6

ShiftsinEquilibrium:
LeChteliersPrinciple

Introduction
Wheneverachemicalreactionoccurs,thereversereactioncanalsooccur.Asthe
originalreactants,ontheleftsideoftheequation,reacttoformproducts,ontherightside
oftheequation,theproductsalsoreacttoreformthereactants. Eventually,apointis
reachedatwhichtheratesofthesetwoopposingprocessesareequal.Bothreactantsand
productsareusedupasfastastheyareformed,andnofurtherchangeintheamountsof
eithertakesplace.Thereactionsystemhasreachedequilibrium.Theequilibriumpoint
isalwaysthemoststable,lowestenergypointthatthereactionsystemcanreach.
If a reaction system that has reached equilibrium is subjected to a change in
conditions,thentheequilibriumpositionmayalsochange.Anewequilibriumposition
may result if the temperature or pressure of the reaction system is altered, or if the
concentrationofanyofthecomponentsofthereactionsystemischanged.
The new equilibrium position will always be the most stable position for the
reactionsystemunderthenewconditions.Thedirectioninwhichthesystemwillshiftto
reachanewequilibriuminresponsetoachangeinconditionscanbepredictedbyLe
Chteliersprinciple. Thisprinciplehasbeenstatedinmanydifferentways,including
thefollowing:

Ifasystematequilibriumisalteredinanyway,thesystemwillshiftsoas
tominimizetheeffectofthechange.
Whenastressisappliedtoasysteminequilibrium,theconcentrationsof
thereactantswillchangeinsuchawaythatthestressispartiallyrelieved.
Ifasystematequilibriumhasanychangeimposedonit,itwillshiftinthe
directionhelpedmostbythatchange.

Chemistry1BExperiment6 13
 Theprinciplecanbeappliedtothespecificcasesofchangesinconcentration,
pressure,andtemperature.
Concentration:
Considerthereaction:
+
U seW or d6. 0co r l
at er t o

NaCl(s) Na (aq)+Cl (aq)

vi ew Mac nt oshpi ct
i ur e.

(whitesolid)(botharecolorlessinsolution)
Supposewestartwithasaturatedsolutionofsodiumchloride;thatis,wehavea
+
solutionofNa (aq)andCl (aq)inequilibriumwithexcesssolidNaCl.Afterlettingthe
excesssolidsettletothebottomofthecontainer,weaddafewdropsofconcentrated
hydrochloric acid (HCl). The solution immediately becomes cloudy, andmore solid
settlesoutofsolution.
These observations can be explained using Le Chteliers principle. Adding

concentrated HCl initially increases the concentration of Cl ions. The resulting
cloudinessshowsthatmoresolidNaClformed(theequilibriumhasshiftedtotheleft),

therebyusingupsomeoftheaddedCl ions.ThenewequilibriumhasmoresolidNaCl
+
(andalowerconcentrationofNa )thantheoriginalequilibrium. Ifweincreasethe
concentration of one component in any equilibrium system, the system will shift to
minimizethechangebyusingupsomeofthatcomponent.
EveryshiftinequilibriumpositionpredictedbyLeChteliersprinciplecanbe
explained in terms of reaction kinetics. In the above example, increasing the

concentration of Cl ions increases the rate of the reverse reaction (precipitation of
NaCl). Therateoftheforwardreaction(dissolutionofNaCl)isinitiallyunaffected,
becauseitdependsonlyonthesurfaceareaofthesolidNaCl.Atthispoint,thesystemis
no longer at equilibrium, because the two opposing rates are not equal. They will
+
becomeequalagainaftersomeNa andCl ionsareusedup(therebydecreasingthe
reversereactionrate)andmoresolidNaClisformed(therebyincreasingtheforward
reaction rate). Again, the new equilibrium position has more solid NaCl, and less
+
dissolvedNa ions.

Pressure:
Forreactionsinvolvinggases,thetotalpressureofthesystemisanimportant
factor.Considerthereaction:
Use W or
d 6.
0 cor l at
er o
t

2NO2(g) N2O4(g)
vi
ew M aci
n osh
t pi
ct ur
e .

