Prof.

PKB Unit 9: Equilibrium

Introduction
Equilibriumisastateofbalancewheretheopposingforcesareinbalance.Atightropewalker carefullyshiftstheweightofhispoletomaintainhisbalanceonthethinwirehemustwalk.In chemistry,anequilibriumisbalancedbetweentworeactions:oneispushingtowardsproducts andtheotherispullingbacktostartingmaterials. Equilibrium. Allreactionshavemirrorimagereactions,wheretheproductsbecomethereactantsandvisa versa.Forexample,theelectrolysisofwaterformshydrogenandoxygen,andthecombustion ofhydrogengiveswater:2H2+O22H2O&2H2O2H2+O2.Thegraphofthese equationsshowsthattheirenergychangeisoppositeaswell.

Energy

2 H2 + O2 2H2O

Energy

2H2O 2H2 + O2

2 H2 + O2

2 H2 + O2

H2O

H2O

Reaction Progress Reaction Progress Mostofthetimetheendothermicreactionistoodifficultforthereversereactiontohappen withoutalargeinputofenergy,liketheelectricityneededtodecomposewater,andby removingthereactantssothattheexothermicreactioncannothappen.Buttherearemany chemicalsystemswherebothreactionsareoccurringinthemixtureatthesametime.These systemsareinequilibriumwithaforwardreactionbeingtheconventionalreactionwith reactantsontheleft,andareversereactionwhichisthereverse,mirrorimagereaction. Achemicalequilibriumisasystemwiththerateoftheforwardreactionequaltotherateof thereversereaction.Amixtureatequilibriumisinastateofbalancewiththeconcentrations ofthereactantsandproductsbeingconstant,thoughusuallynotequal,becauseoftheequal ratesofchangefortheforwardandreversereactions.Anysystematequilibriumhasthese threequalities:1)theratesoftheforwardandreversereactionsareequal,2)theconcentrations

ofproductsandreactantsareequal(butrarelyequal),and3)boththeforwardandreverse reactionscontinuetotakeplace.Whenachemicalequilibriumisestablished,itiscalleda dynamicequilibriumbecausereactionscontinuetochangetheindividualcomponentsofthe mixture,buttheconcentrationsoramountsofsubstanceremainsconstant. Abalancedchemicalequationshowsthatareactionisinequilibriumbyusingdoublearrows, (sometimes),ratherthanthetraditionalforwardarrow,;forexample, 2NO+O22NO2.Theforwardreactionisthereactionwiththereactantsontheleft,like normalreactions(2NO+O22NO2),andthereversereactionisthereactiongoingbackwards withthereactantsontheright(2NO+O22NO2).

ItsAllintheSamePot Theequilibriumequationsthatareshownanddiscussedinthisunitseparatethesubstances intoreactantsandproducts.Butanequilibrium,infactnearlyallreactions,takesplacesothat allthecomponentsareinthesamereactionvesselorcontainer.Whenthetemperatureorthe pressureoranyotherfactorchanges,thechangeistothereactionsolutionandcanaffectany orallofthesubstancesinthechemicalequation. EqualRatesofReaction Thekeytoanequilibriumisto haveasystemwherethereaction ratesareequal.Thisoccurs becausetheforwardreaction depletestheconcentrationof reactants,whichslowsthe reactionrateoftheforward reaction(recallthattherateofa reactionincreaseswith increasingconcentrationsand decreaseswithdecreasing concentrations).Meanwhile,the reactionrateofthereverse reactionincreasesasthe concentrationoftheproducts increases.

Atsomepointtheconcentrationsofthereactantsandthe productswillreachalevelwheretheforwardrateandthe reverserateareequal.However,theconcentrationofthe reactantsandproductsdonothavetobeequal.

Concentration (M)

2M

Equilibrium is reached & maintained

Concentration vs Time H2 + I2 2 HI

Key HI

1M H2 I2

0M

Time (sec, min, hours, etc.)

