CMBYkTI6

6-1

66 EETTmmUU ::DDIINNaammiiccGGssrr II rraaggÁÁ

(( IInnoorrggaanniicc TThheerrmmooddyynnaammiiccss)) esovePAKImI Edlerobrab;BIKImIGsrIragÁenHminEmnRKan;EtCakarsikSaFmμtamYyBIFatu KImI nigsmasFatuCaeRcInrbs;BYkvabegáItenaHeT bu:Enþvak¾Tak;TgpgEdreTAnwgkarBnül;BImUl ehtuEdlsmasFatumYycMnYnGackekIt EtmYycMnYneTotminGackekIt)an. karBnül;CaFm μta manTMnak;TMngeTAnwgktþafamBlEdlCab;Tak;TgenAkñúgkarbegáItsmasFatu. RbFanbTenH CasaxamYyénETmU:DINamic ehIyenAkñúgCMBUkenHeyIgnwgbgðajBIkarENnaMya:ggay²GMBIETmU: DINamicGsrIragÁ. eTaHbICakarGPivDÆxagvis½yKImIPaKeRcInKWsßitenAcRkPBGg;eKøs )araMg nigGaLWm:g; bu:EnþmanCnCatiGaemricBIrnak;)anbgðajBIsarsMxan;enAkñúgkarGPivDÆETm:UDINamic. GñkTImYy KWelak Benjamin Thomson EdlCIvitrbs;Kat;GacbegáIt)anCaExSPaBynþd¾l¥mYy. Kat;)an ekItenAqñaM1753 enA Woburn, Massachusetts ehIy)ankøayCavresnIyRtIenAkñúgkg vresnaFMGaNaniKmTIBIrrbs;cRkPBGg;eKøs ehIybnÞab;mkKat;)aneFIVCaGñkesIubkarN_[ cRkPBGg;eKøs edaykareRbIcMeNHdwgEpñkKImIrbs;Kat;edIm,IepJIsaredayeRbITwkfñaMminGac emIleXIj. enAeBl Boston )anFøak;kñúgkarRKb;RKgrbs;kgkmøaMgbdivtþn_ Kat;)anePosxøÚn eTARbeTsGg;eKøs ehIyeTAkan; Bavaria Edlbc©úb,nñCaEpñkmYyenARbeTsGaLWm:g;. cMeBaH karbric©aKEpñkviTüasaRsþrbs;Kat;eTAdl;kgkmøaMgTahanrbs; Bavaria Kat;)anbegáItkar KNnamYy ehIyKat;)andak;eQ μaHfa Count Rumford. enAeBlenaH kemþARtUv)aneKKitfa CavtßúravmYyRbePT ehIyenAkñúgcMeNamkarrukrksMxan;²CaeRcIn Rumford )anbgðajfa kemþA CalkçN³rUbénrUbFatuminEmnCasmasFaturbs;rUbFatueT. Cak;Esþg eK)anKitfaKat;KWCa ETmU:DINamicviTUdMbUgeKmñak;. RbEhlCaCit 100 qñaMeRkaymk J.Willard Gibbs Edl)anekItenA New Haven,

Connecticut. enAÉsklviTüal½y Yale enAkñúgqñaM1863 Kat;)anTTYlrgVan;fñak;bNÐitdMbUg eKmñak;EdrenAshrdæGaemric. Gibbs CaGñkTImYyEdl)anTajyksmIkarKNitviTüafaCa mUldæanénETmU:DINamicTMenIb. enAeBlenaH bBaØtþiGg;RtUBIRtUv)aneKelIkeLIgenAGWru:b ehIy rUbviTUCnCatiGaLWm:g;KW elak Rudolf Causius )ansegçbBIc,ab;ETmU:DINamicfa : famBlén

ETmU:DINamicGsrIragÁ

6-2

cRkvalenHKWefr Gg;RtUBIéncRkvalmanTMenarGtibrima :. bu:Enþ Clausius nigrUbviTUepSg² eTotmin)anGbGr b¤elIksesIrBIsarsMxan;énbBaØtþiETmU:DINamicenHeT. Gibbs EdlCaGñk bgðajfa GIV²RKb;ya:gEdl)anmkBIPaBGacrlayén]s½μnedIm,IQaneTArklMnwgKImIKWGaRs½y elIktþaGg;RtUBI. enAkñúgkarTTYlsÁal;c,ab;rbs;Kat; famBlesrIETmU:DINamicRtUv)aneKkMNt; nimitþsBaØa G ehIy)anpþl;eQμaHfa famBlesrI Gibbs. 6>1 ETmU:DINamicénkarbegáItsmasFatu smasFatuRtUv)aneKbegáIteLIgBIFatuedayRbtikmμKImI. ]TahrN_ GMbilFm μtaKW sUdüÚmkørYGacRtUv)aneKbegáIteLIgedaykarbBa©ÚlKñaénsUdüÚmEdlCaelah³skmμCamYykør EdlCa]s½μnBN’ébtg ehIyBul³ )(2)()(2 2 sNaClgClsNa →+ edaysarRbtikmμenHGacekIteLIgedayBuMcaM)ac;RtUvkarCMnYyBIxageRkA dUcenHeKehA RbtikmμenHfaCaRbtikmμekIteLIgedayÉkÉg. ¬eTaHbIvaekIteLIgedayÉkÉg bu:EnþeKk¾min Gacdwg)anEdrfa vaCaRbtikmμelOn b¤yWtkMritNaenaHeT¦ RbtikmμRcasKWCakarbMEbksUdüÚm kørY CaRbtikmμEdlminGacekIteLIgedayÉkÉgeT ehIyeyIgk¾mincg;[GMbilEdlenAkñúgpÞH )ayrbs;BYkeyIgbeBa©jnUvBBk]s½μnkørEdlBulenaHEdr. viFImüa:gedIm,ITTYl)anelah³ sUdüÚm nig]s½μnkørRtlb;mkvij KWeK[vaqøgkat;crnþGKÁisnI ¬RbPBfamBlxageRkA¦ tamry³ sUdüÚmkørYrlay³ )()(2)(2 2 gCllNalNaCl +⎯→⎯ karsikSaBImUlehtuEdlbNþal[ekItmanRbtikm μKImIKWCasaxamYyénETmU:DINamic. CMBUkenH nwgpþl;nUvkarENnaMTUeTAgay²énRbFanbTenH enAeBlvaTak;TgnwgkarbegáItsmasFatu GsrIragÁ. dMbUgeyIgRkeLkemIlktþaGg;tal;BI EdlTak;TgnwgkarbegáItsmasFatu. Gg;tal;BI RtUv)aneKkMNt;faCabrimaNkemþAénsmasFatumYy. enAeBlEdlplitplénRbtikmμKImIman Gg;tal;BITabCagGgÁFatuRbtikr enaHRbtikmμbeBa©jkemþAeTAkñúgmCÄdæanCMuvij EdlCadMeNIr karmYyeKehAfa RbtikmμbeBa©jkemþA. RbsinebIplitplmanGg;tal;BIx<s;CagGg;tal;BI GgÁFatuRbtikr enaHfamBlkemþARtUvRsUbBImCÄdæanCMuvij ehIyRbtikm μenHRtUv)aneKehAfaCa

CMBYkTI6

6-3

Rbtikmμ RsUbkemþA. PaBxusKñarvagGg;tal;BIrbs;plitpl ehIynigGg;tal;BIrbs;GgÁFatu RbtikrRtUv)aneKehAfa bERmbRmÜlGg;tal;BI HΔ . k> Gg;tal;BIkMN Gg;tal;BIénsmasFatumYyCaFm μtaRtUv)aneKcuHenAkñúgtaragbBa¢ITinñn½yCatémøGg; tal;BIénkarbegáIt. Gg;tal;BIkMNRtUv)aneKkMNt;faCabERmbRmÜlkñúgbrimaNkemþA enAeBl 1 mol énsmasFatuRtUvbegáItBIFaturbs;va enAkñúgpassþg;darbs;BUkvaKWenAsItuNðPaB 298K nigsm<aF 100 kPa. tamniymn½y Gg;tal;BIkMNénFatuEtmYy KWes μ IsUnü. enHCasþg;daén karbMBanmYy edaysarEtkarkMNt;PUmisaRsþénkMBs;rbs;eyIgRtUvsßitenAx<s;CagkMritnIvUTwk smuRT EdlRbesIrCagenAcMkNþalEpndI. nimitþsBaØasRmab;Gg;tal;BIénkarbegáItenAeRkam lkçxNÐsþg;dax<s;KW o

fHΔ . dUcenH eyIgrktémøenAkñúgtaragTinñn½yman dUcCa ofHΔ (CO2(g))

= -394 kJ.mol-1. karkMNt;enH bgðajfafamBl 394 kJ.mol-1 RtUv)anbeBa©jenAeBl 1

mol énkabUn ¬RkahIVt¦ manRbtikmμCamYy 1 mol én]s½ μnGuksIuEsn enAsItuNðPaB 298 K

nigsm<aF 100 kPa pþl; 1 mol énkabUnDIGuksIut³ )()()( 22 gCOgOsC →+ o

fHΔ = -394 kJ.mol-1 Gg;tal;BIkMNGacRtUv)aneKbBa©ÚlKñaedIm,IKNnabERmbRmÜlGg;tal;BIenAkñúgRbtikm μ KImIepSg²eTot. ]TahrN_ eyIgGackMNt;bERmbRmÜlGg;tal;BIenAeBlkabUnmU:NUGuksIueqH enAkñúgxül;begáIt)anCakabUnDIGuksIut³ )()()( 222

1 gCOgOgCO →+ dMbUgeyIgRtUvRbmUlTinñn½yEdlcaM)ac;BIkñúgtaragTinñn½y³

ofHΔ (CO2(g)) = -394 kJ.mol-1 nig o

fHΔ (CO(g)) = -111 kJ.mol-1 tamniymn½y ofHΔ (O2(g)) = 0. dUcenH bERmbRmÜlGg;tal;BIsRmab;Rbtikm μenHGacTTYl)anBI³

oHΔ ¬Rbtikmμ¦ = ofHΔ∑ ¬plitpl¦ - o

fHΔ∑ ¬GgÁFatuRbtikr¦ dUcenH oHΔ ¬Rbtikmμ¦ = (-394 kJ.mol-1) – (-111 kJ.mol-1) = -283 kJ.mol-1 dUcenH Rbtikm μenHCaRbtikm μbeBa©jkemþA dUceTAnwgRbtikmμcMehHTaMgGs;epSgeTotEdr. x> famBlsm<½n§ ¬Gg;tal;BI¦ témøGg;tal;BIkMNKWgayRsYlNas;sRmab;karKNnaénbERmbRmÜlGg;tal;BIenA kñúgRbtikm μ. bu:EnþKImIGsrIragÁviTUEtgEtmancMNab;Garm μN_kñúgkmøaMgTMnajrvagGatUmenAkñúg

ETmU:DINamicGsrIragÁ

6-4

mU:elKulkUva:Lg; KWGg;tal;BIsm<½n§. BaküenHeKEtgEtehAfa famBlsm<½n§ eTaHbIvamanPaB xusKñatictYcrvagBYkvaTaMgBIr KWedaysarEtniymn½y nigtémøelx. eyIg)anerobrab;rYcmk ehIyBIfamBlsm<½n§enAkñúgGtßbTénkmøaMgsm<½n§kUva:Lg;enAkñúgmU:elKulDIGatUmFmμta ¬CMBUkTI 2¦. famBlsm<½n§RtUv)aneKkMNt;faCafamBlEdlRtUvkaredIm,Ipþac; 1 mol énsm<½n§kUva:Lg; Cak;lak;mYy. famBlRtUv)anbeBa©jenAeBlsm<½n§RtUvkekIt ehIyfamBlRtUv)anpÁt;pÁg; bEnßmenAeBlsm<½n§RtUvpþac;. eyIgGackMNt;BIfamBlsm<½n§[)anBitR)akdsRmab;KUCak;lak;énGatUmEdl)ancUl rYmedaysm<½nkUva:Lg;. ]TahrN_ taragTI 6.1 bgðajBIfamBlsm<½n§enAkñúgmU:elKulDIGatUmén es‘rIGaLÚEsn. RbsinebIeyIgemIlFatuenAkñúgRkum eyIgeXIjfafamBlsm<½n§fycuHelIkElg mYy KWedaysarEtkarekIneLIgénTMhMGatUm nigkarfycuHkñúgPaBRtYtsIuKñaGrb‘Ítal;éndg;sIuet eGLicRtug. eyIgnwg)aneXIjenAkñúgCMBUkenH nigCMBUkbnÞab;eTotfa famBlsm<½n§Tabxus RbRktIrbs; F-F man\T§iBld¾sMxan;kñúglkçN³KImIPøúyGr.

