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ANINTRODUCTIONTOCHEMICAL
EQUILIBRIA

Thispagelooksatthebasicideasunderpinningtheideaofa
chemicalequilibrium.Ittalksaboutreversiblereactionsandhow
theybehaveifthesystemisclosed.Thisleadstotheideaofa
dynamicequilibrium,andwhatthecommonterm"positionof
equilibrium"means.

Reversiblereactions

Areversiblereactionisonewhichcanbemadetogoineither
directiondependingontheconditions.

Ifyoupasssteamoverhotironthesteamreactswiththeironto
produceablack,magneticoxideofironcalledtriirontetroxide,
Fe3O4.

Thehydrogenproducedinthereactionissweptawaybythe
streamofsteam.

Underdifferentconditions,theproductsofthisreactionwillalso
reacttogether.Hydrogenpassedoverhottriirontetroxide
reducesittoiron.Steamisalsoproduced.

Thistimethesteamproducedinthereactionissweptawayby
thestreamofhydrogen.

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Thesereactionsarereversible,butundertheconditions
normallyused,theybecomeonewayreactions.Theproducts
aren'tleftincontactwitheachother,sothereversereaction
can'thappen.

Reversiblereactionshappeninginaclosedsystem

Aclosedsystemisoneinwhichnosubstancesareeither
addedtothesystemorlostfromit.Energycan,however,be
transferredinoroutatwill.

Intheexamplewe'vebeenlookingat,youwouldhaveto
imagineironbeingheatedinsteaminaclosedcontainer.Heat
isbeingaddedtothesystem,butnoneofthesubstancesinthe
reactioncanescape.Thesystemisclosed.

Asthetriirontetroxideandhydrogenstarttobeformed,theywill
alsoreactagaintogivetheoriginalironandsteam.So,ifyou
analysedthemixtureafterawhile,whatwouldyoufind?

Youwouldfindthatyouhadestablishedwhatisknownasa
dynamicequilibrium.Toexplainwhatthatmeans,weare
goingtouseamuchsimplerexample...

Dynamicequilibria

Gettingavisualfeelforadynamicequilibrium

Imagineasubstancewhichcanexistintwoformsablueform
oranorangeformandthateachformcanreacttogivethe
otherone.Wearegoingtoletthemreactinaclosedsystem.
Neitherformcanescape.

Assumethattheblueformturnsintotheorangeonemuchfaster
thantheotherwayround.Inanygiventime,thesearethe
chancesofthetwochangeshappening:

Youcansimulatethisveryeasilywithsomecolouredpapercut
upintosmallpieces(adifferentcolouroneachside),andadice.

Thefollowingaretherealresultsofa"reaction"Ididmyself.I
startedwith16bluesquaresandlookedateachoneinturnand
decidedwhetheritshouldchangecolourbythrowingadice.

Abluesquarewasturnedintoanorangesquare(thebitof
paperwasturnedover!)ifIthrewa4,5or6

AnorangesquarewasturnedintoabluesquareonlyifIthrewa
6whileIwaslookingatthatparticularsquare.

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OnceIhadlookedatall16squares,Istartedtheprocessall
overagainbutobviouslywithadifferentstartingpattern.The
diagramsshowtheresultsofdoingthis11times(plusthe
original16bluesquares).

Youcanseethatthe"reaction"iscontinuingallthetime.The
exactpatternoforangeandblueisconstantlychanging.
However,theoverallnumbersoforangeandofbluesquares
remainremarkablyconstantmostcommonly,12orangeones
to4blueones.

Note:Tobehonest,thiswasaluckyfluke,giventhesmall
numberofsquaresIwasworkingwith.Ifyourepeatedthis
withmuchlargernumberofsquares(say,severalthousand),
youwouldfindthatyourpatternssettleddownquitereliably
closeto75%orangeand25%blue.Ontheotherhand,that
wouldbeseriouslytedious!

Ifyouhadthehugenumbersofparticlestakingpartin
chemicalreactions,theproportionswouldbespoton75%to
25%.

Explainingtheterm"dynamicequilibrium"

Thereactionhasreachedequilibriuminthesensethatthereis
nofurtherchangeinthenumbersofblueandorangesquares.
However,thereactionisstillcontinuing.Foreveryorange
squarethatturnsblue,somewhereinthemixtureitisreplaced
byabluesquareturningorange.

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Thisisknownasadynamicequilibrium.Theworddynamic
showsthatthereactionisstillcontinuing.

Youcanshowdynamicequilibriuminanequationforareaction
bytheuseofspecialarrows.Inthepresentcase,youwould
writeitas:

Itisimportanttorealisethatthisdoesn'tjustmeanthatthe
reactionisreversible.Itmeansthatyouhaveareversible
reactioninastateofdynamicequilibrium.