StressinganEquilibriumandShiftingtheEquilibrium Whenasystemisatequilibriumtheconcentrationsofreactantsandproductsareequal,but thesystemcanbestressedbyaddingandchangingthesystem,byaddingreactants,products, pressure,heatenergy,orbyremovinganyofthese.Whenanequilibriumsystemisstressed, orchanged,thereactionrateofeithertheforwardorreversereactionchangesandthesystem beginstheequilibriumprocessagain.Ifmorereactantsareaddedthentheforwardreaction willincreaseandmoreproductswillbecreated.Wesaythereactionhasshiftedtothe products,ortotheright.Whenmoreproductsareaddedtoamixtureatequilibriumthe reversereactionrateincreasessomorereactantsarecreated.Wesaythereactionhasshiftedto thereactantsortotheleft.

Concentration (M)

Concentration (M)

Equilibrium

Equilibrium

Reactants
Products

Reactant Added

Adding Reactants to an Equilibrium

Equilibrium Reestablished

Adding Products to an Equilibrium

Reactants
Products

Time (sec, min, hours, etc.) Whenareactantisaddedtoanequilibrium thestresscausestheequilibriumtoshiftto theproductsortotheright.

Time (sec, min, hours, e

Whenaproductisaddedtoanequilibrium thestresscausestheequilibriumtoshiftto thereactantsortotheleft.

Whenthetemperatureincreasesinanequilibriummixturethenthereactionrateofthe endothermicreactionincreasesmorethantheexothermicreaction(thereasonforthisis beyondthescopeofthistext).Abalancedchemicalequationcanindicatethattheforward reactionisexothermicbyaddingtheterm+heattotheproductsorbyshowingtheenthalpy ofreaction,Hrxn,whichwillbenegativeforanexothermicreaction.Foranendothermic reactionthe+heattermisinthereactantsortheenthalpyofreaction,Hrxn,ispositive. Example. Exothermic: 2NO2N2O4+heatHrxn=120kJ/mol Endothermic:heat+2PH3+4O23H2O+P2O5Hrxn=120kJ/mol Soaddingheatorincreasingthetemperaturetothefirstexample,2NO2N2O4+heat,will shiftthereactiontothereactants,becausetheendothermicreversereactionincreasesitsrate morethantheforwardexothermicreaction.Inthesecondexample, heat+2PH3+4O23H2O+P2O5,anincreaseintemperaturewillshiftthereactiontothe products. Pressure Increasingordecreasingpressureinagasmixturecanbeaccomplishedbyaddingor removingmolesofeitherreactantsorproducts.Theshiftintheequilibriumisthesameasif theconcentrationincreasestheproductsorreactants.Thepressurecanalsobechangedby changingthevolumeofthecontainerholdingboththereactantsandproducts.Forthe