famBlsm<½n§GaRs½yelIGatUmepSgeTotEd;lmanvtþmanenAkñúgmU:elKul. ]TahrN_ témøfamBlsm<½n§ O-H KW 492 kJ.mol-1 kñúgTwk (HO-H) bu:Enþ 435 kJ.mol-1 enAkñúgemtaNul CH3O-H. edaysarPaBxusKñaenHtaragTinñn½ypþl;nUvfamBlsm<½n§mFümsRmab;sm<½n§ kUva:Lg;Biess. famBlénsm<½n§Cak;lak; dUcCasm<½n§xøaMgekIneLIgenAeBllMdab;sm<½nekIneLIg. taragTI 6.2 bgðajBITMenarenHsRmab;es‘rIénfamBlsm<½n§mFümkabUn-GasUt.

taragTI 6>1 famBlsm<½n§rbs;mU:elKulDIGatUmGaLÚEsn mU:elKul famBlsm<½n§ (kJ.mol-1) F-F 155 Cl-Cl 242 Br-Br 193 I-I 151

CMBYkTI6

6-5

K> famBlbNþaj ¬Gg;tal;BI¦

famBlbNþajCabERmbRmÜlfamBlsRmab;karbegáIt 1 mol énGgÁFaturwgGIuyU:nicBI smasFatuGIuyu:g]sμ ½nrbs;va ¬eyIgBitCakMBugKitBIGg;tal;BIbNþajRtg;enH bu:EnþPaBxusKña minGacTTYlyk)aneT¦. eyIgGacbgðajBIdMeNIrkarCamYysUdüÚmkørY. famBlbNþajén sYdüÚmkørYRbQmnwgbERmbRmÜlfamBlsRmab;³ )()()( sClNagClgNa −+−+ →+ famBlbNþajBitCakarkMNt;mYyénTMnajeGLicRtUsþaTic nigkarbMEbkénGIuyu:genAkñúg bNþajRkam. es‘rIénGnþrkmμenHGacRtUv)aneKbgðajedaybNþajRkamsUdüÚmkørY¬rUbTI 6.1¦.

enACuMvijkacugkNþal KWmanGajú:gcMnYn 6 enAcm¶ay r Edl r Cacm¶ayrvagcMNuc

kNþalénFatuEdlCitbMput. enHCakmøaMgTMnajd¾sMxan;sRmab;cgbNþajCamYyKña. bu:EnþenA cm¶ay(2)1/2r KWmankacugcMnYn 12. kacugTaMgenHnwgpþl;nUvkmøaMgbMEbk. karbEnßmRsTab; énGIuyu:gelIsBI Unit cell eyIgeXIjfamanGajú:gcMnYn 8 eTotenAcm¶ay (3)1/2

r bnÞab;mk mankacugcMnYn 6 eTotenAcm¶ay 2r. dUcenH tulüPaBBiténbnÞúkKWRtUvtagedayes‘rImin kMNt;énkmøaMgTMnaj nigkmøaMgbMEbkqøas;Kña bnÞab;mkkøayCaes‘rIRKbdNþb;mYy. RbePT nImYy²énmbNþajmankarerobcMxus²Kñaénkacug nigGajú:g niges‘rIRKbdNþb;rbs;vapÞal;.

taragTI 6>2 famBlsm<½nmFümsMrab;sm<½n§rvagkabUn-GasUt sm<½n§ famBlsm<½n§ (kJ.mol-1)

C N 305 C N 615 C N 887

rUbTI 6>1 düaRkambNþajGIuyu:génTMrg;sUdüÚmkørY edaybgðajBIbnÞúkGIuyu:g.

ETmU:DINamicGsrIragÁ

6-6

témøelxrbs;es‘rI TaMgenHRtUv)aneKsÁal;faCaefr Madelung A. ]TahrN_énRbePT bNþajFmμtaRtUv)anbgðajkñúgtaragTI 6.3. bEnßmeTAelIkarBwgEp¥kelIRbePTbNþaj famBlbNþajxus²KñaCamYynwgbnÞúkGIuyu:g. PaBeTVdgénbnÞúkBI +1 eTA +2 ¬b¤BI -1 eTA -2 ¦GaceFIV[famBlbNþaj)anRbEhlbIdg. ]TahrN_ famBlbNþajénbU:tasüÚmkørYKW 701 kJ.mol-1 bu:Enþkal;süÚmkørYKW 2237 kJ.mol-1. Cak;Esþg cMeBaHes‘rI MX, MX2, MX3, MX4 famBlbNþajRtUvTak;TgnwgsmamaRt 1:3:6:10. famBlbNþajk¾FMCagEdr RbsinebIGIuyu:gtUcCag CaktþamYyEdleFIV[kan;EtCit GIuyu:gkNþal. eKGackMNt;famBlbNþajénRkamGIuyU:nicBIkarkMNt;tamBiesaFn_ dUcEdleyIgnwg )aneXIjya:gxøI² bu:EnþCajwkjab;eyIgRtUvkarkarsμanTukénfamBlbNþajenAeBlTinñn½y BiesaFminman. edIm,IkMNt;témøtamRTwsþI eyIgGaceRbIsmIkar Born-Lande . smIkarenH )anmkBItémøCak;lak;énfamBlbNþaj, U BIkarbBa©ÚlKñaénGnuKmn_samBaØ. U = )11(

4

2

nrezNAz

oo

−−−+

πε

taragTI 6>3 efr Madelung sMrab;RbePTbNþajFm μta RbePTbNþaj efr Madelung, A Sphalerite, ZnS 1.638 Wurtzite, ZnS 1.641

sUdüÚmkørY, NaCl 1.748

essüÚmkørY, CsCl 1.763 Rutile, TiO2 2.408

PøúyGrIt, CaF2 2.519

taragTI 6>4 tMélsMrab;niTsSn_ Born

sNæaneGLicRtUnicénGIuyu:g niTsSn_ Born, n ]TahrN_ He 5 Li+ Ne 7 Na+, Mg2+, O2-, F- Ar 9 K+, Ca2+, S2-, Cl- Kr 10 Rb+, Br- Xe 12 Cs+, I-

CMBYkTI6

6-7

Edl N CacMnYnGavU:kaRdU (6,023 1023 mol-1), A Caefr Madelung, z+ CabnÞúkkacugTak;Tg, z- CabnÞúkGajú:gTak;Tg, e CabnÞúkeGLicRtugCak;lak; ( 1,602 .10-19 C), 142,3=π , oε Cakar GnuBaØatlMhesrI ( 8,854. 10-12.C2.J-1.m-1), ro CaplbUkénkaMGIuyU:nic nig n CaniTsSn_ Born

mFüm ¬bgðajxageRkam¦. efr Madelung Bnül;BIkmøaMgTMnajrvagGIuyu:gnigGIuyu:g. bu:Enþ enAeBlGIuyu:gxitCit GIuyu:gmYyepSgeTotkan;EtCitEdr enaHGrb‘Ítal;eGLicRtugEdl)anbMeBjrbs;BYkvacab;epþIm bEnßmktþabMEbkEdlekIneLIgya:gxøaMg enAeBléNVyU:BIrxitCitéNVy:UénGIuyu:gmYyeTot. edIm,I Bnül;BIkarbMEbkenH niTsSn_ Born, n RtUv)aneKbBa©ÚleTAkñúgsmIkar Born-Lande. Cak;Esþg plbUkénkaMGIuyU:nictag[TItaMglMnwgrvagTMnajGIuyu:g nigkarbMEbkGnþreGLicRtug. témømYycMnYnénniTsSn_ Born RtUv)anbgðajenAkñúgtaragTI 6.4. edIm,IbgðajBIrebobKNnafamBlbNþajBIsmIkarBorn-LandeeyIgnwgeRbI ]TahrN_ énsUdüÚmkørY. bnÞúksRmab;smasFatuGIuyU:nicenH KW +1 (z+) nig -1 (z-). kaMGIuyU:nicKW 116pm

nig 167pm erogKña Edlpþl;nUvtémø ro KW 283pm b¤ 2,83 .10-10pm. témøefr Born

KWCamFüménGIuyu:gsUdüÚm nigGIuyu:gkørY³ (7+9)/2 = 8. CMnYskñúgsmIkar³ U = 1

1011212

219123

.751)811(

)10.83,2)(..10.854,8.(142,3.4)10.602,1.(1.1.748,1).10.02,6( −

−−−−

−−

−=− molkJmmJC

Cmol

témøenHKWRbEhlKñaeTAnwgtémøenAkñúgkarBIesaFd¾l¥bMputmYyKW -788 kJ.mol-1 ¬PaBlMeGog RtwmEt 4,7 PaKry¦. enAeBlmanPaBxusKñaxøaMgrvagtémøBiesaFn_énfamBlbNþaj nigtémø EdlTTYl)anBIkarKNnatamsmIkar Born-LandevabgðajfaGnþrkmμrvagGIuyu:gKWCaGIuyU:nicmin suT§ bu:Enþk¾manpÞúklkçN³kUva:Lg;d¾sMxan;Edr. smIkarBorn-Lande GacRtUv)aneKeRbIsRmab;EtkarrkfamBlbNþaj RbsinebITRmg; RkaménsmasFatuRtUv)aneKsÁal;. ebIsinCaeKminsÁal; eKeRbIsmIkar Kapustinskii Edl ν CacMnYnénGIuyu:gkñúgrUbmnþtamBiesaFn_ ¬]TAhrN_ kal;süÚmPøúyGrY, ν =3¦ nignimitþsBaØaepSg eTotmann½y nigtémødUcKña enAeBlsmIkar Born-Lande elIkElg ro KitCa pm ³ U = 1

5

.)5,341(..10.202,1 −−+

−− molkJrr

zz

oo

ν

cugeRkay eKGacniyay)anfa RkamTaMgGs;suT§EtmanfamBlbNþaj. cMeBaHsmas FatukUva:Lg;Fm μta famBlbNþajGackMNt;)ancMeBaHTMnajGnþrmU:elKul. cMeBaHsmasFatu kUva:Lg;bNþaj famBlbNþajKWCafamBlénsm<½n§kUva:Lg; cMeBaHelah³ vaCaTMnajEdl

ETmU:DINamicGsrIragÁ

6-8

begáItsm<½n§elah³. bu:Enþ BaküfafamBlsRmab;mU:elKulkUva:Lg;Fmμta eKehAfaGg;tal;BIén rMehIr(enthalpy of sublimation) RbesIrCagkarehAfa famBlbNþaj. X> Gg;tal;BIénGatUmkmμ karrkeXIjd¾sMxan;mYyeTotKWfamBlGatUmkmμ. enHRtUv)aneKkMNt;faCafamBl EdlRtUvkarsRmab;begáIt 1 mol énGatUm]s½μnénFatuenaHecjBIFatuenAkñúgpasFm μtarbs;va enAsItuNðPabbnÞb;. famBlenHRtUv)aneKeRbIedIm,ItMNagkarpþac;sm<½n§elah³enAkñúgelah³ dUc CaTg;Edg³ )()( gCusCu → oHΔ = +337 kJ.mol-1 b¤karpþac;énsm<½n§kUva:Lg; nigkmøaMgGnþrmU:elKulenAkñúgGelah³dUcCaDIGIuyU:d³ )(2)(2 gIsI → oHΔ = +107 kJ.mol-1 enAkñúgkrNIGatUmkmμDIGIuyU:d eKmanCMhanpSMBIrya:genAkñúgdMeNIrkarenH dMbUgkar bMEbkkmøaMgcakp©wtrvagmU:elKul bnÞab;mkpþac;sm<½n§kUva:Lg;kñúgmU:elKul³

)(2)(

)()(

2

22

gIgI

gIsI

→

→

g> bERmbRmÜlGg;RtUBI Gg;RtUBIKWCaTMnak;TMngnwgkMrit\tsNþab;Fñab;énsmasFatu ¬eTaHbIbBaØtþiGg;RtUBIman PaBsaMjauMCagk¾eday¦. dUcenH pasrwgmanGg;RtUBITabCagpasrav bu:Enþpas]s½ μnEdlman clna\tsNþab;Fñab;manGg;RtUBIx<s;. bERmbRmÜlGg;RtUBIRtUv)anbgðajedaynimitþsBaØa SΔ . mindUcCaGg;tal;BIeT Edltémørbs;vaRtUv)aneKcuHkñúgbBa¢I ¬dUcCaGg;tal;BIénkar begáIt¦ rIÉGg;RtUBIRtUv)aneKBiPakSaelImUldæanCak;lak;. dUcenH sUm,IEtFatuk¾témøGg;RtUBI RtUv)aneKcuHenAkñúgbBa¢IEdr. cMNucsUnüRtUv)aneKykCacMNucRkamd¾l¥bMputénsmasFatuenA sItuNðPaBsUnü. eyIgGacKNnabERmbRmÜlGg;RtUBIsþg;dasRmab;RbtikmμmYytamviFIdUcKñ μa eTAnwgbERmbRmÜlGg;tal;BIEdr. ]TahrN_ BImuneyIg)anKNnabERmbRmÜlGg;tal;BIsþg;da sRmab;Rbtikm μ³ )()()( 222

1 gCOgOgCO →+ ehIyeyIgGacKNnabERmbRmÜlGg;RtUBItamviFIdUcKña³ oSΔ ¬Rbtikmμ¦ = oSΔ∑ ¬plitpl¦ - oSΔ∑ ¬GgÁFatuRbtikr¦