(brownsmog) (colorless)
SupposewestartwithapistonfilledwithabrownmixtureofNO 2 andN2O4
gases.Wesqueezethepistontodecreasethetotalvolumeofthereactionmixture.The
browncolorofthereactionmixturefadestocolorless.

14 Chemistry1BExperiment6
 These observations can also be explained using Le Chteliers principle.
Decreasingthevolumeincreasesthetotalpressureofthesystem,whichdependsonthe
totalnumberofgasphasemolecules.Theresultingcolorchangefrombrowntocolorless
showsthatsomeNO2wasusedup(theequilibriumhasshiftedtotheright).Sincetwo
NO2moleculesareusedtomakeonlyoneN2O4molecule,thenewequilibriumhasfewer
gasphasemolecules, andalowerpressure. Ifweincreasethe totalpressureofany
equilibrium system involving gas phase molecules, the system will reduce its total
pressurebyshiftinginthedirectionthatproducesfewergasphasemolecules.
Theobservationscanalsobeexplainedintermsofreactionkinetics.Increasing
thetotalpressureincreasestherateoftheforwardreactionandtherateofthereverse
reaction.Theshiftarisesbecausethetwoopposingratesincreasebydifferentamounts.
Forsimplicity,letsassumethatthereactionoccursallinonestep,sothattheratelawsof
theopposingreactionsfollowthereactionstoichiometry. Doublingthetotalpressure
doubles the concentrations of both NO2 and N2O4. Since the forward reaction is
2
bimolecular,itsrateisproportionalto[NO2] ,andincreasesbyafactoroffour. The
reversereactionisunimolecular,itsrateisproportionalto[N2O4],andincreasesonlyby
afactoroftwo.Atthispoint,thesystemisnolongeratequilibrium,becausetherateof
theforwardreactionisfasterthantherateofthereversereaction.Therateswillbecome
equalagainaftersomeNO2isusedup(therebydecreasingtheforwardreactionrate)and
moreN2O4isformed(therebyincreasingthereversereactionrate).Thisreasoningalso
showsthattheequilibriumshiftstotheright,thesidewithfewergasphasemolecules,so
thatthereismoreN2O4andlessNO2.

Temperature:
Consideragainthereaction:
exothermic
2NO2(g) endothermic N2O4(g)+heat H=55kJ
(brownsmog) (colorless)
SupposewestartwithaflaskfilledwithabrownmixtureofNO 2 andN2O4
gases. Weplacetheflaskinaboilingwaterbath. Thebrowncolorofthereaction
mixtureintensifies.
Ifwethinkaboutincreasingthetemperatureasaddingheattothereaction
mixture,wecanuseLeChteliersprincipletoexplaintheseobservations.Placingthe
flaskintheboilingwaterbathaddedheattothereactionmixture. Theresultingcolor
changetoadarkerbrowncolorshowsthatmoreNO 2wasformed(theequilibriumhas
shiftedtotheleft),therebyusingupsomeoftheaddedheat.Thenewequilibriumhasa
higher concentration of NO2 (and a lower concentration of N2O4) than the original
equilibrium.Ifweincreasethetemperatureofanyequilibriumsystem,thesystemwill
trytouseuptheaddedheatbyshiftingintheendothermicdirection.
Intermsofreactionrates,increasingthetemperatureincreasestherateofthe
forwardreactionandtherateofthereversereaction. Again,theshiftinequilibrium

Chemistry1BExperiment6 15
arises because the twoopposing rates increase bydifferent amounts. The activation
energy in the endothermic direction is greater than the activation energy in the
exothermicdirection.(Why?)Therefore,therateintheendothermicdirectionismore
sensitive to changes in temperature, and increases more when the temperature is
increased.

Inall ofthese examples, making theopposite change will havethe opposite

effect. Decreasingtheconcentrationofonecomponentshiftstheequilibriumtoform
moreofthatcomponent.Loweringthetotalpressurefavorsthesidetheofreactionthat
has more molecules in the gas phase. And, lowering the temperature favors the
exothermicdirection.
Fourreactionsystemswillbeexaminedinthisexperiment. Ineachofthese,
equilibriumwillbeestablishedandthereactionconditionswillthenbechanged. The
directioninwhichtheequilibriumshiftsinresponsetothischangewillbeestablishedby
observingachangeintheconcentrationofoneofthecomponentsofthereaction.Ifthe
concentrationofthiscomponentincreases,theequilibriumhasshiftedtowarditssideof
theequation.Ifitsconcentrationdecreases,equilibriumhasshiftedtowardstheother
side.

