+ lMnaMekIteLIgÉkÉgenA 25oC eTaHbICamankar fycuHPaB\tsNþab;Fñab;kñúgRbBn§½k¾eday (]sμ½n)anbMElgCaeTAGgÁFaturwg) . cUrBnül; ?

59. edayeRbITinñn½ydUcteTA edIm,IkMNt;cMnucrMBuHFmμtaKitCaEklvinén)art. etIkar]bmaGVI EdlGñkRtUveFVIkñúgkarteRmobkñúgkarKNna?

)(lHg : 0=ΔΗ of (tamniymn½y)

molKJS o ./4,77= )(lHg : molkJo

f /78,60=ΔΗ

molKJS o ./7,174= 60. kMedArMhYtCam:UléneGtaNulKW molkJ /3,39 nigcMnucrMBuHéneGtaNulKW 78,3oC. KNna

SΔ sMrab;karrMhYtén 0,50mol eGtaNul ? 61. RbtikmμCak;EsþgKW)ansÁal;mantMél oGΔ -122kJ. etIRbikm μnwgcaM)ac;ekIteLIgRbsinebI

GgÁFatuRbtikrRtUv)anlaycUlKña. 62. kñúglMnaM MondsMrab;karbnSúT§nIEklkabUnm:UNUGuksIutKW)anRbtikmμCamYykMedAedIm,IbegáIt

4)(CONi EdlCa]s μ ½n nigGaRs½ydUecñHGacRtUv)anEjkBIGgÁFaturwgminsuT§. )(4)( gCsNi + 4)(CONi (g)

eK[famBlesrIsþg;daénkMNr CO(g) nig 4)(CONi (g) KW -137,3kJ/mol nig -587,4kJ/mol

erogKña. KNnaefrlMnwgénRbtikm μenA 80oC . ]bmafa ofGΔ minGaRs½ynigsItu-NðPaB.

63. KNna oGΔ nig pK sMrab;lMnaMdUcteTAenA 25oC ÷ (a) )()( 22 lBrgH + )(2 gHBr

(b) )(21)(

21

22 lBrgH + )(gHBr

Bnül;BIPaBxusKñakñúg oGΔ nig pK TTYl)ansMrab; (a) nig (b) .

CMBUkTI18

18-41

64. KNnasMBaFénGuksIuEsn (KicCa atm) elIPaKsMNakén NiO enA 25oC ebI oGΔ = 212kJ sMrab;Rbtikmμ . )(sNiO )(

21)( 2 gOsNi +

65. x 66. x 67. BinitüRbtikmμ )()( 22 gOgN + )(2 gNO

[tMél oGΔ sMrab;Rbtikm μenA 25oC KW 173,4kJ. (a) KNnafamBlesrIsþg;dakMNrén NO

nig (b) KNna pK énRbtikmμ (c) sarFatumYykñúgkarcabepþImkñúgkMNrEpSgKW NO . ]bmafa sItuNðPaBkñúgdMeNIrkareRKOgcRkKW 1100oC TsSTay pK sMrab;Rbtikm μxag elI. (d)

Caksikr yl;fa ebøkbenÞarCYykñúgkarbegáInksipl ehtuGVI ?

68. karkMedATg;Edg (II) GuksIut enA 400oC minGacplitbrimaN[)ansmrmüén Cu :

CuO(s) � Cu(s) + 1/2O2(g) kJGo 2,127=Δ

GaRs½ydUecñH RbsinebIRbtikmμenHKWCaKUedIm,IeFVIkarbMElgBIRkahVIteTAkabUnm:UNUGuksIut vaCaRbtikmμekIteLIgÉkÉg. sresrsmIkarsMrab;lMnaMCaKU nigKNnaefrlMnwgsMrab; KURbtikm μ.

69. xagkñúgm:asIunénrfynþEdlmanTMgn; 1200kg KWRtUv)ankMNt;edIm,IdMenIrkarCamYyGuktan )( 188HC EdlGg;RtUBIéncMNehHKW 5510kJ/mol. ebIrfynþeFVIclnaeLIgTICMralKNna

kMBs;Gtibrima(KitCaEm:Rt) EdlGaceFVI[rfynþebIkbrcMNayEt 1,0 gallon \nÞn³. ]bmafa sItuNðPaBkñúgsILaMgm:asIunKW 2200oC nigsItuNðPaBecj-cUlKW 760oC nigGac ecal)anRKb;sNæanénkarTgÁic. m:asén 1 gallon \nÞn³KW 3,1kg . [Bnül;³ emIl KImIGnuvtþn_TMB½rTI18-13. kmμnþeFVIclnakñúgbMlal;TIénrfynþqøgkat;cMgaybBaÆrKW mgh Edl m Cam:asénrfynþKitCa kg, g CakarbegáInel,OneTAnigTMnajdI (9,81m/s2) nig h

CakMBs;KitCaEm:Rt].

