PHYSICAL CHEMISTRY

TARGET IIT JEE 2010

XII (ABCD)

CHEMICAL EQUILIBRIUM
CONTENTS
" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY Basicprinciplesofsubjects.Anoutlineofthetopicstobe

discussedinclasslectures.
THE ATLAS Basiclayoutofsubject.Aroutemapcorrelatingdifferentsubtopics
incoherentmanner.
EXERCISE I Introductoryproblemstogetfirsthandexperienceofproblem
solving.
PROFICIENCY TEST Tocheckyounewlyacquiredconcepts.
EXERCISE II Acollectionofgoodproblems.
EXERCISE III TestyourskillsasperNew JEE pattern.
EXERCISE IV AcollectionofprevioustenyearsJEEproblems.
 KEY CONCEPTS

TYPES OF REACTION:
(i) Reversible:
(ii) Irreversible

STATE OF EQUILIBRIUM
Mostofthechemicalreactiondonotgotocompletioninaclosedsystemandattainastateofequilibrium.

There are two approaches to understand nature of equilibrium. The One stems from
thermodynaics.EquilibriumcriteriaisexplainedonthebasisofthermodynamicfunctionlikeH(change
inenthalpy),S(changeinentropy)andG(changeinGibb'sfunction).Atequilibriummacroscopic
propertiesofthesystemlikeconcentration,pressureect.becomeconstantatconstanttemperature.

OtherapproachcomesfromkineticsasdevelopedbyGuldbergandWaage(1863).Equilibriumissaid
tohavereachedinaphysicalorchemicalsystemwhenrateofforwardandreverseprocessesareequal.
Atequilibrium
Rateofforwardreaction=Rateofbackwardreaction.

rf

rate
Stateof
equilibrium
rb

time
Example:
N2(g)+3H2(g)2NH3(g)
StartingwithpureH2andN2asreactionproceedsinforwarddirection.Ammoniaisformed.Atinitially
conc.ofH2andN2dropsandattainasteadyvalueatequilibrium.Ontheothershandconc.ofNH3
increasesandatequilibriumattainsaconstantvalue.
Concentrationtimegraphsfor
concentration.

[H2]
[N2]
[NH3]

t
fig(1)

CHEMICAL EQUILIBRIUM [2]

IMPORTANT CHARACTERISTIC OF EQUILIBRIUM
(i) Equilibriumispossibleonlyinclosedsystem.
(ii) Therateofforwardprocessatequilibriumisequaltorateofbackwardprocess.
(iii) Allmeasurablepropertiesofsystemremainconstantovertime.Stateofchemicalequilibriumis
characterisedbyequilibriumconstant.Equilibriumconstanthaveconstantvalueatagiven
temperature.
(iv) Atequilibriumentropyofuniverseismaxmized.
(v) Both,KineticandThermodynamicstheoriescanbeinvokedtounderstandtheextenttowhich
areactionproceedtoforwarddirection.e.g.Ifextentofreactionistoolargeforforwarddirection
(equilibriumistiltedheavilytoforwarddirection)than
(a) Specificrateofforwardreaction>>>specificrateofbackwardreaction
(b) Gibb'sfunctionofproductisvarysmallascomparedtoGibb'sfunctionofreactant.

LAW OF CHEMICAL EQUILIBRIUM OR MASS ACTION (By Guldberg and Waage)

Ageneralequationforareversiblereactionmaybewritten
mA+nBlxC+yD
rateofreactionininforwarddirection(rf)[A]m[B]m;rf=kf[A]m[B]m
rateofreactionininforwarddirection(rb)[C]x[D]y;rb=kb[C]x[D]y
Atequilibrium,rf=rb

[C ]x [ D ] y
KeqorKc= whereKc=kf/kb
[ A ]m [ B]m
whereweuse[]toindicate"molarconcentration."

