CMBYkTI13

13-1

ssuu II eennTTiiccKKIImmII (( CC hh ee mm ii cc aa ll KK ii nn ee tt ii cc ss ))

1 el,ÓnRbtikmµ

suIenTicKImIsuIenTicKImIsuIenTicKImIsuIenTicKImI KWCaEpñkmYyénKImI EdlTak;TgCamYynwgel,Ónrbs;RbtikmµEdlekItman eLIg. Baküfa {sIuenTic} mann½yfamanclna b¤pøas;bþÚr. enAC¿BUkTI5 eyIg)aneGay niymn½yfamBlsIuenTicfaCafamBlEdlekItmaneLIgedaysarclnarbs;vtßúmYy. Baküfa {sIuenTic} enAeBlenHsMedAeTAelIelelelel,,,,ÓnRbtikmµÓnRbtikmµÓnRbtikmµÓnRbtikmµ EdlCabMErbMrYlkMhab;rbs;Rbtikrb¤plitpl CamYyeBlevla (M/s) .

manehtuplCaeRcInsMrab;karsikSael,ÓnRbtikmµ. Cakarcab;epþImmankarcg;dwgfa ehtuGVI)anCaRbtikmµKImImanel,Ónxus²Kñay:agxøaMgdUecñH. dMeNIrkarxøH dUcCadMNak;kaldMbUg énKMehIjnigrsµIsMeyaK nigRbtikmµRcvak;nuyekøEG‘RbRBwtþeTAkñúgry³eBld¾xøI KWBI 10­12s eTA 10­6s. cMENkÉRbtikmµepSgeTot dUcCabMElgeTACasIum:g;nigbMElgBIRkaPIteTACaeBRCRtUv cMNayeBlrab;qñaMb¤rab;lanqñaMedIm,IbBa©b;. kñúgkarGnuvtþ cMeNHdwgBIel,ÓnRbtikmµmansar³ sMxan;Nas;kñúgkarplitfñaMeBTü kñúgkarRKb;RKgkarbMBulbrisßannigkñúgkarEkécñGahar. KImIviTU xag]sShkmµeRcInEtsgát;F¶n;eTAelIkarbegáInel,ÓnRbtikmµCaCagkñúgkarbegáInTinñpl.

eyIgdwgehIyfaRKb;RbtikmµKImITaMgGs;GactagedaysmIkarTUeTAdUcxageRkam³ GgÁFatuRbtikr → plitpl

RbtikmµenHR)ab;eyIgeGaydwgfakñúgeBlRbtikmµRbtikrRtUv)aneRbI ehIyplitplRtUv krekIt. CalT§pleyIgGactamdanemIlBIkarvivDÆénRbtikmµmYyedayBinitüemIlBIkarfycuH kMhab;rbs;Rbtikrb¤karekIneLIgkMhab;rbs;plitpl .

rUbTI1bgðajBIkarvivDÆénRbtikmµsamBaØmYy EdlkñúgenaHm:UelKulARtUv)anpøas;bþÚreTA Cam:UelKulB.

A → B

karfycuHéncMnYnm:UelKul A ehIynigkarekIneLIgénm:UelKul B CamYyeBlevla RtUv)anbgðajenArUbTI2. CaTUeTA vakan;EtgayRsYlkñúgkarbgðajel,ÓnRbtikmµkñúgn½yCa bMErbMrYlkMhab;CamYyeBlevla. dUcenHsMrab;Rbtikmµ A→B eyIgGacrkel,Óneday³

suIenTicKImI

13-2

el,Ón = b¤ el,Ón = Edl ∆[A] nig ∆[B] KWCabMErbMrYlkMhab;¬m:ULarIet¦ kñúgGMLúgeBl ∆t. edaykMhab;

rbs; A fycuHkñúgcenøaHeBlenaH dUcenH ∆[A] mantMélGviC¢man. rUbTIrUbTIrUbTIrUbTI1111³ ³ ³ ³ vivDÆnvivDÆnvivDÆnvivDÆn____énRbtikmµ énRbtikmµ énRbtikmµ énRbtikmµ A →→→→ B kñúgkñúgkñúgkñúgkMlugkMlugkMlugkMlugeeeeBl Bl Bl Bl 10s mþgrhUtdlmþgrhUtdlmþgrhUtdlmþgrhUtdl; ; ; ; 60s. . . . dMbUgmanEtdMbUgmanEtdMbUgmanEtdMbUgmanEt

mmmm:::: UelKul UelKul UelKul UelKul A eTEdlmanvtþman ¬ceTEdlmanvtþman ¬ceTEdlmanvtþman ¬ceTEdlmanvtþman ¬cMnucBN’exµA¦MnucBN’exµA¦MnucBN’exµA¦MnucBN’exµA¦. . . . edayeedayeedayeedayeBlevlaBlevlaBlevlaBlevlaedIredIredIredIreTAmuxeTAmuxeTAmuxeTAmux mmmm:::: UelKul UelKul UelKul UelKul B

¬cM¬cM¬cM¬cMNNNNucBN’¦ cabucBN’¦ cabucBN’¦ cabucBN’¦ cab;;;;epþImepþImepþImepþImkkkkekItekItekItekIt. . . .

rUbTIrUbTIrUbTIrUbTI2222³ ³ ³ ³ elelelel,,,,ÓnRbtikmµ ÓnRbtikmµ ÓnRbtikmµ ÓnRbtikmµ A →→→→ B tagedaykarfycuHénmtagedaykarfycuHénmtagedaykarfycuHénmtagedaykarfycuHénm:::: UelKul UelKul UelKul UelKul A nigkarekIneLIgén nigkarekIneLIgén nigkarekIneLIgén nigkarekIneLIgén

mmmm:::: UelKul UelKul UelKul UelKul B CaCaCaCamYymYymYymYyeBleBleBleBlevlaevlaevlaevla. . . .

el,ÓnRbtikmµmantMélviC¢man dUcenHehIysBaØadkKWRtUvkarkñúgkarbgðajel,ÓnedIm,I

eGayvamantMélviC¢man. pÞúymkvij el,ÓnénkMNplitplmincaM)ac;dak;sBaØadkeT eRBaH ∆[B] KWCacMnYnviC¢man¬kMhab;rbs; B ekIneLIgCamYyeBlevla¦. el,ÓnTaMgenHKWCael,Ón mFüm vaRtUv)aneFVImFümPaKkñúgGMLúgeBlc,as;las; ∆[t].

bnÞab;mkenHeyIgnwgBinitüemIlfaetIel,Ónrbs;RbtikmµRtUv)anTTYltam karBiesaF y:agdUcemþc. tamniymn½y eyIgdwgfaedIm,IkMNt;el,Ónrbs;Rbtikmµ eyIgRtUvtamdankMhab; rbs;Rbtikr¬b¤plitpl¦ CaGnuKmn_eTAnwgeBl. sMrab;RbtikmµkñúgsUluysüúgkMhab;RbePT KImIeRcInEtGacvas;edayviFIs,iúcTsSn_. RbsinebIGIuy:ugcUlrYm bMErbMrYlkMhab;k¾GacRtUv)an

t

A

∆∆− ][

t

B

∆∆ ][

CMBYkTI13

13-3

kMNt;edaykMritcMlgGKÁisnI.RbtikmµEdlman]sµ½ncUlrYmKWgayRsYlbMputedayrgVas;sMBaF. eyIgnwgBinitüemIlRbtikmµyfaRbePTBIr EdlviFIxus²KñaRtUv)aneRbIkñúgkarvas;el,ÓnRbtikmµ. Rbtikmµrbs;RbUmCamYyGasIutprmic

enAkñúgsUluysüúgTwk m:UelKulRbUmmanRbtikmµCamYyGasIutprmicdUcxageRkam³ Br2 (aq) + HCOOH (aq) → 2Br(aq) +2H+ (aq) +CO2 (g)

m:UelKulRbUmmanBN’Rkhmetñat ehIyRbePTKImIdéTeTotenAkñúgRbtikmµenHKµanBN’ eT. enAeBlEdlRbtikmµdMeNIrkar kMhab;rbs;RbUmfycuHy:ageTogTat; ehIyBN’rbs;vak¾ cab;epþIm)at;¬rUbTI3¦. kar)at;BN’dUcenHeFVIeGayeyIgtamdankMhab;ya:ggayedayeRbI s,iúcRtUEm:Rt Edlkt;RtabrimaNénBnøWGacemIleXIjEdlRtUv)anRsUbedayRbUm¬rUbTI4¦.

karvas;bMErbMrYl¬karfycuH¦énkMhab;RbUmenAeBldMbUg nigenAeBlcugbBa©b;GaceGay eyIgkMNt;el,ÓnmFümrbs;RbtikmµkñúgGMLúgeBlenaH³

el,ÓnmFüm

edayeRbITinñn½ykñúgtaragTI1 eyIgGacKNnael,ÓnmFümkñúgcenøaHeBl 50s énRbtikmµdUc xageRkam³ el,ÓnmFüm = RbsinebIeyIgeRCIserIs100s dMbUgCary³eBlcenøaH el,ÓnmFümrbs;vamantMél

el,ÓnmFüm = rUbTIrUbTIrUbTIrUbTI3333³ ³ ³ ³ karfycuHénkMhabkarfycuHénkMhabkarfycuHénkMhabkarfycuHénkMhab;;;;RbUmeTAtamkMeNIneBlRbUmeTAtamkMeNIneBlRbUmeTAtamkMeNIneBlRbUmeTAtamkMeNIneBlbgbgbgbgðajajajajBN’rbsBN’rbsBN’rbsBN’rbs;;;;vafycuHBIeqVgeTAsþaMvafycuHBIeqVgeTAsþaMvafycuHBIeqVgeTAsþaMvafycuHBIeqVgeTAsþaM

t

Br

∆∆

−=][ 2

initialfinal

initialfinal

tt

BrBr

−−

−=][][ 22

sMM

/1080,30,50

)0120,00101,0( 5−×=−−

sMM

/1058,30,100

)0120,000846,0( 5−×=−−

suIenTicKImI

13-4

rUbTIrUbTIrUbTIrUbTI4444³ ³ ³ ³ RkabRkabRkabRkabénkarénkarénkarénkarsMrUbsMrUbsMrUbsMrUbRbUmCamYynwgRbUmCamYynwgRbUmCamYynwgRbUmCamYynwgCMhanCMhanCMhanCMhanrlkrlkrlkrlk

taragTItaragTItaragTItaragTI1111³ ³ ³ ³ elelelel,,,,ÓnRbtikmµrvagmÓnRbtikmµrvagmÓnRbtikmµrvagmÓnRbtikmµrvagm:::: UelKulRbUmnigGasIutprmicenAUelKulRbUmnigGasIutprmicenAUelKulRbUmnigGasIutprmicenAUelKulRbUmnigGasIutprmicenA250C

TIME (s)

[Br2] (M)

el,Ón

0,0 50,0 100,0 150,0 200,0 250,0 300,0 350,0 400,0

0,0120 0,0101 0,00846 0,00710 0,00596 0,00500 0,00420 0,00353 0,00296

4,20 × 10-5

3,52 × 10-5

2,96 × 10-5

2,49 × 10-5

2,09 × 10-5

1,75 × 10-5

1,48 × 10-5

1,23 × 10-5

1,04 × 10-5

3,50 × 10-3

3,549 × 10-3

3,50 × 10-3

3,51 × 10-3

3,51 × 10-3

3,50 × 10-3

3,52 × 10-3

3,48 × 10-3

3,51 × 10-3

rUbTIrUbTIrUbTIrUbTI5555³ ³ ³ ³ elelelel,,,,ÓnÓnÓnÓnCaryCaryCaryCary³³³³énénénénRbtikmµRbtikmµRbtikmµRbtikmµrvagrvagrvagrvagRbUmRbUmRbUmRbUmnignignignigGasIutprmicenA GasIutprmicenA GasIutprmicenA GasIutprmicenA t=100s, 200s, 300s, RtUvRtUvRtUvRtUv))))anpþlanpþlanpþlanpþl;;;;edayRkabedayRkabedayRkabedayRkab

)(][

1

2

−= sBr

ratek

CMBYkTI13

13-5

karKNnaTaMgenHbgðajfa el,ÓnmFümrbs;RbtikmµGaRs½yeTAelIcenøaHeBlevla EdleyIgeRCIserIs.

edayKNnael,ÓnRbtikmµmFümenAcenøaHry³eBlkan;EtxøIeTA² eyIgGacTTYl)an el,ÓnsMrab;ry³eBlCak;lak;Edlpþl;eGayeyIgnUvel,ÓnCary³énRbtikmµkñúgeBlnwg. rUbTI5bgðajBIExSekagénRbUmCamYyeBlevlaedayEp¥kelITinñn½ykñúgtaragTI1. tamRkaPic el,ÓnCary³enA100s bnÞab;BIcMnucc,ab;epþIménRbtikmµRtUv)anpþl;eGayedayExSekagEdlb:H eTAnwgRkabkñúgeBlenaH. el,ÓnCary³enAeBlepSgeTotGacRtUv)anKNnatamviFIdUcKñaEdr. cUrcMNaMfa drabNasItuNðPaBefrel,ÓnCary³EdlRtUv)ankMNt;tamviFIenHnwgmantMélesµIKña Canic©sMrab;RbtikrEdlmankMhab;esµIKña. eyIgmin)ac;)armÖCamYyeRbIcenøaHeBlNaenaHeT. dUcenHeyIgGacehAel,ÓnCary³faCael,Ónk¾)anEdr.

sTisPaB (analogy) énkareFVIdMeNIrteTAenHCYyEbgEckrvagel,ÓnmFümnigel,Ón Cary³. cMgaypøÚvedayrfynþBITIRkugsan;RhVan;sIuskáÚ (San Francisco) eTALsEGnCIlIs (Los Angeles) KW512miles. RbsinebImnusSmñak;RtUvcMNayeBl 11,4ema:gedIm,IeFVIdMeNIrBI rdæmYyeTArdæmYyeTotel,ÓnmFümKW 512/11,4 b¤ 44,9mile kñúgmYyema:g(mph). b:uEnþRbsin ebIrfynþebIkedayel,Ón55,3mph enAry³eBlbIema:gnig26naTIbnÞab;BIecjdMeNIrenaHel,Ón Cary³rbs;vaKW55,3mph. cUrcaMfael,Ónrbs;rfynþenAkñúg]TahrN_rbs;eyIgGacekIneLIg b¤fycuHkñúgeBleFVIdMeNIr b:uEnþel,ÓnCary³rbs;RbtikmµEtgEtfycuHCamYyeBlevla.

el,ÓnénRbtikmµrvagRbUmnigGasIutprmick¾GaRs½yeTAelIkMhab;rbs;GasIutprmic Edr. b:uEnþedaykarbEnßmbrimaNelIsénGasIutprmiceTAkñúgl,ayRbtikmµenaH eyIgGacFana fakMhab;rbs;GasIutprmicenAEtefrdEdlkñúgry³eBlRbtikmµ. kñúgl½kçx½NÐenH bMErbMrYl brimaNGasIutprmicKµan\T§iBlGVIeTAelIel,ÓnRbtikmµEdlRtUv)anvas;eT .

rUbTI6KWCaRkabénel,ÓnCamYynwgkMhab;RbUm. ehtukarN_EdlRkabenHmanragCa bnÞat;Rtg;bgðajfa el,ÓnRbtikmµsmamaRteTAnwgkMhab;RbUm KWkMhab;kan;Etx<s; el,Ónk¾kan; EtelOnEdr.

el,Ón ][ 2Brα = k[Br2]

suIenTicKImI

13-6

rUbTIrUbTIrUbTIrUbTI6666³ ³ ³ ³ RkaRkaRkaRkabénelbénelbénelbénel,,,,ÓnCamYyÓnCamYyÓnCamYyÓnCamYykMhabkMhabkMhabkMhab;;;;RbUmRbUmRbUmRbUmmmmm:::: UelKulsMrabUelKulsMrabUelKulsMrabUelKulsMrab;;;;RbtikmµrvagRbUmmRbtikmµrvagRbUmmRbtikmµrvagRbUmmRbtikmµrvagRbUmm:::: UelKul UelKul UelKul UelKul nignignignigGasIutprmicGasIutprmicGasIutprmicGasIutprmic

GkSr k tageGayefrelefrelefrelefrel,,,,Ón Ón Ón Ón EdlCaefrénsmamaRtrvagel,ÓnRbtikmµnigkMhab;

Rbtikr. eyIgGacTaj)an ³

][ 2Br

ratek =

edaysarel,ÓnRbtikmµKitmanxñat M/s nigkMhab;rbs;RbUmKitCa M dUcenHxñatrbs; k RtUvKitCa 1/s b¤ s-1 kñúgkrNIenH. eyIgKYryl;fa tMél k minrg\T§iBlBIkMhab;rbs;RbUmeT. kalNasItuNðPaBminERbRbYleT enaHtMél k k¾minERbRbYleT. R)akdNas;el,ÓnelOnCag enAkMhab;x<s;CagnigyWtCagenAkMhab;TabCagénRbUm b:uEnþ pleFobénel,Ón/RbUmenAEt dEdl)aneFVIeGaysItuNðPaBminERbRbYl.

tamtaragTI1 eyIgGacKNnaefrel,ÓnsMrab;RbtikmµenH. edayeyIgyktMélt=50s eyIg)an³

13

5

2

1049,30101,0

/1052,3

][

−−−

×=×=

=

sM

sM

Br

ratek

eyIgGaceRbITinñn½yenHsMrab;ry³eBl(t)Nak¾)anEdredIm,IKNnatMélk. bMErbMrYl bnþicbnþÜcrbs;tMél k EdlmankñúgtaragTI1 KWedaysarlMgakkarvas;el,ÓnenAeBlBiesaFn_.

CMBYkTI13

13-7

RbtikmµbMEbkTwkGuksIuEsen RbsinebIplitplmYykñúgcMeNamplitplTaMgLayb¤k¾RbtikrmYykñúgcMeNamRbtikr

TaMgLayCa]sµ½n eyIgGaceRbINaNUEm:RtedIm,Ivas;BIel,ÓnRbtikmµ. cUrBinitüemIlRbtikmµ rbs;TwkGuksIuEsenenAsItuNðPaB200C.

2H2O2 (l) � 2H2O (l) + O2 (g)

kñúgkrNIenH el,ÓnRbtikmµbMEbkGacRtUv)ankMNt;)ankMNt;edaykartamdanel,Ón énkarvivtþGuksIuEsnedayeRbINaNUEm:Rt¬rUbTI7¦. sMBaFrbs;GuksIuEsnGacbþÚrCakMhab;vij )anya:ggaytamsmIkar]sµ½nbrisuT§³

PV = nRT

P= RTORTV

n][ 2=

Edl n/V pþl;m:U:LarIetrbs;]sµ½nGuksIuEsn. erobsmIkareLIgvij eyIg)an³ P

RTO

1][ 2 =

el,Ónrbs;Rbtikmµ Edlpþl;eGayedayplitén]sµ½nGuksIuEsn Gacsresr³ el,Ón =

t

P

RTt

O

∆∆=

∆∆ 1][ 2

rUbTI8bgðajBIkarekIneLIgénsMBaF]sµ½nGuksIuEsnCamYyeBl nigkarkMNt;el,ÓnCa ry³enAxN³t=400naTI. edIm,IKitel,ÓnRbtikmµenHCaxñatFmµtaM/seyIgRtUvbþÚrBImmHg/min

eTACa atm/s bnÞab;mkKuNnwgsmIkarbnÞat;b:H (�P/�t) eday 1/RT dUcEdl)anbgðajenAkñúgsmIkarxagelI. rUbTIrUbTIrUbTIrUbTI7777³³³³ elelelel,,,,ÓnénkarbMEbkTwkGuksIuEsÓnénkarbMEbkTwkGuksIuEsÓnénkarbMEbkTwkGuksIuEsÓnénkarbMEbkTwkGuksIuEsnnnnGacvasGacvasGacvasGacvas;;;;))))anedayeRbIanedayeRbIanedayeRbIanedayeRbI NaNUEmNaNUEmNaNUEmNaNUEm::::RtERtERtERtEdlbgðajBIkarekIneLIgsMBaFGukdlbgðajBIkarekIneLIgsMBaFGukdlbgðajBIkarekIneLIgsMBaFGukdlbgðajBIkarekIneLIgsMBaFGuksIuEsnCasIuEsnCasIuEsnCasIuEsnCamYyemYyemYyemYyeBlBlBlBl evlaevlaevlaevla....

suIenTicKImI

13-8

rUUbTIrUUbTIrUUbTIrUUbTI8888³ ³ ³ ³ elelelel,,,,ÓnÓnÓnÓnCaryCaryCaryCary³³³³sMrabsMrabsMrabsMrab;;;; RbtikmµbMEbkTwkGuksIuEsRbtikmµbMEbkTwkGuksIuEsRbtikmµbMEbkTwkGuksIuEsRbtikmµbMEbkTwkGuksIuEsnnnnenAenAenAenA xNxNxNxN³³³³eBl eBl eBl eBl t=400 min RtUvRtUvRtUvRtUv))))an an an an pþlpþlpþlpþl;;;;eGayedaybneGayedaybneGayedaybneGayedaybnÞatatatat;;;;bbbb::::HHHH....

el,ÓnRbtikmµnigsÞWsüÚemRTI eyIgeXIjfa cMeBaHRbtikmµsÞWsüÚemRTIgay²énRbePTRbtikmµ A�B el,ÓnRbtikmµGac

RtUv)anbBa¢ak;kñúgn½yfakarkMhab;RbtikrCamYyeBlKW -�[A]/�t b¤karekInkMhab;plitpl CamYyeBlKW�[B]/�t. sMrab;RbtikmµsaMjaMuCag eyIgRtUvEtRbugRby½tñkñúgkarsresrel,Ón Rbtikmµ. cUrBinitüemIlRbtikmµCa]TahrN_³

2A � B

m:UelKul A cMnYn2mol RtUv)an)at;bg;sMrab;karkekItmYymUlnImYy²én B KWmann½yfa el,Ónénkar)at;bg; A KWelOnCagBIrdgénkarkekIt B. eyIgGacsresrel,Óneday³

el,Ón = t

A

∆∆− ][

2

1 b¤ el,Ón =t

B

∆∆ ][

CaTUeTAsMrab;Rbtikmµ a A + b B � c C + d D

smIkarel,Óntageday el,Ón =

t

D

dt

C

ct

B

bt

A

a ∆∆=

∆∆=

∆∆−=

∆∆− ][1][1][1][1

]TahrN_dUcxageRkamtMrUveGayeyIgsresrel,ÓnRbtikmµkñúgn½yCaRbtikrnigplitpl. ]]]]TahrNTahrNTahrNTahrN____1111³ ³ ³ ³ cUrsresrsmIkarel,ÓnsMrab;RbtikmµxageRkamenHkñúgn½yCakar)at;bg;Rbtikr nigkarkekItplitpl³

CMBYkTI13

13-9

a. I– (aq) + OCl– (aq) � Cl– (aq) + OI– (aq) b. 3 O2 (g) � 2O3 (g) c. 4 NH3 (g) + 5 O2 (g) � 4NO (g) + 6H2O (l)

cMelIy cMelIy cMelIy cMelIy a. edaysaremKuNsÞWsüÚemRTInImYy²esµI1 eyIgGacsresr³ el,Ón =

t

OI

t

Cl

t

ClO

t

I

∆∆=

∆∆=

∆∆−=

∆∆−

−−−− ][][][][ b. enATIenHemKuNsÞwsüÚemRTIKW 3 nig 2 eyIgGacsresr³ el,Ón =

t

O

t

O

∆∆

=∆

∆−

][

2

1][

3

1 32 c. enAkñúgRbtikmµenH eyIgGacsresr³ el,Ón =

t

OH

t

NO

t

O

t

NH

∆∆

=∆

∆=∆

∆−=

∆∆

−][

6

1][

4

1][

5

1][

4

1 223 lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³³³³ cUrsresrsmIkarel,ÓnsMrab;RbtikmµdUcxageRkam³ CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

2 c,ab;el,Ón eyIg)ansikSarYcmkehIyfa el,Ónrbs;RbtikmµKWsmamaRteTAnwgkMhab;rbs;Rbtikr

ehIyefrsmamaRt k ehAfa efrel,Ón. cccc,,,,abababab;;;;elelelel,,,,ÓnÓnÓnÓn bBa¢ak;BITMnak;TMngénel,ÓnRbtikmµeTA nwgefrel,Ón nigkMhab;rbs;RbtikrEdlRtUv)aneLIgsV½yKuNmYycMnYn. sMrab;RbtikmµTUeTA³

a A + b B � c C + d D c,ab;el,ÓnGacsresr el,Ón = k [A] x[B] y (1) Edl x nig y KWCacMnYnEdlRtUvkMNt;edaykarBiesaF. cUrcMNaMfa CaTUeTA x nig y min

esµIeTAnwgtMélemKuNsÞWsüÚemRTI a nig beT. kalNaeyIgsÁal;tMél x, y nig k eyIgGac KNnael,ÓnRbtikmµ)anedayeRbIsmIkar1 EdleKpþl;eGaynUvkMhab;rbs;A nig B. sV½yKuN x nig y bBa¢ak;BITMnak;TMngrvagkMhab;Rbtikr A nig B nigel,ÓnRbtikmµ. tMél(x + y enHpþl; eGayeyIgnUvlMdablMdablMdablMdab;;;;RbtikmµRbtikmµRbtikmµRbtikmµTaMgmUlEdlRtUv)ankMNt;fa kMhab;rbs;RbtikrenAkñúgc,ab;el,Ón RtUvelIkCasV½yKuN. sMrab;smIkar1 lMdab;RbtikmµTaMgmUlKW(x + y ). eyIgGacniyaymü:ag eTotfa RbtikmµKWlMdab;TI x énRbtikr A lMdab;TI y énRbtikr B niglMdab;TI(x+y) cMeBaHlMdab; RbtikmµTaMgmUl .