70. RkamkabUnm:UNUGuksIut(CO)mYy KW)anrkeXIjmanGg;RtUBIFMCagsUnüenAtMélsItuNðPaB dac;xatsUnü. cUreFVIkarBnül;[)anBIrsMrab;karGegátenH.

71. x

72. es‘rIskmμPaBkñúgCMBUkTI 4 bgðajfaRbtikmμ (a) KWekIteLIgÉkÉgenAeBlEdlRbtikmμ(b)

KWminekIteLIgÉkÉgenA 25oC :

(a) )()(2)( 22 gHaqFeHsFe +→+ ++

(b) )()(2)( 22 gHaqCuHsCu +→+ ++


18-42

eRbITinñn½ykñúgesckþIsegçbTI 3 edIm,IKNnaefrlMnwgsMrab;RbtikmμTaMgenHehIyBIenHbBaa¢k;fa es‘rIskmμPaBKWRtwmRtUv. 73. el,OnefrsMrab;Rbtikm μdMbUgKW 7,1 sM ./109× enA 25oC ÷ )(2)()(2 22 gNOgOgNO →+ etIel,OnefrsMrab;RbtikmμRcasenAsItuNðPaBdUcKñaes μ Ib:un μan ? 74. x 75. cUrBiBN’naBIviFIBIry:agEdlGñkGacvas; oGΔ énRbtikmμ . 76. RbtikmμdUcteTAenHtMNag[karykecjénGUsUnBImNÐlGakass¶b; (stratosphere) . )(2 3 gO )(3 2 gO KNnaefrlMnwg )( pK sMrab;Rbtikm μ. kñúgkarbgðajTMhMénefrlMnwgcUrBnül;ehtuGVIRbtikmμ enHmin)anbBaa¢k;BIPaBbgád¾cMbgénkarbMpøajGUsUncMeBaHmuxskm μPaBmnusSeFVI[RkxVk;dUcCa GasUtGuksIut nig CFCs ? ]bmafa sItuNðPaBén stratosphere KW Co30− nig o

fGΔ KWmin GaRs½yeTAnwgsItuNðPaB. 77. dMuTwkkkTm¶n; 74,6g GENþtkñúgsmuRTGak;Tic. sItuNðPaB nig sMBaFénRbBn§½CMuvijKW 1atm

nig0oC.KNna surrsys SS ΔΔ , nig univSΔ sMrab;karrMlayéndMuTwkkk. etIGñkGacsnñidæany:ag dUemþcGMBIFm μCatiénlMnaMBItMél univSΔ ?(kMedACam:UlénkarrMlayrbs;TwkKW6,01kJ/mol) .

78. eFVIkarBnül;PaBEdlGaceFVI)anéneyabkTg;EdgBIEr: chalcocite (Cu2S) edaykarkMedA ³ )()(2)(2 sSsCusSCu +→

KNna oGΔ sMrab;RbtikmμCasrub RbsinebIlMnaMxagelICalMnaMKUredIm,IeFVIkarbMElgs<an;F½r eTACas<an;F½rDIGuksIut. eK[ molkJSCuGo

f /1,86)( 2 −=Δ . 79. x 80. brimaNd¾eRcInénGIuRdUEsnKW)anRtUvkaredIm,IsMeyaKGam:Ujak;. karerobcMmYyénGIuRdUEsn

Tak;TgeTAnigRbtikmμkabUnm:UNUGuksIutnigcMhayTwkenA 300oCenAcMeBaHmuxkatIkr Cu-Zn )()( 2 gOHgCO + )()( 22 gHgCO +

KNnaefrlMnwg(Kp)sMrab;RbtikmμnigsItuNðPaBenAeBlEdlRbtikm μekIteLIgnUvCOnig H2O. etInwgman Kp FMnwgTTYl)anenAsItuNðPaBdUcKña ebIkatlIkrmansmtßPaBeRcIn)aneRbI ?

81. cUrbgðajGasIutkabuksIulicBIr (GasIutEdlmanRkum COOH− ) : COOHCH 3 (GasIut GaesTic) 5108,1 −×=aK nig ClCOOHCH 2 (GasIutkør:UGaesTic) 3104,1 −×=aK . (a) KNna oGΔ sMrab;GIuy:ugkmμénGasIutTaMgenHenA 25oC.

