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Chemical Energe.

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Thestandardenthalpychangeofareac1on, Hr,istheheatenergyabsorbedorevolved whenmolarquan..esofreactantsasstated inthethermochemicalequa.onreact togetherunderstandardcondi.ons. Thestandardenthalpychangeof combus1on,Hc,istheenergychangewhen onemoleofasubstanceiscompletelyburnt inexcessoxygenunderstandardcondi.ons.


Hcisusuallyexothermic.

Heatevolvedbyfuel=Heatabsorbedbywater=mcT Hc=(+/)Heatevolved/amountoffuelused

Thestandardenthalpychangeofneutralisa1on, Hn,istheenergychangewhenonemoleof waterisformedduringtheneutralisa.onofan acidandanalkaliunderstandardcondi.ons.


Hnisalways exothermic.
Heatevolved=Heatabsorbedbysolu.on=mcT Hn=Heatevolved/amountofwaterformed

Thestandardenthalpychangeofforma1on, Hfistheenergychangewhenonemoleofa compoundisformedfromitscons%tuent elementsintheirstandardstatesunder standardcondi%ons. Hr=nHf(products)mHf(reactants)

Thebonddissocia1onenergy,Hdissisthe energyrequiredtobreakonemoleofcovalent bondbetweentwoatomsinthegaseousstate.


Hdissisalwaysendothermic.

Hr=BE(bondsbroken)BE(bondsformed) Thestandardenthalpychangeof atomisa1on,Hatistheenergychangewhen onemoleofgaseousatomsisformedfrom itselementunderstandardcondi.ons.


Hatisalwaysendothermic

Therstionisa1onenergyofanelementisthe energyneededtoremoveonemoleofoutermost electronsfromonemoleofgaseousatomsto formonemoleofsinglychargedgaseousca.ons.


Ionisa.on Therstelectronanityistheenergy energiesare changewhenonemoleofelectronsis always addedtoonemoleofgaseousatoms endothermic.

toformonemoleofgaseousanions. ThestandardlaAceenthalpy,HlaBisthe energychangewhenonemoleofanionic Note: compoundisformedfromitscons.tuentHlaBis always gaseousionsatstandardcondi.ons. exothermic

wherez+=chargeonca.onz=chargeonanion r++r=interionicdistancebetweennucleiofthetwoions lz+zl LE r +r + ChargeASrac.onLE SizeofionsASrac.onLE

BornHaberCycletoobtainLE 3Steps 1.Atomisa.onofelements 2.Forma.onofgaseousionsfromatoms(I.E.,E.A.) 3.Forma.onofioniclaZcefromgaseousatoms(LE) Na+(g)+Cl(g)


1stI.E. 1STE.A. LE/HlaS

Na(g)+Cl(g)
Hat

Na(s)+Cl2(g)

Hf

NaCl(s)

Thestandardenthalpychangeofhydra1on, Hhydistheenergychangewhenonemoleof gaseousionsissurroundedbywater molecules,formingasolu.onatinnite dilu.onunderstandardcondi.ons.


lzl Alwaysexothermic,lHhydl r

Thestandardenthalpychangeofsolu1on, Hsolistheenthalpychangewhenonemoleof compoundisdissolvedbysolvent(usually water)suchthatfurtherdilu.onproducesno moreheatchangeunderstandardcondi.ons.

Hofdissolu1onofioniccompounds,Hsol Stage1:Theionsarepulledfaraparttoformseparateions=HlaS Stage2:Watermoleculesarebondedtothegaseousionsforminga solu.on=Hhyd

Hsol=HhydHlaB
NaCl(s)+aq

Stage1 HlaS

Hsol

Na+(aq)+Cl(aq)

Na+(g)+Cl(g)+aq

Stage2 Hhyd

Entropy,S,isthemeasureoforderofasystem.
DisorderEntropy S=SnalSini1alUnits=JK1mol1

Factors

Reason

tempentropy Thehigherthetemperature,themoreenergythe systempossesses.Therearemorewaysto distributetheenergypacketsamongthe par.clesnow.Asaresult,thesystembecomes moredisordered,entropyincreases. Changeinphase Thechangefromsolidtoliquidtogasinvolves SolidLiquidGas moleculeshavingamoredisorderedorrandom Entropy arrangementwithinthechemicalsystem.Hence entropyincreases(S>0).Increaseinentropy fromliquidtogasisgreaterthanforsolidtoliquid asithasagreaterincreaseinvolume. No.ofpar.cles Entropy Thegreaterthenumberofmolecules,themore randomanddisorderedthesystembecomes. Therearemorewaysofarrangingthemolecules. Henceentropyincreaseswhenthenumberofgas moleculesincreases.

Factors Mixingof par.cles (Liquids, Gases) Entropy

Reason Whengasesmix,eachgasexpandstooccupythewholecontainer, leadingtohigherstateofdisorder.Therearenowmorewaysof arrangingthegaseouspar.cleswithinthesystem.Henceentropy increases. Thesamereason(forgases)appliestothemixingofliquidswith similarpolari.es.Hence,entropyincreases.

Dissolving Whenanionicsoliddissolvesinwater,theionsexperienceagreat ofSolids increaseindisorderastheybreakawayfromthesolidlaZce, leadingtoincreaseinentropy.However,thewatermolecules Generally, becomemoreorderedaroundtheionsandexperienceadecrease Entropy inthedisorder,causingadecreaseinentropy.Formostionic solidsthataresolubleinwater,thedisorderingprocessesare usuallydominant.Thustheoveralleectisanincreaseindisorder andentropyofthesystemupondissolvinginwater. in volumeof gases Entropy Agasspontaneouslyexpandstooccupythewholecontainer. Expansionofvolumeleadstoincreaseinentropy.Thisisbecause, inalargervolumeofspace,therearemorewaysforthe moleculestoarrangethemselves.

G=HTS
whereT=temperature(inKelvin) Gisthestandardfreeenergy changeneededtoconvertreactants intoproductsatstandardcondi.ons.
IfG<0,reac.ontakesplacespontaneously. IfG>0,reac.oncannottakeplacespontaneously. IfG=0,reac.onreachesequilibrium. Thetemperatureatwhichthereac.onturns fromnonspontaneoustospontaneouscanbe determinedbyseZngG=0andsolvingforT.

Examples
aremetastableunderallcondi.onsandonlyexistbecause theac.va.onenergyofthereac.onissohigh. e.g.organiccombus.onreac.ons,explosives,some decomposi.onreac.ons e.g.Photosynthesis

nega.ve posi.ve Thesereac.onsarefeasibleatalltemperatures.Reactants

posi.ve nega.ve Thesereac.onsarenotfeasibleandhavetobedriven. posi.ve posi.ve Theseareendothermicreac.onswhichmaynotbefeasible

atroomtemperaturebutwillbecomefeasibleifthe temperatureishighe.g.mel.ng,boiling,decomposi.on reac.ons,electrolysis,dissolving(insomecases). AsTincreases,theTStermbecomeslargeenoughto makeGnega.ve.

nega.ve nega.ve Theseareexothermicreac.onswhicharefeasibleatlow

temperaturese.g.condensa.on,freezing,combina.on reac.ons,electrochemicalcells,precipita.on.Atlow temperatures,theTStermbecomessmallerthanthe Htermwhichisnega.ve,inordertomakeGnega.ve.