edIm,IeGaydwgfa etIeyIgRtUvkMNt;c,ab;el,Ónrbs;RbtikmµmYyya:gdUcemþc cUrBinitü emIlRbtikmµrvagPøúyGrnigkørDIGuksIut³

suIenTicKImI

13-10

F2 (g) + 2ClO2 (g) � 2FClO2 (g)

viFImYyedIm,IsikSaBI\T§iBlrbs;kMhab;RbtikreTAelIel,ÓnRbtikmµKWRtUvkMNt;fa etI el,ÓnedImvaGaRs½yeTAelIkMhab;cab;epþImdUcemþc.vamanlkçN³gayRsYlCagkñúgkarvas; el,ÓnenAcMnucdMbUg eRBaHkalNaRbtikmµcab;epþImdMeNIrkarenaHkMhab;rbs;Rbtikrcab;epþIm fycuH ehIyeyIgnwgmankarlM)akkñúgkarvas;bMlas;bþÚreGay)ansuRkit. müa:gvijeTot vak¾ GacmanRbtikmµRtlb;Edr EdlGaceFVIeGaymanPaBlMeGogkñúgkarvas;el,Ón. lkçN³saMjúaM TaMgBIrenHKWGvtþmaneTenAkñúgdMNak;dMbUg²énRbtikmµ.

plitpl � Rbtikr taragTItaragTItaragTItaragTI2222³ ³ ³ ³ Tinñn½yénelTinñn½yénelTinñn½yénelTinñn½yénel,,,,ÓnRbtikmµrvag ÓnRbtikmµrvag ÓnRbtikmµrvag ÓnRbtikmµrvag F2 nig nig nig nig ClO2

kMhab; [F2] (M) kMhab; [ClO2] (M) el,ÓndMbUg (M/s)

1. 0,10 2. 0,10 3. 0,20

0,010 0,040 0,010

1,2 × 10–3 4,8 × 10–3 2,4× 10–3

taragTI2bgðajBIkarvas;el,ÓncMnYnbIsMrab;kMNFClO2. ebIeyIgBinitüemIlkarvas; elIkTI1nigTI3 KWenAeBleyIgbegáInkMhab;rbs;[F2] BIrdgedayrkSakMhab;[ClO2] eGayenA efrel,Ónrbs;RbtikmµekIneLIgeTVr. dUcenHel,ÓnsmamaRtedaypÞal;eTAnwgkMhab;[F2]. dUcKñaenHEdr eyIgBinitüemIlkarvas;elIkTI1nigTIBIrKWrkSakMhab;[F2] eGayenAefrnigbegáIn kMhab;rbs;[ClO2]cMnYnbYndg eyIgeXIjfael,ÓnekIneLIgcMnYnbYndgEdr dUcenHel,Ónrbs; Rbtikmµk¾smamaRtedaypÞal;eTAnwgkMhab;rbs;kørDIGuksIutEdr. eyIgGacsegçbkarsegát rbs;eyIgedaysresrc,ab;el,ÓndUcxageRkam³

el,Ón = k [F2][ClO2]

edaysarTaMg[F2] nig [ClO2]RtUv)aneLIgsV½yKuNmYy RbtikmµenHCalMdab;TImYyén [F2]/ lMdab;TImYyén[ClO2] niglMdab;TIBIr(1+1)sMrab;RbtikmµTaMgmUl. cUrcMNaMfa[ClO2]

RtUv)aneLIgsV½yKuNmYy cMENkemKuNsÞWsüÚemRTIenAkñúgsmIkarTaMgmUlrbs;vaKWBIr. PaBesµI KñaénlMdab;Rbtikmµ¬TImYy¦ nigemKuNsÞWsüÚemRTI¬1¦ KWmankarRtYtsIuKñakñúgkrNIenH.

tamry³kMhab;Rbtikrnigel,ÓnRbtikmµdMbUgeyIgk¾GacKNnaefrel,Ón)anEdr. edayeRbITinñn½yTI1 kñúgtaragTI2 eyIgGacsresr³

CMBYkTI13

13-11

−

−×=

=

sMMM

sM

ClOF

ratek

/2,1)010,0)(10,0(

/102,1

]][[3

22

lMdab;RbtikmµGaceGayeyIgyl;faetIRbtikmµenaHGaRs½yelIkMhab;RbtikrdUcemþc. ]bmafa cMeBaHRbtikmµTUeTA a A + b B � c C + d D eyIgman x =1 , y =2. c,ab;el,ÓnRbtikmµ KW ³

el,Ón = k [A][B] 2

RbtikmµenHKWlMdab;TImYycMeBaH A niglMdab;BIrcMeBaH B niglMdab;bIsMrab;RbtikmµTaMg mUl. eyIgsnµtfakMhab;edImrbs; [A] = 1,0 M nig [B] = 1,0 M. tamc,ab;el,Ón eyIgdwg fa RbsinebIeyIgbEnßmkMhab;rbs; A BIrdgBI 1,0 M eTA 2,0 M nigrkSakMhab;rbs; B efr eyIgk¾)anel,ÓnekIneLIgBIrdgEdr³

cMeBaH [A] = 1,0 M el,Ón1 = k (1,0 M)(1,0 M)2

= k (1,0 M3)

cMeBaH [A] = 2,0 M el,Ón2 = k(2,0 M)(1,0 M)2

= k(2,0 M3)

dUcenH el,Ón2

= 2 el,Ón 1 pÞúymkvij ebIeyIgrkSakMhab;rbs; A nigbEnßmkMhab;rbs; B BIrdg enaHel,Ónrbs;

RbtikmµnwgekIneLIgcMnYn4dg eRBaHmansV½yKuNBIr. cMeBaH [B] = 1,0 M el,Ón1 = k(1,0 M)(1,0 M)2

= k(1,0 M3)

cMeBaH [B] = 2,0 M el,Ón2 = k(1,0 M)(2,0 M)2

= k (4,0 M3)

dUcenH el,Ón 2 = 4 el,Ón 1 sMrab;RbtikmµmYy RbsinebI x = 0 nig y=1 enaHc,ab;el,ÓnKW el,Ón = k [A] 0[B]

= k [B]

RbtikmµenHmanlMdab;sUnücMeBaH A ehIymanlMdab; 1 cMeBaH B nigmanlMdab;1 cMeBaH RbtikmµTaMgmUl. sV½yKuNsUnübBa¢ak;fael,Ónrbs;RbtikmµenHminGaRs½ynwgkMhab;rbs; A

eT. cUrcMNaMfa lMdab;rbs;Rbtikmµk¾GacCacMnYnRbPaKpgEdr. cMnucdUcxageRkamenHsegçbBIkarBiPakSaBIc,ab;el,Ón³

suIenTicKImI

13-12

• Canic©kalc,ab;el,ÓnRtUv)aneKkMNt;edayBiesaFn_. tamry³kMhab;Rbtikr nigel,ÓnRbtikmµdMbUg eyIgGackMNt;lMdab;RbtikmµnigbnÞab;mkefrel,Ónén Rbtikmµ .

• lMdab;RbtikmµEtgEtRtUvkMNt;edaykMhab;Rbtikr¬minEmnplitpleT¦. • lMdab;énRbtikrminTak;TgeTAnwgemKuNsÞWsüÚemRTIrbs;RbtikrenAkñúgsmIkar

lMnwgeT. ]]]]TahrNTahrNTahrNTahrN____2222³³³³ Rbtikmµrbs;GasUtGuksIutnigGIuRdUEsnenAsItuNðPaB 12800C KW³

2NO (g) + 2 H2 (g) → N2 (g) + 2H2O (g)

tamry³Tinñn½yEdl)anRbmUlenAsItuNðPaBenHdUcxageRkam cUrkMNt;c,ab;el,Ón nigefrel,Ónrbs;Rbtikmµ.

BiesaFn_ [NO] [H2] el,ÓndMbUg (M/s)

1 2 3

5,0 × 10–3

10,0 × 10–3 10,0 × 10–3

2,0 × 10–3

2,0 × 10–3

4,0 × 10–3

1,3 × 10–5 5,0 × 10–5 10,0 × 10–5

cMelIycMelIycMelIycMelIy eyIgsnµtfac,ab;el,ÓnGacsresr ³ el,Ón = k [NO]x [H2]

y

BiesaFn_TI1nigTI2bgðajfaenAeBlEdleyIgbEnßmkMhab;[NO] cMnYnBIrdg nigrkSa kMhab;[H2]efr enaHel,Ónrbs;RbtikmµekIneLIg4dg. dUcenHRbtikmµenHmanlMdab;2 cMeBaH NO. BiesaFn_TI2nigTI3bgðajfaenAeBlEdleyIgbEnßmkMhab;GIuRdUEsncMnYnBIrdg nigrkSa kMhab;NOefr enaHel,Ónrbs;RbtikmµekIneLIgBIrdg dUcenHRbtikmµmanlMdab;1 cMeBaH H2. c,ab;el,Óntageday³ el,Ón = k [NO]2[H2]

EdlbgðajfavaCaRbtikmµlMdab; (1+2) cMeBaHRbtikmµTaMgmUl. efrel,Ón k GacRtUv)anKNna)anedayeRbITinñn½yBiesaFn_xagelI³

sM

MM

sMk

./105,2

)100,2()100,10(

/100,5

22

323

5

−

−−

−

×=

×××

=

CMBYkTI13

13-13

cMNaMcMNaMcMNaMcMNaM³ RbtikmµCalMdab;TImYycMeBaH H2 cMENkemKuNsÞWsüÚemRTIrbs;GIuRdUEsnkñúg smIkarlMnwgKW 2.

lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ RbtikmµrvagGuIy:ugEBGuksIuDIs‘ulpat(S2O82-) CamYyGuIy:ugGuIyU:t(I-)

KW S2O82-(aq) + 3I-(aq) → 2SO4

2-(aq) + I3-

cUrkMNt;c,ab;el,Ónnigefrel,Ónrbs;Rbtikmµtamry³Tinñn½yEdl)anRbmUlenA sItuNðPaBmYy.

BiesaFn_ [S2O82-] [I-] el,ÓndMbUg (M/s)

1 2 3

0,080

0,080 0,16

0,034

0,017

0,017

2,2 × 10–4 1,1 × 10–4 2,2 × 10–4

3 TMnak;TMngrvagkMhab;RbtikrnigeBl tamsmIkarc,ab;el,ÓnGaceGayeyIgKNnael,Ónrbs;RbtikmµmYyBIefrel,Ónnig

kMhab;Rbtikr. c,ab;el,Ónk¾GaceGayeyIgKNna)annUvkMhab;rbs;RbtikrenAeBlNamYy kñúgRbtikmµ. eyIgnwgbgðajkarKNnaenHedayBinitüemIlc,ab;el,ÓnBIrd¾samBaØkñúgcMeNam c,ab;el,ÓnTaMgLayenaH KWcMeBaHsmIkarEdlCalMdab;TImYy nigsmIkarlMdab;TI2 énRbtikmµ TaMgmUl. RbtikmµlMdab;TI1

RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITI1111 KWCaRbtikmµEdlel,Ónrbs;vaGaRs½yeTAelIkMhab;rbs;GgÁFatu RbtikrEdlRtUv)aneLIgsV½yKuN1. enAkñúgRbtikmµlMdab;TImYyénRbePT

A → plitpl el,ÓnKW el,Ón =

t

A

∆∆− ][

tamry³c,ab;el,Ón eyIgk¾GacdwgpgEdrfa el,Ón = k [A]

edIm,ITTYl)annUvÉktarbs; k sMrab;c,ab;el,ÓnenH eyIgsresr³ 1/1

/

][−==== ss

M

sM

A

ratek

edayrYmbBa©ÚlsmIkarBIrdMbUg eyIg)an³

suIenTicKImI

13-14

)3(

][

][ln

)2(][][

0 ktA

A

Akt

A

=

=∆

∆−

Edl ln KWCaLÚkarItenEB ehIy [A] 0 nig [A] KWCakMhab;rbs; A enAeBl t=0 nigeBl t = t. eyIgKYrdwgpgEdrfa enAeBlEdl t = 0 vamincaM)ac;RtUveTAnwgcMnuccab;epþIménBiesaFn_ eT nigeyIgGaceRCIserIseBlevlaNak¾)anEdredIm,Icab;epþImtamdanbMErbMrYlkMhab;rbs; A.

smIkar(3) GactMerobeLIgvijdUcxageRkam³ ln [A] 0 – ln [A] = kt

ln [A] = – kt + ln [A]0 (4)

smIkarTI(4) manTMrg;CasmIkarlIenEG‘ y =mx + b Edl m KWCaemKuNénbnÞat; .

bxmy +=

+=bbbb

0[A]ln (t)(-k) [A]ln

dUcenHbnÞat;tageGay ln[A] CamYy t pþl;nUvbnÞat;Rtg;Edlman –k KWCaemKuNbnÞat;. karviPaKRkahVenHGaceGayeyIgKNnanUvefrel,Ón)an. rUbTI9bgðajBIlkçN³rbs;smIkar lMdab;TI1 .

rUbTIrUbTIrUbTIrUbTI9999³ ³ ³ ³ lkçNlkçNlkçNlkçN³³³³RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITI1111. . . . a. karfycuHénkMhabkarfycuHénkMhabkarfycuHénkMhabkarfycuHénkMhab;;;;RbtikrCaRbtikrCaRbtikrCaRbtikrCamYymYymYymYyeTAnwgeBleTAnwgeBleTAnwgeBleTAnwgeBl. . . .

b. TMnakTMnakTMnakTMnak;;;;TMngTMngTMngTMngExSExSExSExSbnÞatbnÞatbnÞatbnÞat;;;;RtgRtgRtgRtg;;;;edImedImedImedIm,,,,ITTYlITTYlITTYlITTYl))))annUvefrelannUvefrelannUvefrelannUvefrel,,,,ÓnÓnÓnÓn-k.... manRbtikmµlMdab;TI1 CaeRcIn. ]TahrN_mYyKWRbtiikmµbMEbkeGtanCabMENkRbtikmµ

x<s;ehAfara:DIkal;emTIl.

C2H6 → 2CH3

RbtikmµbMEbkén N2O5 k¾CaRbtikmµlMdab;TI1 pgEdr 2N2O5 (g) → 4NO2 (g) + O2 (g)

enAkñúg]TahrN_xageRkam eyIgGnuvtþsmIkarTI 3 cMeBaHRbtikmµsrIragÁ. ]]]]TahrNTahrNTahrNTahrN____3333

CMBYkTI13

13-15

RbtikmµbMElgBIsIukøÚRbU)a:neTACaRbUEb:nenAkñúgpas]sµ½nKWCaRbtikmµlMdab;TI1 Edlman efrel,Ón 6,7 ×10-4 s-1 enAsItuNðPaB 5000C.

CH3

CH2 CH2 → CH3 CH = CH2

sIukøÚRbU)a:n RbUEb:n

k> RbsinebIkMhab;edImrbs;sIukøÚRbU)a:nKW 0,25M cUrKNnakMhab;rbs;vabnÞab;BIry³ eBl 8,8min.

x> etIvaRtUvcMNayry³eBlb:unµan edIm,IbnßykMhab;sIukøÚRbU)a:n BI 0,25M eTA 0,15M ? K> etIvaRtUvcMNayry³eBlb:unµan edIm,IbNþÚr 74 % énsIukøÚRbU)a:n?

cMelIy cMelIy cMelIy cMelIy k> tamsmIkar (3)

)min1

60min8,8)(107,6(

][

25,0ln

][

][ln

14

0

ss

A

M

ktA

A

××=

=

−−

edaHRsaysmIkar eyIgTTYl)an³

MA

eA

M

A

M

18,0][

42,1][

25,0

354,0][

25,0ln

354,0

=

==

=

x> edayeRbIR)as;smIkarTI(3) mþgeTot eyIg)an³

min13106,7

)107,6(15,0

25,0ln

2

14

=×=

×= −−

st

tsM

M

K> enAkñúgkarKNnaRbePTenH eyIgmincaM)ac;dwgBIkMhab;BitR)akdénGgÁFatucab;epþIm eT. RbsinebI 74% énGgÁFatuepþImmanRbtikmµ dUcenHbrimaNEdlenAsl;bnÞab;BIry³eBl t

KW (100% –74%) b¤ 26 % . dUcenH [A]/[A] 0 = 26%/100% b¤ 0,26/1,00. tamsmIkar (3)

eyIgGacsresr³ min33102

26,0

0,1ln

107,6

1

][

][ln

1

3

14

0

=×=×

=

=

−− ss

A

A

kt

suIenTicKImI

13-16

lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ Rbtikmµ 2A → B KWCaRbtikmµlMdab;TI1 Edlmanefrel,Ón 2,8 ×10-2 s-1 enA sItuNðPaB800C. etIvaRtUvcMNayry³eBlb:unµan(KitCavinaTI)edIm,IbnßykMhab;A BI 0,88MeTA 0,14M ?

\LÚvenHcUrkMNt;tamRkaPicnUvlMdab;nigefrel,Ónrbs;RbtikmµbMEbkrbs;GasUtb:g; GuksIutenAkñúgFaturMlaykabUnetRtakøra:t enAsItuNðPaB 450C³

2N2O5 (CCl4) → 4NO2 (g) + O2 (g)

taragxageRkambgðajBIbMErbMrYlénkMhab;rbs; N2O5 CamYyeBlnigtMélEdlRtUvKña én ln [N2O5]

t (s) [N2O5] ln[N2O5] 0 300 600 1200 3000

0,91 0,75 0,64 0,44 0,16

–0,094 – 0,29 –0,45 –0,82 –1,83

edayGnuvtþsmIkarTI(4) eyIgGacKUsRkab ln [N2O5] Tl;nwgeBldUcbgðajkñúgrUb TI10. cMNucEdlsßitenAelIbnÞat;Rtg;bgðajfac,ab;el,ÓnKWCalMdab;TImYy. bnÞab;mkeyIg KNnaefrel,ÓnedayeRbIRkab. eyIgeRCIserIscMNucBIrEdlenAq¶ayBIKñaenAelIbnÞat; ehIy dktMél x nig y dUcxageRkam³

Rkab (m) x

y

∆∆

=

14107,5)4002430(

)34,0(50,1 −−×−=−

−−−s

s

eday m = – k eyIg)an k = 5,7 × 10–4 s–1

sMrab;Rbtikmµpas]sµ½n eyIgGacCMnYskMhab;enAkñúgsmIkar (3) CamYynwgsMBaFrbs; RbtikrCa]sµ½n. cUrBinitüemIlRbtikmµlMdab;TI 1 A → plitpl

CMBYkTI13

13-17

rUbTIrUbTIrUbTIrUbTI10101010³ ³ ³ ³ RkaRkaRkaRkabbbb ln [N2O5] TlTlTlTl;;;;nnnnwgeBlwgeBlwgeBlwgeBl. . . . efrelefrelefrelefrel,,,,ÓnGacÓnGacÓnGacÓnGacRtUvRtUvRtUvRtUv))))ananananKNnaKNnaKNnaKNnaBIBIBIBIRkaRkaRkaRkabCabnbCabnbCabnbCabnÞatatatat; ; ; ;

RtgRtgRtgRtg;;;;enHenHenHenH.... edayeRbIsmIkar]sµ½nbrisuT§ eyIgGacsresr PV = nA RT

b¤ RT

PA

V

nA == ][

C¿nYs [A] = P/RT enAkñúgsmIkar(3) eyIg)an³ kt

P

P

RTP

RTP

A

A=== 000 ln

/

/ln

][

][ln

smIkarenHRtUveTAnwgsmIkar (4) EdlGacsresrCa³ ln P = – kt + ln P0 ]TahrN_dUcxageRkambgðajBIkareRbIkarvas;sMBaFedIm,IsikSasuIenTicénRbtikmµ

lMdab;TI1. ]]]]TahrNTahrNTahrNTahrN____4444³ ³ ³ ³ el,ÓnénkarbMEbkGasUemtanRtUv)aneKsikSaedayBinitükMhab;edayEpñkrbs; RbtikrGnuKmn_eTAnwgeBl.

CH3–N = N–CH3 (g) → N2 (g) + C2H6 (g)

Tinñn½yEdlTTYl)anenAsItuNðPaB 3000C manenAkñúgtaragxageRkam³ eBl sMBaFedayEpñkrbs;GasUemtan (mmHg)

0 100 150 200 250

284 220 193 170 150

suIenTicKImI

13-18

etItMélTaMgenaHsmRsbeTAnwgsIuenTiclMdab;TI1rWeT? ebIsmRsbcUrkMNt;efrel,Ón. cMelIy cMelIy cMelIy cMelIy sMBaFedayEpñkrbs;GasUemtaneBlNak¾smamaRtedaypÞal;eTAnwgkMhab;rbs;va (mol/L). dUcenHeyIg C¿nYssMBaFedayEpñksMrab;kMhab;enAsmIkar(4):

ln P = – kt + ln P0

Edl P0 nig P KWCasMBaFedayEpñkrbs;GasUemtanenAeBl t=0 nig t= t . rUbTI11 EdlEp¥kelITinñn½yxageRkambgðajfaRkabén lnP Tl;nwg t )anCaragbnÞat;Rtg; dUcenHRbtikmµ BitCalMdab;TImYy . t (s) ln P 0 100 150 200 250 300

5,649 5,394 5,263 5,136 5,011 4,883

rUbTIrUbTIrUbTIrUbTI11111111³ ³ ³ ³ RkabRkabRkabRkabénénénén ln P TlTlTlTl;;;;nwgeBlnwgeBlnwgeBlnwgeBlsMrabsMrabsMrabsMrab;;;;Rbtikmµ Rbtikmµ Rbtikmµ Rbtikmµ bMEbkGasUemtanbMEbkGasUemtanbMEbkGasUemtanbMEbkGasUemtan....

emKuNR)ab;Tisrbs;bnÞat;enHKW emKuNR)ab;Tis = 131055,2

)3233(

56,505,5 −−×−=−−

ss

tamsmIkarTI (4) emKuNR)ab;Tisrbs;bnÞab;esµInwg – k dUcenH k=2,55 × 10–3 s–1 . lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ RbtikmµbMEbkrbs;GasUemtankñúgpas]sµ½nenAsItuNðPaBCak;lak;

dUcteTAenH C2H6N2 (g) → N2 (g) + C2H6 (g) cUrkMNt;lMdab;Rbtikmµnigel,ÓnRbtikmµBITnñ½ykñúgtaragxageRkam³

t (min) [C2H6N2] (M) 0 15 30 48 75

0,36 0,30 0,25 0,19 0,13

enAeBlRbtikmµdMeNIrkar kMhab;rbs;RbtikrfycuH. rgVas;mYyeToténel,ÓnRbtikmµ

EdlmanTMnak;TMngrvagkMhab;nwgeBl KWryryryry³³³³eBleBleBleBlBakBakBakBak;;;;kNþalRbtikmµkNþalRbtikmµkNþalRbtikmµkNþalRbtikmµ t1/2 EdlCaeBlRtUvkar

CMBYkTI13

13-19

sMrab;eGaykMhab;rbs;RbtikrfycuHBak;kNþalénkMhab;edIm. eyIgGacTTYl)ansmIkarBak; kNþalRbtikmµsMrab;RbtikmµlMdab;TImYydUcxageRkam. tamsmIkar(3) eyIgGacsresr³

][

][ln

1 0

A

A

kt =

tamniymn½yénBak;kNþalRbtikmµ enAeBl t = t1/2 enaH [A] = [A] 0/2 dUcenH

2/][

][ln

1

0

0

2

1 A

A

kt =

b¤ )5(693,0

2ln1

2

1 kkt ==

smIkarTI(5)R)ab;eyIgfaBak;kNþalRbtikmµénRbtikmµlMdab;TImYyminGaRs½yeTAnwg kMhab;edImrbs;RbtikreT. dUcenHedIm,IbnßykMhab;BI 1,0M eTA 0,5M vaRtUvcMNayeBlesµIKña eTAnwgkarfycuHkMhab;BI 0,10M eTA 0,050M ¬rUbTI12¦. karKNnaBak;kNþalRbtikmµ KWCa viFImYykMNt;efrel,Ónrbs;RbtikmµlMdab;TImYy.

sTisPaBteTAenHGacmansar³sMxan;kñúgkaryl;BIsmIkarTI(5). ry³eBlkñúgkar sikSaenAmhaviTüal½ynisSitRtUvcMNayeBl4qñaMedayminKitBIeBlEdlnisSitenaHQb;. dUcenH ry³eBlBak;kNþalénkarsikSaenAmhaviTüal½yKWBIrqñaM. ry³eBlenHBuMb:HBal;dl; cMnYnnisSitEdlcUleronenaHeT. dUcKñaenHEdr ry³eBlBak;kNþalRbtikmµrbs;RbtikmµlMdab; TImYyKWminGaRs½ykMhab;eT.

sar³RbeyaCn_én t1/2 KWvaeFVIeGayeyIgeFVIkar)a:n;sµanTMhMénefrel,Ón. ry³eBl Bak;kNþalRbtikmµkan;EtyWt tMél k kan;EtFM.

rUbTIrUbTIrUbTIrUbTI12121212³³³³ bMbMbMbMErbMrYlénErbMrYlénErbMrYlénErbMrYlénkMhabkMhabkMhabkMhab;;;;RbtikrCamYynwgRbtikrCamYynwgRbtikrCamYynwgRbtikrCamYynwgryryryry³³³³eBleBleBleBl BakBakBakBak;;;;kNþalRbtikmµkNþalRbtikmµkNþalRbtikmµkNþalRbtikmµsMrabsMrabsMrabsMrab;;;;RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;mYymYymYymYy....

suIenTicKImI

13-20

]TahrN_ GIusUtUbviTüúskmµcMnYnBIrEdleKeRbIenAkñúgfñaMeBTünuyekøEG‘KW³ 24Na (t1/2 =

14,7h ) nig 60Co (t1/2 =5,3yr). vac,as;Nas;fa GIusUtUb 24Na qab;BukpuyCag eRBaHvaman Bak;kNþalCIvitxøICag. RbsinebIeyIgcab;epþImCamYy 1g énGIusUtUbnImYy²enaHGIusUtUb 24Na PaKeRcInnigBukpuyGs;kñúgry³eBlmYyGaTitü cMENkÉGIusUtUb 60Co vijGacnwgenAdEdlPaK eRcIn. ]]]]TahrNTahrNTahrNTahrN____5555³³³³

RbtikmµbMEbkeGtaneTACara:DIkal;emTIlKWCaRbtikmµlMdab;TImYy Edlman efrel,Ón 5,36 × 10–4 s–1 enA 700 0C.

