Equilibrium

Background
Allchemicalreactionsarereversible,thatis,theendproductsofareactioncanalwaysbe
transformedbackintotheirrespectivestartingmaterials.Onecanconsideraforwardreaction
whichproducesacompound,calledtheproduct,andareversereactioninwhichtheproduct
decomposesbackintotworeactingspecies,orreactants.Inaclosedsystem,bothreactionscan
2+
occursimultaneously.Forexample,limestone(CaCO
)inwaterwillbreakdownintoCa
and
3
3
CO
ions,whicharesolubleinwaterandwilldissolve:

CaCO
(s)
3

2+
2
Ca
+CO
3(aq)

Astheabovereactionisoccurring,thereversereactionistakingplaceatthesametimeCa2+
andCO3ionsarecombiningtorecreatesolidlimestone:
2+
2
Ca
+CO
3(aq)

CaCO
(s)
3

Thereversibilityofchemicalreactionssuchasthedissolutionoflimestoneinwaterisindicated
bya2wayarrowinthechemicalequation.

ChemicalEquilibrium
Chemicalequilibriumdescribesastateinachemicalreactioninwhichtherateofthe
forwardreactionisequaltothatofareversereaction.Atthispoint,theconcentrationsofthe
startingmaterialsandendproductsareheldconstant.Thisisespeciallyimportantinindustrial
applications,astheratioofproductsandreactantscanvarydependingondifferentconditions.
Beingabletounderstandandmanipulatetheequilibriumpointofareactionisessentialtothe
processofchemicalsynthesis.

Asareactionproceeds,therelativequantitiesofproductsandreactantswillbeginto
approachaparticularratio.Thisisduetothefactthatasmoreproductisformed,thereverse
reactionbecomesmoresignificant.Astheconcentrationofreactantsdecreasesandthe
concentrationofproductsincreases,therespectiveratesofreactionapproacheachother.
Eventually,therateoftheforwardreactionisequaltothatofthereversereaction,and
equilibriumisreached.
Figure1.
Reactionratesoftheforwardandreversereactions,overtime

(Baker,2007)[1]

Itisimportanttonotethatwhiletheconcentrationsofreactantsandproductsisheldconstant,
bothchemicalreactionsarestilltakingplace.Becausetheratesofbothreactionsareequal,there
isnonetchangeincomposition.
Whileallreactionsarereversible,notallreactionsexistatequilibriumtheextentto
whichareactionconvertsreactantsintoproductsdependsontheequilibriumpositionforthat
reaction.Takethecombustionofmethane,inwhichtheequilibriumpositionfavorstheproducts
ofthereactionveryheavily,thusallofthereactantsareconsumedandtransformedintoproduct.

Inthesecases,thechemicalequationreflectstheextentoftheforwardreactionwithaforward
arrow:
CH
+2O
CO
+2H
O
4
2
2
2
ModelingEquilibrium
Achemicalreactionsequilibriumconstantisparticularlyimportantasitrepresentsthe
ratioofproductstoreactantsatequilibrium.Inpractice,theseequilibriumconstantsaredefined
intermsofthereactantandproductconcentrations.Assumingageneralchemicalequationfora
reactionatequilibrium:
aA+bB

cC+dD

Theequilibriumconstantintermsofconcentration(Kc)canbecalculatedbythefollowing
equation
c

[D]
K c = [C]

[A]a[B]b

wherethe[X]representsconcentrationofmaterialXatequilibrium.Thisvalueisdirectly
correlatedtotheamountofproductformedbythereactionatequilibriumthehighertheK
c
value,thehighertheratioofproductstoreactants.Asaresult,itispossibletousetabulatedK
c
valuestoquicklycomparetheyieldoftwodifferentreactions.
Forparticularlycomplexcasesofequilibrium,suchasthosewhichinvolvemultiple
phasesofmatter,itisnotpossibletodescribeachemicalequilibriumusingonlyequilibrium
constants.Forthesemultiphaseequilibria,mathematicalequationsandalgorithmsareusedin
ordertosimulateandmodelthesystem.AccordingtoConorMcDonaldandChristodoulos
Floudas,themethodistoobtainequilibriumsolutionscorrespondingtoaglobalminimumof
theGibbsfreeenergyasefficientlyaspossible,forcaseswheretheliquidphaseorphasescanbe