Note : WeshouldcalculatethevalueofKfromtheactivitiesofthereactantsandproductsratherthanfromtheir
concentrations.However,theactivityofadilutesoluteisusefullyapproximatedbyitsmolarconcentration,
sowewillusemolarconcentrations.However,forgaseswecanusemolarconcentrationsofgasesand
partialpressureinourequilibriumcalculations,Theactivityofapuresolidorpureliquidisconstant,and
theactivityofasolventinadilutesolutionisalsoconstant.Thusthesespecies(solids,liquids,andsolvents)
areomittedfromreactionsquotientsandequilibriumcalculations.

o o
UNIT OF EQUILIBRIUM CONSTANT (K C , K C , K P & K P )
Wehavealreadynotedthatthevalueofanequilibriumconstanthasmeaningonlywhenwegivethe
correspondingbalancedchemicalequation.Itsvaluechangesforthenewequationobtainedbymultiplying
ordividingtheoriginalequationbyanumber.Thevalueforequilibriumconstant,KCiscalculatesubstituting
theconcentrationinmol/LandforKPbysubstitutingpartialpressureinPa,kPa,etc.inatm.Thus,units
ofequilibriumconstantwillturnouttobeunitsbasedonmolarityorpressure,unlessthesumofthe
exponentsinthenumeratorisequaltothesumoftheexponentsinthedenominator.Thusforthereaction:
H2(g)+I2(g)l2HI,KCandKPdonothaveanyunit
N2(g)+3H2(g)l2NH3,KChasunit(mol/L)2andKPhasunitbar2or
N2O4(g)l2NO2,KChasunitmol/LandKPhasunitbar
However,thesedaysweexpressequilibriumconstantsindimensionlessquantitiesbydeviding
concentrationby1Mandpartialpressureby1bar.

* Relationship between KP & KC

KP=KC(RT)ng

CHEMICAL EQUILIBRIUM [3]

TYPE OF EQUILIBRIUM
(a) Homogeneous chemical equilibria
Ahomogeneousequilibriumisequilibriumwithinasinglephasei.e.whenphysicalstateofallthe
reactantsandproductaresame.
(ii) Liquid phase homogeneous equilibrium
Example: (i) I2(aq)+ I (aq)l I3 (aq)

[I 3 (aq)]
Eq.constantsis K=
[ I 2 (aq )][I ( aq)]

(iii) Homogeneous equilibria in gases

Example: (i) C2H6(g)lC2H4(g)+H2(g)
Eq.constantsis
[C 2 H 4 O)][H 2 ] [PC2H 4 ][PH 2 ]
KC= [C 2 H 6 (g )] KP= [PC2H6 ]

[]representsconcentration PC2H 4 &otherarepartialpressureatequilibrium

inmol/litreatequilibrium

(ii) 3O2(g)l 2O3(g)

Eq.constantsis
[O 3 ]2 PO2 3
KC= KP=
[O 2 ]3 PO3 2

(b) Hetrogeneous equilibria

Ifreactantsandproductarefoundintwoormorephases,theequilibriadescribingthemiscalled
hetrogeneousequilibrium.
Example: CaO(s)+ CO2(g)l CaCO3(s)
1 1
Eq.constantsis KP= KC=
P [ CO 2 (g )]
CO 2

CHARACTERSTICS OF EQUILIBRIUM CONSTANT

(i) Theexpressionforequilibriumconstant,Kisapplicableonlywhenconcentrationsofthereactantsand
productshaveattainedtheirequilibriumvaluesanddonotchangewithtime.
(ii) Thevalueofequilibriumconstantisindependentofinitialconcentrationofthereactantsandproduct.
(iii) Equilibriumconstanthasoneuniquevalueforaparticularreactionrepresentedbyabalancedequationat
agiventemperature.
(iv) Theequilibriumconstantforthereversereactionisequaltotheinverseoftheequilibriumconstantforthe
forwardreaction.
H2(g)+I2(g) 2HI(g)
PHI 2
Kp= P .P ;2HI(g) H2(g)+I2(g)
H2 I2

1
KP'= K
P

CHEMICAL EQUILIBRIUM [4]

(v) TheequilibriumconstantK,forareactionisrelatedtotheequilibriumconstantofthecorresponding
reactionwhoseequationisobtainedbymultiplyingordividingtheequation.
1 1
H2(g)+I2(g) 2HI(g) ; H2(g)+ I2(g) HI(g)
2 2
PHI
KP"= P1/ 2 .P1/ 2 = K p
H2 I2

(vi) Ifreactionisperformedissteps
A B;overallreaction
Step-1 :A(g) C(g)+D(g) K p1
Step-2 :C(g) E(g) K p2