Products Added

pressureofagasmixtureatequilibriumtobeincreasedthenthevolumeisdecreased,which increasestheconcentrationofallthegasespresent(sinceconcentrationisn/V,ifthe denominator,V,decreasesthenthefraction,n/V,isalarger).Likewise,adecreaseinpressure byincreasingthevolumewillcausetheconcentrationofallgasestodecrease. Ifalltheconcentrationschangethenbothforwardandbackwardreactionswillincreaseor decreaseinthesameway.Butthesideoftheequilibriumwiththegreatestsumofcoefficients OFGASESwillhavethegreatestchangeinconcentrationandthelargestincreaseinrate. Thus,whenthepressureincreasestheequilibriumshiftstothesideofthereactionwiththe fewestmolesofgasasindicatedbythecoefficientsofthebalancedequation.Forexample,for thereaction2NO2(g)N2O4(g),anincreaseinpressure(causedbyadecreaseinvolume)will shifttheequilibriumtotheproduct,N2O4,ortotheright.Forthedecompositionreactionof solidammoniumchloridetomakegaseousammoniaandhydrochloricacid, NH4Cl(s)NH3(g)+HCl(g),theincreaseinpressurewouldshifttheequilibriumtotheleftor towardsthereactants.Inthisequation,NH4Clisasolidsoitisnotaffectedbypressure. Anotherwaytoaffectpressureistoaddaninertgaslikehelium,argon,xenon,evennitrogen, whicharegasesthatdonotreactwitheitherthereactantsortheproducts.Butwhenthe pressureisincreasedwithagasthatdoesntreact,themolesofthereactantandproductstay thesameandthevolumeofthecontainerstaysthesame.Sothereisnochange.Thereaction rateofeithertheforwardorreversereactions,andtheequilibriumisunchanged. SolidsandLiquidsinanEquilibrium Shiftsinequilibriumarecausedbychangesinreactionratesafterequilibriumhasbeen establishedbythechangeinconcentration,pressure,orheat.Butapuresolid,like undissolvedcarbon,orpureliquid,likeundissolvedchloroform,willnothaveaconcentration. ConsequentlyforequilibriumslikeNH4Cl(s)NH3(g)+HCl(g)willbeunchangedifmore solidNH4Clisaddedorifitisremoved. Furthermore,inawatersolution,oraqueoussolution,thereisnoconcentrationofwater.Water isusuallyinsuchgreatamountsinthemixturethattheadditionofwaterwillnotaffectthe numberofinteractionsbetweenwaterandtheothercomponentsofamixture.Forthisreason changesinwaterconcentration,[H2O],donotaffectequilibria.Forexample,thedissociationof theweakacid,aceticacid,H2O+HCH3COOH3O++CH3COO,doesnotshiftwiththe additionorremovalofwaterinanaqueoussolution(butitwouldmatterinagaseous equilibrium).

Catalyst Acatalystisasubstancethatincreasesthe rateofreactionbychangingthepathwayfor thereaction.Whenthisisgraphedtoshow theactivationenergy(theenergyneededto startareaction)thecatalyticprocessappears asatunnelfromthereactantstothe products.Sinceanequilibriumisboththe forwardandreversereactionthetunnel remainsopenfortheproductstoformthe reactants.Thus,acatalystspeedsupboth reactionsproportionatelyandtheequilibrium remainsunchanged.

Catalyzed Exothermic Equilibrium Energy uncatalyzed equilibrium 2 CO + O2 catalyzed equilibrium - 2 CO2 Reaction Progress

LeChteliersPrinciple Theshiftinequilibriumisremarkablysimilarforthechangesinconcentration,pressure,and temperature.Sowhileunderstandinghowthesefactorschangeinreactionratesindifferent waysandleadtoashiftinequilibrium,itispossibletodevelopsimplerulestodetermine whichwayanequilibriumwillshift.In1884,HenriLeChtelierstatedhisprinciplethat explainedhowanequilibriumbehaveswithachangetotheconcentration,pressure,volume, ortemperatureofasystem:anequilibriumthatisstressedwillrespondbyshiftingthe concentrationstominimizethestresstothesystem.InpracticeLeChteliersPrinciplecanbe paraphrasedto:anincreaseinafactorononesideoftheequilibriumshiftstheequilibrium totheothersideanddecreasingafactorshiftstheequilibriumtowardsthesideofthe decrease.Thisisbecausesometimeschangeshavenoeffectonanequilibrium. RememberthatLeChteliersPrincipleisashortcut,anunderstandingofthechangesinthe reactionratecausedbychangesintheconcentration,pressure,ortemperatureleadstothe sameconclusionsandprovidesamoreaccuratepictureofanequilibrium. StateofMatterandBalancedEquations Asareminder,inabalancedequationthecoefficientisthenumberinfrontofthechemical formula,andthesmallnumberbelowachemicalsymboliscalledthesubscript.Thestateof matterofasubstanceisimportantwhendeterminingtheshiftintheequilibrium,because pressureonlyaffectscompoundsandelementsthataregases.Toindicatethestateofmatter forasubstanceinabalancedequationasetofparentheticallabelsareused:(s)forsolid,(l)for liquid,(g)forgas,and(aq)foraqueoussolution,whichmeansthesubstanceisdissolvedin water.Forexample,theequation2HCl(aq)+Hg(l)H2(g)+HgCl2(s),the2withHClisa coefficientandthe2withH2isasubscript.HClisinawatersolution;Hg,mercury,isaliquid

element;H2,hydrogengasadiatomicmolecule,isagas;andmercury(II)chloride,HgCl2,isa solid.