C2H6 (g) → 2 CH3 (g)

cUrKNnary³eBlBak;kNþalRbtikmµenHCanaTI. cMelIycMelIycMelIycMelIy tamsmIkarTI (5)

min5,211036,5

693,0

693,0

14

2

1

=×

=

=

−− s

kt

lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ cUrKNnary³eBlBak;kNþalrbs;RbtikmµbMEbk N2O5 Edl)anbgðajenATMB½r 13-16. RbtikmµlMdab;TIBIr

RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITIBIrBIrBIrBIrKWCaRbtikmµEdlel,Ónrbs;vaGaRs½yeTAelIkMhab;rbs;RbtikmYy RtUv)anelIkCasV½yKuNBIrb¤enAelIRbtikrBIrepSgKñaEdlRbtikrnImYy²RtUvelIkCasV½yKuN mYy. RbePTEdlsamBaØCagTak;TgEteTAnwgm:UelKulRbtikrmYyRbePT³

A → plitpl Edl el,Ón=

t

A

∆∆ ][

tamc,ab;el,Ón el,Ón = k [A] 2 dUckrNImunEdr eyIgGackMNt;xñatrbs; k edaysresr sM

M

sM

A

ratek ./1

/

][ 22===

RbePTmYyeToténRbtikmµlMdab;TIBIr KW³ A + B → plitpl

CMBYkTI13

13-21

c,ab;el,Óntageday el,Ón = k [A][B] RbtikmµenHCalMdab;TImYycMeBaH A niglMdab;TImYysMrab; B dUcenHRbtikmµTaMgmUlman

lMdab;BIr . tamKNitviTüa eyIgGacTTYl)ansmIkardUcxageRkamcMeBaH “A → plitpl ” cMeBaH

RbtikmµlMdab;TIBIr )6(

][

1

][

1

0

ktAA

+=

¬smIkar “A + B → plitpl} manlkçN³saMjúaMNas;sMrab;karsikSarbs;eyIg ¦. eyIgGacTTYl)ansmIkarBak;kNþalRbtikmµcMeBaHRbtikmµlMdab;TIBIredaytag

[A] = [A] 0/2 enAkñúg smIkarTI (6) .

ktAA

+=00 ][

1

2/][

1

edaHRsayrk t1/2 eyIg)an )7(

][

1

02

1 Akt =

cUrcMNaMfa Bak;kNþalRbtikmµrbs;RbtikmµlMdab;TIBIrsmamaRtpÞúyeTAnwgkMhab;edImrbs;Rbtikr. lT§plenHmanGtßn½yRKb;RKan; eRBaHfaBak;kNþalRbtikmµKYrEtmanry³eBlxøIenAdMNak;kal dMbUgénRbtikmµenAeBlEdlm:UelKulRbtikreRcInCagmanvtþmanedIm,ITgÁicKña. karvas;nUvBak; kNþalRbtikmµrbs;RbtikmµlMdab;TIBIrenAkMhab;edImepSg²Kña KWCaviFImYykñúgkarEbgEckrvag RbtikmµlMdab;TImYy nigRbtikmµlMdab;TIBIr.

karviPaKsIuenTicénRbtikmµlMdab;TIBIrRtUv)anbgðajenA]TahrN_dUcxageRkam³ ]]]]TahrNTahrNTahrNTahrN____6666³³³³ GatUmGIuy:UtTaMgLayrYmbBa©ÚlKñaedIm,IbegáIt)anCam:UelKulGIuy:UtenAkñúgpas]sµ½n³ I (g) + I (g) → I2 (g) RbtikmµenHRtUvnwgsIuenTiclMdab;TIBIrEdlmanefrel,Ónx<s; 7,0 × 109 / M. s enA 23 0C.

k> RbsinebIkMhab;edImrbs;GatUmGIuy:Ut 0,086 M cUrKNnakMhab;rbs;vabnÞab;BI 2

min eRkaymk. x> cUrKNnaBak;kNþalRbtikmµ RbsinebIkMhab;edImrbs;GatUmGIuy:UtKW 0,60M nigebIva

KW 0,42M.

suIenTicKImI

13-22

cMelIy cMelIy cMelIy cMelIy k> tamsmIkarTI (6)

)min1

60min0,2)(./100,7(

086,0

1

][

1

][

1

][

1

9

0

ssM

MA

ktAA

××+=

+=

Edl [A] KWCakMhab;enAeBl t =2, 0min . edaHRsaysmIkareyIg)an [A] = 1,2 ×10–12 M enHKWCakMhab;tUcEdlminGacrkeXIjCak;Esþg. efrel,Ónd¾FMrbs;Rbtikmµmann½yfa

tamkarGnuvtþ GatUmGIuy:UtrYmbBa©ÚlKñaTaMgRsugbnÞab;BIry³eBlBIrnaTI. x> eyIgRtUvkarsmIkarTI(7) cMeBaHEpñkenH

cMeBaH [I] 0 = 0,60 M

sMsM

Akt

10

9

02

1

104,2)60,0)(./100,7(

1

][

1

−×=×

=

=

cMeBaH [I] 0 = 0,42 M

sMsM

t 10

92

1 104,3)42,0)(./100,7(

1 −×=×

=

cMNaMcMNaMcMNaMcMNaM³ ³ ³ ³ lT§plenHbBa¢ak;faBak;kNþalRbtikmµrbs;RbtikmµlMdab;TI2minEmnCaefr bu:EnþvaEp¥k eTAelIkMhab;dMbUgrbs;Rbtikr.

lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ Rbtikmµ 2A → B CalMdab;2 nigefrel,Ón 51/M.min enA 24oC. (a) cab;epþImBI [A] = 0,0092 M etIRtUvkarry³eBlb:unµanrhUtdl;[A] = 3,7 x 10-3 M?

(b) cUrKNnaBak;kNþalRbtikmµ. RbtikmµlMdab;TImYyniglMdab;BIrKWCaRbePTRbtikmµEdlsamBaØbMput. RbtikmµEdlman lMdab;sUnü KWkMrmanNas; A → plitpl

c,ab;el,Óntageday el,Ón = k [A] 0 = k

dUcenHel,Ónrbs;RbtikmµlMdab;sUnüKWCaefr minGaRs½ykMhab;rbs;GgÁFatuRbtikr. RbtikmµlMdab;TIbInigRbtikmµlMdab;x<s;²eTotBitCasaMjúaMNas; vaminRtUv)anbBa©ÚlenAkñúg

CMBYkTI13

13-23

cMnYnTgÁic

esovePAenHeT. taragTI3 segçbBIsIuenTicrbs;RbtikmµlMdab;TImYy nigRbtikmµlMdab;TIBIrén RbePTRbtikmµ A → plitpl

taragTItaragTItaragTItaragTI3333³ ³ ³ ³ segçbsIuenTicrbssegçbsIuenTicrbssegçbsIuenTicrbssegçbsIuenTicrbs;;;;RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITImYyniglMdabmYyniglMdabmYyniglMdabmYyniglMdab;;;;TITITITIBIrBIrBIrBIr lMdab; c,ab;el,Ón smIkarkMhab;–eBl Bak;kNþalRbtikmµ

1 2

el,Ón = k [A]

el,Ón = k [A] 2 ktAA

ktA

A

+=

=

0

0

][

1

][

1

][

][ln

0][

1

693,0

Ak

k

4 famBlskmµnigPaBBwgEp¥keTAelIsItuNðPaBrbs;efrel,Ón el,Ónrbs;RbtikmµekIneLIgCamYynwgkarekIneLIgénsItuNðPaB edayk¾mankrNIelIk ElgmYycMnYntUc. ]TahrN_ ry³eBlEdlRtUvkarkñúgkares¶ars‘utmYymanry³eBlxøIRbsinebI : Rbtikmµ : RbRBwtþeTAenAsItuNðPaB1000C¬RbEhl10naTI¦ CagenAsItuNðPaB800C¬RbEhl 30naTI¦. pÞúymkvij viFId¾manRbsiT§PaBkñúgkarrkSamðÚbGahar KWRtUvTukvaenAsItuNðPaB eRkamsUnüGgSaes Edlbnßyel,ÓnénkarbMEbkrbs;)ak;etrI. rUbTI13bgðajBI]TahrN_ tYy:agénTMnak;TMngrvagefrel,Ónrbs;RbtikrnigsItuNðPaB. edIm,IBnül;lkçN³enH eyIgRtUv EtsYrfa etIRbtikmµcab;epþImdUcemþcenAeBldMbUg.

rUbTIrUbTIrUbTIrUbTI13131313³ ³ ³ ³ PaBBwgEp¥kPaBBwgEp¥kPaBBwgEp¥kPaBBwgEp¥kénénénénefrelefrelefrelefrel,,,,ÓneTAelIsItuNðPaBÓneTAelIsItuNðPaBÓneTAelIsItuNðPaBÓneTAelIsItuNðPaB. . . . efrelefrelefrelefrel,,,,ÓnrbsÓnrbsÓnrbsÓnrbs;;;;RbtikmµRbtikmµRbtikmµRbtikmµPPPPaaaaKKKKeRcInekIneLIgCamYynwg eRcInekIneLIgCamYynwg eRcInekIneLIgCamYynwg eRcInekIneLIgCamYynwg karekIneLIgénsItuNðPaBkarekIneLIgénsItuNðPaBkarekIneLIgénsItuNðPaBkarekIneLIgénsItuNðPaB.... RTwsþITgÁicénsIuenTicKImI

RTwsþIsIuenTicrbs;m:UelKul]sµ½nEcgfa m:UelKul]sµ½nb:HTgÁicKñaCajwkjab;. dUcenH

vahak;dUcCasmehtupledIm,Isnñidæan¬nigCaTUeTABit¦fa RbtikmµKImIekItmaneLIgCalT§pl énkarb:HTgÁicrvagm:UelKulRbtikmµ. tamRTwsþITgÁicrbs;sIuenTicKImI eyIgrMBwgfa el,Ónrbs; RbtikmµsmamaRtedaypÞal;eTAnwgcMnYnb:HTgÁicKñaénm:UelKulkñúgmYyvinaTI b¤PaBjwkjab;énkar b:HTgÁicrbs;m:UelKul.

el,Ón s

α

sItuNðPaB

efrel

,Ón

suIenTicKImI

13-24

TMnak;TMngsamBaØenHBnül;BIPaBBwgEp¥krbs;el,ÓnRbtikmµeTAelIkMhab;Rbtikr . cUrBinitüemIlRbtikmµrvagm:UelKul A nigm:UelKul B edIm,IbegáIt)anCaplitplxøH.

]bmafam:UelKulplitplnImYy²RtUv)anbegáIteLIgedaybnSMénm:UelKul A nigm:UelKul B

edaypÞal;. RbsinebIeyIgbegáInkMhab;rbs; A BIrdg enaHcMnYnénTgÁicrvagm:UelKulA–B k¾ekIn eLIgeTVEdr eRBaHmanm:UelKul A eRcInCagBIrdgEdlGacTgÁicCamYym:UelKul B enAkñúgmaD Edlpþl;eGay¬rUbTI14¦. dUcenHel,Ónk¾GacekIneLIgBIrdgEdr. CamYyKñaenHEdr kMeNIn kMhab;rbs;m:UelKul B cMnYnBIrdgk¾GacbegáInel,ÓnBIrdgEdr. eyIgGacsresrc,ab;el,ÓndUc xageRkam³

el,Ón = k [A][B]

RbtikmµKWCalMdab;TImYyTaMg A nig B ehIyeKarBeTAtamsIuenTiclMdab;TIBIr. RTwsþITgÁicmanlkçN³KYreGaycg;ecHdwgNas; b:uEnþTMnak;TMngrvagel,ÓnnigkarTgÁic

rbs;m:UelKulmanlkçN³saMjúaMCagGVIEdleyIgrMBwgTukeTAeTot. PaBsaMjúaMénRTwsþITgÁicKWfa RbtikmµEtgEtekItmaneLIgenAeBlEdlm:UelKul A nig B b:HTgÁicKña. b:uEnþ minEmnRKb;Etkar TgÁicnaMeGaymanRbtikmµenaHeT. karKNnaedayBwgEp¥keTAelIRTwsþIm:UelKulsIuenTicbgðaj fa enAsMBaFFmµta ¬KW 1atm¦ nigsItuNðPaBFmµta ¬KW 298K¦manm:UelKulcMnYn 1027 b:HTgÁic KñaeTVta¬rvagm:UelKulBIr¦ kñúgmaD 1mL Caerogral;vinaTIenAkñúgpas]sµ½n. karTgÁicenaHvarwt EtmaneRcIneTotkñúgmYyvinaTIkñúgGgÁFaturav. RbsinebIkarTgÁiceTVtanaM eGayekItCaplitpl enaHRbtikmµPaKeRcInnwgRtUv)anbBa©b;enAeBldMNalKñanwgTgÁicenH. enAkñúgkarGnuvtþeyIg eXIjfael,Ónrbs;RbtikmµmanPaBxusKñaya:gxøaMg. enHmann½yfa kñúgkrNICaeRcInkarb:H TgÁicEtÉgminFanafaRbtikmµekItmaneLIgenaHeT.

RKb;m:UelKulEdlmanclnamanfamBlsIuenTic. m:UelKulmanclnakan;Etel,Ón famBlsIuenTickan;EtFM. b:uEnþm:UelKulEdlmanclnaelOnminbMEbkeTACabMENktUc²eday xøÜnvaenaHeT. edIm,IeGaymanRbtikmµ vaRtUvmankarb:HTgÁicCamYym:UelKulepSgeTot. enAeBl Edlm:UelKulb:HTgÁicKña mYyEpñkénfamBlsIuenTicrbs;vaRtUv)anbMEbøgeTACafamBllMj½r. RbsinebIfamBlsIuenTicdMbUgFM enaHm:UelKulEdlTgÁicKñanwgmanlMj½rxøaMg EdlnaMeGayman karpþac;sMB½n§KImImYycMnYn. karbMEbksMB½n§enHKWCaC¿hanTImYyeTArkkMNplitpl. RbsinebI famBlsIuenTicdMbUgtUc m:UelKulnwgRKan;Etpøas;TIecjBIKñaedayBuMmankarxUcxatGVIeLIy. ebIniyaytamn½yfamBl manfamBlTgÁicGb,brmaxøHEdleRkamenHKµanRbtikmµekItman

CMBYkTI13

13-25

eLIg. edaykgVHxatfamBlenH m:UelKulTaMgLaynwgenAdEdl ehIyKµanbMlas;bþÚrGVIekIt maneLIgeTbnÞab;BIkarb:HTgÁic.

eyIgGaceGayCaviFanfa edIm,IeGaymanRbtikmµekItmaneLIgm:UelKulEdlb:HTgÁic RtUvEtmanfamBlsIuenTicsrubesµIeTAnwgb¤FMCag famBlskmµ famBlskmµ famBlskmµ famBlskmµ Ea EdlCafamBlGb,brma EdlRtUvkarcaM)ac;edIm,IepþImRbtikmµKImImYy. enAeBlEdlm:UelKulb:HTgÁicKña vabegáIt)anCa kuMpøicskmµkuMpøicskmµkuMpøicskmµkuMpøicskmµ EdlCaRbePTKImIbeNþaHGasnñkekItedaym:UelKulRbtikrCalT§plénkarb:HTgÁic KñamuneBlEdlvabegáIt)anCaplitpl.

rUbTI15bgðajBIfamBlb:Utg;EsülxusKñaBIrsMrab;Rbtikmµ A + B → C + D

RbsinebIplitplmanesßrPaBCagRbtikr enaHRbtikmµnwgnaMmkCamYynUvkarbeBa©j kMedAKWRbtikmµbeBa©jkMedA¬rUbTI15a¦. pÞúymkvij RbsinebIplitplmanesßrPaBticCag RbtikrenaH kMedAnwgRtUvRsUbedayl,ayFatuRbtikmµBIbriyakasCuMvij ehIyeyIgnwgTTYl)an RbtikmµRsUbkMedA¬rUbTI15b¦. enAkñúgkrNITaMgBIr eyIgKUsRkabtagfamBlb:Utg;Esülén RbB½n§FatuRbtikmµTl;nwgkarvivtþénRbtikmµ. ebItamKuNPaBRkabTaMgenHbgðajBIbMErbMrYl famBlb:Utg;EsüledayRbtikrRtUv)anbMEbøgeTACaplitpl.

rUbTIrUbTIrUbTIrUbTI14141414³ ³ ³ ³ PaBBwgEp¥kPaBBwgEp¥kPaBBwgEp¥kPaBBwgEp¥kénénénénTgÁicTgÁicTgÁicTgÁicmYycMnYnmYycMnYnmYycMnYnmYycMnYneTAelIkMhabeTAelIkMhabeTAelIkMhabeTAelIkMhab;;;;. . . . enATIenHenATIenHenATIenHenATIenH eyIgRKaneyIgRKaneyIgRKaneyIgRKan;;;;EtBiEtBiEtBiEtBinitüemIlnitüemIlnitüemIlnitüemIlkarbkarbkarbkarb::::HTgÁicrvag HTgÁicrvag HTgÁicrvag HTgÁicrvag A–B EdlGacEdlGacEdlGacEdlGacnaMeTAdlnaMeTAdlnaMeTAdlnaMeTAdl;;;; kMNkMNkMNkMNplitplplitplplitplplitpl. . . . (a) mankarbmankarbmankarbmankarb::::HTgÁiccMnYn bYnrvagmHTgÁiccMnYn bYnrvagmHTgÁiccMnYn bYnrvagmHTgÁiccMnYn bYnrvagm:::: UelKul UelKul UelKul UelKul A nig nig nig nig B cMnYnBIrcMnYnBIrcMnYnBIrcMnYnBIr²²²².... (b)karbegáIncMnYnBIrdgénkarbegáIncMnYnBIrdgénkarbegáIncMnYnBIrdgénkarbegáIncMnYnBIrdgénRbePTRbePTRbePTRbePT¬b¬b¬b¬b:::: uEnþminEmnuEnþminEmnuEnþminEmnuEnþminEmn RbePTTaMgBIrRbePTTaMgBIrRbePTTaMgBIrRbePTTaMgBIr¦¦¦¦énménménménm:::: UelKulUelKulUelKulUelKulEdlEdlEdlEdlbegáIncMnYnTgÁicrhUteTAdlbegáIncMnYnTgÁicrhUteTAdlbegáIncMnYnTgÁicrhUteTAdlbegáIncMnYnTgÁicrhUteTAdl;;;;8888. . . . (c) karbegáIncMnYnBIrdgkarbegáIncMnYnBIrdgkarbegáIncMnYnBIrdgkarbegáIncMnYnBIrdgénénénénmmmm:::: UelKul UelKul UelKul UelKul A nig nig nig nig B EdlbEdlbEdlbEdlbegáIncMnYnegáIncMnYnegáIncMnYnegáIncMnYn TgÁicrhUtdlTgÁicrhUtdlTgÁicrhUtdlTgÁicrhUtdl;;;;eTAeTAeTAeTA16161616. . . .

suIenTicKImI

13-26

rUbTIrUbTIrUbTIrUbTI15151515³ ³ ³ ³ RkabtagfamBlbRkabtagfamBlbRkabtagfamBlbRkabtagfamBlb:::: UtgUtgUtgUtg;;;;EsülEsülEsülEsülsMrabsMrabsMrabsMrab;;;; (a) RbtikmµbeBa©jkMedA RbtikmµbeBa©jkMedA RbtikmµbeBa©jkMedA RbtikmµbeBa©jkMedA (b) RbtikmµRbtikmµRbtikmµRbtikmµRsUbkMedA RsUbkMedA RsUbkMedA RsUbkMedA

eyIgGacKitfafamBlskkmµCar)aMgkarBarm:UelKulEdlmanfamBlticmineGayman

Rbtikmµ. eRBaHEtcMnYnm:UelKulRbtikrenAkñúgRbtikmµFmµtaFMxøaMg el,ÓnehIynwgfamBl sIuenTicrbs;m:UelKulERbRbYlya:gxøaMg. CaFmµta manEtbrimaNtictYcénm:UelKulEdlb:HKña eT ¬m:UelKulmanclnaelOn¦ manfamBlsIuenTicRKb;RKan;elIsfamBlskmµ. dUcenH m:UelKulTaMgenHGaccUlrYmkñúgRbtikmµ. karekIneLIgénel,Ón¬b¤efrel,Ón¦ CamYysItuNðPaB \LÚvenHGacBnül;)anfa³ el,Ónm:UelKuleKarBtamr)ay Maxwell Edl)anbgðajkñúgrUbTI 15. cUreRbobeFobr)ayel,ÓnenAsItuNðPaBxusKñaBIr. edaym:UelKulEdlmanfamBlx<s; CagmanvtþmanenAsItuNðPaBx<s;Cagel,ÓnénkMNplitplk¾elOnCagEdrenAsItuNðPaBx<s; Cag. smIkarGaerjIs

PaBBwgEp¥keTAelIsItuNðPaBrbs;efrel,ÓnGactagedaysmIkardUcxageRkam Edl eyIgehAfasmIkarGaerjIs RTEaAek /−= (8)

Edl Ea KWCafamBlskmµrbs;RbtikmµKitCa kJ/mol/ R efr]sµ½n (8,314J/K.mol) T

sItuNðPaBdac;xat ehIyCa e eKalmaRtdæanLÚkarItenEB. brimaN A tMNageGayPaB jwkjab;énkarb:HTgÁicehAfaktþaénPaBjwkjab;. vaGacRtUv)anKitCaefrsMrab;cMeBaHRbB½n§ RbtikmµEdlpþl;eGayenAkñúgcenøaHsItuNðPaBd¾TUlay. smIkarTI(8)bgðajfaefrel,Ónsma- maRtedaypÞal;CamYy A ehIynwgPaBjwkjab;énkarb:HTgÁic. CagenHeTAeTot edaysar EtsBaØadkenAelIsV½yKuN Ea/RT efrel,ÓnfycuHCamYynwgkarekIneLIgénfamBlskmµnig

CMBYkTI13

13-27

karekIneLIgénsItuNðPaB. smIkarenHGacsresredayTMrg;gayeRbIR)as;CagedaybMBak; LÚkarItenEBeTAelIGgÁTaMgBIr³

)9(ln

lnln /

RT

EA

Aek

a

RTEa

−=

= −

smIkarTI (9) GacsresrCasmIkarlIenEG‘³

bxmy

ATR

Ek a

+=

+

−=

bbbb

ln1

ln

dUcenHRkabén ln k Tl;nwg 1/T manragCabnÞat;Rtg; EdlemKuNR)ab;Tis m esµInwg –Ea/R ehIy b CYbG½kSGredaenCa ln A.