Step-3 :D(g)+E(g) B(g) K p3

A(g) B(g) Kp thenKp= K p1 . K p2 . K p3

APPLICATION OF EQULIBRIUM CONSTANT.
Nowwewillconsidersomeapplicationsofequilibriumconstantanduseittoanswerquestionlike:
(i) predictingtheextentofareactiononthebasisofitsmagnitude.
(ii) predictingthedirectionofthereaction,and
(iii) calculatingequilibriumconcentration.
(i) Predicting the extent of a reaction
Themagnitudeofequilibriumconstantisveryusefulespeciallyinreactionsofindustrialimportance.An
equilibriumconstanttellsuswhetherwecanexpectareactionmixturetocontainahighorlowconcentration
ofproduct(s)atequilibrium.(Itisimportanttonotethatanequilibriumconstanttellsusnothingaboutthe
rateatwhichequilibriumisreached).IntheexpressionofKCorKP,productoftheconcentrationsof
productsiswritteninnumeratorandtheproductoftheconcentrationsofreactantsiswrittenindenominator.
Highvalueofequilibriumconstantindicatesthatproduct(s)concentrationishighanditslowvalue
indicatesthatconcentrationoftheproduct(s)inequilibriummixtureislow.
Forreaction,H2(g)+Br2(g)l2HBr(g),thevalueof
(PHBr ) 2
KP= 18
(PH )(PBr ) =5.410
2 2
Thelargevalueofequilibriumconstantindicatesthatconcentrationoftheproduct,HBrisveryhighand
reactiongoesnearlytocompletion.
Similarly,equilibriumconstantforthereactionH2(g)+Cl2(g)l2HCl(g)aty300Kisveryhighand
reactiongoesvirtuallytocompletion.
[ HCl ]2
KC= =4.01031
[ H 2 ][Cl 2 ]
Thus,largevalueofKPorKC(largerthanabout103),favourtheproductsstrongly.Forintermedicate
valuesofK(approximatelyintherangeof103to103),theconcentrationsofreactantsandproducts
arecomparable.Smallvaluesofequilibriumconstant(smallerthan103),favourthereactantsstrongly.
At298Kforreaction,N2(g)+O2(g)l2NO(g)
[ NO ]2
KC= =4.81031
[ N 2 ][O 2 ]
TheverysmallvalueofKCimpliesthatreactantsN2andO2willbethepredominantspeciesinthe
reactionmixtureatequilibrium.
CHEMICAL EQUILIBRIUM [5]
(ii) Predicting the direction of the reaction.
Theequilibriumconstantisalsousedtofindinwhichdirectionanrabidityreactionmixtureofreactants
andproductswillproceed.Forthispurpose,wecalculatethereactionquotient,Q.Thereactionquotient
isdefinedinthesamewayastheequilibriumconstant(withmolarconcentrationstogiveQC,orwith
partialpressuretogiveQP)atanystageofreaction.Forageneralreaction:
aA+bBlcC+dD
[C]c [D]d
QC=
[A]a [B]b
Then, ifQC>Kc,thereactionwillproceedinthedirectionofreactants(reversereaction).
ifQC<Kc,thereactionwillmoveinthedirectionoftheproducts
ifQC=Kc,thereactionmixtureisalreadyatequilibrium.
Inthereaction,H2(g)+I2(g)l2Hl(g),ifthemolarconcentrationsofH2,I2andHIare0.1molL1
respectivelyat783K,thenreactionquotientatthisstageofthereactionis
[ HI]2 (0.4) 2
QC= = =8
[ H 2 ][I 2 ] (0.1)(0.2)
KCforthisreactionat783Kis46andwefindthatQC<KC.Thereaction,therefore,willmovetoright
i.e.moreH2(g)andI2(g)willreacttoformmoreHI(g)andtheirconcentrationwilldecreasetill
QC=KC.

(iii) Calculating equilibrium concentration.

(a) A + B C
attimet=0 a b
atequlb. ax bx x

x
PT
(x / V ) a b x
Kc= ; Kp=
a x b x ax b x
PT PT
V V a b x a b x

(b) Equilibriumconstantexpressionsintermof''
PCl5(g)PCl3(g)+Cl2(g)
Initialpartialpr. 1
At.Eq. 1
[p PCl3 ( g) ][ pCl2 ( g) ] 2 1
KP= ; KC=
p [ PCl5 ( g )] 1 V

. PT
KP=
1 (1 )

2
KP= P
1 2 T

CHEMICAL EQUILIBRIUM [6]

(IV) Degree of dissociation in terms of molar mass and vapour density

(a) A(g) l nB(g)

MT M O DT DO
or
M O ( n 1) D O (n 1)
MT=Theoreticalmolarmassofreactant
MO=Observedmolarmassofmixture
MT MO
DT= and DO=
2 2