UsingLeChteliersPrinciple Intheexamplesbelow,LeChteliersPrinciplecausestheequilibriumtoshiftawayfromthe sideoftheaddedconcentration,pressure,orheat.Ifoneofthesefactorsisremovedthe equilibriumshiftstowardsthesidewherethesubstanceorenergyisremoved.Exothermic reactionsproduceheatsoanincreaseintemperatureshiftstheequilibriumawayfromthe product,whileendothermicreactionshaveheatasareactantandincreasedtemperatureshifts thereactiontowardstheproducts.Forsystemsthathavegases,thehighestpressureat equilibriumisthesidewiththelargestsumofcoefficientsforcompoundsthataregases (ignoresubstancesthatarelabeledliquids,solids,andaqueoussolutions),soaddedpressure shiftstheequilibriumawayfromthisside. Example1. ForeachchangelistedbelowfortheequilibriumN2(g)+3H2(g)2NH3(g)+heat,statethe shiftinequilibriumandthechangesinconcentrationtothethreesubstances(theforward reactionisexothermic).

Change
Increase in H2

Shift
shift to products shift to the right shift to reactants shift to the left

[N2]
decrease

[H2]
increase
(increases less than the amount added)

[NH3]
increase increase

Increase in NH3

increase

increase decrease

(but there is less than was added)

Decrease in N2

shift to reactants shift to the left

increase

(decreases less than the amount removed)

decrease

decrease Increase in Temperature shift to reactants shift to the left increase increase
(Temperature increase is not favored by an exothermic reaction)

Increase in Pressure

shift to products shift to the right

decrease

decrease

increase

Change
Decrease in Pressure

Shift
shift to reactants shift to the left

[N2]
increase

[H2]
increase

[NH3]
decrease

Example2. Fortheequilibriumheat+CaCO3(s)CaO(s)+CO2(g)determinetheshiftinthe equilibriumforeachofthechangeslistedbelow. NoticethattheCaCO3andCaOdonothave[]sbecausesolidsdonothaveconcentrations.

Change
Increase in Temperature Decrease in CaCO3 Increase in CaO Increase in Pressure

Shift
shift to products shift to the right no change to equilibrium no change to equilibrium shift to reactants shift to the left

CaCO3
decrease in mass decrease in mass no change increase

CaO
increase in mass no change increase in mass decrease

[CO2]
increase no change no change decrease

Example3.FortheequilibriumCO(g)+H2O(g)CO2(g)+H2(g),determinetheshiftinthe equilibriumforeachchangeandgivethechangesinconcentrationforeachmolecule.

Change

Shift
shift to products shift to the right

[CO]

[H2O]

[CO2]

[H2]
decrease
(but less than removed)

Removal of H2

decrease

decrease

increase

Addition of CO

shift to products shift to the right

increase
(but less than added)

decrease

increase

increase

If the forward reaction is shift to reactants to exothermic, then an shift to the right Increase in Temperature

increase

increase

decrease

decrease

Change

Shift
no change
(the coefficients of gas are equal on both sides of the equilibrium)

[CO]

[H2O]

[CO2]

[H2]