The"forwardreaction"andthe"backreaction"

Thechangefromlefttorightintheequation(inthiscasefrom
bluetoorangeasitiswritten)isknownastheforwardreaction.
Thechangefromrighttoleftisthebackreaction.

Positionofequilibrium

Intheexamplewe'veused,theequilibriummixturecontained
moreorangesquaresthanblueones.Positionofequilibriumisa
wayofexpressingthis.Youcansaythingslike:

"Thepositionofequilibriumliestowardstheorange."

"Thepositionofequilibriumliestowardstherighthand
side."

Iftheconditionsoftheexperimentchange(byalteringthe
relativechancesoftheforwardandbackreactionshappening),
thecompositionoftheequilibriummixturewillalsochange.

Forexample,ifchangingtheconditionsproducedmorebluein
theequilibriummixture,youwouldsay"Thepositionof
equilibriumhasmovedtotheleft"or"Thepositionofequilibrium
hasmovedtowardstheblue".

Note:Ifyoucanbebothered,trytheeffectonthepositionof
equilibriumofincreasingthechancesofanorangesquare
turningbluefrom1in6to2in6.Inotherwords,allowitto
changeifyouthroweithera5ora6withyourdice.

Reachingequilibriumfromtheotherside

Whathappensifyoustartedthereactionwithorangesquares
ratherthanblueones,butkeptthechancesofeachchange
happeningthesameasinthefirstexample?Thisistheresultof
my"reaction".

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Onceagain,youcanseethatexactlythesamepositionof
equilibriumisbeingestablishedaswhenwestartedwiththe
bluesquares.Yougetexactlythesameequilibriummixture
irrespectiveofwhichsideoftheequationyoustartfrom
providedtheconditionsarethesameinbothcases.

Remember:Youcan'tgetthenumberstoworkoutexactly
usingthissmallnumberofparticles.Chancefluctuationsare
toonoticeable.Onceagain,ifyouusedreallylargenumbers
ofparticles,theequilibriummixturewouldcontain75%
orangeand25%blue.Giventhenumberofparticleswe're
workingwith,the"reaction"isremarkablyclosetothaton
average.

Amoreformallookatdynamicequilibria

Thinkingaboutreactionrates

Thisistheequationforageneralreactionwhichhasreached
dynamicequilibrium:

Howdiditgettothatstate?Let'sassumethatwestartedwithA
andB.

Atthebeginningofthereaction,theconcentrationsofAandB
wereattheirmaximum.Thatmeansthattherateofthereaction
wasatitsfastest.

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AsAandBreact,theirconcentrationsfall.Thatmeansthatthey
arelesslikelytocollideandreact,andsotherateoftheforward
reactionfallsastimegoeson.

Inthebeginning,thereisn'tanyCandD,sotherecan'tbeany
reactionbetweenthem.Astimegoeson,though,their
concentrationsinthemixtureincreaseandtheyaremorelikely
tocollideandreact.

Withtime,therateofthereactionbetweenCandDincreases:

Eventually,theratesofthetworeactionswillbecomeequal.A
andBwillbeconvertingintoCandDatexactlythesamerateas
CandDconvertbackintoAandBagain.

Atthispointtherewon'tbeanyfurtherchangeintheamountsof
A,B,CandDinthemixture.Asfastassomethingisbeing
removed,itisbeingreplacedagainbythereversereaction.We
havereachedapositionofdynamicequilibrium.

Asummary
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Adynamicequilibriumoccurswhenyouhaveareversible
reactioninaclosedsystem.Nothingcanbeaddedtothe
systemortakenawayfromitapartfromenergy.

Atequilibrium,thequantitiesofeverythingpresentinthemixture
remainconstant,althoughthereactionsarestillcontinuing.This
isbecausetheratesoftheforwardandthebackreactionsare
equal.

Ifyouchangetheconditionsinawaywhichchangestherelative
ratesoftheforwardandbackreactionsyouwillchangethe
positionofequilibriuminotherwords,changetheproportions
ofthevarioussubstancespresentintheequilibriummixture.
Thisisexploredindetailonotherpagesinthisequilibrium
section.

Questionstotestyourunderstanding

Ifthisisthefirstsetofquestionsyouhavedone,pleasereadthe
introductorypagebeforeyoustart.YouwillneedtousetheBACKBUTTON
onyourbrowsertocomebackhereafterwards.

questionsontheintroductiontoequilibria

answers

Wherewouldyouliketogonow?

Totheequilibriummenu...

TothePhysicalChemistrymenu...

ToMainMenu...

JimClark2002(modifiedApril2013)

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