(b) nA (g) l An (g)

Initialconn a 0
a
ateqm 1(1)
n
MT MO

1
M O 1
n

FACTOR'S AFFECTING EQUILIBRIA (Le-chatelier's principle)

(i) Effect of change in concentration on equilibrium
Achemicalsystematequilibriumcanbeshiftedoutofequilibriumbyaddingorremovingonemoreof
reactantsorproducts.Shiftingoutofequilibriumdoesn'tmeanthatvalueofequilibriumconstantchange.
Anyalterationofconcentrationofreactantorproductwilldisturbtheequilibriumandconcentrationof
reactantandproductonereadjusttooneagainattainequilibriumconcentration.
Inotherword,asweaddorremovereactant(orproduct)theratioofequilibriumconcentrationbecome
'Q'(reactionquotient)anddependingupon.
Q<K : equilibriumwillshiftinforwarddirection.
Q>K : equilibriumwillshiftinbackwarddirection.
Example: Fe (a)+SCN(aq)lFe(SCN)2+(aq)
3+

[ Fe(SCN ) 2 ]
(i) addingFe3orSCNwillmore =QlessthenKCandequilibriawillshiftinforward
[ Fe3 ][SCN ]
direction.
(ii) RemovingFe(SCN)2+willhavesameeffect
(iii) AddingFe(SCN)2+fromoutsidesourceinequilibriummixturewillhaveeffectofincreasing'Q'hence
reactionshiftinbackwarddirection.

CHEMICAL EQUILIBRIUM [7]

(ii) Effect of change in pressure
Sometimeswecanchangethepositionofequilibriumbychangingthepressureonasystem.However,
changesinpressurehaveameasurableeffectonlyinsystemwheregasesareinvolvedandthenonly
whenthechemicalreactionproducesachangeinthetotalnumberofgasmoleculesinthesystem.
Asweincreasethepressureofagaseoussystematequilibrium,eitherbydecreasingthevolumeofthe
systemorbyaddingmoreoftheequilibriummixture,weintroduceastressbyincreasingthenumberof
moleculesperunitofvolume.InaccordancewithLeChatelier'sprinciple,achemicalreactionthat
reducesthetotalnumberofmoleculesperunitofvolumewillbefavoredbecausethisrelievesthestress.
Thereversereactionwouldbefavouredbyadecreaseinpressure.
ConsiderwhathappenswhenweincreasethepressureonasysteminwhichNO,O2andNO2arein
equilibrium.
Example: 2NO(g)+O2(g)l2NO2(g)
TheformationofadditionalamountsofNO2decreasesthetotalnumberofmoleculesinthesystem,
becauseeachtimetwomoleculesofNO2form,atotalofthreemoleculesofNOandO2react.This
reducesthetotalpressureexertedbythesystemandreduces,butdoesnotcompletelyrelieve,thestress
oftheincreasedpressure.On theotherhand,adecreaseinthepressure onthesystemfavors
decompositionofNO2intoNOandO2whichtendstorestorethepressure.
Letusnowconsiderthereaction

N2(g)+O2(g)l2NO(g)
Becausethereisnochangeinthetotalnumberofmoleculesinthesystemduringreaction,achangein
pressuredoesnotfavoreitherformationordecompositionofgaseousnitricoxide.
(iii) Effect of change in temperature on equilibrium
Changingconcentrationorpressureupsetsanequilibriumbecausethereactionquotientisshiftedaway
fromtheequilibriumvalue.Changingthetemperatureofasystematequilibriumhasadifferenteffect:A
changeintemperaturechangesthevalueoftheequilibriumconstant.However,wecanpredicttheeffect
ofthetemperaturechangebytreatingitasastressonthesystemandapplyingLeChatelier'sprinciple.
Whenhydrogenreactswithgaseousiodine,energyisreleasedasheatisevolved.
H2(g)+I2(g)l2I(g) H=9.4kJ(exothermic)
Becausethisreactionisexothermic,wecanwriteitwithheatasaproduct.