]TahrN_xageRkambgðajBIviFIRkaPickñúgkarkMNt;famBlskmµrbs;Rbtikmµ. ]]]]TahrNTahrNTahrNTahrN____7777 efrel,ÓnénkarbMEbkGal;edGIutprmic RtUv)aneKvas;enAsItuNðPaB5xus²Kña. CH3CHO (g) → CH4 (g) + CO (g)

cUrKUsRkabén ln k Tl;nwg 1/T nigkMNt;famBlskmµ¬CakJ/mol) sMrab;RbtikmµenH. RbtikmµenHCaRbtikmµlMdab;TI 3/2 cMeBaH CH3CHO dUcenH k manxñat 1/M1/2 .s .

rUbTIrUbTIrUbTIrUbTI16161616³ ³ ³ ³ RkabRkabRkabRkabénénénén ln k TlTlTlTl;;;;nwg nwg nwg nwg 1/T

k (1/M1/2.s) T (K) 0,011 0,035 0,105 0,343 0,789

700 730 760 790 810

suIenTicKImI

13-28

cMelIycMelIycMelIycMelIy³ ³ ³ ³ eyIgcg;KUsRkab ln k enAelIG½kSGredaenTl;nwg 1/T enAelIG½kSGab;sIus. tamry³ Tinñn½ykñúgbMrab; eyIg)an³

ln k 1/T (K–1) – 4,51 – 3,35 – 2,254 – 1,070 – 0,237

1, 43 × 10–3

1, 37 × 10–3

1, 32 × 10–3

1, 27 × 10–3

1, 23 × 10–3

karKUsRkabénTinñn½yTaMgenHpþl;nUvRkabdUckñúgrUbTI16. emKuNR)ab;Tisrbs;bnÞat; RtUv)anKNnaBIcMnYnkUGrDINasüúgBIrKU³

emKuNR)ab;Tis = KK

4

131009,2

10)24,141,1(

)45,0(010,4×−=

×−−−−

−−

tamsmIkarlIenEG‘TI (9) emKuNR)ab;Tis = K

R

Ea 41009,2 ×−=− Ea = (8,314 J/K.mol)(2,09 × 104 K) = 1,74 × 105 J/mol = 1,74 × 102 kJ/mol

snñidæan³ cUrcMNaMfa eTaHCaefrel,Ónmanxñat 1/M1/2 .s k¾edayk_tMél ln k BuMmanxñat eT . cMNaMcMNaMcMNaMcMNaM³ ³ ³ ³ eTaHbICaefrel,Ónmanxñat l/M 1/2.s b:uEnþ ln k Kµanxñat. lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn_ _ _ _ ³³³³ eK)anvas;efrel,ÓnénRbtikmµlMdab;TI2rbs;RbtikmµbMEbk N2O eTACa N2

nigGatUmGuksIuEsnenAsItuNðPaBepSg²xus²KñadUcxageRkamenH. k (l/M.s) t (oC) 1.87 x 10-3 0,0113 0,0569 0,244

600

650

700

750

cUrkMNt;famBlskmµedayRkabsMrab;RbtikmµenH. smIkarEdlTak;TgeTAnwgefrel,Ón k1 nig k2 enAsItuNðPaB T1 nig T2 GaceRbIedIm,I

KNnafamBlskmµ b¤edIm,Irkefrel,ÓnenAsItuNðPaBepSgeTot RbsinebIfamBlskmµRtUv )aneKR)ab;. eyIgGacsresrsmIkarkñúgkarKNnaenHtamry³smIkarTI(9) dUcteTA³

2

2

11

lnln

lnln

RT

EAk

RT

EAk

a

a

−=

−=

CMBYkTI13

13-29

dkGgÁnigGgÁénsmIkarTaMgBIreyIg)an

)10(

ln

11lnln

21

21

21

21

2

1

1221

−=

−=

−=−

TT

TT

R

E

TT

TT

R

E

k

k

TTR

Ekk

a

a

a

]TahrN_xageRkambgðajBIkareRbIR)as;smIkarEdleTIbnwgTaj)anxagelI. ]]]]TahrNTahrNTahrNTahrN____8888³ efrel,Ónrbs;RbtikmµlMdab;TImYyKW 3,46×10–2s–1enAsItuNðPaB 298K. etIefr el,ÓnenAsItuNðPaB 350K esµIb:unµan RbsinebIfamBlskmµrbs;RbtikmµesµInwg 50,2kJ/mol? cMelIycMelIycMelIycMelIy smµtikmµKW k1 = 3,46 × 10–2 s–1 k2 ? T1 = 298 K T2 = 350 K

C¿nYsmIkarTI (10) eyIg)an

12

01,3

2

2

2

12

3

2

12

702,0

0493,01046,3

01,31046,3

ln

)350)(298(

350298

./314,8

/102,501046,3ln

−

−−

−−

−−

=⇒

==×

⇔

−=×

⇔

−×=

×

sk

ek

k

s

KK

molKJ

molJ

k

s

cMNaMcMNaMcMNaMcMNaM³ ³ ³ ³ eyIgdwgehIyRbsinsItuNðPaBkan;Etx<s; efrel,Ónkan;EtFM dUecñHcMelIyeyIg)anTTYl KWsmehtupl. lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ efrel,ÓnlMdab;TI1rbs;RbtikmµrvagemTIlkørY(CH3Cl) nigTwkedIm,Iplit emtaNul (CH3OH) nwgGasIutkørIRDic (HCl) KW 3,32 x 10-10 enA 25oC. cUrKNnaefrel,Ón enA 40oC ebIfamBlskmµesµInwg 116 kJ/mol.

rUbTIrUbTIrUbTIrUbTI17171717³³³³ kartMrgkartMrgkartMrgkartMrg;;;;TisTisTisTiseFobéneFobéneFobéneFobénmmmm:::: UelKulRbtikmµUelKulRbtikmµUelKulRbtikmµUelKulRbtikmµ. . . . manEteBlGatUmbmanEteBlGatUmbmanEteBlGatUmbmanEteBlGatUmb:::: UtasüÚmTgÁicUtasüÚmTgÁicUtasüÚmTgÁicUtasüÚmTgÁic

edaypÞaledaypÞaledaypÞaledaypÞal;;;;CamYyGatUmGIuyCamYyGatUmGIuyCamYyGatUmGIuyCamYyGatUmGIuy:::: UteTUteTUteTUteT EdlRbtikmµGaceEdlRbtikmµGaceEdlRbtikmµGaceEdlRbtikmµGacekItmaneLIgkItmaneLIgkItmaneLIgkItmaneLIg. . . .

suIenTicKImI

13-30

cMeBaHRbtikmµgay²¬dUcCaRbtikmµrvagGatUmTaMgLay¦ eyIgGacRbdUcktþaénPaB jwkjab;(A) enAkñúgsmIkarGaerjIsCamYynwgPaBjwkjab;énkarb:HTgÁicrvagRbePTKImIcUlrYm Rbtikmµ. cMeBaHRbtikmµmanlkçN³saMjúaM eyIgRtUvEtKitBIktþaedATis KWmann½yfa etIGgÁFatu RbtikmµRtUv)anedATisdUcemþcTak;TgKñaeTAvijeTAmk. RbtikmµrvagGatUmb:UtasüÚm nigemTIl GIuy:UDY edIm,IbegáItCab:UtasüÚmGIuy:UDY nigra:DIkal;emTIlbgðajBIcMnucenH³

K + CH3I → KI + CH3

RbtikmµenHGMeNayplbMputenAeBlEdlGatUmb:UtasüÚmTgÁicCamYynwgGatUmGIuy:Ut kñúgm:UelKulemTIlGIuy:UDY¬rUb17¦ ebIBuMdUcenHeTmanplitpltictYc b¤k¾KµanplitplnwgekIt maneLIgeT. RbePTénktþaedATisenHRtUv)andMeNIrkary:agl¥CamYykarsikSaBIsuIenTicKImI kMritx<s;Cag. 5 clnkarRbtikmµ

dUcEdleyIg)aneXIjBIxagedImrYcehIy smIkarlMnwgKImITaMgmUlmin)anR)ab;eyIg eGay)aneRcInfaetIRbtikmµekItmanya:gNaenaHeT. enAkñúgkrNICaeRcIn vaRKan;EttageGay C¿hansrubdMbUgC¿hansrubdMbUgC¿hansrubdMbUgC¿hansrubdMbUgmYycMnYnb¤RbtikmµdMbUg²EdlCaesrIénRbtikmµsamBaØtageGayvivtþn_én RbtikmµTaMgmUlenAkMritm:UelKul. BaküsMrab;erobrab;BIlMdab;C¿handMbUg²EdlnaMeTAdl;kMN plitplehAfa clnakarRbtikmµclnakarRbtikmµclnakarRbtikmµclnakarRbtikmµ. clnakarRbtikmµKWRbdUceTAnwgkareFVIdMeNIrtampøÚvkñúg ry³eBleFVIdMeNIreTATisedANamYyehIysmIkarKImIsrubbBa¢ak;EtBIRbPBedImnigTIedA.

cUrBinitüemIlRbtikmµrvagGasUtm:UNUGuksIutCamYyGuksIuEsn Ca]TahrN_mYyén clnakarénRbtikmµ³

2NO (g) + O2 (g) → 2NO2 (g)

eyIgdwgfa plitplminRtUv)anekIteLIgedaypÞal;edaykarTgÁicrvagBIrm:UelKul GasUtm:UNUGuksIutnigmYym:UelKulGuksIuEsneT eRBaH N2O2 RtUv)anrkeXIjkñúgdMeNIrkarRbti kmµenH. eyIgsnµtfaRbtikmµekItmaneLIgtamC¿hanBIr dUcxageRkam³

2NO (g) → N2O2 (g) N2O2 (g) + O2 (g) → 2 NO2 (g) enAkñúgCMhanTImYy m:UelKulGasUtm:UNUGuksIutcMnYnBIrTgÁicKñaedIm,IbegáIt)anCamYy

m:UelKul N2O2. RbtikmµbnÞab;KWCaRbtikmµrvagm:UelKul N2O2 CamYynwgGuksIuEsn. smIkar srubEdltageGayRbtikmµTaMgmUl KWCasmIkarsrubrvagsmIkarTaMgBIr.

CMhanTI1 NO + NO → N2O2 C¿hantI2 N2O2 + O2 → 2NO2

CMBYkTI13

13-31

smIkarsrub 2NO + N2O2 + O2 → 2 NO2 + N2O2

RbePTKImIdUcCaN2O2 ehAfaFatukNþalFatukNþalFatukNþalFatukNþal eRBaHvaekIteLIgenAkñúgclnakarrbs;Rbtikmµ ¬enaHKWCaC¿handMbUg¦ b:uEnþminEmnekIteLIgenAkñúgsmIkarlMnwgTaMgmUlenaHeT. cUrcaMfa Fatu kNþalEtgEtekIteLIgenAkñúgC¿handMbUg ehIyvaRtUvmanRbtikmµbnþeTotenAC¿hanbnÞab;.

mmmm:::: UelKulLarIeténRbtikmµUelKulLarIeténRbtikmµUelKulLarIeténRbtikmµUelKulLarIeténRbtikmµ KWCacMnYnm:UelKulEdlcUlrYmRbtikmµenAkñúgC¿handMbUg. m:UelKulTaMgenHGacmanRbePTdUcb¤xusKña. C¿handMbUgnImYy²EdleyIg)anniyayxagelI ehAfa Rbtikmµb‘ÍmRbtikmµb‘ÍmRbtikmµb‘ÍmRbtikmµb‘Ím:: :: UelKulUelKulUelKulUelKul EdlCMhandMbUgmanBIrm:UelKulcUlrYm. ]TahrN_mYyén RbtikmµRbtikmµRbtikmµRbtikmµ ÉkmÉkmÉkmÉkm:::: UelKulUelKulUelKulUelKul EdlCMhandMbUgRtUv)ancUlrYmedaym:UelKulRbtikmµEtmYy KWRbtikmµbMElgBIsIukøÚ RbU)a:neTACaRbUEb:nEdl)ansikSaxagelI. RbtikmµRbtikmµRbtikmµRbtikmµETmETmETmETm:::: UelKul UelKul UelKul UelKul EdlekItmanedaym:UelKulcMnYn bIenAC¿handMbUgmantictYcNas; BIeRBaHkarTgÁicKñarvagm:UelKulbIvaBuMsUvmandUckarTgÁicKña rvagm:UelKulBIr. c,ab;el,ÓnnigC¿handMbUg²

kardwgBIrC¿handMbUg²rbs;RbtikmµmYyGacCYyeGayeyIgKNnac,ab;el,Ón)an. ]bmafaeyIgmanRbtikmµCMhandMbUgdUcxageRkam³

A → plitpl edaysarEtmanvtþmanEtmYym:UelKul enHKWCaRbtikmµénm:UelKul. kalNaman

vtþmanm:UelKul A kan;EtFM enaHel,ÓnkñúgkarbegáItplitplk¾kan;EtelOnEdr. dUcenHel,Ón énRbtikmµÉkm:UelKulsmamaRtedaypÞal;eTAnwgkMhab;én ArWCalMdab;TI1én A³

el,Ón = k [A]

cMeBaHRbtikmµC¿handMbUgbIm:UelKulmankarcUrlrYmBIm:UelKul A nig B

A + B → plitpl el,ÓnénkMNplitplGaRs½yeTAelIkarTgÁicrvagm:UelKul A nig B jwkjab;y:agNa

ehIy vak¾GaRs½yeTAnwgkMhab;rbs;A nig B Edr. dUcenHeyIgGacsresrel,ÓndUcxageRkam³ el,Ón = k [A][B]

dUcKñaenHEdrsMrab;RbtikmµC¿handMbUg b‘Ím:UelKulénRbePT A + A → plitpl

rW 2A → plitpl

suIenTicKImI

13-32

el,Ónrbs;vakøayCa el,Ón = k [A] 2

]TahrN_xagelIbgðajfalMdab;RbtikmµsMrab;RbtikrnImYy²enAkñúgRbtikmµ C¿handMbUg esµInwgemKuNsÞWsüÚemRTIenAkñúgsmIkarKImIénC¿hanenaH. CaTUeTAeyIgminGacdwgedayRKan; EtemIleTAelIsmIkarlMnwgfaetIvaCaRbtikmµekIteLIgdUc)anbgðaj b¤k¾RbtikmµekIteLIgCaes‘rI C¿hanenaHeT. karkMNt;enHRtUv)aneFVIenAkñúgbnÞb;BIesaF.

rUbTIrUbTIrUbTIrUbTI18181818³ ³ ³ ³ lMdablMdablMdablMdab;;;;C¿hankñúgkarsikSaclnakarRbtikmµ C¿hankñúgkarsikSaclnakarRbtikmµ C¿hankñúgkarsikSaclnakarRbtikmµ C¿hankñúgkarsikSaclnakarRbtikmµ

enAeBlEdleyIgsikSaBIRbtikmµmYyEdlmanCMhandMbUgeRcInCagmYy c,ab;el,Ón sMrab;lMnaMRbtikmµTaMgmUlRtUv)anpþl;eGayeday CMhankMNtCMhankMNtCMhankMNtCMhankMNt;;;;elelelel,,,,ÓnÓnÓnÓn EdlCaCMhand¾yWtCageK bMputenAkñúglMdab;énC¿hanEdlnaMeTAdl;kMNplitpl. C¿hankMNt;el,ÓnGaceRbobeTAnwg kareFVIcracrenAelIpøÚvd¾ceg¥ótmYy. edaysnµtfarfynþminGacva:Kña)aneTenAelIpøÚvenH dUcenH el,ÓnEdlrfynþTaMgenaHeFVIcracrKWGaRs½yeTAelIrfynþEdlebIkyWtCageKbMput.

karsikSaBiesaFn_BIclnakarRbtikmµcab;epþImedaykarRbmUlTinñn½ybnÞab;mkeyIg viPaKTinñn½y edIm,IkMNt;efrel,Ón lMdab;rbs;Rbtikmµ nigsresrc,ab;el,Ón. TIbBa©b;eyIg esñIeLIgnUvclnakarsmRsbsMrab;RbtikmµkñúgC¿handMbUg²¬rUbTI18¦ CMhandMbUgTaMgenaHRtUv EteKarBeTAtamtMrUvkarcaM)ac;cMnYnBIr³

- CMhandMbUg²srubRtUvEtpþl;nUvsmIkarlMnwgTaMgmUlsMrab;RbtikmµenaH. - CMhankMNt;el,ÓnKYrEtBüakrN_nUvc,ab;el,ÓndUcKñaeTAnwgkarkMNt;edayBiesaFn_.

cUrcgcaMfasMrab;KMeragRbtikmµesñIeLIgeyIgRtUvEtGacrkeXIjvtþmanénFatukNþal EdlkekIteLIgenAkñúgCMhandMbUgmYy b¤eRcIn.

RbtikmµbMEbkGIuRdUEsnEBGuksIutnigkMNGIuRdUEsnGIuy:UDYBIm:UelKulGIuRdUEsnnigm:UelKul GIuy:UtbgðajBIPaBc,as;las;rbs;clnakarRbtikmµedaykarsikSaBiesaFn_.

karvas;el,Ón Rbtikmµ

begáItc,ab;el,Ón EcgclnakarRbtikmµ EdlsmRsb

CMBYkTI13

13-33

RbtikmµbMEbkGIuRdUEsnEBGuksIutRbtikmµbMEbkGIuRdUEsnEBGuksIutRbtikmµbMEbkGIuRdUEsnEBGuksIutRbtikmµbMEbkGIuRdUEsnEBGuksIut RbtikmµbMEbkGIuRdUEsnEBGuksIutRtUv)ansMrYledayGIuy:ugGIuy:UDY¬rUbTI19¦.

rUbTIrUbTIrUbTIrUbTI19191919³ ³ ³ ³ RbtikmµbMEbkRbtikmµbMEbkRbtikmµbMEbkRbtikmµbMEbkGIuRdUEsnEBGuksIut RtUvGIuRdUEsnEBGuksIut RtUvGIuRdUEsnEBGuksIut RtUvGIuRdUEsnEBGuksIut RtUv))))ankatalIsankatalIsankatalIsankatalIseday eday eday eday GIuyGIuyGIuyGIuy:::: ugGIuyugGIuyugGIuyugGIuy:::: UDYUDYUDYUDY....

smIkarsrubKW³ 2H2O2 (aq) → 2H2O (l)+ O2 (g)

tamry³BiesaFn_ c,ab;el,ÓnRtUvrkeXIjdUcxageRkam³ el,Ón = k [H2O2][I

–]

dUcenHRbtikmµKWCalMdab;TImYycMeBaH H2O2 nig I– . GñkGaceXIj ehIyfa karbMEbkTwkGuksIuEsenminekIteLIgkñúgC¿handMbUgEt

mYyEdlRtUvnwgsmIkarsrubeT. RbsinebIvaekIteLIgEtmYyC¿handMbUg enaHRbtikmµGacCa lMdab;BIrcMeBaHTwkGuksIuEsen¬CalT§plénkarTgÁicrvag m:UelKulTwkGuksIuEsenBIr¦. CagenHeTAeTot GIuy:ugGIuy:Ut EdlminmanenAkñúgsmIkarlMnwgKWmanenAkñúgkenSamc,ab;el,Ón. etIeyIgGacbgðajehtukarN_enHya:gdUcemþc)an? dMbUgeyIgRtUvKitBI c,ab;el,ÓnEdl)ansegátedaysnµtfaRbtikmµekItmaneLIgkñúgBIrCMhandMbUgEdlCMhannImYy²KWCab‘Ím:UelKulcUlrYm³

CMhanTI1 H2O2 + I– → 1k H2O + IO– CMhanTI2 H2O2 + IO– → 2k H2O + I– + O2

RbsinebIeyIgsnµtbnþeTotfa C¿hanTImYyKWCaC¿hankMNt;el,Ón dUcenHel,Ónrbs; RbtikmµGacRtUv)ankMNt;BIC¿hanTImYyEtÉg³

el,Ón = k1[H2O2][I-]

cUrcaMfa IO- KWCaFatukNþal eRBaHvaBuMmanenAkñúgsmIkarlMnwgsrubeT. eTaHCaGIuy:ug GIuy:UtBuMmanenAkñúgsmIkarlMnwgk¾edayEtvaxusBI IO- Rtg;vamanvtþmanenAeBlcab;epþImRbtikmµ ehIyenAeBlRbtikmµcb;k¾vamanvtþmanEdr. muxgarrbs;GIuy:ugGIuy:UtKWbegáInel,ÓnRbtikmµEdl eyIgehAfa katalIkr katalIkr katalIkr katalIkr . eyIgnwgsikSaBIkatalIkrenAEpñkbnÞab;.

suIenTicKImI

13-34

RbtikmµbegáItGIuRdUEsnGIuyRbtikmµbegáItGIuRdUEsnGIuyRbtikmµbegáItGIuRdUEsnGIuyRbtikmµbegáItGIuRdUEsnGIuy:::: UDÜUDÜUDÜUDÜ clnakarRbtikmµTUeTAKWCaclnkarEdlrYmmanC¿handMbUgya:gticcMnYnBIr kñúgenaH

C¿handMbUgTI1 KWelOnNas;TaMgRbtikmµeTAnigRbtikmµRtlb; ebIeRbobeFobCamYynwgCMhan dMbUgTIBIr. ]TahrN_mYyxageRkamKWCaRbtikmµrvagm:UelKulGIuRdUEsnnigm:UelKulGIuy:UtedIm,I begáIt)anCaGIuRdUEsnGIuy:UDY.

H2 (g) + I2 (g) → 2HI (g)

tamBiesaFn_ el,ÓnRbtikmµesµInwg el,Ón = k [H2][I 2]

rbs;CaeRcInqñaM eKKitfaRbtikmµekItmaneLIgdUcsmIkarEdleK)ansresr KWCaRbtikmµ b‘Ím:UelKulénGIuRdUEsnnigGIuy:UtdUcbgðajxagelI. EtenATsvtSqñaM1960 KImIviTU)anrkeXIj nUvclnakarRbtikmµBitR)akdEdlmanlkçN³saMjúaMCag. clnakarBIrC¿hanRtUv)anesñIeLIg

C¿hanTI1 I2 → 2I

CMhanTI2 H2 + 2I → 2k 2HI Edl k1, k-1 , nig k2 KWCaefrel,ÓnsMrab;RbtikmµTaMgenH. GatUmGIuy:UtKWCaFatukNþal

enAkñúgRbtikmµenH. enAeBlRbtikmµcab;epþIm vtþmanGatUmGIuy:UttictYcNas; b:uEnþenAeBlEdlDIGIuy:Ut

bMEbkkMhab;rbs;DIGIuy:UtfycuH cMENkkMhab;rbs;GatUmGIuy:UtekIneLIg. dUcenH el,ÓnkekIt énC¿hanTImYyfycuH ehIyel,ÓnRbtikmµRtlb;ekIneLIg. bnÞab;mkel,ÓnTaMgBIresµIKñaehIy begáIt)anCalMnwgKImI. edaysarEtRbtikmµdMbUgkñúgCMhanTI1elOnCagRbtikmµdMbUgkñúgCMhan TI2 enaHlMnwgekItmaneLIgmuneBlRbtikmµsMxan;CamYyGIuRdUEsnekItmaneLIg ehIyvaenArkSa dUecñHrhUtRbtikmµcb;.

enAkñúgl½kçx½NÐlMnwgC¿hanTI1 el,ÓnRbtikmµkMNplitplesµIeTAnwgel,ÓnRtlb;³

k1[I2] = k-1[I]2

][][ 21

12 Ik

kI

−

=

el,Ónrbs;RbtikmµenHRtUvkMNt;edayCMhankMNt;el,ÓnyWt enaHKWCMhanTI2³ el,Ón = k2[H2][I]

2

C¿nYs [I] 2 eTAkñúgc,ab;el,ÓnenH eyIg)an³

CMBYkTI13

13-35

el,Ón = ]][[]][[ 22221

21 IHKIHk

kk =−

Edl k =k1k2/k–1. dUcEdleyIgGaceXIjehIy clnakarBIrC¿hanenHk¾pþl;nUvc,ab; el,ÓnRtwmRtUvEdrsMrab;RbtikmµenH. karyl;RBmenHCamYynwgkarsegátFatukNþalGatUm GIuy:Utpþl;nUvPsþútagd¾xøaMgfaclnkarénRbtikmµKWCaclnakarRtwmRtUv.

TIbMputeyIgkt;sMKal;fa minEmnRKb;RbtikmµTaMgGs;manC¿hankMNt;el,ÓnEtmYy enaHeT. RbtikmµmYyGacmanC¿hanyWtRbhak;RbEhlKñaBIrb¤eRcIn. karviPaKsIuenTicrbs; RbtikmµenH CaTUeTARtUv)ancUlrYmEfmeTot.