ExperimentalProcedure
SAFETYPRECAUTIONS: WearyourSAFETYGOGGLES.Washyourhandsand
clothingimmediatelywithcopiousamountsofwater,ifyouspillanyofthesolutionson
them.Beparticularlycarefulwiththesilvernitratesolution(PartII)andtheconcentrated
hydrochloricacid(PartIII).Thesilvernitrate(AgNO3)producespermanentblackstains
on skin and clothing; these stains appear gradually after exposure to sunlight. The
concentratedhydrochloricacid(12MHCl)hasirritatingvaporsandishighlycorrosive.
Ifyouspillanyofthisacidonthelabbench,neutralizeitwithsodiumbicarbonatebefore
wipingitup.
WASTE DISPOSAL: Pour the solutions from Part I and Part IV down the drain,
followedbyplentyofrunningwater.PourthesolutionsfromPartIIandPartIIIintothe
INORGANICWASTEcontainersinthefumehood.

PartI.DissociationofAceticAcid
CH3COO(aq)+H+(aq)
Use Wo d
r 6.
0c or l at
er t o

CH3COOH(aq)
vi
ew M aci
nt osh pi
ct ur
e.

aceticacid acetateion hydrogenion

Aceticacidistypicalweakacid.Inwater,itdissociatesslightlytoproducealow
concentrationofions.Unlikeionicsalts,itdoesnotdissociatecompletelywhenaddedto
water. This reaction reaches equilibrium with most of the acetic acid remaining
undissociated (thatis,equilibrium lies tothe left). Acetic acid solutions are weakly

16 Chemistry1BExperiment6
acidic because some hydrogen ions are released into solution. The concentration of
hydrogenionscanbemonitoredwithanacidbaseindicator.
Tosetupthisreactionsystem,youwilladdaceticacidtowatercontainingafew
dropsofbromophenolblueindicator,untilthebluecolorjustchangescolorfromblueto
+ 4
green(onitswaytoyellow). Thegreencolormeansthat[H ]isabout10 M. The
+ +
coloroftheindicatorwilltellyouif[H ]changes.Iftheindicatorturnsyellow,[H ]has
4 +
increasedtomorethan10 M. Iftheindicatorturnsblue,[H ]hasdecreasedtoless
4
than10 M.
Youwillmakeonechangetothisequilibriumsystem:
Addingsolidsodiumacetate(CH3COONa),whichisatypicalionicsalt.

Procedure
Fillabeakerabouthalffullwithwater. Addafewdropsofbromphenolblue
solution.Thenaddaceticacidfromadroppertothebeakeruntiltheindicatorchanges
colorfrombluetogreen.
Addasmallamountofsolidsodiumacetatetothebeakerandstirtodissolveit.
Recordyourobservations.

2+
PartII.FormationoftheFe(SCN) ComplexIon
3+ 2+
Use Wo d
r 6.
0c or l at
er t o

Fe (aq) + SCN (aq) FeSCN (aq)

vi
ew M aci
nt osh pi
ct ur
e.

ferricion thiocyanateion complex

(lightyellow) (colorless) (deepred)
3+
Ferric ion, Fe , reacts with thiocyanate ion, SCN , to form the deep red,
2+ 2+
complex ion, FeSCN . The intensity of the red color will tell you if [FeSCN ]
changes.
Youwillmakethreechangestothisequilibriumsystem:
Addingsolidpotassiumthiocyanate(KSCN),
Adding silver nitrate (AgNO3), which removes one of the ions from the
equilibriumsystembyforminganinsolublesilversalt,and
Heatingandcoolingthesystem.

Procedure
Addapproximately50mLof0.001Mpotassiumthiocyanate(KSCN)solutionto
abeakerorflask.Addabout10dropsof0.1Mferricnitrate[Fe(NO 3)3]solution,and
stir.Thisshouldgivearedcolorwhichisintenseenoughtoseebutnotsointensethat
changesinthecolorcannotbenoticed.
Pourapproximately1/4ofthesolutionintoeachoffourtesttubes.