H2(g)+I2(g)l2HI(g)+9.4kJ
Increasingthetemperatureofthereactionincreasestheamountofenergypresent.Thus,increasingthe
temperaturehastheeffectofincreasingtheamountofoneoftheproductsofthisreaction.Thereaction
shiftstothelefttorelievethestress,andthereisanincreaseintheconcentrationofH2andI2anda
reductionintheconcentrationofHI.Whenwechangethetemperatureofasystematequilibrium,the
equilibriumconstantforthereactionchanges.LoweringthetemperatureintheHIsystemincreasesthe
equilibriumconstantfrom50.0at400Cto67.5at357C.Atequilibriumatthelowertemperature,the
concentrationofHIhasincreasedandtheconcentrationsofH2andI2havedecreased.Raisingthe
temperaturedecreasesthevalueoftheequilibriumconstantfrom67.5at357Cto50.0at400C.
van't Hoff equation
d(nK) H
(a) =
dT RT 2
K2 1 1
ln = H
K1 R T2 T1

CHEMICAL EQUILIBRIUM [8]

(iv) Effect of catalyst on equilibrium
Acatalysthasnoeffectonthevalueofanequilibriumconstantoronequilibriumconcentrations.The
catalystmerelyincreasetheratesofboththeforwardandthereversereactionstothesameextentsothat
equilibriumisreachedmorerapidly.
Alloftheseeffectschangeinconcentrationorpressure,changeintemperature,andtheeffectofa
catalystonachemicalequilibriumplayaroleintheindustrialsynthesisofammoniafromnitrogenand
hydrogenaccordingtotheequation.
N2 + 3H2 l 2NH3
OnewaytoincreasetheyieldofammoniaistoincreasethepressureonthesysteminwhichN2,H2and
NH3areinequilibriumorarecomingtoequilibrium.
N2(g)3H2(g)l2NH3(g)
Theformationofadditionalamountsofammoniareducesthetotalpressureexertedbythesystemand
somewhatreducesthestressoftheincreasedpressure.
AlthoughincreasingthepressureofamixtureofN2,H2andNH3increasetheyieldammonia,atlow
temperaturestherateofformationofammoniaisslow.Atroomtemperature,forexample,thereaction
issoslowthatifwepreparedamixtureofN2andH2,nodetectableamountofammoniawouldform
duringourlifetime.Attemptstoincreasetherateofthereactionbyincreasingthetemperatureare
counterproductive.Theformationofammoniafromhydrogenandnitrogenisanexothermicprocess:
N2(g)+3H2(g)2NH3(g) H=92.2kJ
Thusincreasingthetemperaturetoincreasetheratelowerstheyield.Ifwelowerthetemperaturetoshift
theequilibriumtotherighttofavourtheformationofmoreammonia,equilibriumisreachedmoreslowly
becauseofthelargedecreaseofreactionratewithdecreasingtemperature.
Partoftherateofformationlostbyoperatingatlowertemperaturescanberecoveredbyusingacatalyst
toincreasethereactionrate.Ironpowderisonecatalystused.However,aswehaveseen,acatalyst
servesequallywelltoincreasetherateofareversereactioninthiscase,thedecompositionofammonia
intoitsconstituentelements.Thustheneteffectoftheironcatalystonthereactionistocauseequilibrium
tobereachedmorerapidly.

A THERMODYNAMIC RELATIONSHIP :

G=G+RTlnQ [Q=Reactionquotient]
G=RTlnKeq (Ateqm.(G)T,P=0)
G=HTS
ForExothermicreaction
r H rS
lnKeq= +
RT R
rS r H
lnK1= RT lnK
R 1

rS r H
lnK2= KT
R 2
1/T
K 2 H 1 1
ln =
K1 R T1 T2

CHEMICAL EQUILIBRIUM [9]

EQUILIBRIUM CONSTANT AS PER KINETICS :
Kf
A(g) Kb B(g)+C(g)

d (A)
=Kf[A]Kb[B][C]
dt
d[A ] K f [ B][C]
Ateqm =0 Kc
dt Kb [A]

where k=A e E a / RT ; A:pre-expotentialfactor

Ea ( f ) / RT
kf=Af e Ea:activationenergy
E a ( b ) / RT
kb=Ab e

Ea(f) Ea(b)
E / RT P.E.
kf A f .e a ( f )
Keq= k = E / RT
b A b .e a ( b )
H

ReactionCoordinate

k=AeH/RT
whereH=Ea(f)Ea(b)
H
lnK1=lnA RT
1

H
lnK2=lnA RT
2

K 2 H 1 1
ln
K1 R T1 T2

SIMULTANEOUS EQUILIBRIA :
X(s) l A(g)+B(g) K P1 ( x y) x
(x+y) x
Y(s) l A(g)+C(g) K P2 ( x y) y
(y+x) y
K P1 x
Ptotal 2x 2 y
K P2 y