CMBYkTI6

6-9

dUcenH oSΔ = [So(CO2(g))]-[So(CO(g) + ½ So (O2(g))] = {(+214)-(+198)-1/2(+205)} J.mol-1.K-1 = -86 J.mol-1.K-1 eyIgGacrMBwgBIkarfycuHénGg;RtUBIsRmab;RbB½n§kñúgdMeNIrkarenH eRBaHvaTak;Tgnwg kar)at;bg; ½ mol én]s½ μn. eKk¾GacsμandwgBIsBaØaénbERmbRmÜlGg;RtUBIedaykarrab;mU:lén ]s½ μnenAkñúgEpñknImYy²énsmIkar eRBaHRbePTKImIkñúgpas]s½μnmanGg;RtUBIFMCagxøaMgenAkñúg pasrwg rav b¤pasTwk. c> famBlesrI³ kmøaMgCMrujénRbtikm μ sRmab;Rbtikm μEdlekIteLIgedayÉkÉg BitCamankarekIneLIgénGg;RtUBI ¬EdlbMEr bMrYlGg;RtUBIénsklRtUvEtmantémøviC¢man¦. sklcMeBaHKImIrUbviTU KWmanRbtikm μ ¬RbB½n§¦ EdleyIgkMBugsikSa nigmCÆdæanCuMvijrbs;va. vamanPaBgayRsYlenAkñúgkarkMNt;bERmbRmÜl Gg;RtUBIénRbtikmμ bu:EnþenAkñúgmCÆdæanCuMvijBitCamankarBi)akkñúgkarkMNt;edaypÞal;. eTaHbI Caya:gNad¾eday bERmbRmÜlGg;RtUBIénmCÆdæanCuMvijCaFm μtabNþalmkBIkemþAEdl)an beBa©j b¤RsUbkñúgRbtikm μ. kemþAEdl)anbeBa©ajeTAkñúgmCÆdæanCuMvij ¬RbtikmμbeBa©jkemþA¦ nwgekIneLIgGg;RtUBIenAmCÆdæanCuMvij rIÉkarRsUbkemþA¬Rbtikm μRsUbkemþA¦ nwgbnßyGg;RtUBIeTA kñúgmCÆdæanCuMvij. dUcenH eyIgGackMNt;faetIRbtikmμmYyGacekIteLIgedayÉkÉgBIbERm bRmÜlGg;RtUBI nigGg;tal;BIénRbtikmμenaH. karbBa©ÚlKñaénsBaØaEdlGacmansRmab;muxgar ETmU:DINamicRtUv)ansegçbenAkñúgtaragTI 6.5. TMnak;TMngbrimaNrvagnaTITaMgbIenHKW ³

ooo STHG Δ−Δ=Δ ]TahrN_ eyIgGacKNnabERmbRmÜlfamBlesrIsRmab;Rbtikmμ³ )()(2/1)( 22 gCOgOgCO →+ EdleyIg)anTajmkBIbERmbRmÜlGg;tal;BI (-283 kJ.mol-1) nigbERmbRmÜlGg;RtUBI (-86

kJ.mol-1) edayeRbIsItuNðPaB 25 oC³ oGΔ = (-283 kJ.mol-1) –(698K)(-0,086 kJ.mol-1.K-1) = -257 kJ.mol-1 edaytémø oGΔ GviC¢man enaHRbtikmμGacekIteLIgedayÉkÉgtamETmU:DINamicenA sItuNðPaBenH.

ETmU:DINamicGsrIragÁ

6-10

famBlesrIénRbtikmμenAsItuNðPaB 298 K GacRtUv)aneKKNnaBIplbUkBiCKNit

énfamBlesrIrbs;Rbtikm μenAkñúglkçN³RsedogKñaeTAnwgkarKNnasRmab;Gg;tal;BI³ oGΔ ¬Rbtikmμ¦ = o

fGΔ∑ ¬plitpl¦ - ofGΔ∑ ¬GgÁFatuRbtikr¦

dUcEdl)aneXIjenAkñúgtaragTI 6.5 sRmab;karbBa©ÚlKñaénΔΗ nig SΔ viC¢man nigΔΗ nig SΔ GviC¢man RbtikmμKWGaRs½yelIsItuNðPaB. enHk¾edaysarEtktþasItuNðPaBenAkñúgsmIkar

famBlesrI. Cak;Esþg eyIgGaceRbIsmIkarfamBlesrIedIm,ITTYl)antMé;lkan;EtCak;lak;énsItuNð PaBEdlRbtikmμmYyERbRbYlBIkarekIteLIgedayÉkÉgeTACaminGacekIteLIgedayÉkÉg)an b¤pÞúymkvij. karbMEbkedaykemþAénemSABN’Rkhmrbs;)art(II)GuksIuteTACaRKab;tUc²én elah³)art nig]s½ μnGuksIuEsnGacRtUv)aneKeRbICa]TahrN_³ )()(2)(2 2 gOlHgsHgO +⎯→⎯Δ bERmbRmÜlGg;RtUBI nigGg;tal;BIsþg;daKW +91 kJ.mol-1 nig +108 kJ.mol-1erogKña dUcenH oGΔ = (+91 kJ.mol-1) – T(+0,108 kJ.mol-1)

enAcMNuceBlEdlTisedARbtikmμERbRbYl oGΔ = 0 enaH T = 91/0.108 . K-1 = 843 K = 570 oC

Cak;Esþg )art(II)GuksIutbMEbkenAsItuNðPaBcenøaHBI 350 oC eTA 500oC. PaBxus KñaBIkarKNnarbs;eyIgKWK μanGIVKYr[PJak;ep¥IleT. mYyEpñk PaBxusKñaenHKWedaysarEt RbtikmμCak;lak;RtUvekIteLIgenAkñúgsm<aFbriyakasGuksIuEsn 20 kPa minEmnenA 100 kPa

sm<aFGuksIuEsnEdl)an)a:n;sμanenAkñúgkarKNnafamBlesrIeT. TMnak;TMngfamBlesrIk¾

taragTI 6>5 ktþaEdlman\T§iBlelIRbtikmμedayÉkÉg

HΔ SΔ GΔ lT§pl GviC¢man viC¢man GviC¢manCanic© ekIteLIgedayÉkÉg viC¢man GviC¢man viC¢manCanic© minekIteLIgedayÉkÉgeT viC¢man viC¢man GviC¢manenA Tx<s; ekIteLIgÉkÉgenA T x<s; GviC¢man GviC¢man GviC¢manenA T Tab ekIteLIgedayÉkÉgenA T Tab

CMBYkTI6

6-11

Gacs μan)anEdrfa bERmbRmÜlGg;tal;BI ΔΗ KWGaRs½yelIsItuNðPaB enAeBlkarBitvaman PaBGaRs½yelIsItuNðPaBtictYc. 6>2 karbegáItsmasFatuGIuyU:nic enAeBlsmasFatuGIuyU:nicmYyRtUvkekItBIFaturbs;va enaHCaFmμta vamankarfycuHén Gg;RtUBI EdlsRmab;PaBlMdab; smasFatuRkamrwgmanGg;RtUBId¾Tab ehIyEtgEtCaRbtikr Gelah³dUcCaGuksIuEsn b¤kørEdlCa]s½ μnmanGg;RtUBIx<s;. ]TahrN_ enAkñúgEpñkmun eyIg)an kMNt;fabERmbRmÜlGg;RtUBIsRmab;karbegáItsUdüÚmkørYKWGviC¢man. dUcenH sRmab;karbegáIt smasFatu EdlmanesßrPaBETmU:DINamicBIFatupSMrbs;va bERmbRmÜlGg;RtUBIGviC¢manén RbtikmμCaFmμta BitCacaM)ac;. vaCakarbeBa©jkemþAEdlkøayCakmøaMgCMrujRbtikm μ. edIm,Iyl;BImUlehtuEdlsmasFatuBiessGacekIteLIg nigsmasFatuepSgeTotmin GacekIteLIg eyIgnwgbMEbkdMeNIrkarbegáIténsmasFatuGIuyU:niceTACaes‘rIénCMhanRTwsþIKW dMbUgpþac;sm<½n§énGgÁFatuRbtikr bnÞab;mkbegáItplitpl. tamviFIenH eyIgGacbBa¢ak;BIktþa Gg;tal;BINaEdlsMxan;cMeBaHRbtikmμEdlekIteLIgedayÉkÉg. eyIgBicarNamþgeTotBIkar begáItsUdüÚmkørY³ )()(2/1)( 2 sNaClgClsNa →+ o

fHΔ = -411 kJ.mol-1 1> sUdüÚmnwgRtUvbMElgeTACaGatUmsUdüÚm ¬]s½ μn¦esrI. dMeNIrkarenHRtUvkarGg;tal;BIGatUm kmμ³ )()( gNasNa → oHΔ = +108 kJ.mol-1 2> mU:elKul]s½ μnkørRtUv)anbMEbkeTACaGatUm. bMElgenHRtUvkarfamBlsm<½n§Bak;kNþalén mU:elKulkør³ )()(2/1 2 gClgCl → oHΔ = +121 kJ.mol-1 3> GatUmsUdüÚmRtUvbMEbkeTACaGIuyu:g. dMeNIrkarenHRtUvkarfamBlGIuyu:gkm μdMbUg. ¬Rbsin ebIeyIgmanelah³EdlbegáItkacugDIva:Lg; dUcCakal;süÚm enaHeyIgnwgRtUvbEnßmfamBl GIuyu:gkmμTaMgBIrKWTImYy nigTIBIr¦ −+ +→ egNagNa )()( oHΔ = +502 kJ.mol-1 4> GatUmkørRtUvEtekIneGLicRtug. témøenHCaTMnak;TMngeGLicRtugénGatUmkør³ )()( gClegCl −− →+ oHΔ = -349 kJ.mol-1 témøsRmab;karbEnßmeGLicRtugdMbUg CaFm μtaKWbeBa©jkemþA rIÉkarbEnßmeGLicRtugelIkTIBIr CakarRsUbkemþA ¬dUcCakarbegáIt O2- BI O-¦.

ETmU:DINamicGsrIragÁ

6-12

5> bnÞab;mkGIuyu:gesrIbBa©ÚlKñabegáItCasmasFatuGIuyU:nicrwg. karbBa©ÚlKñaénGIuyu:genHCa dMeNIrkarbeBa©jkemþAd¾xøaMgkøamYyKWfamBlbNþaj. famBlbNþajGacRtUv)aneKcat;Tuk CakMlaMCMrujsRmab;karbegáItsmasFatuGIuyU:nic³ )()()( sNaClgClgNa →+ −+ oHΔ = -793 kJ.mol-1 Appendix1manpÞúkTinñn½yGg;tal;BI Gg;RtUBI nigfamBlesrIsRmab;elah³ nigsmas FatuCaeRcIneTot. Tinñn½ymYycMnYndUcCafamBlGIuyu:gkmμKWGaRs½yelIkarKNnaCak;lak; bu:Enþ famBlbNþajminGacrk)anedaykarKNnaCak;lak;)aneT. BYkvaGacRtUv)aneKkMNt;)an tamvdþ Born –Haber b¤karKNnatamRTwsþI. elIsBIenH karkMNt;mYycMnYnminRtUv)aneK sÁßal;BIkMritx<s;énPaBRtwmRtUvCak;lak;eT. CalT§pl karKNnaCaeRcInKWGaRs½yelITinñn½y ETmU:DINamicEdlpþl;EtcMelIyRbhak;RbEhl bu:EnþtémøbrimaNBak;kNþalEbbenHGacpþl; RbeyaCn_cMeBaHesßrPaB nigRbtikmμKImI. 6>3 vdþ Born-Haber CaFm μtavamanPaBgayRsYlCagkñúgkarsikSaBIBt’man RbsinebIvabgðajCaRkahVIc. kartagenHGacRtUv)aneKeFIVeLIgsRmab;smasFatutamRTWsþIénkarbegáItsmasFatuGIuuyU:nicBI Faturbs;va. RBYjeLIgelIRtUv)aneKeRbIedIm,IbgðajBICMhanRsUbkemþAenAkñúgdMeNIrkarRbtikmμ ehIyRBYjcuHeRkam bgðajBICMhanbeBa©jkemþA. düaRkamlT§plRtUv)aneKehAfavdþ Born-

Haber. rUbTI 6.2 bgðajBIvdþEbbenHsRmab;karbegáItsUdüÚmkørY. Na+ Cl- (s)

Na(g)+Cl(g)

Na(g)+1/2Cl2(g)

Na(s)+1/2Cl2(g)

+121 kJ

+108 kJ -793 kJ

Na+ (g) + Cl- (g)

-349 kJ+502 kJ

Na+ (g) + e- + Cl (g)

-411 kJ

rUbTI 6>2vdþ Born-Haber

sMrab;karbegáItsUdüÚmkørY.