]TahrN_dUcxageRkambgðajBIkarsikSaclnaRbtikmµEdlgay². ]]]]TahrNTahrNTahrNTahrN____9999³³³³ karbMEbkrbs;DIGasUtGuksIutkñúgpas]sµ½n N2O ekItmaneLIgCaBIrC¿han³ CMhanTI1 ONON k +→ 2

12

C¿hanTI2 222

2 ONOON k +→+ c,ab;el,ÓnBiesaFn_esµInwg k [N2O]. k> cUrsresrsmIkarRbtikmµsrub. x> cUrkMNt;FatukNþal. K> etIeyIgGacniyayBIel,ÓneFobénCMhanTImYynigCMhanTI2 dUcemþc? cMelIycMelIycMelIycMelIy ¬k¦> edaykarbUksmIkarkñúgCMhanTI1nigCMhanTI2 eyIg)ansmIkarRbtikmµsrub 2N2O → 2N2 + O2 ¬x¦> edayGatUmGuksIuEsnekIteLIgenACMhanTI1dMbUg ehIyvaKµanenAkñúgsmIkarlMnwg srub dUcenHGatUmGuksIuEsnKWCaFatukNþal. ¬K¦> RbsinebIeyIgsnµtfa C¿hanTI1KWCaC¿hankMNt;el,ÓnRbtikmµ ¬enHmann½yfa ebI k2 >> k1) dUcenHel,Ónrbs;smIkarRbtikmµsrubKW

el,Ón = k1[N2O] nig k = k1

lMhatlMhatlMhatlMhat;;;;GnuvtþnGnuvtþnGnuvtþnGnuvtþn__ __³ ³ ³ ³ Rbtikmµrvag NO2 nig CO Edlplit NO nig CO2 RtUv)aneKeCOfaman dMeNIkarBIrCMhan³ CMhanTI1 NO2 + NO2 → NO + NO3

CMhanTI2 NO3 + CO → NO2 + CO2

c,ab;el,ÓnBiesaFn_esµInwg k[NO2]2. k> cUrsresrsmIkarRbtikmµsrub.

x> cUrkMNt;FatukNþal K> etIeyIgGacniyayBIel,ÓneFobénCMhanTI1 nigCMhanTI2dUcemþc?

suIenTicKImI

13-36

karKaMRTedayBiesaFn_cMeBaHclnkarRbtikmµ etIeyIgGacdwgfaclnaEdleyIgesñIeLIgsMrab;RbtikmµNamYyRtwmRtUvenaH? kñúgkrNI

RbtikmµbMEbkGIuRdUEsnEBGuksIut eyIgGacrkeXIjvtþmanrbs; IO– edayviFIs,úicRtUTsSn_. Psþútagénvtþmanrbs;vaGacKaMRTKMeragRbtikmµ. CamYyKñaenHEdr sMrab;RbtikmµbegáItGIuRdUEsn GIuy:UDY karrkeXIjGatUmGIuy:UtGacnwgKaMRTclnkarRbtikmµBIrC¿hanenaH. ]TahrN_ karbMEbkm:UelKulGIuy:UteTACaGatUmGIuy:UtenAeBlvaRtUv)an)aj;kaMrsµIGacemIleXIj. dUcenH eyIgGacBüakrN_fa karbegáItGIuRdUEsnGIuy:UDYBIm:UelKulGIuRdUEsnnigm:UelKulGasUtnwgGac begáInelOnenAeBlEdleKbEnßmGaMgtg;sIuetBnøW eRBaHkareFVIdUcenHGaceFVIeGaykMhab;rbs; GatUmGIuy:UtekIneLIg. tamBitenHRKan;EtCakarsegátb:ueNÑaH.

kñúgkrNImYy KImIviTUcg;dwgfaetIsm<½n§ C–O mYyNaRtUv)anpþac;enAkñúgRbtikmµrvag emTIlGaestatnigTwk edIm,Iyl;EfmeTotBIclnkarrbs;Rbtikmµ

lT§PaBEdlGacekItmancMnYnBIrKW

(a) (b)

edIm,IEbgEckTMrg;(a)nig(b)KImIviTU)aneRbITwkEdlmanGIusUtUbGuksIuEsn18 CMnYseGay TwkFmµtaEdlmanEtGIusUtUbGuksIuEsn16. enAeBlEdleKeRbITwkEdlmanGIusUtUbGuksIuEsn 18 manEtTMrg;GasIutGaesTiceTEdlmanGuksIuEsnEdlmanGIusUtUb18 .

dUcenHRbtikmµRtUvEtekItmaneLIgenAelITMrg; (a) eRBaHplitplEdlekItmaneLIgtam

TMrg;smasFatu (b)GacmanGatUmGuksIuEsnedImdEdl. ]TahrN_mYyepSgeTotKWrsµIsMeyaK EdlCadMeNIrkarmYykñúgenaHrukçCatiébtgplitKøúykUsBIkabUnDIGuksIutnigTwk.

6CO2 + 6H2O → C6H12O6 + 6O2 sMNYrEdlelIkeLIgenaHKWfa etIm:UelKulGuksIuEsnEdlekItmaneLIgenaH)anmkBITwk

]sµ½nkabUnic b¤k¾)anmkBIsmasFatuTaMgBIrenH. edayeRbITwkEdlmanGIusUtUbGuksIuEsn18 vabgðajfaGuksIuEsnEdlekItmaneLIgKW)anmkBITwk ehIyKµanGuksIuEsnEdl)anmkBI]sµ½n

CMBYkTI13

13-37

kabUniceT eRBaHGuksIuEsnmanEtGIusUtUbGuksIuEsn18eT. lT§plenHKaMRTclnkarRbtikmµ EdlkñúgenaHm:UelKulGuksIuEsnRtUv)anbMEbkedayBnøW.

2H2O + hv → O2 + 4H+ + 4e–

Edl hv tageGayfamBlpUtug . pUtugnigeGLicRtugRtUv)aneRbIedIm,InaMeGay manRbtikmµxøaMgkøaminGMeNaypl EdlcaM)ac;sMrab;karlUtlas;nigmuxgarrbs;rukçCati.

]TahrN_TaMgenHpþl;nUvKMnitxøHEdlfaetIKImIviTUmanKMnitbegáItfµIRtUvEtsikSaBIclnkar RbtikmµdUcemþc. b:uEnþ cMeBaHRbtikmµsaMjúaMvaBitCaminGacbgðajBIPaBmanEtmYyKt;én clnkaredayELkNamYyeT. 6 katalIs

cMeBaHRbtikmµbMEbkTwkGuksIuEsen eyIgeXIjfael,ÓnRbtikmµGaRs½yeTAelIkMhab; rbs;GIuy:ugGuIy:Ut eTaHCaGIuy:ugGIuy:UtBuMmanenAkñúgsmIkarsrubk¾eday. eyIgkMnt;faGIuy:ugGIuy:Ut edIrtYCakatalIkrkñúgRbtikmµenH. katalIkr katalIkr katalIkr katalIkr KWCasarFatuEdlbegáInel,Ónrbs;RbtikmµKImI b:uEnþ vaminRtUv)aneRbIR)as;eT. katalIkrGaccUlrYmRbtikmµedIm,IbegáItCaFatukNþal b:uEnþvaekIt eLIgvijenAkñúgCMhanbnÞab;énRbtikmµ.

enAkñúgTegVIGuksIuEsnm:UelKulkñúgTIBiesaFb:UtasüÚmkøra:tRtUv)andutkMedA. RbtikmµenaH KW³ 2KClO3 (s) → 2KCl (s)+ 3O2 (g)

b:uEnþRbtikmµbMEbkedaykMedAenHyWtNas;ebIKµankatalIkr. el,ÓnénRbtikmµbMEbk ekIneLIgya:gqab;rh½sedaykarbEnßmbrimaNtictYcénkatalIkrm:g;kaENsDIGuksIutEdlCa emSABN’exµA. MnO2 TaMgGs;ekItmaneLIgvijenAeBlRbtikmµcb; dUcGIuy:ugGIuy:UtEdlenAsl; bnÞab;BIRbtikmµbMEbkTwkGuksIuEsenEdr.

katalIkrbegáInel,ÓnRbtikmµedaybegáIt)anCaes‘rIénCMhandMbUgEdlmanlkçN³sIuenTicRbesIrCagRbtikmµEdlKµankatalIkr. tamsmIkarTI(8) eyIgdwgfaefrel,Ónk rbs;Rbtikmµ GaRs½yeTAnwgktþaénPaBjwkjab; A nigfamBlskmµ Ea. kalNatMél A kan;EtFMb¤tMél Ea

kan;EttUc enaHel,Ónkan;EtelOn. kñúgkrNICaeRcIn katalIkrbegáInel,ÓnRbtikmµedaybnßy nUvfamBlskmµsMrab;RbtikmµenaH.

cUrsnµtfaRbtikmµdUcxageRkammanefrel,ÓnCak;lak;mYy k ehIyfamBlskmµ Ea. A + B DCk +→

b:uEnþedaysarvtþmanénkatalIkr efrel,ÓnKW kc ¬ehAfa efrel,ÓnkatalIkr¦.

suIenTicKImI

13-38

DCBA ck +→+ tamniymn½ykatalIkr el,ÓnkatalIkr > el,ÓnKµankatalIkr

rUbTIrUbTIrUbTIrUbTI20202020³ ³ ³ ³ kareRbobeFobénrkareRbobeFobénrkareRbobeFobénrkareRbobeFobénr))))aMgfamBlskmµénRbtikmµEdlmankatalIkr nigRbtikmµ aMgfamBlskmµénRbtikmµEdlmankatalIkr nigRbtikmµ aMgfamBlskmµénRbtikmµEdlmankatalIkr nigRbtikmµ aMgfamBlskmµénRbtikmµEdlmankatalIkr nigRbtikmµ EdlKEdlKEdlKEdlKµankatalIkrµankatalIkrµankatalIkrµankatalIkr. . . . katalIkrbnßyrkatalIkrbnßyrkatalIkrbnßyrkatalIkrbnßyr))))aMgfamBlaMgfamBlaMgfamBlaMgfamBl bbbb:::: uEnþmineFVIeGaybuEnþmineFVIeGaybuEnþmineFVIeGaybuEnþmineFVIeGayb::::HBalHBalHBalHBal;;;;dldldldl;;;;famBlBitfamBlBitfamBlBitfamBlBit RRRR))))akdakdakdakdrbsrbsrbsrbs;;;;Rbtikrb¤plitpleLIyRbtikrb¤plitpleLIyRbtikrb¤plitpleLIyRbtikrb¤plitpleLIy. . . . eTaHCaplitplnigeTaHCaplitplnigeTaHCaplitplnigeTaHCaplitplnigRbtikrdUcKñaenAkñúgkrNIRbtikrdUcKñaenAkñúgkrNIRbtikrdUcKñaenAkñúgkrNIRbtikrdUcKñaenAkñúgkrNITaMgBIrTaMgBIrTaMgBIrTaMgBIr k¾edayk¾edayk¾edayk¾eday k¾clnkarRbtikmµnigck¾clnkarRbtikmµnigck¾clnkarRbtikmµnigck¾clnkarRbtikmµnigc,,,,abababab;;;;elelelel,,,,ÓnxusKñaEdr enAkñúgÓnxusKñaEdr enAkñúgÓnxusKñaEdr enAkñúgÓnxusKñaEdr enAkñúg(a) nignignignig(b)....

rUbTI20bgðajBIfamBlb:Utg;Esülrbs;RbtikmµTaMgBIr. cUrcMNaMfa famBlsrub rbs;Rbtikr (A nig B ) nigrbs;plitpl (C nig D ) minrg\T§iBlBIkatalIkreT. PaBepSgKña EtmYyrvagRbtikmµTaMgBIrKWkarfycuHénfamBlskmµBI Ea eTA Ea

’. edaysarEtfamBlskmµ rbs;RbtikmµRtlb;k¾RtUv)anbnßy dUcenHkatalIkrbegáInel,ÓnRbtikmµbegáItplitplnig RbtikmµRtlb;vijesµIKña.

mankatalIsbIRbePTTUeTA GaRs½yeTAelIRbePTsarFatubegáInel,ÓnRbtikmµ³ katalIeGetr:UEsn katalIkrGUm:UEsn nigkatalIsGg;sIum.

katalIseGetr:UEsn ¬katalIsminesµIsac;¦ kñúgkatalIkreGetr:UEsn katalIkrmanpasxusBIRbtikr. CaFmµtakatalIkrCaGgÁFatu

rwg ehIyRbtikrCa]sµ½nb¤GgÁFaturav. katalIseGetr:UEsnKWCaRbePTkatalIsmansar³sMxan; bMputenAkñúgKImI]sSahkmµ CaBiessenAkñúgkarsMeyaKnUvFatuKImIsMxan;². eyIgnwgelIkyknUv ]TahrN_Cak;lak;cMnYnbIénkatalIseGetr:UEsnEdlCYyeGayFatuKImIrab;etanRtUv)anplitCa erogral;qñaMenAkMrit]sSahkmµ.

CMBYkTI13

13-39

sMeyaKhaEb‘sMeyaKhaEb‘sMeyaKhaEb‘sMeyaKhaEb‘(Haber)rbsrbsrbsrbs;;;;GamGamGamGam:::: UjUjUjUj::::akakakak;;;; Gam:Uj:ak;KWCasaFatuGsrIragÁd¾mantMél EdlRtUv)aneRbIenAkñúg]sSahkmµCI eragcRk

pliteRKOgpÞúH nigkareRbIR)as;epSgeTot. ry³eBlCitmYystvtSmkenH KWmIviTU)anxitxM sMeyaKGam:Uj:ak;BIGasUtnigGIuRdUEsn. GasUtKWCa]sµ½nEdleRbIminecHGs;EdlmanenAkñúg briyakasehIy]sµ½nGIuRdUEsnGacRtUv)anplitedaykarbBaöÚncMhayqøgFüÚgRtUv)andutkMedA.

H2O (g) + C (s) → CO (g) + H2 (g)

GIuRdUEsnk¾CaplitplénkarcMraj;eRbg\n§n³Edr. kMNGam:Uj:ak;BIGasUtnigGIuRdUEsn KWCaRbtikmµRsUbkMedA³ N2 (g) + H2 (g) → 2NH3 (g) �H0 = –92,6 kJ

b:uEnþ RbtikmµenHCaRbtikmµyWtNas;enAkñúgsItuNðPaBbnÞb;. kñúgkarGnuvtþCaRTg;RTay FMRbtikmµRtUvEtekItmaneLIgedayel,ÓnKYrsm ehIyvaRtUvEtmanTinñplénplitplx<s;tam EdlRtUvkar. kartMeLIgsItuNðPaBBitCabegáInel,ÓnRbtikmµxagelIenH b:uEnþ enAeBlCamYy KñaenaHvak¾CMrujRbtikmµbMEbkGam:Uj:ak;eTACaGasUtnigGIuRdUEsnpgEdr dUcenHvaGaceFVIeGay fycuHnUvTinñplGam:Uj:ak;.

enAqñaM1905 bnÞab;BIkareFVIetsþedaypÞal;nUvsmasFaturab;ryenAsItuNðPaBnigsMBaF xus²Kñamk Fritz Haber )anrkeXIjfaEdkpSMCamYynwgb:UtasüÚm nigGaluymIj:ÚmGuksIutBIr bIPaKryGackatalIsRbtikmµrbs;GIuRdUEsnCamYyGasUt ehIyTTYl)anGam:Uj:ak;enAsItuNð- PaB 5000C. dMeNIrkarenHehAfa dMeNIrkarhaEb‘.

enAkñúgkatalIseGetr:UEsn épÞrbs;katalIkrrwgCaFmµtaCatMbn;Rbtikmµ. C¿handMbUg enAkñúgdMeNIrkarhaEb‘Tak;TgeTAnwgkarbMEbkGasUtnigGIuRdUEsneTAelIépÞelah³¬rUbTI21¦. eTaHCaRbePTKImIEdlRtUv)anbMEbkminEmnCaGatUmesrIBitR)akdk¾eday k¾RbePTKImITaMgenaH skmµya:gxøaMg eRBaHvaRtUv)ancgsm<½n§CamYynwgépÞelah³. m:UelKulRbtikrTaMgBIrman skmµPaBxusKñaenAelIépÞkatalIkr.

suIenTicKImI

13-40

rUbTIrUbTIrUbTIrUbTI21212121³ ³ ³ ³ GMeBIkatalIkrenAkñúgRbtikmµsMeyaKGamGMeBIkatalIkrenAkñúgRbtikmµsMeyaKGamGMeBIkatalIkrenAkñúgRbtikmµsMeyaKGamGMeBIkatalIkrenAkñúgRbtikmµsMeyaKGam:::: UjUjUjUj::::akakakak;;;;. . . . dMbUgmdMbUgmdMbUgmdMbUgm:::: UelKulGIuRdUEsn UelKulGIuRdUEsn UelKulGIuRdUEsn UelKulGIuRdUEsn

nigGasUtnigGasUtnigGasUtnigGasUtPPPPöabababab;;;;eTAelIépÞrbseTAelIépÞrbseTAelIépÞrbseTAelIépÞrbs;;;;katalIkrkatalIkrkatalIkrkatalIkr. . . . GnþrkmµenHeFVIeGaysmGnþrkmµenHeFVIeGaysmGnþrkmµenHeFVIeGaysmGnþrkmµenHeFVIeGaysm<<<< ½n§kUva½n§kUva½n§kUva½n§kUva:: ::LgLgLgLg;;;;fycuHenAkñúg fycuHenAkñúg fycuHenAkñúg fycuHenAkñúg mmmm:::: UelKulUelKulUelKulUelKul ehIyTIbMputeFVIeGaymehIyTIbMputeFVIeGaymehIyTIbMputeFVIeGaymehIyTIbMputeFVIeGaym:::: UelKulUelKulUelKulUelKulbMEbkxøbMEbkxøbMEbkxøbMEbkxøÜn.... GatUmGasUtnigGIuRdUEGatUmGasUtnigGIuRdUEGatUmGasUtnigGIuRdUEGatUmGasUtnigGIuRdUEsnEdlskmµsnEdlskmµsnEdlskmµsnEdlskmµxøaMgpSMxøaMgpSMxøaMgpSMxøaMgpSM KñayaKñayaKñayaKñaya::::grh½sedImgrh½sedImgrh½sedImgrh½sedIm,,,,IbegáItIbegáItIbegáItIbegáIt))))anCaGamanCaGamanCaGamanCaGam:::: UjUjUjUj::::akakakak; ; ; ; rYck¾pþacrYck¾pþacrYck¾pþacrYck¾pþac;; ;;ecjBIépÞkatalIkrvij ecjBIépÞkatalIkrvij ecjBIépÞkatalIkrvij ecjBIépÞkatalIkrvij ....

karsikSabgðajmU:elKulfaGIuRdUEsnbMEbkeTACaGatUmGIuRdUEsnenAsItuNðPaB–1960C

¬cMnucrMBuHrbs;GasUtrav¦. pÞúymkvij m:UelKulGasUtbMEbkeTACaGatUmGasUtenAsItuNðPaB RbEhl5000C. GatUmGasUtnigGIuRdUEsnEdlskmµxøaMgpSMKñaya:gqab;rh½senAsItuNðPaBx<s; edIm,IbegáItCam:UelKulGam:Uja:k; EdleyIgcg;)an³

N + 3H → NH3 karplitGasIutnIRTic karplitGasIutnIRTic karplitGasIutnIRTic karplitGasIutnIRTic

GasIutnIRTicKWCaGasIutmYykñúgcMeNamGasIutGsrIragÁsMxan;CageK. vaRtUv)aneKeRbI enAkñúgkarplitCI fñaMlab fñaMeBTü nigeRKOgpÞúH. viFI]sSahkmµd¾sMxan;kñúgkarplitGasIutnIRTic KWdMeNIrkarGUsv:l(Ostwald). vtßúFatuedImKWGam:Uj:ak;nigm:UelKulGuksIuEsnEdlRtUv)andut kMedACamYyvtþmanén)øaTIn-r:UdüÚmCakatalIkr¬rUbTI22¦enAsItuNðPaBRbEhl8000C.

4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)

GasUtGuksIuteFVIGuksIutkmµedayKµankatalIkredIm,IbegáItCaGasUtDIGuksIut³ 2NO (g) + O2 (g) → 2NO2 (g) enAeBlRtUv)anrMlaykñúgTwk NO2 begáIt)anCaGasIutnIRtWnigGasIutnIRTic³

CMBYkTI13

13-41

2NO2(g) + H2O (l) → HNO2(aq) + HNO3(aq)

edaykardutkMedA GasIutnIRtWRtUv)anbMEbkeTACaGasIunIRTicdUcxageRkam³ 3HNO2 (aq) → HNO3 (aq) + H2O (l) + 2NO (g)

NO GacykeTAeRbIeLIgvijedIm,IbegáIt)anCaGasUtDIGuksIutenAkñúgC¿hanTI2. rUbTIrUbTIrUbTIrUbTI22222222³ ³ ³ ³ katalIkrkatalIkrkatalIkrkatalIkr))))aøTInaøTInaøTInaøTIn–rUdüÚmrUdüÚmrUdüÚmrUdüÚmRtUvRtUvRtUvRtUv))))an an an an eRbIenAkñúgdMeNIrkar eRbIenAkñúgdMeNIrkar eRbIenAkñúgdMeNIrkar eRbIenAkñúgdMeNIrkar Ostwald....

RbdabRbdabRbdabRbdab;;;;bMElgbMElgbMElgbMElgkkkkatalIatalIatalIatalIssss(Catalytic Converters)

enAsItuNðPaBx<s;enAkñúgma:sIunrfynþkMBugrt; ]sµ½nGasUtnigGuksIuEsnmanRbtikmµ edIm,IbegáIt)anCaGasUtm:UNUGuksIut³

N2 (g) + O2 (g) → 2NO (g)

enAeBlEdlbeBa©jeTAkñúgbriyakas NO pSMya:gqab;CamYyGuksIuEsnedIm,IbegáItCa NO2. GasUtDIGuksIutnig]sµ½ndéTeTotEdlbeBa©jedayrfynþ dUcCakabUnm:UNUGuksIut(CO)

nigGIuRdUkabYEdlmineqHepSg²GacCaRbPBmYyd¾sMxan;énkarbMBulxül;. rfynþfµI²PaKeRcInRtUv)anbMBak;eTAedayRbdab;bMElgkatalIs¬rUbTI23¦. Rbdab;

bMElgkatalIsd¾manRbsiT§PaBRtUv)aneRbIkñúgeKalbMNgBIrya:g³ vaeFVIGuksIutkmµeTAelIkabUn m:UNUGuksIutnigGIuRdUkabYEdlmineqHeTACa]sµ½nkabUnicnigTwk nigvaeFVIerdukmµ NOnigNO2eTACa N2nigO2. ]sµ½nEpSgekþAEdlRtUvbeBa©jRtUvqøgkat;bnÞb;TImYyénRbdab;bMElgmYyedIm,IbegáIn cMehHsBVGIuRdUkabY nigbnßykarbeBa©j]sµ½nCO. b:uEnþ edaysItuNðPaBx<s;begáInkarplit NO

eTIbmanbnÞb;TIBIrEdlpÞúkkatalIkrepSgeTot¬elah³qøgb¤GuksIutrbs;elah³qøg dUcCa CuO

rWCr2O3¦ ehIykatalIkrenHdMeNIrkarenAsItuNðPaB TabCagEdlRtUvkaredIm,IbMEbkNO eTACa N2 nig O2 muneBlEdl]sµ½nEpSgenHRtUv)anbeBa©jeTAtambMBg;EpSg.

suIenTicKImI

13-42

rUbTIrUbTIrUbTIrUbTI23232323³ ³ ³ ³ RbdabRbdabRbdabRbdab;;;;bMElgbMElgbMElgbMElgkatalIkatalIkatalIkatalIssssBIrdMNakBIrdMNakBIrdMNakBIrdMNak;;;;kalsMrabkalsMrabkalsMrabkalsMrab;;;;rfynþrfynþrfynþrfynþ....

katalIsGUm:UEsn ¬katalIsesµIsac;¦ enAkñúgkatalIkrGUm:UEsn katalIkrnigRbtikrRtUv)anBRgaykñúgpasEtmYy CaFmµta

KWGgÁFaturav. katalIsGasIutnig)asKWCaRbePTd¾sMxan;bMputénkatalIsGUm:UEsnenAkñúg sUluysüúgrav. ]TahrN_ RbtikmµeGTIlGaestatCamYyTwkedIm,IbegáIt)anCaGasIutGaes- TicnigeGtaNulCaFmµtaekItmanyWteBksMrab;karvas;.

edayGvtþmankatalIkr c,ab;el,ÓnGacsresrCa el,Ón = k [CH3COOC2H5]

EtRbtikmµenHGacRtUv)ankatalIsedayGasIut. CamYynwgvtþmanrbs;GasIutGIuRdUkøric el,Ón RbtikmµelOnCag ehIyc,ab;el,Óntageday

el,Ón = kc[CH3COOC2H5][H+]

cUrcMNaMfaedaysar kc > k , el,ÓnRtUv)ankMNt;edayEpñkEdlrgkatalIskñúgRbtikmµ.

rUbTIrUbTIrUbTIrUbTI24242424³ ³ ³ ³ TMrgTMrgTMrgTMrg;;;;rbsrbsrbsrbs;;;;RbdabRbdabRbdabRbdab;;;;bMElgkatabMElgkatabMElgkatabMElgkata---- lIslIslIslIs. . . . bMBgbMBgbMBgbMBg;;;;enHpenHpenHpenHpÞúkkkk))))aøTIn baøTIn baøTIn baøTIn b:::: ULÚdüÚm nig ULÚdüÚm nig ULÚdüÚm nig ULÚdüÚm nig rrrr:: :: UdüÚm EdlkatalIscMehHUdüÚm EdlkatalIscMehHUdüÚm EdlkatalIscMehHUdüÚm EdlkatalIscMehHCO nigGIuRdUnigGIuRdUnigGIuRdUnigGIuRdU---- kabYkabYkabYkabY....