CHEMICAL EQUILIBRIUM [10]

SEQUENTIAL EQUILIBRIUM :
A(s)B(g)+C(g) K C1 ( x )( x y)
ax xxy

y
C(g)D(g) K C2
xy
xy y

PHASE DIAGRAM FOR WATER:

P
Solid Liquid

O Gas

CHEMICAL EQUILIBRIUM [11]

 THE ATLAS

CHEMICAL EQUILIBRIUM [12]

 EXERCISE I

Reaction quotient and equilibrium constant

Q.1 Theinitialconcentrationsorpressureofreactantsandproductsaregivenforeachofthefollowing
systems.Calculatethereactionquotientanddeterminethedirectionsinwhicheachsystemwillshiftto
reachequilibrium.
(a) 2NH3(g)lN2(g)+3H2(g) K=17
[NH3]=0.20M;[N2]=1.00M;[H2]=1.00M
(b) 2NH3(g)lN2(g)+3H2(g) Kp=6.8104atm2
Initialpressure:NH3=3.0atm;N2=2.0atm;H2=1.0atm
(c) 2SO3(g)l2SO2(g)+O2(g) K=0.230atm
[SO3]=0.00M;[SO2]=1.00M;[O2]=1.00M
(d) 2SO3(g)l2SO2(g)+O2(g) Kp=16.5atm
Initialpressure:SO3=1.0atm;SO2=1.0atm;O2=1.0atm
(e) 2NO(g)+Cl2(g)l2NOCl(g) K=4.6104
[NO]=1.00M;[Cl2]=1.00M;[NOCl]=0M

Q.2 AmongthesolubilityrulesisthestatementthatallchloridesaresolubleexceptHg2Cl2,AgCl,PbCl2,andCuCl.
(a) Writetheexpressionfortheequilibriumconstantforthereactionrepresentedbytheequation.
AgCl(s)lAg+(aq)+Cl(aq)
IsKgreaterthan1,lessthan1,oraboutequalto1?Explainyouranswer
(b) Writetheexpressionfortheequilibriumconstantforthereactionrepresentedbytheequation
Pb2+(aq)+2Cl(aq)lPbCl2(s)
IsKgreaterthan1,lessthan1,oraboutequalto1?Explainyouranswer.

Q.3 Amongthesolubilityrulesisthestatementthatcarbonates,phosphates,borates,arsenates,andarsenites,
exceptthoseoftheammoniumionandthealkalimetalsareinsoluble.
(a) Writetheexpressionfortheequilibriumconstantforthereactionrepresentedbytheequation
CaCO3(s)lCa2+(aq)+CO32(aq)
IsKgreaterthan1,lessthan1,oraboutequalto1?Explainyouranswer
(b) Writetheexpressionfortheequilibriumconstantforthereactionrepresentedbytheequation.
3Ba2+(aq)+2PO43(aq)lBa3(PO4)2(s)
IsKgreaterthan1,lessthan1,oraboutequalto1?Explainyouranswer.

Q.4 Benzeneisoneofthecompoundsusedasoctaneenhancersinunleadedgasoline.Itismanufacturedby
thecatalyticconversionofacetylenetobenzene.
3C2H2 C6H6
WouldthisreactionbemostusefulcommerciallyifKwereabout0.01,about1,orabout10?Explain
youranswer.

Q.5 Showthecompletechemicalequationandthenetionicequationforthereactionrepresentedbytheequation
KI(aq)+I2(aq)lKI3(aq)
givethesameexpressionforthereactionquotient.KI3iscomposedoftheionsK+andI3.

Using the equilibrium constant

Q.6 Whichofthefollowingreactionsgoesalmostallthewaytocompletion,andwhichproceedshardlyatall?
(a) N2(g)+O2(g)l2NO(g); Kc=2.71018
(b) 2NO(g)+O2(g)l2NO2(g); Kc=6.01013

CHEMICAL EQUILIBRIUM [13]

Q.7 Forwhichofthefollowingreactionswilltheequilibriummixturecontainanappreciableconcentrationof
bothreactantsandproducts?
(a) Cl2(g)l2Cl(g); Kc=6.41039
(b) Cl2(g)+2NO(g)l2NOCl(g); Kc=3.7108
(c) Cl2(g)+2NO2(g)l2NO2Cl(g); Kc=1.8

Q.8 ThevalueofKcforthereaction3O2(g)l2O3(g)is1.71056at25C.Doyouexpectpureairat
25CtocontainmuchO3(ozone)whenO2andO3areinequilibrium?Iftheequilibriumconcentration
ofO2inairat25Cis8103M,whatistheequilibriumconcentrationofO3?