Increase in Pressure

no change

no change

no change

no change

EquilibriumConstantExpression Equilibriumsolutionswillhavehigherconcentrationproductsthanreactantsorahigher concentrationofreactantsthanproducts.Usuallytheequilibriumfavorsonesideofthe equilibriumovertheotherbyquiteabitanditisonlyrarelythattheconcentrationofthetwo willbeequalornearlyequal.Anequilibriumconstantexpression,Keq,isaratioofthe concentrationsoftheproductstotheconcentrationofthereactantsthatprovidesameasureof howfartheequilibriumisontheproductsideoronthereactantside.Fortheequation aA+bBcC+dDtheequilibriumconstantexpressionistheratio:Keq=[C] c[D] d [A]a[B]b Bypluggingintheconcentrationsofthedifferentsubstancestheequilibriumconstant,Keqcan becalculated(theexpressionistheformulaandtheconstantisthevalue).Iftheequilibrium favorstheproducts,thenthenumeratorislargeandKeq>1andiftheequilibriumfavorsthe reactants,thenthedenominatorKeq<1. Also,recallthatchangingamountsofpuresolids,pureliquids,andwaterinwatersolutions didnotshifttheequilibriumandthesesubstancesdonothaveaconcentration.Forthisreason anyofthesetypesofmatterareleftoutofanequilibriumconstant. Example1.WritetheequilibriumconstantexpressionforC(s)+CO2(g)2CO(g). Keq=Products=[CO] 2 =[CO] 2 Reactants[C][CO2][CO2] ThepuresolidC,carbon,isremovedfromtheequilibrium. Thecoefficientbecomesanexponent. Example2.FindtheKeqfortheequilibrium,N2+3H22NH3giventheequilibrium concentrationsat400C:[N2]=0.14M;[H2]=3.5M;&[NH3]=2.5M. Variables |Formula |Work(filledinformula) |Answer&Units 2 2 Keq=x Keq=[NH3 Keq=(2.5M) ] 603 3 3 [N2]=0.14M [N2][H2] (0.14)(0.42) nounitsforKeq [H2]=0.42M [NH3]=2.5M ThisequilibriumfavorstheproductsbecausetheKeq>1.Iftheequationwasreversed 2NH3N2+3H2thenthevalueforKeqforthereversedequationwouldbe1/603=1.7X103.

Example3.TheKeqfortheweakacid,aceticacid,HCH3CO2,is1.8X105findtheconcentration ofHCH3CO2given[H3O+]=1.3X103M,[CH3CO2]1.3X103M.Theequilibriumis: HCH3CO2+H2OH3O++CH3CO2 Variables |Formula |Work(filledinformula) |Answer 5 + 5 3 3 Keq=1.8X10 Keq=[H3 O ][CH3 1.8X10 =(1.3X10)(1.3X10)x=0.094M CO ] [HCH3CO2]=x [H2O][HCH3CO2] x + 3 [H3O ]=1.3X10 M [HCH3CO2]=0.94M 3 [CH3CO2 ]=1.3X10 M Pureliquids,puresolids,andwaterinwatersolutionsdonothaveconcentrationsandarenot includedintheequilibriumconstant,sowaterisremovedfromtheequilibriumexpression. ThisequilibriumfavorsthereactantsbecausethegivenKeq<1. WeakAcidsandKeq OneofthemostcommonusesofKeqistocomparethestrengthsofweakacids.Fortheweak acidHFtheequilibriumisHFH++ForHF+H2OH3O++F.Theweakacidthathasthe greatestconcentrationofH3O+,orH+,thestrongeritwillbe.SincetheconcentrationofH3O+is inthenumerator,thentheweakacidwithaKeqthatislargerandcloserto1willbethe strongeracid.ThiscomparisonissocommonthattheKeqtermischangedtoKa,andcalled theaciddissociationconstant,butitisjustthesameaKeq.Inthetablebelowthetopacidisthe strongestandthebottomacidistheweakest. Some Weak Acids and Their Kas

Weak Acid
oxalic acid, H2C2O4 (first H) sulfurous acid, H2SO3 hydrofluoric acid, HF acetic acid, HCH3CO2 carbonic acid, H2CO3 (first H) hydrocyanic acid, HCN boric acid, H3BO3 hydrogen carbonate ion HCO3 5.8 X 102 1.4 X 102 6.3 X 104 1.8 X 105 4.5 X 107 6.2 X 10-10 5.4 X 1010 4.7 X 1011