CMBYkTI6

6-13

düaRkamGg;tal;BITaMgenHGacRtUv)aneKeRbItamviFIBIrya:gKW (1) begáItBIrYbPaBEdl GacemIleXIjénGg;tal;BIsMxan;²enAkñúgkarbegáItsmasFatunig (2) kMNt;témøGg;tal;BIEdl minsÁal;enAkñúgvdþETmU:DINamic EdleyIgsÁal;faplbUkénFatupSMKYrEtesμ InwgbERmbRmÜlGg; tal;BIsrubsRmab;lMnaMénkarbegáIt. CMhanRsUbkemþAd¾sMxan;KWbNþalmkBIGIuyu:gkmμénGatUmelah³ rIÉCMhanbeBajkemþA)an mkBIkarbegáIténbNþajRkamGIuyU:nic. tulüPaBenHCamYyfamBlbNþajEdlelIs famBl GIuyu:gkmμCasmasFatuGIuyU:nicesßrPaB. ma:ejsüÚmPøúyGrY, MgF2 GacRtUv)aneKeRbI edIm,I bgðajBIcMNucenH. plbUkénGIuyu:gkm μTImYynigTIBIrénGIuyu:gma:ejsüÚmKW +2190 kJ.mol-1 EdlFMCagfamBlGIuyu:gkm μeTalrbs;GIuyu:gsUdüÚmmU:NUviC¢man. bu:EnþGIuyu:gma:ejsüÚmEdltUc nigmanbnÞúkx<s; k¾manfamBlbNþajx<s;CagEdrKW -2880 kJ.mol-1. karbBa©ÚlKñaepSgeTot BIvdþGg;tal;BI[plCaGg;tal;BIGviC¢manFMénkarbegáItma:ejsüÚmPøúyGrY³ -1100 kJ.mol-1. RbsinebIfamBlbNþajekIneLIgxøaMgCamYynwgbnÞúkkacugFMCag etiehtuGIV)anCama:ej süÚm nigPøúyGrbegáIt MgF2 minbegáIt MgF3? RbsinebIeyIgs μanTuknUvGg;tal;BIkMN MgF3 famBlbNþajk¾FMCag MgF2Edr eRBaHEtTMnajeGLicRtUsþaTicFMCagedayGIuyu:g Mg3+. bu:EnþcMeBaHma:ejsüÚm eGLicRtugEdlRtUvrgGIuyu:gkm μbegáItCaGIuyu:g 3+ KWeGLicRtug kNþal ehIyfamBlGIuyu:gkm μTIbIKWFMxøaMg (7740 kJ.mol-1) EdlFMCagkarekIneLIgBIfamBl bNþaj. karbBa©ÚlKñaCamYyGg;RtUBIGviC¢man enaHK μanCMerIsmYyNaEdlsmasFatuenHGacmanvtþman enaHeT.

taragTI 6>6 ktþaETmU:DINamickñúgkarbegáIténma:ejsüÚmPøúyGrYbIya:gEdlGacman ktþaGg;tal;BI (kJ.mol-1) MgF MgF2 MgF3

GIuyu:gkmμ Mg +150 +150 +150

famBlsm<½n§ F-F +80 +160 +240

GIuyu:gkmμ Mg ¬srub¦ +740 +2190 +9930

TMnak;TMngeGLicRtug F -330 -660 -990

famBlbNþaj ≈ -900 -2880 ≈ -5900 0fHΔ ¬sμanTuk¦ -260 -1040 +3430

ETmU:DINamicGsrIragÁ

6-14

pÞúyeTAvij ehtuGIVma:ejsüÚm nigPøúyGrbegáIt MgF2 ehIyminGacbegáIt MgF? dUcEdleyIg)aneXIjBImunmk ktþafamBlFMbMputBIrya:g KWfamBlGIuyu:gkmμénma:ejsüÚm ¬RsUbkemþA¦ nigfamBlbNþaj ¬beBa©jkemþA¦. eKRtUvkarfamBlticCagedIm,IeFIVGIuyu:gkm μ eGLicRtugEtmYybegáIt)anGIuyu:gma:ejsüÚmmU:NUviC¢manCaCagGIuyu:gDIviC¢man. bu:Enþ famBl bNþajKWGaRs½yelIbnÞúkd¾x<s; dUcenHkacugmU:NUviC¢mannwgpþl;[nUvfamBlbNþajtUcCag. taragTI 6.6 eRbobeFobtémøelxénsmasFatuETmU:DINamicénvdþ Born-Haber sRmab;kar begáIt MgF, MgF2 nig MgF3. TaMgenHbgðajfakarbegáIt MgF2 KWmanTMenarCageKbg¥s; edaysarktþaGg;tal;BI. vdþ Born-Haber cMnYnbIGacRtUv)aneKeRbobeFobtamRkahVic Edl sarsMxan;éntulüPaBrvagfamBlGIuyu:gkmμ nigfamBlbNþajmanlkçN³c,as;las;¬rUbTI 6.3¦.

RbsinebI MgF2 manTMenarCag MgF enaHeyIgGacrMBwgTukBIsmasFatuénsUdüÚm nig PøúyGr[køayCa NaF2 minEmnCa NaF. bu:EnþenAkñúgkrNIsUdüÚm eGLicRtugTIBIrRtUvrgGIuyu:g kmμ CaGIuyu:gkNþalmYy EdlCaRbtikm μRsUbkemþAya:gxøaMgkøa. famBlGIuyu:gkmμd¾eRcInelIs lubGacnwgminmantulüPaBedayfamBlbNþajEdl)anekIneLIg. vak¾manktþabnÞab;bnSMBIr EdleFIV[Gg;tal;BIkMN NaF KWGviC¢manCag GIVEdleyIgrMBwgTukcMeBaH MgF. CamYy nwg Zff TabCag eyIgeXIjfafamBlGIuyu:gkmμTImYyénsUdüÚmKWRbEhl 200 kJ.mol-1 ticCag ma:ejsüÚm. elIsBIenH GIuyu:g Mg + CamYyeGLicRtug 3s mYyEdlenAsl;KWCakacugFMCag GIuyu:g Na+. dUcenH famBlbNþajén NaF nwgGacx<s;Cag MgF. karbBa©ÚlKñaénfamBl

rUbTI 6>3 RkahiVceRbobeFobvdþ Born- Haber sMrab;ma:ejsüÚm PøúyGrYTaMgbI.

CMBYkTI6

6-15

GIuyu:gkmμTabCag nigfamBlbNþajx<s;Cag begáItCaGg;tal;BIkMNcMeBaHsUdüÚmkørYKW -574

kJ.mol-1 ebIeRbobeFobeTAnwgtémøEd;lsμanTukKW -260 kJ.mol-1 sRmab; MgF. 6>4 ETmU:DINamicénkarbegáItsUluysüúgénsmasFatuGIuyU:nic edaysarkarbegáItsmasFatuBIFatupSMrbs;vaGacRtUv)aneKcat;TukCaes‘rIénCMhanRTwsþI dUcenHkarbegáItsUluysüúgGacRtUv)aneKEckCaeRcInCMhan. cMeBaH karviPaKenHdMbUgeyIg emIleXIjfa GIiuyu:genAkñúgbNþajRkamRtUvEbkExJkeTACapas]s μ ½n bnÞab;mkenAkñúgCMhanmYy epSgeTotEdlmU:elKulTWkenACMuvijGIuyu:g]s½μnbegáIt)anCaGIuyu:gGIuRdat. dUcenH Gnþrkmμrvag GIuyu:g-GIuyu:g ¬sm<½n§GIuyU:nic¦RtUvpþac; ehIyGnþrkmμGIuyu:gDIbU:lRtUv)anbegáIt. bnÞab;mk kMrit rlayKWGaRs½yelItulüPaBénktþaTaMgBIrenH EdlnImYy²manTaMgGg;tal;BI nigGg;RtUBI. vamanlkçN³xusKñad¾sMxan;mYyrvagFatuviPaKTaMgBIr. enAkñúgkarviPaKsmasFatu eyIgeRbIktþaETmU:DINamicya:gsamBaØedIm,IkMNt;faetIsmasFatumYyGacekIteLIgedayÉk Ég b¤eT. CamYynwgETmU:DINmicénkarbegáItsUluysüúg eyIgRtUvykcitþTukdak;CamYykMrit rlayEdlsmasFatumYyRtUvenAbnþbnÞab;KñaKWBIPaBrlayxøaMg eTArlay rlaytic nigmin rlay eTAdl;PaBminrlayd¾xøaMg. sUm,IEtcMeBaHsmasFatud¾minrlaymYy k¾mansmamaRt EdlGackMNt;énGIuyu:gTwkEdlmanvtþmanenAkñúglMnwgCamYysmasFaturwg. k> famBlbNþaj edIm,Ipþac;GIuyu:g[esrIBIbNþajKWsm<½n§GIuyU:nic KWRtUvkarfamBld¾FM. témøénfamBl bNþajGaRs½yelIkmøaMgénsm<½n§GIuyU:nic ehIyminTak;TgnwgbnÞúk nigTMhMGIuyu:geT. ma:ejsüÚmGuksIutCamYyGIuyu:gDIviC¢mannwgmanfamBlbNþajFMCagsUdüÚmPøúyGrYCamYyGIuyu:g mU:NUviC¢manrbs;va ¬3933 kJ.mol-1 nig 915 kJ.mol-1 erogKña¦. enAeBlRsbKñaenaH ktþaGg;RtUBInwgmanTMenard¾x<s; enAeBlRbB½n§ERbRbYlBIRkamrwglMdab;x<s;eTACapas]sμ ½nK μan sNþab;Fñab;. dUcenH TaMg SΔ nig HΔ sRmab;karbMEbkbNþaj KWviC¢manCanic©.

x>famBlGuIRdatkmμ kñúgsUluysüÚmTwk GuIyu:gRtUv)anBT§½CuMvijedaymU:elKulTwkEdlb:UEl. EsV‘GuIRdatkm μ dMbUgmYyénm:UelKulTwk¬CaFm μtacMnYn6¦ B½TæCMuvijkacugCamYynwgEpñkénGatUmGuksuIwEsnGviC¢ manEbrmuxeTArkkacug. RsedogKñaenHEdr Gaj:úgk¾RtUvBTæ½CMuvijedaym:UelKulTwkCamYynwg EpñkGatUmGIuRdUEsnviC¢manEbrmuxeTArkGaj:úg. hYsBIRsTab;TImYyénm:UelKulTwk eyIgeXIj

ETmU:DINamicGsrIragÁ

6-16

RsTab;bEnßménm:UelKulTwkeTot¬rUbTI6>4¦. cMnYnsrubénm:UelKulTwkEdlBT§½CMuvij GIuy:ug mYyy:agmanRbsiT§PaBRtUv)aneKehAfacMnYnGIuRdatkmμ.

GIuy:ugEdlmanbnÞúkx<s;CagnigtUcCagnwgmancMnYnm:UelKulTwkeRcInCagkñúgEs‘VGIuRdat. CalT§plTMhMRbsiT§PaBénGIuy:ugGIuRdatkñúgsUluysüúgGacxusKñaBIkñúgpasrwg. TMhMxusKñaenH RtUv)anbgðajenAkñúgtaragTI6>7. TMhMtUcCagénGIuy:ugb:UtasüÚmGIuRdatGaceFIV[xøÜnvaqøgkat; PñasekasikaCIv³)any:agl¥CagGIuy:ugsUdüúmGIuRdatEdlFMCag.

karbegáItGnþrkmμGuIyu:gDIb:UlénGuIy:ugGuIRdatKWCadMeNIrkarbeBa©jkemþAy:agxøaMg. Témø

Gg;tal;BIGuIRdatkm μk¾GaRs½yelIbnÞúknigTMhMGuIy:ugEdr EdlvaCadg;suIetbnÞúk. taragTI6>8 bgðajBITMnak;TMngvay:agxøaMgrvagGg;tal;BIGuIRdatkmμ nigdg;suIetbnÞúkcMeBaHkacuges‘rIGuIsU eGLicRtUnic. Gg;RtUBIGuIRdatkmμk¾GviC¢manEdr KWedaysarEtmU:elKulTwkEdlenACuMvijGuIy:ugman sNþab;Fñab;CageBlBYkvaenACamU:elKulTwkesrI. cMeBaHkacugEdlmanbnÞúkx<s;Cag nigTMhMtUc dUcCam:aej:süÚmnigGaluymIjÚ:mEsV‘GuIRdatkmμKWFMCagsUdüÚm dUcenHvamansNþab;Fñab;d¾l¥én

rUbTI 6>4 EsV‘GIuRdatkmμTImYy nigTIBIr énkacugelah³.

taragTI 6>7 \T§iBlGIuRdatkm μelITMhMénGIuyu:gsUdüÚm nigbU:tasüÚm GIuyu:g kaM (pm) GIuyu:gGIuRdat kaMGIuRdat (pm) Na+ 116 Na(OH2)13

+ 276 K+ 152 K(OH2)7

+ 232

CMBYkTI6

6-17

mU:elKulTwkCuMvijkacug EdlmanbnÞúkx<s;CagBIr. cMeBaHkacugTaMgenHmankarfycuHd¾xøaMgén Gg;RtUBIkñúgdMeNIrkarGuIRdatkm μ.