Chemistry1BExperiment6 17
 Test 1: To one of the test tubes, add a few crystals of solid potassium
thiocyanate(KSCN).Recordyourobservations.
Test 2: To another tube, add several drops of 0.1 M silver nitrate solution
(AgNO3).Recordyourobservations.
Test3: Placeoneoftheremainingtesttubesinabeakerfilledwithiceand
water.Placetheothertesttubeinabeakerhalffilledwithwater,andthenheatthewater
whilesupportingthebeakeronaringstand.Recordyourobservations.

2
III.FormationoftheCoCl4 ComplexIon
2+ 2
Use Wo d
r 6.
0c or l at
er t o

Co (aq) + 4Cl (aq) CoCl4 (aq)

vi
ew M aci
nt osh pi
ct ur
e.

cobaltIIion chlorideion complex

(pink) (deepblue)
2+
SolutionscontainingcobaltIIion,Co ,dissolvedinwaterareordinarilypinkor
red.Thisisthecolorofthecobaltionwhenitisassociatedwithwatermolecules.Inthe
2+ 2
presenceofchlorideion,however,Co reactstoformthebluecomplexionCoCl4 .
Tosetupthisreactionsystem,youwilladdchlorideionstoasolutioncontaining
cobaltIIionsuntilthepinkcolorchangestopurple(inbetweenpinkandblue). The
2+ 2
purplecolorshowsthatbothpinkCo ionsandblueCoCl4 ionsarepresent.Color
2+ 2
changesfrompurpletopinkorfrompurpletobluetellyouif[Co ]and[CoCl4 ]
change.
Youwillmaketwochangestothisequilibriumsystem:
Dilutingthesystemwithwater,and
Heatingandcoolingthesystem.

Procedure
Addabout5to6mLof0.3Mcobaltnitrate[Co(NO 3)2]solutiontoatesttube.
AddconcentratedHClinverysmallportionsuntilthecolorhaschangedtopurple.BE
CAREFUL!!ConcentratedHCl(12Mhydrochloricacid)ishighlycorrosive!
Addabouthalfofthesolutiontoasecondtesttubetokeepforcomparison.
Test1:Tooneofthetubes,veryslowlyaddalittlewater.Addjustenoughwater
toobserveasignificantcolorchange.Recordyourobservations.
Test2:Placethetesttubetowhichthewaterhasbeenaddedinabeakerpartly
filledwithwater.Heatthebeakerwhilesupportingitonaringstand.Comparethecolor
tothatoftheothertesttube.Ifyoulike,tryheatingthistesttubeaswell.Recordyour
observations.

18 Chemistry1BExperiment6
IV.BicarbonateIonCarbonDioxideEquilibrium
+
U s
e W or d6. 0cor at er t
l o

CO2(aqandg)+H2O(l) H (aq)+HCO3 (aq)

vi ew Maci nt
o h
s pi ct
ur e.

carbondioxide water hydrogenion bicarbonateion

Whencarbondioxide(CO2)gasdissolvesinwater,aweaklyacidicsolutionis
+
created, with a small concentration of H ions in solution. You will set up this
equilibrium,startingfromtheothersideofthereaction.Byaddingasmallamountofa
strongacid(HCl)toasolutionofsodiumbicarbonate(NaHCO3),carbondioxidewillbe
produced. Atequilibrium,carbondioxidegaswillbepresentbothwithinthesolution
(aqueousphase)andinthevaporphaseabovethesolution. AsinPartI,shiftsinthe
+
positionoftheequilibriumcanbeobservedbyfollowingtheH ionconcentration.The
indicatorbromothymolbluewillbeused.
Youwilladdhydrochloricacidtoasolutioncontainingbicarbonateionsanda
fewdropsofbromothymolblue,untilthebluecolorjustchangescolorfrombluetogreen
+ 7
(onitswaytoyellow).Thegreencolormeansthat[H ]isabout10 M.Thecolorof
+ +
the indicator will tell you if [H ] changes. If the indicator turns yellow, [H ] has
7 +
increasedtomorethan10 M. Iftheindicatorturnsblue,[H ]hasdecreasedtoless
7
than10 M.
Youwillmakeonechangetothisequilibriumsystem:
Loweringthetotalpressure.