modeledbyNRTL,UNIQUAC,UNIFAC,Wilson,modifiedWilson,andASOGequations[2].
Conditions
Chemicalreactionsaredependentonanumberofenvironmentalfactors,andasaresult,
theirequilibriumsarealsoaffectedbythesefactors.Forinstance,theabovecalculationsforthe
equilibriumconstantK
areeffectivesolongasthephysicalenvironmentisheldconstantforthe
c
system.ChrisTsokosandS.W.Hinkleylistseveralfactorswhichalterachemicalreactions
equilibriumwhenconsideringanonlaboratoryconditions:changesintemperatureand
pressure,presenceofcatalyticagentsandthedegreeofheterogeneityoftheenvironment[3].
Notonlythis,butI.Yamamotoetal.havefoundthatalthoughtheeffectsofmagneticfieldson
achemicalequilibriumofareactionhavebeenthoughttobenegligiblysmallcomparedwith
thoseduetootherintensiveparameterssuchastemperatureandpressure...theequilibrium
pressureandhydrogencompositionforferromagneticLaCo
H
werechangedinthemagnetic
5
x
fieldsof12and26Tatroomtemperature[4].Thiswouldindicatethattherearecertain
scenariosinwhichvaryingthemagneticfieldaroundareactioncaninfluencethecompositionof
anequilibriumtoasignificantdegree.
LeChatliersPrinciple
Chemicalequilibriumisadynamicstatewhileareactionatequilibriummaybestable
withregardstothecompositionofthesystem,changesarestilloccurringthroughoutinorderto
maintainthestablestate.Infact,areactionwillresistanydisturbancetothesysteminorderto
maintainequilibrium.Ifthetemperature,pressure,orconcentrationofanyspeciesofareaction
atequilibriumisaltered,thepositionoftheequilibriumwillshiftinawaythatneutralizesthat
change,thusreestablishingequilibrium.Thedirectioninwhichthepositionofequilibriumshifts

canbepredictedbyLeChatelier'sPrinciple,whichEmilioTorresstatesasfollows:Ifa
chemicalsystemissubjectedtoaperturbation,theequilibriumwillbeshiftedsuchastopartially
undothisperturbation[5].Essentially,ifyouchangetheconcentrationofeitherareactantor
productspecies,thereactionwillproceedinadirectionwhichbalancesoutthatdisturbance.For
example,forthehypotheticalreaction

aA+bB

cC+dD

iftheconcentrationsofeitherAorBareincreased,theequilibriumpositionwillshiftright,in
thedirectionoftheproducts,inordertoincreaseproductconcentrationandreestablish
equilibrium.Viceversa,iftheconcentrationsofCorDareincreased,theequilibriumposition
shiftsleft,andmoreofreactantsAandBareformed.Thisprincipleisinvaluableinsynthesisas
itallowsforthecontrolofthedirectionofachemicalreactionifoneconstantlyremovesthe
productsCandDastheyareproduced,theequilibriumpositionwillconsistentlyshiftrightin
ordertomakemoreproducts.Inthisway,thereactionwillnotreachequilibriumandwill
continuetoproducethedesiredproductforaslongasthereareenoughstartingmaterialsto
react.

References
[1]Baker,A.(2007).Reactionratesoftheforwardandreversereactions,overtime[Online
image].
RetrievedOctober1,2012from
http://wikis.lawrence.edu/display/CHEM/Introduction+to+Equilibrium++Baker

[2]C.M.McDonaldandC.A.Floudas,'"GLOPEQ:Anewcomputationaltoolforthephaseand
chemicalequilibriumproblem,"
Computers&ChemicalEngineering
,vol.21,no.1,1997,
pp.123.
[Online].Available:Inspec,http://inspecdirectservice.theiet.org.[AccessedSept.
24,2012].

[3]S.W.HinkleyandC.P.Tsokos,'"Astochasticmodelforchemicalequilibrium,"
Mathematical
Biosciences
,vol.21,no.12,10,1974,pp.85102.
[Online].Available:Inspec,
http://inspecdirectservice.theiet.org.[AccessedSept.24,2012].

[4]I.Yamamoto,N.Deguchi,M.Yamaguchi,Y.Shimazu,F.IshikawaandS.Miura,
'"Chemical
equilibriuminmagneticfieldsforferromagnetichydrideandhydrogensystem,"
PhysicaB:
CondensedMatter
,vol.246247,no.0,1998,pp.404407.
[Online].Available:Engineering
Village,www.engineeringvillage2.org.[AccessedOct.1,2012].

[5]E.M.Torres,'"EffectofaPerturbationontheChemicalEquilibrium:ComparisonwithLe
Chatelier's
Principle,"
JournalofChemicalEducation
,vol.84,no.3,2007,pp.516.
[Online].Available:
EngineeringVillage,www.engineeringvillage2.org.[AccessedSept.25,2012].