CMBYkTI13

13-43

katalIsGUm:UEsnk¾GacekItmanenAkñúgpas]sµ½npgEdr. ]TahrN_mYyEdleKsÁal; eRcInénRbtikmµkatalIspas]sµ½nKWdMeNIrkarbnÞb;sMN EdlCaeRcInqñaMmkehIyCaviFIsMxan; énkarplitGasIuts‘ulpYric. edaycab;epþImBIs<an;F½r eyIgGacrMBwgTukkarplitGasIuts‘ulpYric tamC¿handUcxageRkam³

S (s) + O2 (g) → SO2(g) 2SO2(g) + O2 (g) → 2SO3 (g) H2O (l) + SO3(g) → H2SO4(aq)

b:uEnþtamBits<an;F½rDIGuksIutminRtUv)anbMEbøgedaypÞal;eTACas<an;F½rRTIGuksIuteTKW GuksIutkmµenHRtUv)andMeNIrkaredayRbsiT§PaBCagCamYynwgvtþmanrbs;katalIkrGasUtDI GuksIut.

2SO2(g) + 2NO2(g) → 2SO3(g) + 2NO (g) 2NO (g) + O2(g) → 2NO2(g) __________________________

smIkarsrub 2SO2(g) + O2(g) → 2SO3(g)

cUrcMNaMfaKµankar)at;bg; NO2 c,as;las;kñúgRbtikmµsrubeT dUcenHGasUtDIGukeqøIy tbeTAnwglkçN³vinicä½yénkatalIkr.

enAeBlfµI²enH KImIviTU)anRbwgERbgya:gxøaMgedIm,IplitsmasFatuelah³mYyfñak; edIm,IeFVICakatalIkrGUm:UEsn. smasFatuTaMgenHrlayenAkñúgFaturMlaysrIragÁepSg² ehtudUcenHvaGackatalIsRbtikmµkñúgpasdUcKñanwgRbtikrEdlrlay. dMeNIrkarCaeRcInEdl vakatalIsKWsmasFatusrIragÁ. ]TahrN_ smasFatu RkhmsVayénrU:düÚm[(C6H5)3P]3RhCl

katalIsbMElgsm<½n§BIrCan;rbs;kabUneTACasm<½n§kabUnmYyCan;vij. C=C + H2 → –C–C–

katalIsGUm:UEsnmanGtßRbeyaCn_mYycMnYnCagkatalIseGetr:UEsn. GtßRbeyaCn_ mYyKWRbtikmµGacRbRBwtþeTAenAkñúglkçxNÐbriyakasFmµta dUcenHvaGacsnSMsMéctMélkñúgkar plit ehIynigbnßyRbtikmµbMEbkplitplenAsItuNðPaBx<s;. CagenHeTAeTot katalIs GUm:UEsnGacRtUv)anbegáIteLIgedIm,IdMeNIrkarmuxgarcMedayeRCIserIssMrab;RbePTedayELk

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13-44

énRbtikmµehIykatalIsGUm:UEsnmantMélefakCagelah³éfø² dUcCa)aøTIn nigmasEdlRtUv )aneRbIkñúgkatalIseGetr:UEsn.

katalIsGg;sIum kñúgdMeNIrkarTaMgGs;EdlTak;TgeTAnwgRbB½n§manCIvit KµanGVIEdlmansar³sMxan;Cag

Gg;sIumeT. GgGgGgGg;;;;sIum sIum sIum sIum KWCakatalIkrCIv³. ehtukarN_KYreGaycab;GarmµN_BIGg;sIumenaHKWfa vaminRtwmEtGacbegáInel,ÓnRbtikmµKWmICIv³BI106 eTA1012 b:ueNÑaHeT b:uEnþvaEfmTaMgmanlkçN³ yfaRbePTCak;lak;eTotpg. Gg;sIummYymanGMeBIEteTAelIm:UelKulCak;lak;mYyb:ueNÑaHEdl eyIgehAfa s‘ubRsþa¬Rbtikr¦ EtRbB½n§déTeTotminrg\T§iBlGVIeT. eK)an)a:n;sµanfa ekasika rs;CamFümGacmanGg;sIumRbEhl3000epSg²Kña Gg;sIumnImYy²katalIsRbtikmµyfa RbePTEdlkñúgenaHs‘ubRsþaRtUv)anbMEbøgeTACaplitplsmRsb. katalIsGg;sIum KWGUm:UEsn eRBaHTaMgs‘ubRsþanigGg;sIummanvtþmanenAkñúgsUluysüúgTwk.

CatYy:agGg;sIumCam:UelKulRbUetGIund¾FMEdlmanmNÐlskmµmYyrWeRcInEdlGnþrkmµ CamYys‘ubRsþaekItmaneLIg. mNÐlenHmanTMrg;RtUvCamYym:UelKuls‘ubRsþayfaRbePTdUc kUnesaRtUvnwgemesarbs;vaGBa©wgEdr. tamBit sBaØaNénTMrg;Gg;sIumrwgbwugGaccgsm<½n§ CamYyEtm:UelKulNaEdlTMrg;m:UelKulKñaCamYynwgmNçlskmµ KWCamUldæanénRTwsþIdMbUgén katalIsGg;sIum. rbs;EdlehAfaRTwsþIkUnesa nigemesaRtUv)anGPivDÆedayKImIviTUGaløWm:g; Emil Fischer enAqñaM1894¬rUbTI25¦. smµtikmµrbs; Fischer Bnül;BIPaByfaRbePTén Gg;sIum b:uEnþvapÞúyeTAnwgPsþútagénkarRsavRCavEdlfaGg;sIummYycgPöab;CamYysu‘b®sþaEdl manTMhMnigragxus²Kña. \LÚvenH KImIviTUdwgfam:UelKulGg;sIum¬b¤ya:gehacNas;mNÐlskmµ rbs;va¦ manTMrg;bt;EbnxøH ehIyGacEkERbTMrg;rbs;vaedIm,IeGayRtUvnwgs‘ubRsþaelIsBImYy RbePT.

rUbTIrUbTIrUbTIrUbTI25252525³ ³ ³ ³ KMrUemsaKMrUemsaKMrUemsaKMrUemsa nigkUnesaénPaBnigkUnesaénPaBnigkUnesaénPaBnigkUnesaénPaByfaRbePTyfaRbePTyfaRbePTyfaRbePTrbsrbsrbsrbs;;;;GgGgGgGg;;;;sIumcMeBaHmsIumcMeBaHmsIumcMeBaHmsIumcMeBaHm:::: UelKuls‘ubRsþa UelKuls‘ubRsþa UelKuls‘ubRsþa UelKuls‘ubRsþa

CMBYkTI13

13-45

karKitKUrtamKNitviTüaénsIuenTicGg;sIummanlkçN³saMjúaMNas; eTaHbIeyIgdwgBI C¿handMbUg²kñúgRbtikmµk¾eday. KMeraggayRtUv)anpþl;eGayedayCMhandMbUg²dUcxageRkam³

E + S ES ES → 2k E + P

Edl E, S nig P tageGayGg;sIum s‘ubRsþa nigplitpl ehIy ES KWCaFatukNþal rvagGg;sIumnigs‘ubRsþa. eKeRcInsnµtfakMN ES nigkarbMEbkrbs;vaeTACam:UelKulGg;sIum nigs‘ubRsþavijekItmanya:gqab;rh½s ehIyC¿hankMNt;el,ÓnKWkMNplitpl. rUbTI26bgðaj BIfamBlb:Utg;EsüsMrab;RbtikmµenaH.

rUbTIrUbTIrUbTIrUbTI26262626³ ³ ³ ³ kareRbobeFobrkareRbobeFobrkareRbobeFobrkareRbobeFobrvagvagvagvag (a)RbtikmµRbtikmµRbtikmµRbtikmµminrgminrgminrgminrgkatalIkatalIkatalIkatalIssss nig nig nig nig (b)RbtikmµdUcKña RbtikmµdUcKña RbtikmµdUcKña RbtikmµdUcKña

EtEtEtEtrgrgrgrgkatalIkatalIkatalIkatalIsBIGsBIGsBIGsBIGgggg;;;;sIumsIumsIumsIum. . . . ExSekagkñúg ExSekagkñúg ExSekagkñúg ExSekagkñúg (b)bgðajfaRbtikmµbgðajfaRbtikmµbgðajfaRbtikmµbgðajfaRbtikmµrgrgrgrgkatalIkatalIkatalIkatalIsmanclnkarsmanclnkarsmanclnkarsmanclnkarBIrC¿han BIrC¿han BIrC¿han BIrC¿han EdlkñúgenaHC¿hanTIBIrEdlkñúgenaHC¿hanTIBIrEdlkñúgenaHC¿hanTIBIrEdlkñúgenaHC¿hanTIBIr(ES → E+P)KWCaCMhanKWCaCMhanKWCaCMhanKWCaCMhankMNtkMNtkMNtkMNt;;;;elelelel,,,,ÓnÓnÓnÓn....

CaTUeTAel,Ónrbs;RbtikmµEbbenHtagedaysmIkar³ el,Ón =

t

P

∆∆ ][

= k [ES]

kMhab;rbs;FatukNþal ES smamaRteTAnwgbrimaNs‘ubRsþaEdlmanvtþman ehIyExS ekagtageGayel,ÓnTl;nwgkMhab;rbs;s‘ubRsþamandUcrUbTI27.

k1

k2

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13-46

eBldMbUg el,ÓnekIneLIgya:gqab;rh½sCamYynwgkarekIneLIgénkMhab;s‘ubRsþa. b:uEnþ

enAxagelIkMhab;Cak;lak;mYy mNÐlskmµTaMgGs;RtUvCab;rvl;Gs; ehIyRbtikmµkøayCa Rbtikmµ lMdab;sUnüenAkñúgs‘ubRsþa. m:üavijeTot el,ÓnenAEtdEdleTaHbIkMhab;rbs;s‘ubRsþa ekIneLIgk¾eday. enAcMNucenHb¤elIsBIcMNucenH el,ÓnkMNplitplGaRs½yeTAelIfaetI FatukNþal ES bMEbkelOnb:uNÑa minEmnGaRs½yeTAelIcMnYnm:UelKuls‘ubRsþaEdlmanvtþman enaHeT.

KImIGnuvtþn_ karkMNt;Gayukalrbs;kMNat;rMusaksBenATurIn

(Determining the Age of the Shroud of Turin)

etIGñkviTüasaRsþGackMNt;Gayukalrbs; vtßúburaN Edl)anCIkrukrkrbs;GñkburaNviTüaya:g dUcemþc? RbsinebImaneKcg;lk;rUbcMlak;rWsila carwkmYyeGayGñk ehIyeKR)ab;GñkfavaCavtßúEdl sl;taMgBI1000qñaMmunK>s etIGñkGaceCOCak;favtßú buraNenHBitCamanGayukal1000qñaMmunK>s)an ya:gdUcemþc? etIkMNat;rMusaksBEdlrkeXIjenA BIra:mIténRbeTseGsIubBitCamanGayukalrab;Ban; qñaMEmnrWeT? etIkMNat;rMusB ( shroud )enATurIn (Turin) EdlRtUv)aneKniyayGYtfa CakMNat;ruMsB rbs;RBHeysU‘RKwsþenaH KWCakarBitrWeT? cemøIyeTA nwgsMnYrxagelI b¤sMnYrEdlRbhak;RbEhlKñaenH GacRtUv)anrkeXIjedaykarGnuvtþsIuenTic KImI nigbec©keTskMnt;GayukalénkabUnviTüúskmµ.

rUbTIrUbTIrUbTIrUbTI27272727³ ³ ³ ³ ExSekagtagelExSekagtagelExSekagtagelExSekagtagel,,,,ÓnkMNplitplTlÓnkMNplitplTlÓnkMNplitplTlÓnkMNplitplTl; ; ; ; nwgkMhabnwgkMhabnwgkMhabnwgkMhab;;;;rbsrbsrbsrbs;;;;s‘ubRsþaenAkñúgRbtikmµrgkatalIss‘ubRsþaenAkñúgRbtikmµrgkatalIss‘ubRsþaenAkñúgRbtikmµrgkatalIss‘ubRsþaenAkñúgRbtikmµrgkatalIsGgGgGgGg;;;;sIumsIumsIumsIum. . . .

CMBYkTI13

13-47

briyakasEpndIRtUv)an)aj;bMEbkCaRbfacaMedaykaMrsµIcRkvaLénfamBleRCotcUl y:agx<s;bMput. kaMrsµITaMgenHEdlmanRbPBBIlMhxageRkAmaneGLicRtug NWRtug nigéNVyU: GatUm. RbtikmµmYyd_sMxan;rvagbriyakas nigkaMrsµIcRkvaLKWCakarcab;ykNWRtugeday GatUmGasUtkñúgbriyakas(GuIsUtUb 14N ) eGayCaFatuviTüúskmµ KWGIusUtUb 14C nigGIuRdUEsn. enATIbBa©b;GatUmkabUnminefrbegáItCaTMrg; 14CO2 EdllayCamYykabUnDIGuksIutedIm 12CO2 enAkñúgxül;. enAeBlEdlGIusUtUb12CO2 rgnUvkarbMEbkvabeB©ajPaKl¥it β (e-). el,Ónénkar bMEbkenH ¬vas;edaykarbeBa©jcMnYneGLicRtugkñúgmYyvinaTI¦ eKarBtamsIuenTiclMdab;TImYy. c,ab;el,ÓnénkarsikSakarbMEbkviTüúskmµRtUv)ansresr

el,Ón= KN

Edl K KWCaefrel,ÓnlMdab;TImYy ehIy N CacMnYnéNVy:Urbs; 14C Edlmanvtþman. Bak;kNþalCIviténkarbMEbk t1/2 KW 5,73× 103 qñaM dUcenHtamsmIkar (7) eyIgGacsresr³

123

1021,11073,5

692,0 −−×=×

= yryr

K

GIusUtUb 14C cUleTAkñúgmNÐlCIv³enAeBlEdl CO2RtUv)ancab;ykedayrukçCatieday rsµIsMeyaK. rukçCatiRtUv)ansIuedaystV ehIybeBa©j 14C kñúgTMrg;Ca CO2. enAeBlcugeRkay 14C )ancUlrYmeRcInTidæPaBénvdþkabUn. 14C EdlRtUv)an)at;bg;edaykarbMEbkviTüúskmµRtUv )anbMeBjeLIgvijCaRbcaMedaykarplitGuIsUtUbfµIkñúgbriyakas. kñúglMnaMbMEbk-bMeBjeLIg vijenH lMnwgDINamicRtUv)anbegáIteLIgedaypleFobén 14C eTA 12C enAefrkñúgrUbFatuman CIvit. b:uEnþenAeBlEdledImeQImYyb¤stVmYysøab;GIusUtUb 14C kñúgsarBagÁkayvaelgbMeBj eLIgvijehIy dUcenH pleFobfycuHenAeBl 14CbMEbkxøÜn. karERbRbYldUcKñaenH ekItman eLIgenAeBlEdlGatUmkabUnRtUv)ansßitenAkñúgFüÚgfµ eRbgkateqA eQIenAkñúgdI nigsaksB enAeGsIub. bnÞab;BIry³eBleRcInqñaM eK)anrkeXIjfaéNVy:Urbs;GatUm14C kñúgsaksBman smamaRtticCagmnusSrs;.

enAqñaM1955 elak Willard.F.Libby )anesñIeLIgfaehtukarN_enHGacRtUv)aneRbIedIm,I )a:n;RbmaNry³eBlénGIusUtUb 14C kñúgbdirUbedayELkRtUvkarbMEbkedayKµankarbMeBjeLIg vij. edayeRbIsmIkarTI3 eyIgGacsresr³

ktN

N=0ln

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13-48

EdlN0 nigN KWCacMnYnéNVy:Urbs; 14CmanvtþmanenAt=0 nigt=t erogKña. edayel,Ón énkarbMEbkKWsmamaRteTAnwgcMnYnéNVy:U14C manvtþmansmIkarxagelIGacRtUv)ansresreLIg vijdUcxageRkam³

N

N

kt 0ln

1= ln

1021,1

114 −−×

=yr

ln1021,1

114 −−×

=yr

edaydwgtMél k nigel,ÓnénkarbMEbkrbs;PaKsMNakRss;nigPaKsMNakcas; eyIg GacKNna t EdlCaGayukalrbs;PaKsMNakcas;. bec©keTsd_l¥enHKWBwgEp¥kelIKMnitgay bMput. eCaKC½yrbs;vaGaRs½yelIPaBRtwmRtUvEdleyIgGacvas;)anBIel,ÓnénkarbMEbk. kñúgPaKsMNakRss; pleFob 14C/12C KWRbEhlCa 1/1012 dUcenH]bkrN_edIm,Itamdankar bMEbkviTüúskmµRtUvEtrYsbMput. PaBCak;lakKWBi)akCagcMeBaHPaKsMNakcas; eRBaHvamanpÞúk éNVy:U 14C tictYc. eTaHbICaya:gNak_edaykarkMNt;GayukalkabUnviTüúskmµ)ankøayeTACa ]bkrN_d¾mantMélbMputsMrab;kar)a:n;RbmaNGayukalrbs;vtßúburaN pÞaMgKMnUr nig]bkrN_ manGayukalBI 1000 eTA 50000qñaM. karGnuvtþn_d¾sMxan;fµI²enHénkarkMNt;GayukalkabUnviTüúskmµKWkarkMNt;Gayukal rbs;sMBt;ruMsBenATurIn. enAqñaM1988 TIBiesaFcMnYnbIenAGWr:ub nigshrdæGaemricEdl)aneFVIkar viPaKelIPaKsMNakEdlmanbrimaNticCag 50mg énRkNat;rMusaksB)anbgðajtamkarkMnt; GayukalkabUn 14C faGayurbs;RkNat;rMusaksBenaHKWsßitenAcenøaH 1260 nig 1390 qñaMmun K>s. dUcenHkMNat;rMusaksBenHminEmnCaRkNat;EdlrMuedIm,IbBa©úHsBrbs;RBHeysU‘RKWsþeT. segçbsmIkarKnøwH el,Ón = k [A] x[B] y (1) c,ab;el,Ón. karbUk (x + y )pþl;eGayeyIgnUvlMdab;Rbtikmµ TaMgmUl.

)3(][

][ln 0 kt

A

A= TMnak;TMngrvagkMhab;nigry³eBlkñúgRbtikmµlMdab;TI1.

el,ÓnénkarbMEbkenA t=0

el,ÓnénkarbMEbkenA t=t

el,ÓnénkarbMEbkkñúgPaKsMNakRss;

el,ÓnénkarbMEbkkñúgPaKsMNakcas;

CMBYkTI13

13-49

ln [A] = – kt + ln [A]0 (4) smIkarsRmab;kMNt; k rbs;RbtikmµlMdab;1edayKUrRkab. )5(

693,0

2

1k

t = Bak;kNþalRbtikmµrbs;RbtikmµlMdab;TI1.

)6(][

1

][

1

0

ktAA

+= TMnak;TMngrvagkMhab;nigry³eBlkñúgRbtikmµlMdab;TI2. RTEaAek /−= (8) smIkarGaerjIs EdlbgðajBIPaBBwgBak;énefrel,ÓneTAelI

famBlskmµnigsItuNðPaB. A

TR

Ek a ln

1ln +

−= (9) smIkarsRmab;kMNt;famBlskmµedayKUrRkab.

)10(ln21

21

2

1

−=TT

TT

R

E

k

k a TMnak;TMngrvagefrel,ÓnenAsItuNðPaBBIrxusKña.

segçbehtukarN_nigbBaØtþi 1. el,ÓnRbtikmµKImIKWCabERmbRmYlkMhab;Rbtikrb¤plitplkñúgGMLúgeBl.

el,ÓnRbtikmµminefreT b:uEnþvaERbRbYlCanic©eTAtambERmbRmYlénkMhab;. 2. c,ab;el,Ón)anbgðajBITMnak;TMngel,ÓnRbtikmµeTAnwigefrel,Ón nigkMhab;rbs;RbtikrRtUv

)anelIksV½yKuNsmRsb. efrel,Ón k sMrab;Rbtikmµpþl;eGayERbRbYlEtCamYynwg sItuNðPaB.

3. lMdab;RbtikmµKWCasV½yKuNEdlkMhab;Rbtikrpþl;eGay)anRtUvelIkeLIgtamc,ab;el,Ón. lMdab;énRbtikmµsrubKWCaplbUks½VyKuNEdlkMhab;énRbtikrRtUv)anelIkeLIgtamc,ab; el,Ón. c,ab;el,ÓnniglMdab;RbtikmµminGackMnt;)antamsÞWsüÚemRTIénsmIkarRbtikmµ srub)aneT KWvaRtUv)ankMnt;tamBiesaFn_. sMrab;RbtikmµlMdab;sUnüel,ÓnRbtikmµesµInwg efrel,Ón.

4. Bak;kNþalCIviténRbtikmµ¬ry³eBlcaM)ac;sMrab;eGaykMhab;RbtikrfycuHBak;kNþal¦ GacRtUv)aneRbIkñúgkarkMnt;efrel,Ónrbs;RbtikmµlMdab;TI1.

5. tamRTwsþITgÁic RbtikmµekItmanenAeBlEdlmU:elKulTgÁicKña edaymanfamBlRKb;RKan; EdlehAfafamBlskmµ edIm,IbMEbksm<½n§KImInigcab;epIþmRbtikmµ. efrel,ÓnnigfamBl skmµmanTMnak;TMngCamYyKñaedaysmIkarGaerjIs.

6. smIkarlMnwgsrubsMrab;RbtikmµmYyGacCaplbUkes‘rIénRbtikmµgay ehAfaCMhandMbUg². clnakarRbtikmµ KWCaes‘rIénCMhandMbUg²TaMgGs;sMrab;RbtikmµenaH.

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7. RbsinebICMhanmYyénclnakarRbtikmµPaByWtCagCMhanepSgeToteRcIn vaCaCMhankMNt; el,Ón.

8. katalIkrbegáInel,ÓnRbtikmµedaykarbnßytMélEa. katalIkr GacekItmkvijedaymin pøas;bþÚreT enATIbBa©ab;énRbtikmµ.

9. kñúgkatalIkseGetrU:Esn¬mansar³sMxan;xøaMgNas;kñúgvis½y]sSahkmµ¦katalIkrCaGgÁ- Faturwg nigRbtikrGgÁFaturavb¤]s½µn. kñúgkatalIsGUmU:Esn katalIkrmanpasdUcpasrbs; Rbtikr. Gg;sIumKWCakatalIkrkñúgRbB½n§CIvit.

BaküKnøwH kuMpøicskmµkuMpøicskmµkuMpøicskmµkuMpøicskmµ Activated complex 13-25

famBlskmµ famBlskmµ famBlskmµ famBlskmµ Ea Activation energy 13-25

Rbtikmµb‘ÍmRbtikmµb‘ÍmRbtikmµb‘ÍmRbtikmµb‘Ím:: :: UelKulUelKulUelKulUelKul Bimolecular reaction 13-31

katalIkrkatalIkrkatalIkrkatalIkr Catalyst 13-37

suIenTicKImIsuIenTicKImIsuIenTicKImIsuIenTicKImI Chemical kinetics 13-1

C¿hanC¿hanC¿hanC¿handMbUgdMbUgdMbUgdMbUg² Elementary steps 13-30

GgGgGgGg;;;;sIum sIum sIum sIum Enzyme 13-44

RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITI1111 First-order reaction 13-13

ryryryry³³³³eBlBakeBlBakeBlBakeBlBak;;;;kNþalRbtikmµkNþalRbtikmµkNþalRbtikmµkNþalRbtikmµ Half-life 13-18

FatukNþalFatukNþalFatukNþalFatukNþal Intermediates 13-31

LarIeténRbtikmµLarIeténRbtikmµLarIeténRbtikmµLarIeténRbtikmµ Molecularity of a reaction 13-31

efrelefrelefrelefrel,,,,Ón Ón Ón Ón Rate constant 13-6

CMhankMNtCMhankMNtCMhankMNtCMhankMNt;;;;elelelel,,,,ÓnÓnÓnÓn Rate determining step 13-32

cccc,,,,abababab;;;;elelelel,,,,ÓnÓnÓnÓn Rate law 13-9

clnakarRbtikmµclnakarRbtikmµclnakarRbtikmµclnakarRbtikmµ Reaction mechanism 13-30

lMdablMdablMdablMdab;;;;RbtikmµRbtikmµRbtikmµRbtikmµ Reaction order 13-9

elelelel,,,,ÓnRbtikmµÓnRbtikmµÓnRbtikmµÓnRbtikmµ Reaction rate 13-1

RbtikmµlMdabRbtikmµlMdabRbtikmµlMdabRbtikmµlMdab;;;;TITITITIBIrBIrBIrBIr Second order reaction 13-20

RbtikmµÉkmRbtikmµÉkmRbtikmµÉkmRbtikmµÉkm:::: UelKulUelKulUelKulUelKul Unimolecular reaction 13-31

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sMnYrniglMhat; el,ÓnRbtikmµ sMNYrrMlwkemeron 1. dUcemþcEdlehAfael,ÓnRbtikmµ? etIGVICaxñatrbs;el,ÓnRbtikmµ? 2. etIel,ÓnmFümnigel,ÓnCary³xusKñadUcemþc? etIel,ÓnmYyNakñúgcMeNamel,ÓnTaMgBIr

Edlpþl;eGayeyIgnUvkarvas;el,ÓnedayKµanPaBlMeGog? ehtuGVI? 3. etIkarvas;el,ÓnenAeBldMbUgrbs;RbtikmµmanGtßRbeyaCn_GVIxøH? 4. etIGñkGacesñIeLIgnUvRbtikmµBIrEdlyWtxøaMg¬RbtikmµekItmanrab;éf¶¦ nigRbtikmµBIrEdl

elOnxøaMg ¬RbtikmµEdlekItmanrab;naTIb¤vinaTI¦? lMhat; 5. cUrsresrkenSamel,ÓnRbtikmµdUcteTAenH sMrab;kar)at;bg;RbtikrnigkarkrekItplitpl³

a. H2 (g) + I2 (g) → 2HI (g) b. 5Br– (aq) + BrO3

– (aq)+ 6H+ (aq) → 3Br2(aq) + 3H2O (l)

6. cUrsresrkenSamel,ÓnRbtikmµdUcteTAenH sMrab;kar)at;bg;RbtikrnigkarkekItplitpl³ a. 2H2 (g) + O2 (g) → 2H2O (g) b. 4NH3 (g) + 5O2(g) → 4NO(g) + 6H2O (l)

7. cUrBinitüemIlRbtikmµ 2NO (g) + O2 (g) → 2NO2 (g)

]bmafa kñúgry³eBlmYykñúgeBlRbtikmµ GasUtm:UNUGuksIutmanRbtiikmµkñúgel,Ón 0,066 M/s . ¬k¦ etIGasUtDIGuksIutkekItenAel,Ónb:unµan?