CMBUkTI18

18-43

(b) BIsmIkar ooo STG Δ−ΔΗ=Δ eyIgeXIjfakarpþl;[eTAelIBakü oGΔ KWCa oΔΗ

nigry³eBlsItuNðPaB ( oSTΔ ). karpþl;[nUvtMélTaMgenH)anerobCatarag sMrab;GasIut TaMgBIr ³

)(kJoΔΗ )(kJST oΔ

ClCOOHCHCOOHCH

2

3 7,457,0

−−

1,216,27

−−

etIBaküBakü]tþmPaBNamYyeRbIsMrab;eFVIkarkMNt;tMélén oGΔ (ehIyBIenH aK énGasIutb¤ ?)

(c) etIlMnaMGVIpþl;[eTAelI oΔΗ ? (eFVIkarbBaa¢k;énGasIutdUcCaRbtik μGasIut)as) (d)

cUrBnül;etIehtuGVI oSTΔ KWmantMélGviC¢manCagsMrab; COOHCH 3 ? cMelIylMhat;Gnuvtþn_ 1. (a) Gg;RtÚBIfycuH (b) Gg;RtÚBIfycuH (c) Gg;RtÚBIekIneLIg (d) Gg;RtÚBIekIneLIg 2. (a) -173,6 J/K (b) -139,8 J/K (c) 215,3 J/K 3. (a) ΔS<0 (b) ΔS<0 (c) ΔS≈0 4. (a) -106,4 J/K (b) -2935,0 kJ 5. ΔSfus = 16 J/K.mol ; ΔSvap = 72 J/K.mol

6. 1,93 x 1057 7. 33 kJ 8. ΔG = 0,97 kJ ; BIxagsþaMeTAxageqVg. cMelIylMhat 6. (a) 0,02 (b) 9x10-19 (c) 2x10-181 10. (c)<(d)<(a)<(e)<(b) 12. (a) 47,5 J/K (b) -12,5 J/K (c) -242,8 J/K 14. (a) ΔS<0 (b) ΔS>0 (c) ΔS>0 d) ΔS<0

18. (a) -1139 kJ (b) -140,0 kJ (c) -2935,0 kJ 20. (a) enAsItuNðPaBTaMGs; (b) eRkam 111K 24. 8x104 J 26. 4,5x10-81 28. (a) -24,6 kJ (b) -1,10 kJ 30. -341 kJ/mol 32. -2,87 kJ 36. 1x103 38. (a) 8,0x104 J (b) 4,0x104 J (c) -3,2x104 J

(d) 6,4x104 J 40. (i) RbtikmμminGacekIteLIgeRBaHΔG > 0 (ii) RbtikmμenaHRtUvkarfamBl skmμ. (iii) RbtikrenAkMhab;lMnwgehIy. 42. kñug (a), (b) nig (c) ΔH > 0, ΔS > 0; sRmab; (a) ΔG < 0, (b) ΔG =0, (c) ΔG > 0 44. ΔS > 0 46. (b) ΔHvap FMCagsRmab; eGtaNul nigTwkedaysarmansm<½n§GIuRdUEsn. 48. (a) 2CO + 2NO → 2 CO2 + N2

(b) Pñak;garGuksIutkmμKW NO ; Pñak;garerdukmμKW CO (c) 1x10121 (d) 1,2x1018 BIxageqVg eTAxagsþaM (e) eT 50. 2,6x10-9 52. 976 K 54. ΔS < 0 ; ΔH < 0 56. 55 J/K

58. kMeNInGg;RtUBIrbs;brisßanCMuvij GacTUTat;karfycuHGg;RtUBIrbs;RbB½n§Rbtikm μ. 60. 56 J/K 62. 4,5x105 64. 4,5x10-75 atm. 66. x 68. C + CuO � CO + Cu ; 6.1

70. TMrg;RkamminmansNþab;Fñab; b¤minsuT§. 72. (a) 7,6x1014 (b) 4,1x10-12 74. x

76. 1,8x1070 RbtikmμenaHRtUvkarfamBlskmμeRcIn. 78. -214,3 kJ 80. Kp = 36 ;

981K ; eT

Documents

Gg;RtUB I famBlesrI nig lMn wg...CMBUkTI18 18-1 Gg;RtUB I famBlesrI nig lMn wg Entropy, Free Energy, and Equilibrium m ETm:UDINamicKWCalkçN³FMeFgehIyBi)akQandl;sMrab;karcUlrYmEbbviTüasaRsþEdl