Procedure
ObtainaheavywalledErlenmeyerflaskwithasidearm,arubberstopperthat
fitstheflask,andapieceofthickwalledrubbertubing.Connectoneendofthetubingto
thesidearmoftheflask.Clamptheflaskinplaceonaringstandnearawaterfaucet
withanaspirator.
Add50100mLof0.4Msodiumbicarbonatesolutiontotheflask,andthenadd
afewdropsofbromthymolblue.Add3MHCltotheflaskdropbydrop,justuntilthe
indicatorcolorhasbecomelightgreen. (DonotaddsomuchHClthattheindicator
becomesyellow.)AssoonasenoughHClhasbeenadded,placethestoppersecurelyon
theflask.
Turnontheaspirator,attachtherubbertubingfromthesidearmoftheflaskto
theaspirator,andobservetheeffectofreducingpressureontheequilibriumposition.
Recordyourobservations.

Analysis
Inthedataanalysissectionofyourreport,youshoulddescribehowtheresultsof
eachtestperformedinthisexperimentareconsistentwithLeChteliersPrinciple,and
you should also explain them using your knowledge of reaction kinetics. You may

Chemistry1BExperiment6 19
organizethisdiscussioninanylogicalwayyouchoose.Herearespecificquestionsthat
youshouldansweraspartofyourdiscussionofeachtest:
Howweretheconcentrationsofeachreactioncomponentinitiallyaffectedafteryou
madethespecifiedchange?
Youwereabletoseechangesintheconcentrationofanothercomponent.Asaresult
ofthischange,diditsconcentrationincreaseordecrease? Youranswershouldbe
supportedbytheobservationsrecordedinyourlabnotebook. Didtheequilibrium
shifttotheleftortotheright?
Was the observed shift in equilibrium consistent with Le Chteliers Principle?
Explain.
Useyourknowledgeofkineticstoexplainwhytheequilibriumsystemshiftedinthis
way.
YourdiscussionofthereactionsinPartIIandPartIIImaybealittlebitdifferent,asyou
maynothavebeenabletopredicttheresponsetotemperaturechangesinadvance.For
eachofthesereactions,youshouldbeabletodeducefromyourobservationswhetherthe
forwardreactionisendothermicorexothermic.

PreLabQuestion
UseLeChteliersPrincipletopredicthowthefourequilibriumsystemswillrespondto
thechangesyouwillmake:
CH3COO(aq)+H+(aq)
U s
e W or d6. 0cor at er t
l o

I. CH3COOH(aq)
vi ew Maci nt
o h
s pi ct
ur e.

How will adding sodium acetate (CH3COONa) initially change [CH3COOH],

+
[CH3COO ], and [H ]? How should the equilibrium system respond to this
change?
3+ 2+
U s
e W or d6. 0cor at er t
l o

II. Fe (aq)+SCN (aq) FeSCN (aq)

vi ew Maci nt
o h
s pi ct
ur e.

3+
1. How will adding potassium thiocyanate (KSCN) initially change [Fe ],
2+
[SCN ],and[FeSCN ]? Howshouldtheequilibriumsystemrespondtothis
change?
3+
2. Howwilladdingsilvernitrate(AgNO3) initially change[Fe ],[SCN ],and
2+
[FeSCN ]?Howshouldtheequilibriumsystemrespondtothischange?
2+ 2
Use W or
d 6.
0 cor l at
er o
t

III. Co (aq)+4Cl (aq) CoCl4 (aq)

vi
ew M aci
n osh
t pi
ct ur
e .

2+ 2
Howwilldilutingwithwaterinitiallychange[Co ],[Cl ],and[CoCl4 ]?How
shouldtheequilibriumsystemrespondtothischange?
+
Use W or
d 6.
0 cor l at
er o
t

IV. CO2(aqandg)+H2O(l) H (aq)+HCO3 (aq)

vi
ew M aci
n osh
t pi
ct ur
e .

Howshouldtheequilibriumsystemrespondwhenthepressureislowered?

20 Chemistry1BExperiment6