K> bERmbRmÜlfamBlénkarbegáItsUluysüúg

eyIgGaceRbIdMeNIrkarbegáItsUluysüúgénsUdüÚmkørYedIm,IbgðajBIGg;tal;BIvdþsUluy süúg. kñúgdMeNIrkarenH TMnajGuIyU:nicenAkñúgbNþajRtUvEtQñHedayGnþrkmμGuIyu:gDIb:Ul CamYy mU:elKulTwk ³

( ) ( ) ( )aqClaqNasClNa −+−+ +→ pþac;dMeNIrkarenHCaCMhan² edaydMbUgbNþajRtUv)aneKrMhYt ¬bMEbkeTACaGuIyug]s½ μn¦³

( ) ( ) ( ) 10 .788 −−+ +=Δ+→ molkJHgClgNasNaCl bnÞab;mkGuIyu:gRtUv)anrgGuIRdatkm μ ³ ( ) ( )

( ) ( ) 10

10

.378.406

−−−

−++

−=Δ→

−=Δ→

molKlHaqClgClmolkJHaqNagNa

dUcenHbERmbRmÜlGg;tal;BI 0HΔ sRmab;karbegáItsUluysüúgKW ³ ( ) ( ) ( ) 1.4378406788 −+=−+−++ molkJ

dMeNIrkarenHRtUv)anbgðajkñúgdüaRkam ¬rUbTI 6>5¦.

taragTI 6>8 Gg;tal;BIGIuRdatkmμ nigdg;sIuetbnÞúksMrab;GIusUeGLicRtUnicbIRbePT GIuyu:g Gg;tal;BIGIuRdatkm μ (kJ.mol-1) dg;sIuetbnÞúk(C.mm-3) Na+ -406 24 Mg2+ -1920 120 Al3+ -4610 364

Na+ Cl- (s)

Na+ (g) + Cl- (g)

Na+ (aq) + Cl- (g)

Na+ (aq) + Cl- (aq)

+788 kJ

-378 kJ

-406 kJ

+4 kJ

rUbTI 6>5 vdþGg;tal;BItamRTwsþIsMrab; dMeNIrkarbegáItsUluysüúgsUdüÚmkørY.

ETmU:DINamicGsrIragÁ

6-18

bERmbRmÜlGg;tal;BICaFmμtaFMCagbERmbRmÜlGg;RtUBIenAsItuNðPaBFmμta. bu:Enþkñúg krNIenHbERmbRmÜlGg;tal;BId¾FM KWelIkElg[KñaeTAvijeTAmkEdleFVI[bERmbRmÜlGg;RtUBI CaktþasMxan;mYykñúgkarkMNt;kMritrlayénsUdüÚmkørY. dUcenHeyIg\LÚvRtUveFVIkarKNnaRs edogKña mYysRmab;ktþaGg;RtUBI EdleFVI[eyIgGaceRbobeFoblT§plCamYytémøGg;tal;BI EdleyIgeRbITinñn½y 0STΔ enA 298k. dMbUg bNþajRtUv)aneKrMhYt ³ ( ) ( ) ( ) 10 .68 −−+ +=Δ+→ molkJSTgClgNasNaCl bnÞab;mkGuIyu:gRtUvrgGuIRdatkmμ ³ ( ) ( )

( ) ( ) 10

10

.28.27

−−−

−++

−=Δ→

−=Δ→

molkJSTaqClgClmolkJSTaqNagNa

dUcenHbERmbRmÜlGg;RtUBI ¬ 0STΔ ¦sRmab;dMeNIrkarbegáItsUluysüúgKW ³ ( ) ( ) ( ) 1.13282768 −+=−+−++ molkJ dMeNIrkarRtUv)aneKbgðajkñúgdüaRkam¬rUbTI 6>6¦.

rUbTI 6>6 vdþGg;RtUBItamRTwsþI ¬ oSTΔ ¦sRmab;karbegáItsUluysüúgsUdüÚmkørY bnÞab;BIkarKNnabERmbRmÜlfamBlesrIsRmab;dMeNIkarbegáItsUluysüúg eyIg eXIjfa vaCabERmbRmÜlGg;RtUBIEdlmanTMenarbegáItsUluysüúg rIÉbERmbRmÜlGg;tal;BIK μan TMenarenaHeT EdlBImunKWFMCagtémøeRkaymk. dUcenHdUcEdleyIg)andwgBIkarBiesaF sUdüúÚmkørY KWrlayxøaMgkñúgTwkenAsItuNðPaB 298 K.

( ) ( )1

11

000

.9.13.4

−

−−

−=

+−+=

Δ−Δ=Δ

molkJmolkJmolkJ

STHG

6>5 karbegáItsmasFatukUva:Lg; edIm,IsikSaBIETm:UDINamuicénkarbegáItsmasFatukUv:aLg; eKGacKUrvdþEdlRsedogKña nwgvdþ Born-Haber EdleyIgeRbIsRmab;smasFatuGuIyUnic. bu:EnþvamanlkçN³xusKñay:ag

Na+ Cl- (s)

Na+ (g) + Cl- (g)

Na+ (aq) + Cl- (g)

Na+ (aq) + Cl- (aq)

-27 kJ

-28 kJ+68 kJ

+13 kJ

Na+ (aq) + Cl- (aq)

Na+ (aq) + Cl- (g)

Na+ Cl- (s)

CMBYkTI6

6-19

xøaMg vdþenHminTak;TgnwgkarbegáItGuIyu:g pÞúyeTAvijeyIgRtUvykcitþTukdak;CamYyfamBl sm<½n§kUva:Lg;eTAvij. dMeNIrkarGacRtUv)aneKbgðajsRmab;karbegáItGas‘UtRTIPøúyGrY. karKNnanwgepþateTAelIktþaGg;tal;BIehIyktþaGg;RtUBInwgRtUvBicarNabnÞab;BIenaH. ( ) ( ) ( )gNFgFgN 322 2

32

1 →+ 1> sm<½n§bICan;manDIGasUtRtUv)ankat;pþac;. karkat;pþac;RtUv)ankarfamBlsm<½n§ NN ≡ knøH ³ ( ) ( ) 10

2 .47121 −+=Δ→ molkJHgNgN

2> sm<½n§eTalDIPøúyGrRtUv)ankat;pþac;Edr. sRmab;esÞItüÚebRTIvaRtUvkarfamBlsm<½n§ F-F

bIPaKBIr ³ ( ) ( ) 10

2 .232323 −+=Δ→ molkJHgFgF

3> sm<½n§rvagGasUt PøúyGrRtUv)ankekIt. dMeNIrkarenHbeBa©jfamBlsm<½n§rvag N-

FbIdgedaysar Et 3molénsm<½n§RtUv)anbegáIt ³ ( ) ( ) ( ) 10

3 .8283 −−=Δ→+ molkJHgNFgFgN düaRkamGg;tal;BIsRmab;karbegáItGasUtRTIPøúyGrYRtUv)aneKbgðajenAkñúgrUbTI6>7. bERm bRmÜlGg;tal;BIsrubEdlTTYl)ansRmab;RbtikmμKW ³

( ) ( ) ( ) 1032 .1252

32

1 −−=Δ→+ molkJHgNFgFgN f

rUbTI 6>7 vdþGg;tal;BItamRTwsþIsRmab;karbegáItGasUtRTIPøúyGrY.

Rtlb;eTAktþaGg;RtUBIkñúgkarbegáItGasUtRTIPøúyGrYBIFaturbs;va KWmankarfycuH 1mol én]s μ ½n. dUcenHkarfycuHGg;RtUBIGacRtUv)aneKrMBwgTuk. Cak;EsþgkñúgkrNIenHmanbERm

N(g) + 3F (g)

N(g) + 3/2 F2 (g)

1/2 N2(g) + 3/2 F2 (g)

NF3 (g)

+232 kJ

+471 kJ

-125 kJ

-828 kJ

ETmU:DINamicGsrIragÁ

6-20

bRmÜlGg;RtUBIsrubKW -140kJ.mo-1.k-1¬edaykareRbITinñn½yBI Appendix 1¦. bERmbRmÜl famBlesrIEdlTTYl)anKW

( ) ( )( )1

111

000

.83.140.0298.125

−

−−−

−=

−−−=

Δ−Δ=Δ

molkJkmolkJkmolkJ

STHG fff

CatémømYybgðajfasmasFatuenHmanesßrPaBETmU:DINamic.

esdækic©GuIRdUEsn ³ The Hydrogen Economy

GuIRdUEsnCafamBlrkSaTukmYykñúgry³eBld¾yUr. famBlGacRtUv)aneKbegáIteLIg edayRbtikm μrbs;GuIRdUEsnCamYyGuksuIEsnkñúgbriyakas³ ( ) ( ) ( )gOHgOgH 222 2

1 →+ edaykareRbItémøfamBlsm<½n§ eyIgGacbgðajfakarbegáItTwk ¬]s½ μn¦ BIGuIRdUEsn nigGuksuIEsn KWCaRbtikmμbeBa©jkemþAy:agxøaMg ³

( ) ( )[ ] ( )[ ]

[ ] [ ] 11

0

.239.459249421432

221

−− −=×−×+

−Δ−=Δ+−Δ=Δ

molkJmolkJ

HOHOOHHHHH f

eyIgRtUvpþac;kareRbIR)as;RbPBfamBlGuIRdUkabYmYyEpñk eRBaHkarpÁt;pÁg;rbs;vaman kMNt; ehIymYyEpñkedaysarEtkardutpUsuIl\nÞn³eFVI[mankarERbRbYlGakasFatuCaskl. GuIRdUkabYravk¾mantMéledaysartMrUvkarsRmab;]sSahkmμKImIedIm,IeFVIkarsMeyaKb:UlIEmfñaMeBTü nigsmasFatukMupøicsrIragÁepSg²eTot. karRbkYtRbECgTImYyKWRbPBénGuIRdUEsn. eKmanCMerIsmYyKWGKÁisnIviPaKTwkenAkñúg BileGLicRtUlIt ³ katUt ³ ( ) ( ) ( )gHaqOHelOH 22 222 +→+ −− GaNUt ³ ( ) ( ) ( ) −− ++→ egOlOHaqOH 22

12 22 RbPBd¾sMxan;énfamBlGKÁisnInwgGacCava eRBaHGKÁisnIRtUv)aneKbegáIteLIgRKb;eBl evla ehIyenAeBltMrUvkarepSgeTotmanticdUcCakmøaMgxül; b¤Twkrlk. varIGKÁisnInig eragcRkfamBlnuyekøEG‘EdlmanPaBcMrUgcMras;d¾xøaMgk¾RtUv)aneKelIkeLIgEdr. CMerIsepSgeTotKWkarsMeyaKKImIénGuIRdUEsnBIemtan. CMhanRbtikmμRtUv)anbkRsay kñúgCMBUk TI 15 EpñkTI 15>6 bu:EnþRbtikmμsrubKW ³

CMBYkTI6

6-21

( ) ( ) ( ) ( ) ( )gHgCOgOHgOgCH 22224 321 +→++

RbPBenHkan;Etminc,as;las;eTAeTot CaBiessva)anbegáIteLIgbEnßmnUvkabUnDIGuksuIt. karKNnaETmU:DINamick¾bgðajEdrfaRbtikmμenHbeBa©jkemþAEdlmanTMhMeTAdl;-77kJ.mol-1. dUcenHkñúgkarbegáItén]s½μnGuIRdUEsnCabrimaNfamBlEdlmanRtUv)an)at;bg;. bu:EnþeKGac niyay)anfakarbegáItsMNl;kabUnDIGuksuItCamaDenAkñúgeragcRkKImIGacsþúkTukeRkamdIrIÉenA kñúgrfynþva)anPayecjeTAkñúgbriyakasedaypÞal;. karsþúkTukGuIRdUEsnk¾CabBaðamYyEdr. DIGuIRdUEsnEdlmanma:sm:UltUcCageKbg¥s; kñúgcMeNam]s½ μn KWmandg;suIetTabbMput. dUcenHmaDd¾FMén]s½ μnenHKWtMrUv[mankic©kareRbob eFobeTAnwgmaDén\n§n³ravEdlpþl;famBldUcKña. viFImü:agsRmab;sþúkTukGuIRdUEsn[)ankan; Etl¥RbesIr KWkarGPivDÆGagsþúkEdlFn;nwgsm<aFxøaMg. GagEbbenHRtUv)aneKGPivDÆ bu:EnþvabEnßmTMgn;eTAdl;yanynþ nigsuITItaMgFMCagmun. GuIRdUEsnrav KWCaPaBxusKñamYyeTot b:uEnþCamYycMNucrMBuH -252 GgSaes GuIRdUEsnnwgRtUv)at;bg;edaykarrMehIr RbsinebIK μan karkarBar. viFIrkSaTukfμImYyKWCakareRbIR)as;elah³ GuIRdY¬CMBUkTI10 EpñkTI10>4¦. elah³EdledIrtYCaeGb:ugGuIRdUEsn EdlGuIRdUeEsnGacbeBa©jmkvijedaykardut. bu:Enþ elah³TaMgenHéføxøaMgNas;. viFIrkSaTukmüa:geTotKWkareRbIR)as;kabUn nanotube ¬CMBUkTI 14 EpñkTI 14>2¦. mU:elKulGuIRdUEsnGacRtUv)anRsUbeTAkñúgbMBg;TaMgenH eTaHbIkarTajyk ecjmkvijminTan;RtUv)aneKbgðajenAeLIyk¾eday. vIFIbegáItGKÁisnIBIGuksuItkmμGuIRdUEsnkMBugRtUv)aneKeFVIkarRsavRCavya:gxøagkøa. bec©kviTüaenHKWGaRs½yeTAelIfμBil\n§n³ CaBiessdMeNIrkarGKÁisnIviPaKRcasEdl)anniyay xagelI KWfamBlKImIBIGuksuItkm μGuIRdUEsnRtUvbMElgeTACafamBlGKÁisnI. bnÞab;mkfamBl GKÁisnIRtUv)aneKeRbIedIm,IdMeNIrkarmU:tUGKÁisnIEdlk)anP¢ab;eTAnwgkg;rbs;yanynþ. rhUtmkdl;bc©úb,nñ plvi)akcMeBaHbrisßanénkareRbIR)as;GuIRdUEsnd¾eRcInRtUv)aneK emIlrMlg. GuIRdUEsnmYycMnYnnwgelcecjeTAkñúgbriyakasedayeCosminrYc ehIyKImIbrisßan viTU)ansnñidæanfakarbEnßmbrimaNtictYcén]s½μnGuIRdUEsneTAkñúg Troposphere nig Stratosphere nwgminticeT. CaBiessDIGuIRdUEsnbMpøajra:DIkal;GuIRduksuIl ¬CMBUkTI16 EpñkTI 16> 10¦ EdlCaRbePTKImId¾sMxan;bMputsRmab;kMcat;m:UelKulkxVk;kñúgbriyakas. bMElgénsgÁmrbs;BYkeyIgeTACaEbbenHRtUv)aneKeXIjfa CadMeNaHRsayry³ eBlEvg b¤xøIcMeBaHkarRbkYtRbECgbrisßan. karvinieyaKTunCaeRcInsn§wksn§ab;nwgRtUv)an