¬x¦ etIm:UelKulGuksIuEsnmanRbtikmµenAel,Ónb:unµan? 8. cUrBinitüemIlRbtikmµ

N2 (g) + 3H2 (g) → 2NH3 (g)

]bmafa kñúgry³eBlmYykñúgeBlRbtikmµ m:UelKulGIuRdUEsnmanRbtiikmµkñúgel,Ón 0,074 M/s . ¬k¦ etIGam:Uj:ak;kekItenAel,Ónb:unµan?

¬x¦ etIm:UelKulGasUtmanRbtikmµenAel,Ónb:unµan? c,ab;el,Ón sMNYrrMlwkemeron 9. dUcemþcEdlehAfac,ab;el,Ónrbs;Rbtikmµ?

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10. dUcemþcEdlehAfalMdab;Rbtiikmµ? 11. etIefrel,Ónrbs;RbtikmµlMdab;TI1 nigRbtikmµlMdab;TI2 manxñatGVIxøH? 12. cUrBinitüemIlRbtikmµlMdab;sUnü³ A → plitpl.

¬k¦ cUrsresrc,ab;el,Ónrbs;Rbtikmµ? ¬x¦ etIefrel,ÓnmanxñatGVI? ¬K¦ cUrKUsRkabénel,ÓnRbtikmµTl;nwg[A] .

13. efrel,Ónrbs;RbtikmµlMdab;1 KW 66 s-. cUrbMEbøgefrel,ÓnenHCanaTI. 14. etIefrel,ÓnGaRs½yeTAelIlkçN³GIVxøHkñúgcMeNamlkçN³dUcteTAenH³

¬k¦ kMhab;Rbtikr ¬x¦RbePTRbtikr ¬K¦ sItuNðPaB. lMhat; 15. c,ab;el,ÓnsMrab;Rbtikmµ

NH4+ (aq) + NO2

–(aq) → N2 (g) + 2H2O (l) tagedayel,Ón = k[NH4

+][ NO2–] enAsItuNðPaB 25 0C ehIyefrel,ÓnesµInwg

3,0×10–4 /M.s. cUrKNnael,Ónrbs;RbtikmµenAsItuNðPaBenH RbsinebI [NO2

–]= 0,080 M nig [NH4+] = 0,26 M.

16. cUreRbITinñn½ykñúgtaragTI2 edIm,IKNnael,Ónrbs;RbtikmµenAeBlEdl [F2]= 0,010 M nig [ClO2]=0,020 M.

17. cUrBinitüemIlRbtikmµ A + B → plitpl tamry³Tinñn½yEdlTTYl)anenAsItuNðPaB Cak;lak;mYy. cUrkMNt;lMdab;EnRbtikmµnigefrel,ÓnRbtikmµ!

18. cUrBinitüemIlRbtikmµ X + Y → Z

tamry³Tinñn½ydUcxageRkamEdlTTYl)anenAsItuNðPaB 360K. ¬k¦ cUrkMNt;lMdab;Rbtikmµ?

[A] [B] el,Ón (M/s)

1,50 1,50 3,00

1,50 2,50 1,50

3,20 × 10–

3,20 × 10–

6,40 × 10–

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¬x¦cUrkMNt;el,ÓndMbUgénkar)at;bg; X enAeBlEdlkMhab;rbs; X =0,30 M nigkMhab;rbs; Y= 0,40M.

19. cUrkMNt;lMdab;RbtikmµsrubEdlel,ÓnxageRkamRtUv)anGnuvtþ. ¬k¦ el,Ón= k[NO2]

2 ¬x¦ el,Ón= k ¬K¦ el,Ón= k[H2][Br2]

1/2 ¬X¦ el,Ón = k[NO]2[O2] 20. cUrBinitüemIlRbtikmµ

A → B

el,ÓnRbtikmµenHesµInwg 1,6 × 10-2 M/s enAeBlEdlkMhab;rbs; A =0,35 M . cUrKNna efrel,Ónrbs;RbtikmµebI ¬k¦ RbtikmµCaRbtikmµlMdab;TImYykñúg A

¬x¦ RbtikmµlMdab;TI2 kñúg A.

21. sIukøÚb‘uytanbMEbkeTACaeGTIELntamsmIkarxageRkam³ C4H8 (g) → 2C2H4 (g)

cUrkMNt;lMdab;Rbtikmµ nigefrel,ÓnedayEp¥kelIsMBaFdUcxageRkam EdlRtUv)ankt;Rta enAeBlEdleKeFVIBiesaFn_enAsItuNðPaB 430 0C enAkñúgepIgmaDefr?

22. Rbtikmµkñúgpas]sµ½ndUcxageRkamRtUv)ansikSaenAsItuNðPaB 2900C edaykarBinitüemIl bMErbMrYlsMBaFCamYynwgeBlenAkñúgepIgmaDefrmYy³

ClCO2CCl3(g) → 2COCl2 (g)

cUrKNnalMdab;Rbtikmµnigefrel,ÓntamTinñn½yteTAenH.

el,ÓndMbUgkñúgkar)at;bg; X (M/s) [X] [Y]

0,053 0,127 1,02 0,254 0,509

0,10 0,20 0,40 0,20 0,40

0,50 0,30 0,60 0,60 0,30

ry³eBl (s) P(C4H8) (mmHg)

0 2000 4000 6000 8000 10000

400 316 248 196 155 122

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TMnak;TMngrvagkMhab;Rbtikrnigry³eBl sMNYrrMlwkemeron 23. cUrsresrsmIkarEdlTak;TgeTAnwgkMhab;Rbtikr A enAcenøaHBI t=0 eTA t=t cMeBaH

RbtikmµlMdab;TI1. cUreGayniymn½yRKb;Bakü ehIynigxñatrbs;vapg. sMnYrdUcKñaenH Edr cMeBaHRbtikmµlMdab;TI2.

24. dUcemþcEdlehAfaBak;kNþalRbtikmµ? cUrsresrsmIkarEdlBak;kNþalRbtikmµrbs; RbtikmµlMdab;TI1 Tak;TgeTAnwgefrel,Ón.

25. cUrsresrsmIkarEdlBak;kNþalRbtikmµrbs;RbtikmµlMdab;TI2 Tak;TgeTAnwgefrel,Ón. etIsmIkarenHxusBIsmIkarlMdab;TImYydUcemþc ?

26. cMeBaHRbtikmµlMdab;TI1 etIvaRtUvcMNayry³eBlb:unµanedIm,IeFVIeGaykMhab;rbs;Rbtikr fycuHrhUtdl; 1/8 énkMhab;edImrbs;va? cUrbgðajcMelIyrbs;Gñkkñúgn½yBak;kNþalRbti kmµnigefrel,Ón k. lMhat;

27. cUrKNnaBak;kNþalRbtikmµrbs;smasFatumYy RbsinebIPaKsMNakcMnYn75%rbs;va RtUvrgRbtikmµbMEbkkñúgry³eBl 60mn. snµtfavaCaesenTiclMdab;TI1.

28. RbtikmµbMEbkedaykMedArbs; PH3 eGayeTACa P4 nig H2 CaRbtikmµlMdab;TI1³ 4PH3 (g) → P4 (g) + 6H2(g)

Bak;kNþalRbtikmµrbs;vaesµInwg 35,0 s enAsItuNðPaB 680 0C. cUrKNna ¬k¦efrel,Ónrbs;RbtikmµlMdab;TImYyrbs;Rbtikmµ ¬x¦eBlevlaEdlRtUvkarcaM)ac;edIm,IbMEbk PH395% .

29. efrel,Ónrbs;RbtikmµlMdab;TI2esµInwg 0,80/M.s enAsItuNðPaB 100C. 2NOBr(g) → 2NO (g) + Br2 (g)

¬k¦ edaycab;epþImBIkMhab; 0,086 M cUrKNnakMhab;rbs; NOBr bnÞab;BIry³eBl 22s. ¬x¦ cUrKNnaBak;kNþalRbtikmµenAeBlEdl[NOBr]0=0,072M nig [NOBr]0=0,054M.

ry³eBl (s) P(ClCO2CCl3) (mmHg)

0 181 513 1164

15,76 12,64 8,73 4,44

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30. efrel,Ónrbs;RbtikmµlMdab;TI2esµInwg 0,54/M.s enAsItuNðPaB 3000C. 2NO2(g) → 2NO (g) + O2 (g)

¬k¦etIvaRtUvkarry³eBlb:unµanedIm,IeFVIeGaykMhab;rbs; NO2¬KitCavinaTI¦ fycuHBI0,62M eTA 0,28M?

famBlskmµ sMNYrrMlwkemeron 31. dUcemþcEdlehAfa famBlskmµ? etIfamBlskmµmantYnaTIGVIkñúgsuIenTicKImI? 32. cUrsresrsmIkarGaerjIs nigkMNt;BaküTaMgGs;? 33. cUreRbIsmIkarGaerjIsedIm,Ibgðajfa ehtuGVI)anCaefrel,ÓnRbtikmµ

¬k¦ fycuHenAeBlEdlfamBlskmµkmµekIneLIg. ¬x¦ ekIneLIgenAeBlEdlsItuNðPaBekIneLIgEdr.

34. cMehHemtankñúgGuksIuEsnKWCaRbtikmµbeBa©jkMedAya:gxøaMg. b:uEnþl,ay]sµ½nemtannig GuksIuEsnGacrkSaTukCamYyKñaedayKµanbMErbMrYlGVIesaH. cUrBnül;.

35. cUrKUsRkabtagfamBlb:Utg;EsülCamYynwgkarvivtþrbs;RbtikmµxageRkam³ a. S (s) + O2 (g) → SO2 (g) ∆H0 = –296,06 kJ b. Cl2 (g) → Cl (g) + Cl(g) ∆H0 = 242,7 kJ

36. Rbtikmµ H + H2 →H2 + H RtUv)aneKsikSaCaeRcInqñaM. cUrKUsfamBlb:Utg;EsülCamYy nwgdüaRkanénkarvitþsMrab;RbtikmµenH.

lMhat; 37. bMErbMrYlénefrel,ÓnCamYysItuNðPaBRtUv)anpþl;eGaykñúgtaragdUcxageRkamcMeBaH

RbtikmµlMdab;TI1 . cUrkMNt;tamRkaPicnUvfamBlskmµrbs;Rbtikmµ. 2N2O5 (g) → 2N2O4(g) + O2 (g)

38. eKeGaykMhab;RbtikrdUcKñarbs;Rbtikmµ CO (g) + Cl2 (g) → COCl2 (g)

T (K) k (s-1)

298 308 318 328 338

1,74 × 10–5

6,61 × 10–5 2,51 × 10–4 7,59 × 10–4 2,40 × 10–3

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el,Ónrbs;vaenAsItuNðPaB 2500C elOnCag 1,50×103 dgénel,Ónrbs;RbtikmµenHenA sItuNðPaB 1500C. cUrKNnafamBlskmµrbs;RbtikmµenH. snµtfaktþaénkarb:HTgÁicKña efr.

39. cMeBaHRbtikmµ ³ NO(g) + O3(g) → NO2(g) + O2(g)

ktþaénPaBjwkjab;KW 8,7×1012 s-1ehIyfamBlskmµrbs;vaesµInwg63kJ/mol. cUrKNna efrel,ÓnRbtikmµenHenAsItuNðPaB 75 0C.

40. efrel,Ónrbs;RbtikmµlMdab;TI1 esµInwg 4,60×10–4 s–1 enAsItuNðPaB 350 0C. Rbsin ebIfamBlskmµrbs;vaesµInwg 104kJ/mol cUrKNnasItuNðPaBenAeBlEdlefrel,Ónrbs; vaesµInwg 8,80 × 10–4 s –1.

41. efrel,Ónrbs;RbtikmµmYycMnYnekIneLIgBIrdgCamYynwgral;karekIneLIgsItuNðPaB100C. snµtfaRbtikmµekItmaneLIgenAsItuNðPaB 295K nwg 305K. etIvaRtUvmanfamBlskmµ b:unµan edIm,IeGayefrel,ÓnekIneLIgdUckarerobrab;xagelI?

42. el,ÓnénkaryMrbs;stVcRgitesµInwg 2,0×102 kñúgmYynaTI enAsItuNðPaB270C b:uEnþ el,Ón enHmantMélRtwmEt 39,6 enAsItuNðPaB 50C. tamry³Tinñn½yenH cUrKNnafamBlskmµ éndMeNIrkaryMenH?

clnkarRbtikmµ sMNYrrMlwkemeron 43. dUcemþcEdlehAfaclnkarRbtikmµ? 44. dUcemþcEdlehAfaC¿handMbUg? dUcemþcEdlehAfam:UelKulLarIetrbs;Rbtikmµ?

cUrcat;fñak;RbtikmµdUcteTAenHfaetIvaCaRbtikmµÉkm:UelKul Rbtikmµb‘Ím:UelKul rWRbtikmµ ETmU:elKul³ a. 2NO + Br2 → 2NOBr b. CH3NC → CH3CN c. SO + O2 → SO2 + O

45. RbtikmµKImIGaccat;fñak;CaÉkm:UelKul b‘Ím:UelKul>>>. ehtuGVI)anCaKµanRbtikmµsUnüm:Uel- Kul? cUrBnül;faehtuGVI)anCaRbtikmµbIm:UelKulminsUvman?

46. etIGVICaC¿hankMNt;el,ÓnRbtikmµ? cUrpþl;sTisPaBerobral;éf¶ edIm,IbgðajBIGtßn½yrbs; {karkMNt;el,Ón}.

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47. smIkarcMehHeGtantageday ³ 2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l)

cUrBnül;faehtuGVI)anCasmIkarenHminGactageGayC¿handMbUgsMrab;RbtikmµenH. 48. cUrbBa¢ak;faetIRbePTKImIxageRkamenH RbePTKImINaEdlminGacEjkecjBIRbtikmµ³

kMpøicskmµ/ plitpl/ FatukNþal. lMhat; 49. c,ab;el,Ónrbs;Rbtikmµ 2NO(g) + Cl2(g) → 2NOCl(g)

tagedayel,Ón= k [NO][Cl 2]. ¬k¦ etIRbtikmµenHCaRbtikmµlMdab;b:unµan? ¬x¦ clnkarEdlmankarcUlrYmBIC¿handMbUg²)anRtUvesñIeLIgsMrab;Rbtikmµ³ NO (g) + Cl2(g) → NOCl2(g) NOCl2 (g) + NO (g) → 2NOCl (g)

RbsinebIclnkarenHRtwmRtUv etIeyIgGacniyay)anfaya:gdUcemþccMeBaHel,ÓneFobén C¿hanTaMgBIrenH?

50. cMeBaHRbtikmµ³ X2 + Y + Z → XY + XZ eKrkeXIjfakalNaeKbegáInkMhab;rbs; X2

BIrdg enaHel,ÓnRbtikmµk¾ekIneLIgBIrdgEdr kalNabegáInkMhab; Y bIdgenaH el,Ón Rbtikmµk¾ekIneLIgbIdgEdr EtebIeKbegáInkMhab;rbs; Z BIrdgeKBuMeXIjmanGVIERbRbYleT.

k> etIGVICac,ab;el,Ónrbs;RbtikmµenH. x> ehtuGVI)anCaeKeFVIkarpøas;bþÚrkMhab;rbs; Z KµanGVIERbRbYleTAelIel,ÓnRbtikmµ?

K> cUreGayclnkarrbs;RbtikmµenHeGayRtUvKñanwgc,ab;el,Ón. 51. c,ab;el,Ónrbs;RbtikmµbMEbkGUsUneTACaGuksIuEsnm:UelKultageday³ 2O3 →3O2

el,Ón ][

][

2

23

O

Ok=

clnkartagRbtikmµenHGactageday O3 O + O2 O + O3 → 2O2

cUrsresrc,ab;el,ÓnBIC¿handMbUgTaMgenH. cUrbBa¢ak;eGayc,as;BIkarsnµtrbs;Gñkkñúg karsresrenH. cUrBnül;faehtuGVI)anCael,ÓnfycuHenAeBlEdlkMhab;rbs;GuksIuEsn ekIneLIg.

52. c,ab;el,Ónrbs;Rbtikmµ 2H2(g) + 2NO(g) → N2(g) + 2H2O(g)

k-1

k1

k2

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KWel,Ón = k[H2][NO]2. etIclnakarNamYykñúgcMeNamclnkarxageRkamenHGacRtwmRtUv cMeBaHel,ÓnEdl)ansegát?

clnkarTI1 H2+ NO → H2O + N ¬yWt¦ N + NO → N2 + O ¬elÓn¦ O + H2 → H2O ¬elÓn¦ clnkarTI2 H2 + 2NO → H2O + N2O ¬yWt¦ N2O + H2 → H2O + N2 ¬elÓn¦ clnkarTI3 2NO ⇋ N2O2 ¬lMnwgelOn¦ N2O2 + H2 → N2O + H2O ¬yWt¦ N2O + H2 → N2 + H2O ¬elOn¦

katalIkr sMNYrrMlwkemeron 53. etIkatalIkrbegáInel,ÓnRbtikmµdUcemþc? 54. etIkatalIkrmanlkçN³dUcemþcxøH? 55. RbtikmµmYyRtUv)aneKdwgfamandMeNIrkarya:gyWtenAsItuNðPaBbnÞb;. etIeyIgGac

begáInel,ÓnRbtikmµedayBuMeFVIkarpøas;bþÚrsItuNðPaB)anEdrb¤eT? 56. etIkatalIsGUm:UEsn nigkatalIseGetr:UEsnxusKñadUcemþc? cUrBnül;. cUrerobrab;

dMeNIrkar]sSahkmµsMxan;² 3EdleRbIkatalIseGetr:UEsn? 57. etIRbtikmµkatalIsGg;sIumCa]TahrN_énkatalIseGetr:UEsnb¤katalIkrGUm:UEsn.

cUrBnül; ? 58. kMhab;rbs;Gg;sIumenAkñúgekasikaCaFmµtamantMéltUcNas;. etIsar³sMxan;CIvsa®sþén

ehtukarN_enHKWGVI?

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lMhat; 59. RbtikmµPaKeRcIn rYmTaMgRbtikmµkatalIsGg;sIum mandMeNIrkarya:gelOnenAsItuNðPaB

x<s;. b:uEnþ sMrab;Gg;sIumpþl;eGaymYy el,Ónrbs;RbtikmµfycuHya:gelOnenAsItuNðPaB BitR)akdmYy. cUrBnül;BIlkçN³enH.

60. cUrBinitüemIlclnakarrbs;RbtikmµkatalIsGg;sIum³ E + S ES ¬elOnenAcMNuclMnwg)

ES → E + P ¬yWt¦ cUrsresrkenSamc,ab;el,Ónrbs;Rbtikmµtamry³kMhab;rbs; E nig S.

lMhat;bEnßm 61. cUreGaynUvviFIBiesaFn_ EdlkñúgenaHel,Ónrbs;RbtikmµxageRkamenH RtUv)anbnþ³

a. CaCO3(s) → CaO (s) + CO2 (g) b. Cl2 (g) + 2Br- (aq) → Br2 (aq) + 2Cl- (aq) c. C2H6(g) → C2H4 (g) + H2 (g) d. C2H5I (g) + H2O (l) → C2H5OH (aq) + H+(aq) + I- (aq)

62. cUreGayktþabYnEdlman\T§iBleTAelIel,ÓnRbtikmµ. 63. efrel,Ónrbs;Rbtikmµ NO2 (g) + CO (g) → NO (g) + CO2(g) esµInwg 1,64×10-6/M.s.

etIkareBalenHmanGVIEdlmineBjelj? 64. enAkñúgdMeNIrkar]sSahkmµEdlTak;TgeTAnwgkatalIkreGetr:UEsn maDrbs;katalIkr

¬katalIkrmanragEsV‘¦esµInwg10,0cm3. cUrKNnaépÞrbs;katalIkr? RbsinebIEsV‘enH bMEbkeTACaEsV‘8tUc²EdlEsV‘nImYy² manmaD 1,25cm3 etIEsV‘TaMgenaHmanépÞsrubb:unµan vij? etIragFrNImaRtTaMgBIrénkatalIkrmYyNamanRbsiT§PaBCag?¬rUbmnþépÞEsV‘4πr2¦

65. cUreRbITinñn½ykñúg]TahrN_TI4 edIm,IkMNt;tamRkaPicnUvBak;kNþalRbtikmµ. 66. Tinñn½ydUcxageRkamRtUv)anRbmUlenAkñúgRbtikmµrvagGasUtm:UNUGuksIutnigGIuRdUEsnenA

sItuNðPaB7000C. 2H2 (g) + 2NO(g) → 2H2O (g) + N2(g)

BiesaFn_ [H2] [NO] el,ÓndMbUg (M/s)

1 2 3

0,010 0,0050 0,010

0,025 0,025 0,0125

2,4 × 10–6

1,2 × 10–6 0,60 × 10–6

k-1

k1

k2

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k> cUrkMNt;lMdab;Rbtikmµ. x> cUrKNnaefrel,Ón. K>cUreGayclnkarRbtikmµEdlRtUvnwgc,ab;el,Ón¬GatUmGuksIuEsnCaFatukNþal¦

67. enAeBlEdlemTIlpUsVatRtUv)aneKdutkMedAedaymanvtþmansUluysüúgGasIut vaman RbtikmµCamYyTwk

CH3OPO3H2 + H2O → CH3OH + H3PO4 RbsinebIRbtikmµekItmaneLIgenAkñúgTwkEdlsMbUrGatUmGuksIuEsn18 GatUmGIusUtUb GuksIu Esn-18RtUv)aneKeXIjmankñúgGasIutpUsVric b:uEnþKµankñúgemtaNuleT. etIvaR)ab;eyIgBI clnkarrbs;RbtikmµdUcemþc?

68. el,Ónrbs;Rbtikmµ CH3COOC2H5(aq) + H2O(l) → CH3COOH(aq) + C2H5OH(aq)

bgðajfavaCaRbtikmµlMdab;TI1 Edlel,Ón = k[CH3COOC2H5] eTaHCaRbtikmµenHCa RbtikmµlMdab;BIrk¾eday. cUrBnül;.

69. cUrBnül;faehtu)anCaelah³PaKeRcInEdleRbIkñúgkatalIsCaelah³qøg. 70. Rbtikmµ³ 2A + 3B → C CaRbtikmµlMdab;TImYycMeBaH A nig B. enAeBlEdlkMhab;dMbUg

[A] = 1,6×10–2 M nig [B] = 2,4 × 10-3 M el,Ónrbs;RbtikmµesµInwg 4,1× 10-4 M/s. cUrKNnaefrel,Ónrbs;RbtikmµenH?

71. RbtikmµbUkRbUmrbs;GaestUnRtUv)ankatalIsedayGasIut³ CH3COCH3 + Br2

−+ ++→+

BrHBrCOCHCHH23

el,Ónénkar)at;bg;RbUmRtUv)aneKvas;sMrab;kMhab;epSg²Kñarbs;GaestUn RbUm nigGuIy:ug H+ enAsItuNðPaBCak;lak;mYy.

k> cUrKNnac,ab;el,Ónrbs;Rbtikmµ. x> cUrkMNt;efrel,Ón

[CH3COCH3] [Br2] [H+] el,Ón)at;bg;RbUm (M/s)

(a) (b) (c) (d) (e)

0,30 0,30 0,30 0,40 0,40

0,050 0,10 0,050 0,050 0,050

0,050 0,050 0,10 0,20 0,050

5,7 × 10–5

5,7 × 10–5 1,2 × 10–4

3,1 × 10–4

7,6 × 10–5

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72. RbtikmµbMEbkrbs; N2O eTACa N2 nig O2 KWCaRbtikmµlMdab;TI1. enAsItuNðPaB 730 0C Bak;kNþalRbtikmµenHesµInwg 3,58 × 103min. RbsinebIsMBaFedImrbs;]sµ½nDIGasUt GuksIutesµInwg 2,10 atmenA 7300C cUrKNnasMBaF]sµ½nsrubbnÞab;BIBak;kNþalRbtikmµ. snµtfamaDrbs;vaenAefr.