Ka

Summary. Areactioninequilibriumhasequalratesoftheforwardreaction,wherereactantschangeto products,andthereversereaction,whereproductschangebacktoreactants.The concentrationoftheproductsandreactantsdoesnothavetobeequalusuallytheyarenot equalbuttheconcentrationsofthereactantsandproductsremainconstantatequilibrium. Moreover,sincechemicalequilibriumisdynamic,theforwardandreversereactionscontinue evenafterequilibriumisreached.Thiscausestheindividualatoms,molecules,andionsto changefromreactantstoproductsandback,buttheconcentrationofreactantsandofproducts remainsconstant. Sincetherateofareactionisincreasedbyincreasingconcentrationsanddecreasedby decreasingconcentrations,theequilibriumisshiftedbychangestoconcentrationof substances,topressureofthegasesinvolvedintheequilibrium,andtochangesinthe temperatureofthereaction.Ifachangecausesthereactiontoincreasetheconcentrationof productsanddecreasetheconcentrationofthereactantsthenwesaythattheequilibrium favorstheproductsorthattheequilibriumshiftstoproductsorthattheequilibriumshiftsto theright.Ifachangeincreasesthereactantconcentrationthentheequilibriumfavorsreactants orisshiftedtothereactantsorisshiftedtotheleft. LeChteliersprincipleisawayofexaminingtheeffectofachangeandstatingthechangein equilibrium.Ifanadditionofasubstanceincreasestheconcentrationofthereactantsthe equilibriumshiftstotheproducts.Iftheadditionofasubstanceincreasestheconcentrationof theproductsthenthereactionshiftstothereactants.Ifasubstanceisremovedfromthe reactantsthenthereactionshiftstothereactantsandshiftstotheproductswhenproductsare removed.Whentemperatureincreases,thereactionshiftstoreactantsforexothermicreactions andtoproductsforendothermicreactions.Also,LeChteliersPrinciplestatesthatfora reactionwithgases,anincreaseinpressureshiftsthereactionawayfromthesidewiththe greatestnumberofgasparticlesinthebalancedequation(ifthenumberofgasparticlesisthe samethenthereisnochangeintheequilibrium).Finally,whenacatalystisusedinan equilibriumreactionbothforwardandreversereactionratesareincreased,sothatthe equilibriumisunchanged. Equilibriumreactionseachhaveanequilibriumexpression,whichisaratioofthe concentrationoftheproductsdividedbytheconcentrationofthereactants: FortheequationaA+bBcC+dDtheequilibriumconstantexpression=Keq=[C] c[D] d [A]a[B]b AvalueforKeqisdeterminedbyusingtheabovegenericexpressionandsubstitutinginthe concentrationofthereactantsandproductsandusingthecoefficientsofthebalancedequation astheexponentsofeachconcentration.WhenKeq<1thentheequilibriumisfavorsthe

reactants,becausethereactantshavethelargestconcentration,andwhenKeq>1thenthe equilibriumfavorstheproductsbecausetheirconcentrationislarger.Thesevaluesprovidea comparisonforequilibriumreactionsincludingthoseofweakacidswherethestrongestweak acidhasalargerKeqthantheweakeracid.

ChemicalEquilibrium 9.Chemicalequilibriumisadynamicprocessatthemolecularlevel.Asabasisfor understandingthisconcept: a.StudentsknowhowtouseLeChateliersprincipletopredicttheeffectofchangesin concentration,temperature,andpressure. b.Studentsknowequilibriumisestablishedwhenforwardandreversereactionratesare equal. c.*Studentsknowhowtowriteandcalculateanequilibriumconstantexpressionforareaction. Starred standards are non-tested standards on the California Standards Test Contributed by Kenneth Pringle Edited by Kathleen Duhl Formatted and Wiki Contribution by Christine Mytko