ETmU:DINamicGsrIragÁ

6-22

eFVIkñúgeragcRksMeyaK nigrkSaTukGuIRdUEsn. ehIyGuIRdUEsnnigBitCakøayCa\n§n³ fitefrmYy sRmab;esdækic©. eKmanpøÚvq¶ayRtUvedIr bu:EnþCMhanTImYyKWkMBugsßitenAkEnøgCamYyshKmn_ gnþrCatisRmab;famBlGuIRdUEsnEdlsMrbsMrYlCamunelIBiPBelakkñúgbec©kviTüaGuIRdUEsn.

6>6 ktþaETmU:DINamic nigktþasuIenTic

ETmU:DINamicRtUv)aneKykcitþTukdak;CamYynwgPaBGacekIteTA)anénRbtikm μ KWTItaMg lMnwg nigesßrPaBénsmasFatu. eKKμanBt’manGMBIel,ÓnRbtikmμEdlCaEpñksuIenTic. el,Ón RbtikmμEdlmanTMhMFMRtUv)aneKkMNt;edayfamBlskmμkmμsRmab;RbtikmμEdlr)aMgfamBl )anTak;TgkñúgdMeNIrkarsRmab;begáItsmasFatu. bBaØtiþenHRtUv)anbgðajkñúgrUbTI6>8.

]TahrN_d¾samBaØmYyén\T§iBlfamBlskmμkmμRtUv)anpþl;edaysRmUbTaMgBIrrbs; kabUn KWRkahVItnigeBRC. eBRCKWGesßrPaBETmU:DINamicCamYynwgkareKarBcMeBaHRkahVIt ³ C¬eBRC¦→C¬RkahVIt¦ 10 .3 −−=Δ molkJG b:uEnþ eBRCenAkñúgvg;eBRCminbMEbkCaemSABN’exμAeT eRBaHEtfamBlskmμkmμx<s;xøaMg rbs;vaRtUvkaredIm,IerobcMeLIgvijnUvsm<½n§kUva:Lg;BIkarerobcMragctumuxkñúgeBRCeTACaTRmg;bøg; kñúgRkahVIt. elIsBIenHeTAeTot TRmg;TaMgGs;énkabUnGesßrPaBETm:UDINamicCamYYy kareKarBnwgGuksuItkmμCakabUnDIGuksuItkñúgvtþmanDIGuksuIEsn. famBlskmμkmμenHehIy EdlkarBareBRCkñúgvg; nigRkahVIt¬sMN¦ kñúgex μAédBIkarpÞúHkñúgePøIg ³ ( ) ( ) ( ) 10

22 .390 −−=Δ→+ molkJGgCOgOsC

rUbTI 6>8 ktþafamBlsIuenTic nig ETmU:DINamicenAkñúgRbtikmμKImI

CMBYkTI6

6-23

karBiteyIgGaceRbIsuIenTicedIm,I[pliplénRbtikmμKImIxusKña)an. ]TahrN_d¾sMxan; mYyKWcMehHGamU:ja:k;. GamU:ja:k;eqHkñúgxül;begáIt)anCaDIGasUt nigcMhayTwk ³ ( ) ( ) ( ) ( )gOHgNgOgNH 2223 6234 +→+ enHCadMeNIrkarETmU:DINamicEdlmanbERmbRmÜlfamBlesrI -1306kJ.mol-1. enA eBlcMehHekIteLIgkñúgvtþmanénkatalIkrfamBlskmμkmμénRbtikmμRbkYtRbECg EdlbegáIt GasUtm:UNUGuksuIt KWTabCagRbtikm μEdlbegáIt]s½μnDIgasUt ³ ( ) ( ) ( ) ( )gOHgNOgOgNH 2223 6454 +→+ RbtikmμbNþaj EdlCaCMhand¾sMxan;kñúgkarEjkGasuItnIRTickñúg]sSahkm μekIteLIg sUm,IEtbERmbRmÜlfamBlesrIénRbtikmμmanRtwmEt -958kJ.mol-1. dUcenHeyIgkMBugeRbI suIenTicedIm,IRtYtBinitüplitplénRbtikmμnigkMBugTat;ecaldMeNIrkarETmU:DINamic¬rUbTI6>9¦

eKGacsMeyaKsmasFatuEdlmankarbegáItfamBlesrIviC¢man. ]TahrN_ RTIGuksuIEsn ¬GUsUn¦ nigGuksuItrbs;GasUtTaMgGs;begáItfamBlesrIviC¢man. karsMeyaKénsmasFatu EbbenHGacekIteLIg)anRbsinebImandMeNIrkarmYyEdlTak;TgnwgkarfycuHénfamBlesrI ehIyRbsinebIkarbMEbkénsmasFatuyWttamsuIenTic. pÞúyeTAvijvaRtUvEtmandMeNIrkarmYy EdlKitBIfamBlbEnßmBIxageRkAdUcCaBnøWkñúgkrNIrsμ IsMeyaK nigfamBlGKÁisnIkñúgkrNI GKÁisnIviPaK. ]TahrN_³d¾KYr[cab;Garm μN_mYyRtUv)anpþl;edayGasUtRTIkørY. eyIg)aneXIj enAkñúgEpñkmunfaGasUtRTIPøúyGrYmanesßrPaBETmU:DINamic. pÞúyeTAvijGasUtRTIkørY GesßrPaBETmU:DINamic bu:EnþvaBitCamanvtþman ³

rUbTI 6>9 düaRkam ¬minEmnCaTMhM¦ énktþafamBlsIuenTic nigETmU:DINamic kñúgdMeNIrkarBIréncMehHGamU:ja:k;

ETmU:DINamicGsrIragÁ

6-24

( ) ( ) ( ) 10322 .842

32

1 −−=Δ→+ molkJGgNFgFgN f ( ) ( ) ( ) 10

322 .24023

21 −+=Δ→+ molkJGgNClgClgN f

edIm,Iyl;BIPaBxusKñaenH eyIgRtUveRbobeFoblkçN³sMxan;²enAkñúgvdþfamBl nImYy². dMbUg erdukmμkñúgcMnYnm:Ulén]s½μnBIGgÁFatuRbtikr eTACaplitplmann½yfakñúgkrNI TaMgBIktþaGg;RtUBI nigmantémøGviC¢man. dUcecñHsRmab;RbtikmμekIteLIgedayÉkÉg bERmbRmÜlGg;tal;BIRtUvEtGviC¢man. kñúgkarsMeyaKGasUtRTIPøúyGrY sm<½n§rvagPøúyGr-PøúyGrRtUvpþac;KWexSay (158kJ.mol-1)

rIÉsm<½n§rvagGasUt-PøúyGr EdlRtUvkekItKWxøaMg (276kJ.mol-1). CalT§plGg;tal;BI énkarbegáItGasUtRTIPøúyGrYKWviC¢manxøaMg. sm<½n§rvagkør-kør (242kJmol-1) xøaMgCagsm<½n§rvag PøúyGr-PøúyGr ehIysm<½n§rvagGasUt-kør (188kJmol-1)kñúgGasUtRTIkørY KWexSayCagsm<½n§ rvagGasUt-PøúyGrkñúgGasUtRTIPøúyGrY. CalT§plbERmbRmÜlGg;tal;BIsRmab;karbegáIt GasUtRTIkørYKWviC¢man ¬rUbTI6>10¦ ehIyCamYybERmbRmÜlGg;RtUBIGviC¢manpþl;nUv-TΔS

viC¢man. enaHbERmbRmÜlfamBlesrInwgviC¢man.

rUbTI 6>10 vdþGg;tal;BItamRTwsþIénkarbegáItGasUtRTIkørY etIeKGacerobcMsmasFatuEbbenHdUcemþc? RbtikmμrvagGamU:ja:k;nigDIkørbegáIt)anCa GasUtRTIkørYnigGuIRdUEsnkørYEdlmanbERmbRmÜlfamBlesrIGviC¢mantictYcedaysarEt karbegáIténsm<½n§rvagGuIRdUEsn-kørxøaMg ³

N (g) + 3 Cl (g)

N (g) +3/2 Cl2 (g)

1/2N2(g) + 3/2 Cl2 (g)

NCl3 (g)

NCl3 (l)

+240 kJ

-30 kJ

-564 kJ

+363 kJ

+471 kJ

CMBYkTI6

6-25

( ) ( ) ( ) ( )gHCllNClgClgNH 33 323 +→+ GesßrPaBETMU:DINamicénGasUtkørYbMEbky:agxøaMgkøaeBldutkemþA ³ ( ) ( ) ( )gClgNlNCl 223 32 +→ bnÞab;mkETmU:DINamic KWmanRbeyaCn_sRmab;karyl;BIKImI. eyIgKYrEtcg;dwgfaktþa suIenTicGaceFVI[plitplkøayeTACaFatuepSgCagFatuEdlmanesßrPaBETmU:DINamic ¬dUckñúg krNIénGuksuItkmμGamU:ja:k;¦. elIsBIenHeTAeTot CYnkaleKGacsMeyaKsmasFatuEdlman karbegáItfamBlesrIviC¢man Edl)anpþl;viFIsMeyaKTak;TgnwgkarfycuHénfamBlesrI nig karbMEbkénsmasFatu KWyWttamsuIenTic¬dUceyIg)aneXIj sRmab;vtþmanénGasUtRTIkørY ¦. BaküKnøwH famBlGatUmkmμ atomization energy 6-8

famBlsm<½n§ bond energy 6-4

niTsSn_ Born Born exponent 6-7

vdþ Born-Haber Born-Haber cycle 6-12

smIkar Born-Lande Born-Lande equation 6-6

Gg;tal;BIkMN enthalpy of formation 6-3

Gg;RtUBI entropy 6-8

famBlesrI free energy 6-10

cMnYnGIuRdatkmμ hydration number 6-16

smIkar Kapustinskii Kapustinskii equation 6-7

famBlbNþaj lattice energy 6-5

famBlbNþaj lattice energy 6-15

efr Madelung Madelung constant 6-6

RbtikmμekIteLIgedayÉkÉg spontaneous reaction 6-2

bBaØtþisMxan; - RbtikmμKImIGaRs½yelItulüPaBénbERmbRmÜlGg;tal;BI nigGg;RtUBI. - karbegáIténsmasFatuGIuyU:nicmYyGacRtUv)aneKcat;TukfaekIteLIgenAkñúges‘rIén

CMhaneTAtamRTwsþI.

ETmU:DINamicGsrIragÁ

6-26

- düaRkamGacRtUv)aneKKUseLIgedIm,IbgðajBICMhanénTMnak;TMngfamBlenAkñúgvdþén karbegáIt ¬Born-Haber¦.