73. Rbtikmµ S2O82– + 2I– → 2SO4

2– + I2 mandMeNIrkarya:gyWtenAkñúgsUluysüúgTwk b:uEnþ vaGacRtUv)ankatalIsedayGIuy:ug Fe3+. ebI Fe3+ GaceFVIGuksIutkmµ I– nig Fe2+ GaceFVI erdukmµ S2O8

2– cUrsresrclnaBIrC¿hanrbs;RbtikmµenH. cUrBnül;fa ehtuGVI)anCa RbtikmµminRtUv)ankatalIksyWt?

74. etIefrel,Ónrbs;RbtikmµlMdab;TI3manxñatCaGVI? 75. c,ab;el,ÓnsMrab;RbtikmµlMdab;sUnü A →B KW [A] = [A] 0 – kt. cUrKUsRkab

¬k¦ el,ÓnTl;nwg [A] ¬x¦ [A] Tl;nwg t?

76. EkvmYyrYmmanl,aysmasFatu A nig B. smasFatuTaMgBIrrgRbtikmµbMEbktamsmIkar sIuenTiclMdab;TI1. Bak;kNþalRbtikmµrbs; A KW 50,0min nig B KW 18,0min. RbsinebI kMhab;edImrbs; A nig B esµIKña etIvaRtUvcMNayry³eBlb:unµansMrab;kMhab;AmantMél4dg énkMhab; B.

77. eyagtam]TahrN_TI4 cUrBnül;rebobvas;sMBaFedayEpñkrbs;GasUemtanGnuKmn_eTA nwgeBledayBiesaFn_.

78. c,ab;el,Ónrbs;Rbtikmµ 2NO2 (g) → N2O4(g) KWel,Ón = k[NO2]2. etIbMErbMrYlNakñúg

cMeNambMErbMrYldUcteTAenH EdlGacpþas;bþÚrtMél k? ¬k¦ sMBaFrbs;GasUtDIGuksIutRtUvbegáInBIrdg. ¬x¦ RbtikmµekItmaneLIgkñúgFaturMlaysrIragÁ. ¬K¦ maDrbs;EkvRtUv)anbegáInBIrdg. ¬X¦ sItuNðPaBRtUv)anbnßy. ¬g¦ bEnßmkatalIkreTAkñúgEkv.

79. Rbtikmµrvag G2 nig E2 edIm,IbegáItCa 2GE KWCaRbtikmµbeBa©jkMedA ehIyRbtikmµrvag G2

CamYy X2 edIm,IbegáItCa 2GX CaRbtikmµRsUbkMedA. famBlskmµrbs;RbtikmµbeBa©j

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kMedAFMCagfamBlskmµrbs;RbtikmµRsUbkMedA. cUrKUrfamBlb:Utg;EsülcMeBaHRbtikmµ TaMgBIrenHenAelIRkabEtmYy.

80. enAkñúg]sSahkmµnuyekøEG‘ kmµkreRbIviFanemédEdlFatuviTüúskmµecjBIPaKsMNaknwg Elgman\T§iBlb:HBal;dl;suxPaBbnÞab;Bak;kNþalRbtikmµcMnYn10. cUrKNnaRbPaK rbs;PaKsMNakviTüúskmµ EdlenAsl;bnÞab;BIry³eBlenH.

81. cUrBnül;edaysegçbBI\T§iBlrbs;katalIkreTAelI ¬k¦ famBlskmµ ¬x¦ clnkarRbtikmµ ¬K¦ Gg;tal;BIrrbs;Rbtikmµ ¬X¦ el,ÓnénCMhaneTAmux ¬g¦ el,ÓnénCMhanRtLb;.

82. enAeBlEdleKbEnßms½gásIRKab; 6g eTAkñúgsUluysüúgGasIutkørIRDic 2 M eTAkñúgEkvebEs‘ eKsegáteXIjman]sµ½nGIuRdUEsnkekIteLIg. sMrab;bMErbMrYlnImYy²énbMErbMrYldUcteTA enH¬maDGasIutefr¦ cUrbBa¢ak;fael,Ónvivtþn_]sµ½n H2 faetIekIneLIg fycuH b¤enAdEdl ¬k¦ emSAs½gásI 6g RtUv)aneRbI ¬x¦ s½gásIRKab; 4g RtUv)aneRbI ¬K¦ GasIutGaesTic 2M RtUv)aneRbICMnYsGasIutnIRTic 2M ¬X¦ tMeLIgsItuNðPaBdl;eTA 400C.

83. niyayaedayRtg;eTA c,ab;el,ÓnEdl)anBIlMhat;TI66 eRbI)ancMeBaHEtkMhab;H2Cak;lak; b:ueNÑaH. CaTUeTAc,ab;el,ÓnénRbtikmµmanTMrg;Cael,Ón

][1

][][

22

22

1

HK

NHNOK

+=

Edl K1 nig K2 KWefr. cUrTajykkenSamc,ab;el,ÓneRkamlkçxNçkMhab; H2 TabxøaMg nigx<s;xøaMg. etIlT§plEdl)anBIlMhat;66 RsbCamYyGVIEdleyIgbgðajBIel,Ónkñúg lMhat;enHEdrrWeT?

84. RbtikmµlMdab;TImYy KW35.5PaKrycb;sBVRKb;kñúgry³eBl4,90min enAsItuNðPaB250C. cUrKNnaefrel,Ónrbs;va.

85. RbtikmµbMEbk N2O5 RtUv)ansikSakñúgFaturMlaykabUnetRtakørYenAsItuNðPaBCak;lak;³ 2N2O5 → 4NO2 + O2

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cUrkMNt;tamRkaPicnUvc,ab;el,Ónrbs;Rbtikmµ nigKNnaefrel,Ón.

86. RbtikmµbMEbkedaykMedArbs;N2O5eKarBeTAtamsuIenTicKImIlMdab;TI1. enAsItuNðPaB

450C ExSekag ln[N2O5] Tl;nwg t pþl;nUvemKuNR)ab;Tisén -6,18×10-4 min-1. cUrKNna

Bak;kNþalRbtikmµ. 87. enAeBlEdll,ayemtannigRbUmdak;eGayRtUvBnøW RbtikmµdUcxageRkamekItmaneLIg

ya:gyWt³ CH4(g) + Br2(g) → CH3Br(g) + HBr (g)

cUreGayclnkarrbs;RbtikmµenH. 88. el,Ónrbs;RbtikmµGIuRdUEsnCamYyGasUtedIm,IbegáIt)anCa HI ekIneLIgCamYynwgGaMgtg;

sIuetrbs;BnøWEdlGacemIleXIj. cUrBnül;faetIehtuGVI)anCaehtukarN_enHKaMRTclnkar BIrCMhanEdlpþl;eGay. cUrBnül;ehtuGVI)anCaBnøWGacemIleXIjKµan\T§iBlGVIkñúgkar begáItGatUmGIuRdUEsn.

89. el,OnbMEbkrbs;kabUn-14 kñúgPaKsMNakmYyRkamBIkUnedImeQIKW 0,260 karEbkecjkñúg mYyvinaTI. PaKsMNakeQImYyRkamepSgeTot)anmkBIvtßúbraNmanel,OnbMEbkrbs;va 0,186 karEbkecjkñúgmYyvinaTI. eKeGaydwgfa el,OnbMEbkrbs;FatuviTüúskmµ KWeKarB tamsIuenTiclMdab;1 ehIy t½

14C = 5,73 x 10-4 qñaM . etIeQIvtßúburaNmanGayub:unµan. 90. cUrBinitüemIlC¿handMbUgcMeBaHRbtikmµ X + 2Y → XY2

k> cUrsresrmc,ab;el,ÓnsMrab;RbtikmµenH. x> RbsinebIel,ÓndMbUgsMrab;kMN XY2 esµInwg 3,8 × 10-3 M/s ehIykMhab;dMbUgrbs; X

nig Y esµInwg 0,26 M nig 0,88 M cUrKNnaefrel,Ónrbs;RbtikmµenH. 91. enAeBlfµI²enHGUsUnenAkñúgmNÐlGakass¶b;RtUv)anbMpøajKYreGayRBYy)armÖedayCFCs.

m:UelKul CFC dUcCa CFCl3 GacrgRbtikmµbMEbkedaykaMrsµIUV³ CFCl3 → CFCl2 + Cl

bnÞab;mkra:DIkal;kørmanRbtikmµCamYyGUsUndUcxageRkam³

[N2O5] el,ÓndMbUg (M/s)

0,92 1,23 1,79 2,00 2,21

0,95 × 10–5

1,2 0× 10–5 1,93 × 10–5

2,10 × 10–5

2,26 × 10–5

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Cl + O3 → ClO + O2 ClO + O → Cl + O2

k> cUrsresrsmIkarsrubsMrab;CMhanBIrcugeRkay. x> etI Cl nig ClOmantYnaTICaGIV? K> ehtuGVI)anCara:DIkalPøúyGrKµansar³sMxan;kñúgclnkarRbtikmµ? X> sMeNImYyedIm,Ibnßyra:DIkal;kør KWRtUvbEnßmGIuRdUkabYdUcCaeGtan(C2H6) eTAkñúgmNÐl Gakass¶b;. etIvaGacdMeNIrkar)anya:gdUcemþc?

92. kørGuksIut EdledIrtYya:gsMxan;kñúgkareFVIeGayRsTab;GUsUnkan;EtesþIgeTA )anbMEbkya:g qab;rh½senAsItuNðPaBbnÞb;tamsmIkar³ 2ClO (g) → Cl2 (g) + O2(g) tamry³Tinñn½ydUcxageRkam cUrkMNtlMdab;Rbtikmµ nigKNnaefrel,Ónrbs;Rbtikmµ.

93. smasFatu X rgRbtikmµbMEbklMdab;bImYydMNalKñaBIrdUcteTA³ X → Y Edlmanefr el,Ón k1 nig X → Z Edlmanefrel,Ón k2. pleFob k1/k2 enAsItuNðPaB 400C esµInwg 8,0. etIpleFobenHesµIb:unµanenAsItuNðPaB 3000C?

94. ]bmafarfynþmYymanbMBak;eTAedayRbdab;bMElgkatalIs. ry³eBl5naTIdMbUgbnÞab; BIkarcab;epþImbeBaöHrfynþKWCakarbMBulxøaMgbMput. ehtuGVI?

95. rUbdUcxageRkamtageGayGgÁFatu A RtUv)anbMEbøgeTACa B ehIybnÞab;mkeTot B RtUv)an bMEbøgeTACa C eKehAfaRbtikmµbnþbnÞab;³ A → B → C. edaysnµtfaC¿hanTaMgBIrKWCa lMdab;TImYy cUrKUsRkabenAelIRkaPicEtmYyBIbMErbMrYlén [A], [B] nig[C] CamYyeBl?

96. a) etIGñkGacsnñidæan)anya:gdUcemþccMeBaHfamBlskmµrbs;RbtikmµmYy ebIefrel,Ón rbs;vaERbRbYlya:gxøaMgCamYynwgkarpøas;bþÚrsItuNðPaBtictYc? b) RbsinebIRbtikmµb‘Ím:UelKulekItmanral;eBlEdlm:UelKul A nig B TgÁicKña etIGñkGac niyay)anya:gdUcemþccMeBaHktþatMrg;Tis nigfamBlskmµrbs;RbtikmµenH?

97. c,ab;el,Ónrbs;RbtikmµxageRkamtageday³ el,Ón = k [NO2]2

CO (g) + NO2(g) → CO2(g) + NO (g)

ry³eBl (s) [ClO]

0,12 × 10–3

0,96× 10–3 2,24 × 10–3

3,20 × 10–3

4,00 × 10–3

8,49 × 10–6

7,1 0× 10–6 5,79 × 10–6

5,20 × 10–6

4,77 × 10–6

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cUreGayclnkarsMrab;RbtikmµenH ebIRbePTminefr NO3CaFatukNþal. 98. FatuviTüúskmµBøúytUj:Úmman t1/2 = 2,44 × 105qñaMRtUv)aneKeRbIenAkñúgerGak;T½rnuyekøEG‘ nig

RKab;EbkGatUmic. RbsinebImanGIusUtUb 5,0 × 102g enAkñúgRKab;EbkGatUmictUcmYy etI sarFatuenHRtUvkarry³eBlb:unµanedIm,IeGayvabMEbkmkdl; 1,0 × 102 g EdlCabrimaN tictYcelakkñúgkareFVIeGayRKab;EbkmanRbsiT§PaB?

99. RbtikmµCaeRcInEdlmankarcUlrYmBIkatalIkreGetr:UEsnKWCalMdab;sUnümann½yfael,Ón = k. ]TahrN_mYykñúgkrNIenHKWRbtikmµbMEbkrbs;pUshVIneRkam katalIkrtg;Esþn(W):

4PH3 (g) → P4 (g) + 6H2(g)

eKrkeXIjfaRbtikmµenHminGaRs½yeTAelI[PH3]eT drabNasMBaFrbs;pUshVInFM (≥ 1atm). cUrBnül;.

100. tal;lüÚmrgerdukmµedayesrüÚm (iv) dUcsmIkarxageRkam³ Tl+ + 2Ce4+ → Tl3+ + 2Ce3+

C¿handMbUgkñúgvtþmanénGIuy:ugm:g;kaENstagedaysmIkardUcxageRkam³ Ce4+ + Mn2+ → Ce3+ + Mn3+ Ce4+ + Mn3+ → Ce3+ + Mn4+ Tl+ + Mn4+ → Tl3+ + Mn2+

k> cUrkMNt;katalIkr FatukNþal nigC¿hankMNt;el,Ón RbsinebIc,ab;el,Ónrbs; vaesµInwgel,Ón=k[Ce4+][Mn2+] .

x> cUrBnül;fa ehtuGVI)anCaRbtikmµenHyWt RbsinebIKµankatalIkr. K> etICaRbePTkatalIkrGVI¬GUm:UEsnrWeGetr:UEsn¦?

101. s‘ucRkUs (C12H22O11) rgRbtikmµGIuRdUlIsedIm,IbegáIt)anCaRhVúctUs (C6H12O6) nig KøúykUs (C6H12O6).

C12H22O11 + H2O → C6H12O6 + C6H12O6

RbtikmµenHsMxan;xøaMgNas;kñúg]sSahkmµsárRKab;. dMbUgRhVúctUsEp¥mCags‘ucRkUs. bnÞab;mkl,ayRhúVctUsnigs‘ucRkUsEdleKehAfa sárbMElgmineLIgRkameT dUecñHsár RKab;EdlmansárenHnwgs¥it EtBuMRsYydUcsárEdlmansárs‘ucRkUseT. k> tamTinñn½yxageRkam cUrkMNt;lMdab;Rbtikmµ. x> etIvaRtUvcMNayry³eBlb:unµanedIm,IeFVIGIuRdUlIs 95 %éns‘ucRkUs? K> cUrBnül;fa ehtuGVI)anCac,ab;el,ÓnminbBa©Úl [H2O]EdlCaRbtikrEdr?

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ry³eBl ¬naTI¦ [C12H22O11]

0 60,0 96,4 157,5

0,500 0,400 0,350 0,280

102. efrel,Ónrbs;RbtikmµlMdab;TImYysMrab;RbtikmµbMEbkDIemTIleGETesµInwg 3,2×10-4s-1

enA4500C. (CH3)2O(g) → CH4(g) + CO(g) RbtikmµenHekItmaneLIgenAkñúgEkvmaD efr. dMbUgmanEtDIemTIleGETeTnigsMBaFKW 0,35atm. etIRbB½n§enHmansMBaFb:unµanbnÞab; BIry³eBl 8 naTI?

103. b:UlIeGTIELnRtUv)aneKeRbIenAkñúgkarplitrbs;rbreRbIR)as;CaeRcIn dUcCabMBg;Twk tukáta Ekv GIusULg;GKÁisnI nigeRsamsMbuRt. vaKICab:UlIEm EdlCam:UelKulmanma:s m:UelKulFMbgáeLIgedaym:UelKuleGTIELnCaeRcInP©ab;Kña. CMhandMbUgtageday³

•→ RR k 212 dMNak;kaldMbUg

ra:DIkal; R• manRbtikmµCamYym:UelKuleGTIELn (M) edIm,IbegáItCara:DIkal;mYyepSgeTot R• + M → M1•

Rbtikmµrbs; M1• CamYym:UNUEmmYyeTotbNþaleGaybnøayExSkan;EtEvgeLIg³ M1• + M → pk

M1• dMNak;kaldal C¿hanenHGacbnþrhUtdl;eTAm:UelKulm:UNUEmrab;ry. dMNak;kaldalnwgbBa©b;enAeBl Edlra:DIkal;BIrrYmbBa©ÚlKña³ '''''' MMMM tk −→•+• dMNak;kalbBa©b; FatuepþImEdleRbIenAkñúgRbtikmµb:UlIEmkmµenHKWbg;sUGIulEBGuksIut [(C6H5COO)2]

[(C6H5COO)2] → 2C6H5COO•

enHCaRbtikmµlMdab;TImYy. Bak;kNþalCIvitrbs;bg;sIulEBGuksIutenAsItuNðPaB 1000C KW 19,8naTI . (a) cUrKNnaefrel,ÓnKitCa min-1 rbs;Rbtikmµ. (b) RbsinebIBak;kNþalCIvitrbs;bg;sIulEBGuksIutesµInwg 7.30ema:g b¤438naTIenA 700C cUrKNnafamBlskmµKitCa kJ/mol rbs;RbtikmµbMEbkbg;sIulEBGuksIut. (c) cUrsresrc,ab;el,ÓnsMrab;CMhandMbUgenAkñúgdMeNIrkarb:UlIEmkmµ nigkMNt;Rbtikr plitpl nigFatukNþal.

CMBYkTI13

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(d) etIkñúglkçx½NÐGVIEdlGacCYyeGayExSb:UlIEmenHeLIgEvg? 104. cUUrBinitüCMhandMbUgénRbtikmµbnþbnÞab;xageRkamenH

A B C

a) sresrsmIkarsMrab;bMErbMrYlel,Ónén B

b) cUrTajsmIkarrbs;kMhab; B eRkamlkçxNçefr ( steady-state) eBlEdl B bMEbk eTACa C edayel,ÓndUc A bMEbkeTACa B.

105. eGtaNulKWCasarFatuBulEdlenAeBleyIgeRbIvaelIskMritGacb:HBal;dMNkdegðIm nigtYnaTIebHdUgedaykareRCotERCkeTAkñúgGñkbBaöÚnsarRbsaTénRbB½n§RbsaT. enAkñúg sarBagÁkaymnusS eGtaNulrgemtabUlIsedayGg;sIumGal;kuledGIuRdUEsNaseGay CaGal;edGIut EdlbNþaleGayQWk,alenAeBlhUbRsaeRcIn. a) eyagtamcMenHdwgBIsIuenTicGg;sIum cUrBnül;faehtuGVI)anCakarpwkRsaeRcIn nigelOn eBkGaceFVIeGaysøab;. b) emtaNulKWmankMritBulxøaMgCageGtaNul. vak¾rgemtabUlIsedayGg;sIumGal;kul edGIuRdUEsNaseGayCahVm:al;edGuIt EdlGacbNþaleGayxVak;rWsøab;. fñaMbnSabkar BulemtaNulKWeGtaNul. cUrBnül;BIdMenIrkarenH.

106. sIuenTicénRbtikmµeGetr:UEsnrvagelah³m:aejsüÚm nigGasIutkørIRDic³ Mg(s) + 2H+(aq) Mg2+(aq) + H2O (aq)

GacsikSaedaykarvas;karekIneLIgénsMBaF]s½µnH2GnuKmn_eTAnwgry³eBl(∆P/∆t). c,ab;el,ÓnénRbtikmµRtUv)anpþl;eday³ el,Ón= K[ épÞrbs; Mg]a[H+]b

Tinñn½yBiesaFn_enAsItuNðPaB 320C RtUv)anbgðajdUcxageRkam³ BiesaFn_ [H+](M) épÞrbs; Mg(mm2) ∆P/∆t(torr/s)

1 2 3 4 5

1,0 0,20 0,50 1,0 1,0

70 70 70 140 35

2,07 0,0749 0,446 3,70 0,970

a) cUrkMNt;c,ab;el,ÓnénRbtikmµ ( kMNt;tMél a nig b nigtMélmFümrbs; K)

K1 K2

suIenTicKImI

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b) kñúgkarBiesaFmYy 0,0083gén Mg manRbtikmµCamYyHClelIs. sMBaFcugeRkay nigmaDén]s½µnGIuRdÚEsn KW93,2torr nig69,5ml enAsItuNðPaB320C. cUrKNnalMeGog PaKrysMrab;]s½µn H2 BIsÞWsüÚemRTIénRbtikmµenH.

107. cUrKUsfamBlb:Utg;EsülTl;nwgdüaRkamvivtþn_RbtikmµsMrab;RbtikmµbeBa©jkMedABIr C¿hanEdlC¿hanTI1 CaCMhankMNt;el,Ón.

cMelIylMhat;Gnuvtþn_ 1. el,Ón =

t

OH

t

CO

t

O

t

CH

∆∆=

∆∆=

∆∆−=

∆∆− ][

2

1][][

2

1][ 2224 2. el,Ón = k[S2O8

2-][I-] ; k = 8,1 x 10-2 /M.s 3. 66 s. 4. 2,3 × 10–4 s-1

5. 1,2 × 103 s 6. (a) 3,2 min (b) 2,1 min 7. 240 kJ/mol 8. 3,13 × 10–9 s-1

9. (a) NO2 + CO → NO + CO2 (b) NO3 (c) CMhankMNt;el,ÓnKWCMhanTImYy.

cMelIylMhat;elxKU 6) a. el,Ón

t

OH

t

O

t

H

∆∆

=∆

∆−=

∆∆

−=][

2

1][][

2

1 222

b. el,Ón t

OH

t

NO

t

O

t

NH

∆∆

=∆

∆−=∆

∆−=

∆∆

−=][

6

1][

4

1][

5

1][

4

1 223

8) a. 0,049M/s , b. –0,025M/s 16) el,Ón = K[F2][ClO2] × 2,4×10-27M/s

18) a. el,Ón = K[X2][Y] , b. 0,38M/s 20) a. 0,046s-1 , b. 0,13M-1s-1

22) lMdab;TI 1 28) a. 0,0198s-1 , b. 151s 30) 3,6s , 38) 135Kj/mol

40) 641K 42) 51,0Kj/mol 50) a. el,Ón = K[X2][Y] , b. Z

KWCaRbtikmµlMdab;sUnü c. X2 + Y XY + X ( yWt ) , X + Z XZ (elOn )

52) clnakar I 60) el,Ón ]][[1

21 SEK

KK

−

= 62) sItuNðPaB/ famBlskmµ /

kMhab;Rbtikr/ katalIkr 64) 22,6em2 ; 44,9em2 enAeBlRKab;FBaØaCatipÞúHkan; EtxøaMgépÞénkMeTcFBaØCatiFM 66) a. el,Ón = K[H2][NO] 2 , b. 0.38M-2s-1

c. H2 + 2NO N2 + H2O + O (yWt ) , O + H2 H2O (elOn )

68) enAeBlmanvtþman H2O elIs enaHkMhab;minpøas;bþÚrxøaMgeT 70) 10,7M-1s-1

72) 2,63atm 74) M-2s-1 76) 56,4min 78) b , d ,e , 80) 0,098%

82) a. ekIn b. fy c. fy d. ekIn 84) 0,0896min-1 86) 1,12×103 min

CMBYkTI13

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88) a. I2 RsUbBnWøemIleXIjedIm,IbegáItCaGatUm I , b. BnøW UV RtUvkaredIm,IEjk H2

90) a. el,Ón = K[X][Y] 2 , b. 1,9×10-2M-2s-1 92) RbtikmµlMdab; 2 , 2,4×107M-1s-1

94) edaysarEtma:sIuncuHRtCak; dUcenH]sµ½nEdlbeB©ajmkminmanRbtikmµeBjeljCamYy Rbdab;bMElgkatalIseT 96) a. RbtikmµmanfamBlskmµFM b. famBlskmµKWtUcbMput ehIyktþaEdl)anbgðajKWKµansar³sMxan; 98) 3,9×105 qñaM , 13,100 , a. Mn2+ , b. KµankatalIkr RbtikmµETmU:elKul (Thermolecular) , c. GUmU:Esn

102) 0,45atm 104) a. K1[A]-K 2[B] , b. [b]= (K1/K2)[A]

106) el,Ón = K[épÞrbs; Mg][H+]2 , b. 0,32%