- dMeNIrkarsUluysüúgGacRtUv)aneKBicarNaedaysarEtvdþfamBl. - karbegáItsmasFatukUva:Lg;GacRtUv)anbgðajedayry³RkahVic. - RbtikmμKImIRtUv)aneKRtYtBinitüedayktþasIuenTic bEnßmBIelIktþaETmU:DINamic. lMhat;

1/ cUrkMNt;niymn½yén³ k> RbtikmμÉkÉg x> Gg;RtUBI K> karbegáItGg;tal;BIsþg;da

2/ cUrkMNt;niymn½yén³ k> Gg;tal;BI x> famBlsm<½n§mFüm K> Gg;tal;BIGIuRdatkm μ

3> sRmab;karbegáItkal;süÚmGuksIutrwgKWwecjBIkal;süÚmrwwg nig]s½ μnGuksIuEsn etIvaman sBaØadUcemþcénbERmbRmÜlGg;RtUBI? bnÞab;mk etIsBaØaénbERmbRmÜlGg;tal;BIRtUvman dUcemþcRbsinebIkarbegáIteLIgénplitplRtUvekIteLIgedayÉkÉg? edaymin[man karemIlelItarag. 4> enAsItuNðPaBd¾x<s; TwknwgbMEbkeTACa]sμ ½nGIuRdUEsn nigGuksIuEsn. cUrBnül;faehtuGIV )anCaeKGacrMBwgTuk)annUvlT§plenH ebIfamBlesrIEdlTak;TgnwgrUbmnþCamYymuxgar ETmU:DINamicBIrepSgeTot. edaymineRbItarag. 5> edayeRbIGg;tal;BIkMN nigtémøGg;RtUBIBitR)akdBItaragTinñn½yenAkñúg Appendix 1

cUrkMNt;Gg;tal;BI Gg;RtUBI nigfamBlesrIénRbtikmμxageRkam. edayeRbIBt’manenH cUrbBa¢ak;faetIRbtikm μenHGacekIteLIgedayÉkÉgEdrb¤eTenAsItuNðPaB nigsm<aFFmμta³

)()()( 2221

2 lOHgOgH →+ 6> edayeRbIGg;tal;BIkMN nigtémøGg;RtUBIBitR)akdBItaragTinñn½yenAkñúg Appendices

cUrkMNt;Gg;tal;BI Gg;RtUBI nigfamBlesrIénRbtikmμxageRkam. edayeRbIBt’manenH cUrbBa¢ak;faetIRbtikm μenHGacekIteLIgedayÉkÉgEdrb¤eTenAsItuNðPaBnigsm<aFFmμta³ )()()( 2222

1 gNOgOgN →+ 7> cUrrkfaetIkarsMeyaKéns‘ulpYrIl kørY, SO2Cl2 ( o

fGΔ (SO2Cl2(g) ) = -314 kJ.mol-1)

KWRbRBwtþeTAtamETmU:DINamic)anEdrb¤eT BIpUsVrb:g;takørY nigs<an;F½rDIGuksIut? plitplepSg

CMBYkTI6

6-27

eTot KWpUsVrIlkørY POCl3. edayeRbItémøfamBlesrIénkarbegáItBItarag Tinñn½yenAkñúg Appendix 1. 8> edayeRbItémøfamBlesrIénkarbegáItBItaragTinñn½yenAkñúg Appendix 1 cUrkMNt; faetIRbtikmμdUcteTAenHGacRbRBwtþeTAtamETmU:DINamicEdr b¤eT³ )(4)()(4)( 4325 gHClsPOHlOHgPCl +→+ 9> etIsm<½n§mYyNarvag N-N b b¤ N NEdlxøaMgCag? edaymineRbItaragTinñn½y. cUrBnül;. 10> mU:elKulDIGasUt nigkabUnmU:NUGuksIutCaGIusUeGLicRtUnic. bu:Enþ famBlsm<½n§rbs; C O (1072 kJ.mol-1) KWxøaMgCagfamBlsm<½n§rbs; N N (942 kJ.mol-1). cUrBnül;. 11> edayeRbITinñn½yfamBlsm<½n§enAkñúg Appendix 3 cUrKNnatémøRbEhlén Gg;tal;BIrbs;Rbtikm μ³ )(4)()(4 2822 gHgSgSH +→ 12> edayeRbITinñn½yfamBlsm<½n§enAkñúg Appendix 3 cUrbBa¢ak;faRbtikm μdUcteTA enHGacekIteLIgtamETmU:DINamicEdr b¤eT? )(4)()(4)( 424 gHFgCFgFgCH +→+ 13> cUrtMerobsmasFatudUcteTAenHtamlMdab;famBlbNþajekIneLIg³ ma:ejsüÚm GuksIut lIcUmPøúyGrY nigsUdüÚmkørY nigBnül;BIlMdab;EdlGñkerob. 14> cUrKNnaefr Madelung sRmab;FatubIdMbUgénes‘rIsRmab;bNþajsUdüÚmkørY? etIenH GaceRboobeFobCamYytémøkMNt;dUcemþc? 15> cUrKNnaefr Madelung sRmab;FatuBIrdMbUgénes‘rIsRmab;bNþajessüÚmkørY? etIenH GaceRbobeFobCamYytémøkMNt;dUcemþc? 16> edayeRbIsmIkar Born-Lande cUrKNnafamBlbNþajénessüÚmkørY. 17> edayeRbIsmIkar Born-Lande cUrKNnafamBlbNþajénkal;süÚmPøúyGrY. 18> cUrKUrvdþ Born-Haber sRmab;karbegáIténGaluymIjÚ:mPøúyGrY edayminmankarKNna TaMgGs;. 19> cUrKUrvdþ Born-Haber sRmab;karbegáIténma:ejsüÚms‘ulpY edayminmankarKNna TaMgGs;.

ETmU:DINamicGsrIragÁ

6-28

20> KNnaGg;tal;BIkMNTg;Edg (I) PøúyGrY smasFatuenHTTYlTRmg;es<or. 21> famBlbNþajrbs;sUdüÚmGIuRdYKW 2782 kJ.mol-1. edayeRbITinñn½ybEnßmBI Appendices cUrKNnatémøsRmab;TMnak;TMngeGLicRtugénGatUmGIuRdUEsn. 22> enAkñúgkarBiPakSaénktþaETmU:DINamic nigktþasIuenTic eyIg)aneRbobeFobRbtikmμcMnYn BIrKW³

)(6)(4)(25)(4

)(6)(2)(3)(4

23

2223

gOHgNOgOgNH

gOHgNgOgNH

+→+

+→+

edaymineRbItaragTinñn½y³ k> etImanPaBxusKñaGIV b¤eTkñúgktþaGg;RtUBIrvagRbtikmμTaMgBIr? cUrBnül;. x> edayeyagelIcMelIyBIsMnYr ¬k¦ ehIynigkarBitEdlfafamBlesrIsRmab;Rbtikm μTIBIrKW GviC¢manticCagRbtikmμTImYy cUrrksBaØaénGg;tal;BIkMNrbs;GasUtmU:NUGuksIut, NO . 23> TMnak;TMngeGLicRtugrbs;GatUmGuksIuEsnKW

1

2

1

mol.kJ744)g(Oe)g(O

mol.kJ141)g(Oe)g(O−

−

−−

−−−

+→+

−→+

RbsinebITMnak;TMngeGLicRtugTIBIrKWCaRbtikm μRsUbkemþA ehtuGIV)anCaGuksIutGIuyU:nicmanPaB TUeTAemø:H? 24> cMeBaHsmasFatuGIuyU:nicmYy MX manfamBlbNþaj 1205 kJ.mol-1 ehIy Gg;tal;BIénsUluysüúgKW -90 kJ.mol-1. RbsinebIGg;tal;BIGIuRdatkm μénkacugKW 1.5 dgén Gajú:g etIGg;tal;BIGIuRdatkm μénGIuyu:ges μ Ibu:nμan? lMhat;bEnßm 25> smIkar Born-Haber eRbIsMnYnBakümYyEdleKehAfa EBmITIvIeténlMhesrI(permitivity

of free space). cUreRbIGtßbTrUbviTüaediIm,IBnül;BIsarsMxan;énsMnYnenHenAkñúg viTüasaRsþ rUbviTüa? 26> KNnaGg;tal;BIkMNkal;süÚmGuksIut edayeRbIvdþ Born-Haber. TTYlTinñn½yTaMgGs; BIkñúgtaragTinñn½y. cUreRbobeFobtémøEdlGñkrkeXIjCamYynwgtémøBitR)akdén o

fGΔ

(CaO(s)) bnÞab;mkKNnavdþEdlRsedogKñaedaysnμtfakal;süÚmGuksIutKW manTMenarCa

CMBYkTI6

6-29

Ca+O- CagTRmg; Ca-O- KW -800 kJ.mol-1. cUrBiPakSafaehtuGIV)anCaKrNITIBIrmanTMenar Gg;tal;BIticCag? 27> cUrKUrvdþ Born-Haber sRmab;smasFatuRTwsþI NaCl2 nig NaCl3? cUrKNna Gg;tal;BIkMNsRmab;smasFatuTaMgBIrenH edayeRbItaragTinñn½yenAkñúg Appendices

RBmTaMgtémødUcteTA³ famBlbNþajtamRTwsþI NaCl2 = -2500 kJ.mol-1, NaCl3 = -5400

kJ.mol-1 famBlGIuyu:gkmμTIBIr (IE), Na = 4569 kJ.mol-1 nigTIbI IE, Na = 6919 kJ.mol-1. cUreRbobeFobvdþTaMgBIr nigelIkeLIgfaehtuGIV)anCa NaCl2 nig NaCl3 minmanTMenarkñúgkar begáIt)anCaplitpl? 28> famBlbNþajrbs;sUdüÚmetRtaGIuRdIdUbra:t (III) NaBH4 = 2703 kJ.mol-1. edayeRbI Tinñn½ybEnßmenAkñúg Appendices cUrKNnaGg;tal;BIkMNGIuyu:getRtaGIuRDIdYbra:tK. 29> ma:ejsüÚmkørYrlayenAkñúgTwkya:gxøaMg bu:Enþma:ejsüÚmGuksIutminrlayenAkñúgTwkeT. cUrBnül;sRmab;PaBxusKñaenHtamry³CMhanETmU:DINamicéndMeNIrkarsUluysüúg. edaymineRbItaragTinñn½y. 30> edayeRbItémøfamBlbNþaj nigGg;tal;BIGIuRdatkmμBItaragTinñn½y cUrkMNt; Gg;tal;BI énsUluysüúg³

k> lIcUmkørY x> ma:ejsüÚmkørY cUrBnül;BIPaBxusKñakñúgtémøTaMgBIredayCMhanRTwsþI. 31> cUrKUrdüaRkamfamBl EdlRsedogKñaeTAnwgvdþ Born-Haber sRmab;karbegáItkabUn etRtaPøúyGrY. bnÞab;mkKNnaGg;tal;BIkMNBICMhanTaMgenH edayeRbItémøelxBItarag Tinñn½y. cugeRkay eRbobeFobtémørbs;GñkCamYytémøenAkñúgtaragén o

fGΔ (CF4(g)). 32> cUrKUrdüaRkamfamBl EdlRsedogKñaeTAnwgvdþ Born-Haber sRmab;karbegáIts<an;F½r GiucsaPøúyGrY? bnÞab;mkKNnaGg;tal;BIkMNBICMhanTaMgenH edayeRbItémøelxBItarag Tinñn½y. cugeRkay eRbobeFobtémørbs;GñkCamYytémøenAkñúgtaragén o

fGΔ (SF6(g)). 33> cUrKNnafamBlsm<½n§rvagkør-PøúyGr enAkñúgkørmU:NUPøúyGrY, ClF edayeRbIdüaRkam famBl. 34> edayeRbIGg;tal;BIkMN nigtémøGg;RtUBIBitR)akdenAkñúgtaragTinñn½y cUrkMNt;famBl esrIénkarbegáItsRmab;RbtikmμdUcteTA³

ETmU:DINamicGsrIragÁ

6-30

)()()(

)()()(

3223

22

gSOgOsSgSOgOsS

→+→+

k> cUrrksBaØaénbERmbRmÜlGg;RtUBIenAkñúgkarbegáIts<an;F½rRTIGuksIut? x> etIcMehHmYyNaEdlnaMeTAdl;karbnßyfamBlesrIxøaMgbMput ¬etIRbtikm μmYyNa Edlman TMenartamETmU:DINamic?¦. K> etIGuksIuténs<an;F½rmYyNaEdleKEtgEtykmkBiPakSa. X> cUrBnül;BICemøaHrvagcMelIyrbs;GñkeTAnwgsMnYr ¬x¦ nig ¬K¦.

35> eTaHbICafamBlGIuRdatkm μénGIuyu:gkal;süÚm Ca2+ FMCagGIuyu:gbU:tasüÚm K+ bu:Enþ kMritrlaymU:lénkal;süÚmkørYKWexSayCagbU:tasüÚmkørY. cUrBnül;. 36> Gg;tal;BIkMNCasUluysüúgrbs;sUdüÚmkørY KW +4 kJ.mol-1 bu:EnþR)ak;kørYKW +65 kJ.mol-1.

k> etIGñkKitdUcemþcrvagkareRbobeFobkMritrlayénsmasFatuTaMgBIr? enAkñúg karsniñdæanenH etIGñkGacTaj)andUemþc.

x> edaykareRbITinñn½yGg;tal;BIGIuRdatkmμ cUrKNnatémøfamBlbNþajTaMgBIr? ¬smasFatuTaMgBIrTTYlykTRmg;sUdüÚmkørY¦.

K> cUrKNnatémøfamBlbNþaj edayeRbIsmIkar Born-Haber nigeRbobeFobeTA nwgtémø EdlrkeXIjenAkñúgsMnYr ¬x¦. cUrBnül;BIPaBxusKñakñúgkrNIsmasFatuNamYy. 37> edayeRbITinñn½ydUteTAenH RBmTaMgTinñn½yepSgeTotenAkñúg Appendices KNna témøcMnYnbIsRmab;Gg;tal;BIGIuRdatmμénGIuyu:gs‘ulpat. etItémøTaMgenaHmanEdr b¤eT? 38> vaBitCaGackñúgkarKNnasþg;daGg;tal;BI¼Gg;RtUBIéntémøsUluysüúgBIPaBxusKñarvag sþg;daGg;tal;BI¼Gg;RtUBIénkarbegáIténsmasFaturwg nigsþg;daGg;tal;BI¼Gg;RtUBIénkarbegáIt GIuyu:gTwkpSM. dUcenH cUrkMNt;famBlesrIénsUluysüúgkal;süÚmpUsVatenAsItuNðPaB 20oC. cUrelIkeLIgfaetItémørbs;GñkrkeXIjenaHmann½ydUcemþcénkMritrlayrbs;kal;süÚmpUsVat.

sUluysüúg oHΔ famBlbNþaj smasFatu (kJ.mol-1) (kJ.mol-1) CaSO4 -17.8 -2653 SrSO4 -8.7 -2603 BaSO4 +19.4 -2423

CMBYkTI6

6-31

39> ma:ejsüÚm nigsMNmanfamBlGIuyu:gkmμTImYy nigTIBIrRsedogKña bu:EnþRbtikm μrbs; BYkvaCamYyGasIutxusKñaya:gxøaMg. )()()(2)( 2

2 gHaqMaqHsM +→+ ++ Edl M = Mg, Pb. cUrKUrvdþEdlGacman edayeRbITinñn½yBItarag appendices ¬karENnaM³ edaysarEterdukmμénGIuyu:gGIuRdUEsnKWGacmanenAkñúgvdþTaMgBIr dUcenHGñkRtUvKitfamanEt karbegáItkacugelah³kñúgTwwk¦ bnÞab;mk cUrrkktþaEdlbNþal[manRbtikmμPaBxusKña? Bnül;CaeKal²BIPaB xusKñaenH.

40> sRmab;FatuenAkñúgRkumem KWCasmasFatuEdlmanesßrPaBtamETmU:DINamic enAeBl Ed;leGLicRtugva:Lg;TaMgGs;RtUv)an)at;bg;. bu:EnþminEmnsRmab;FatuenAkñúgGMbUrLg;tanIt TaMgGs; EdlcMnYnGuksIutkmμ 3+ pþl;nUvesßrPaBbMput. cUrBnül;edayEp¥kelIfamBl GIuyu:gkmμ nigc,ab;rbs;BYkvaenAkñúgvdþ Born-Haber? 41> edayeRbIsmIkar Kapustinskii cUrKNnafamBlbNþajsRmab;essüÚmkørY nigeRbob eFobvaeTAnwgtémøtamBIesaFn_ nigeTAnwgtémøEdlTTYl)anBIsmIkar Born-Haber ¬lMhat;TI 16¦. 42> talüÚmmancMnYnGuksIutkmμBIrKW +1 nig +3. edayeRbIsmIkar Kapustinskii cUrKNna témøénfamBlbNþajén TlF nig TlF3. kaMrbs; Tl+ nig Tl3+ KW 164 pm nig 102 pm erogKña. 43> enAeRkamsm<aFd¾x<s; ruyb‘ÍdüÚmkørYnwgTTYlnUvTMrgessüÚmkørY. cUrKNnabERmbRmÜl Gg;tal;BIsRmab;karcmøgBITRmg;bNþajsUdüÚmkørYrbs;va eTACaTRmg;bNþajessüÚmkørY. 44> karbgðajd¾Gs©arübMputmYyKWCaRbtikmμ Thermite ¬CaRbtikmμrvagemSAGaluymIjÚ:m nigemSAEdk (III) GuksIut¦ ³ )(2)()()(2 3232 lFesOAlsOFesAl +→+ RbtikmμenHKWbeBa©jkemþAya:gxøaMgEdlbegáIt)anCaEdkrlay ehIyBImuneKeRbICaviFIsRmab; pSarpøÚvrfePøIg. edayeRbItaragTinñn½yenAkñúg appendices cUrBnül;BIkarbeBa©jkemþAd¾xøaMgkøa énRbtikm μenH? 45> cUrKNnaTMnak;TMngRbUtugenAkñúgGamU:ja:k;³ )()()( 43 gNHgHgNH ++ →+

ETmU:DINamicGsrIragÁ

6-32

RtUvpþl;nUvGamU:jÚ:mPøúyGrY NH4F EdleFIV[manRkamenAkñúgTRmg; wurtzite Edlmancm¶ay 256 pm rvagGIuyu:gGamU:jÚ:m nigGIuyu:gPøúyGrYkNþal ehIykareBalrbs; Born sRmab;bNþaj RkamKW 8. famBlGIuyu:gkm μsRmab;GatUmGIuRdUEsnKW +1537kJ.mol-1. smÁal;³enAkñúgcMeNam Tinñn½y GñknwgRtUvkarBItarag appendices bEnßmKWGg;tal;BIkMNGamU:ja:k; GIuRdUEsnPøúyGrY nig GamU:jú:mPøúyGrY. 46> RbtikmμdUcteTAenHeTUv)aneKelIkeLIgfaCaviFIETmU:DINamicmYysRmab;pl;itkmμénDIGIuRdU Esn nigDIGuksIuEsnBITwk. KNnabERmbRmÜlfamBlesrIsRmab;CMhannImYy²enAsItuNðPaB 289 K nigdMeNIrkar³

)()()(

)()()()()()()(2)(

)(2)()()(

221

22

22

22

gOlHgsHgO

sCaBrsHgOsCaOsHgBrgHsHgBrgHBrgHg

gHBrsCaOgOHsCaBr

+⎯→⎯

+→++⎯→⎯+

+⎯→⎯+

Δ

Δ

Δ

cUrelIkeLIgBImUlehtuEdldMeNIrkarGacRbRBwtþeTA)antictYccMeBaHkarTTYlykkñúgCMnYj. 47> sm<½n§GIuyU:nicEtgEtRtUv)aneKniyayfaekIteLIgedaysarelah³cg;e)aHbg;eGLicRtug. cUrriHKn;nUvkarelIkeLIgenHedayeRbItémøETmU:DINamicEdlsmrmü.

cemøIy 6.1 (a) RbtikmμmYyEdlekIteLIgedayKμankarCYyBIxageRkA b¤CaRbtikmμEdlman ΔG°

GviC¢man. (b) TMhMmYyénPaBKμanlMdab;. (c) bERmbRmÜlGg;tal;BI enAeBlmYymU:lénsmasFatuRtUvekItBIrFaturbs;vakñúg

passþg;darbs;BYkvaenA 298 K nig 100 kPa. 6.5 ΔHf° = −286 kJ·mol−1;

ΔSf° = [1 × (70) − 1 × (131) − ½ × (205)] J·mol−1·K−1

= −163 J·mol−1·K−1 = −0.163 kJ·mol−1·K−1 ΔGf° = −286 kJ·mol−1 − (298K)(−0.163 kJ·mol−1·K−1)

= −237 kJ·mol−1

RbtikmμKWekIteLIgedayÉkÉgenA SATP.

6.9 sm<½n§rvag N=N nwgxøaMgCag eRBaHsm<½n§eRcInCan;xøaMgCagsm<½n§mYyCan;rvagFatudUcKña.

CMBYkTI6

6-33

6.13 sUdüÚmkørY lIcUmPøúyGrY ma:ejsüÚmGuksIut. LiF nwgxøaMgCag NaCl eRBaH LiF man GIuyu:gtUcCag dg;sIuetbnÞúkx<s;Cag. MgO nwgx<s;bMputeRBaHbnÞúkx<s;Cag¬nigdg;sIuetbnÞúk¦.

6.17 ⎟⎠⎞

⎜⎝⎛ −

×⋅⋅×××××××××

−= −−−−

−−

811

)m1031.2)(mJC10854.8(142.34)C10602.1(12519.2)mol1002.6(

1011212

219123

U

= −2649 kJ·mol−1

6.21 Na(s) rMhYt = +107 kJ·mol−1

½ H2 famBlsm<½n§ = +216 kJ·mol−1

Na(g) famBlGIuyu:gkmμdMbUg = +502 kJ·mol−1

H(g) PaBdUcKñaéneGLicRtug (EA H) = karrk

Na+H− famBlbNþaj = −782 kJ·mol−1 ΔHfº(NaCl(s)) = −411 kJ·mol−1 −411 kJ·mol-1 = [+107 + 216 + 502 + (EA H) − 782] kJ·mol−1 (EA H) = −454 kJ·mol−1

6.25 EBmITIvIeténlMhesrI “the permittivity of free space” CaefrEdlTak;Tgnwg kmøaMgTMnajrvagcMNucbnÞúkBIr. rUbmnþKNitRtUv)aneKsÁal;Cac,ab;KULúMehIyvamanrUbmnþ³

221

041

rqqF

πε=

Edl F CakmøaMg, q1 nig q2 Cama:ej:TIténcMNucbnÞúk, r Cacm¶ayrvagbnÞúk nig ε0

CakarGnuBaØaténlMhesrI. karGnuBaØaténlMhesrICaefrEdlmansarsMxan;RKb;smIkarEdl Tak;TgnwgbnÞúkGKÁisnI nigrlkeGLicRtUma:ej:Tic. TMnak;TMngEdlmansarsMxan;bMputKW

00

2 1με

=c

Edl c el,OnBnøW ehIy μ0 CakarGnuBaØaténlMhesrI. dUcenH el,OnBnøWRtUvTak;Tgnwgefr rUbepSgeTotTaMgBIrenH. 6.29 ma:ejsüÚmGuksIut RtUvbBa¢ÚlGIuyu:g 2+/2−, nwgmanfamBlbNþajx<s;CagkarbBa©Úl GIuyu:g 2+/1− énma:ejsüÚmkørY. famBlEfmenHRtUvEtFMCagfamBlEdlbeBa©jBIGIuRdatkm énGIuyu:g.

ETmU:DINamicGsrIragÁ

6-34

6.33 BIdüaRkamfamBldUcteTAenH ¬edayeRbItémø ΔHfº BI Appendix 2),

dUcenHfamBlsm<½n§rvag Cl−F RtUv)anKNnaKW 250 kJ·mol−1.

6.37 cMeBaHkal;süÚms‘ulpat: −17.8 kJ·mol−1 = 2653 kJ·mol−1 − (1650 + ΔHhydr(SO4

2−)) kJ·mol−1 ΔHhydr(SO4

2−) = −1021 kJ·mol−1

cMeBaHRsþg;cUms‘ulpat: −8.7 kJ·mol−1 = 2603 kJ·mol−1 − (1480 + ΔHhydr(SO4

2−)) kJ·mol−1 ΔHhydr(SO4

2−) = −1132 kJ·mol−1

cMeBaH)arüÚms‘ulpat: +19.4 kJ·mol−1 = 2423 kJ·mol−1 − (1360 + ΔHhydr(SO4

2−)) kJ·mol−1 ΔHhydr(SO4

2−) = −1044 kJ·mol−1

témøenHefrrhUt kñúgPaBminRbRktIénTinñn½y. 6.41 edayeRbIsmIkar Kapustinskii :

CMBYkTI6

6-35

⎟⎠⎞

⎜⎝⎛ −

××××−=

3485.341

34811210202.1 5

U = −622 kJ·mol−1

eRbobeFobCamYy −668 kJ·mol−1 tamkarBiesaF nig −636 kJ·mol−1 BIsmIkar Born-Landé. 6.45 dMbUg eyIgRtUvKNnafamBlbNþajén NH4F:

⎟⎠⎞

⎜⎝⎛ −

×⋅⋅×××××××××

−= −−−−

−−

811

)m1056.2)(mJC10854.8(142.34)C10602.1(11641.1)mol1002.6(

1011212

219123

U

= −778 kJ·mol−1

bnÞab;mkeyIgGacKUsvdþ Born-Haber :

ΔH RbtikmμGacRtUv)anKNnaBIPaBxusKñakñúgGg;tal;BIkMN: ΔH = [(−464) − (−273) − (−46)] kJ·mol−1 = −145 kJ·mol−1

famBlGIuyu:gkmμénGIuRdUEsn (+1537 kJ·mol−1)RtUvpþl;kñúgsMNYr Bt’manepSgeTotRtUvkaredIm,IbMeBjvdþ elIkElgsRmab; NH3(g) + H+(g) + F−(g) → NH4

+(g) + F−(g)

RtUv)aneXIjkñúg appendices:

famBlsm<½n§ (H−F) = +565 kJ·mol−1

eGLicRtugdUcKña F = −328 kJ·mol−1 −145 kJ·mol−1 =

[(+565) + (+1537) + (−328) + (RbUtugdUcKña) + (−778)] kJ·mol−1

RbtugdUcKña = −1141 kJ·mol−1