Q.9 At1400K,Kc=2.5103forthereactionCH4(g)+2H2SlCS2(g)+4H2(g).A10.0Lreaction
vesselat1400Kcontains2.0molofCH4,3.0molofCS2,3.0molofH2and4.0molofH2S.Isthe
reactionmixtureatequilibrium?Ifnot,inwhichdirectiondoesthereactionproceedtoreachequilibrium?

Q.10 Thefirststepintheindustrialsynthesisofhydrogenisthereactionofsteamandmethanetogivewater
gas,amixtureofcarbonmonoxideandhydrogen.
H2O(g)+CH4(g)lCO(g)+3H2(g) Kc=4.7at1400K
Amixtureofreactantsandproductat1400Kcontains0.035MH2O,0.050MCH4,0.15MCO,and
0.20MH2.Inwhichdirectiondoesthereactionproceedtoreachequilibrium?

Q.11 AnequilibriummixtureofN2,H2,andNH3at700Kcontains0.036MN2and0.15MH2.Atthis
temperature,KcforthereactionN2(g)+3H2(g)l2NH3(g)is0.29.WhatistheconcentrationofNH3?

Q.12 The air pollutant NO is produced in automobile engines from the high temperature reaction
N2(g)+O2(g)l 2NO(g);Kc=1.7103at2300K.IftheinitialconcentrationsofN2andO2at
2300Kareboth1.40M,whataretheconcentrationsofNO,N2,andO2whenthereactionmixture
reachesequilibrium?

Q.13 Atacertaintemperature,thereactionPCl5(g)l PCl3(g)+ Cl2(g)hasanequilibriumconstant

Kc=5.8102.CalculatetheequilibriumconcentrationsofPCl5,PCl3andCl2ifonlyPCl5ispresent
initially,ataconcentrationof0.160M.

Q.14 At700K,Kp=0.140forthereactionClF3(g)lClF(g)+F2(g).Calculatetheequilibriumpartial
pressureofClF3,ClF,andF2ifonlyClF3ispresentinitially,atapartialpressureof1.47atm.

Homogeneous equilibria degree of dissociation, vapour density and equilibrium constant

Q.15 ThedegreeofdissociationofN2O4intoNO2at1.5atmosphereand40Cis0.25.Calculateits
Kpat40C.Alsoreportdegreeofdissociationat10atmosphericpressureatsametemperature.

Q.16 At46C,KpforthereactionN2O4(g)l2NO2(g)is0.667atm.Computethepercentdissociation
ofN2O4at46 Catatotalpressureof380Torr.

Q.17 When36.8gN2O4(g)isintroducedintoa1.0-litreflaskat27C.Thefollowingequilibrium
reactionoccurs: N2O4(g)l2NO2(g);Kp=0.1642atm.
(a) CalculateKcoftheequilibriumreaction.
(b) WhatarethenumberofmolesofN2O4andNO2atequilibrium?
(c) Whatisthetotalgaspressureintheflaskatequilibrium?
(d) WhatisthepercentdissociationofN2O4?

CHEMICAL EQUILIBRIUM [14]

Q.18 Atsometemperatureandunderapressureof4atm,PCl5is10%dissociated.Calculatethe
pressureatwhichPCl5willbe20%dissociated,temperatureremainingsame.

Q.19 InamixtureofN2andH2intheratioof1:3at64atmosphericpressureand300C,thepercentageof
ammoniaunderequlibriumis33.33byvolume.Calculatetheequilibriumconstantofthereactionusing
theequation.N2(g)+3H2(g)l2NH3(g).

Q.20 ThesystemN2O4 l2 NO2maintainedinaclosedvesselat60C&apressureof5atmhasanaverage

(i.e.observed)molecularweightof69,calculateKp.Atwhatpressureatthesame
temperaturewouldtheobservedmolecularweightbe(230/3) ?

Q.21 ThevapourdensityofN2O4andNO2mixtureatacertaintemperatureis30.Calculatethepercentage
dissociationofN2O4atthistemperature.N2O4(g)l2NO2(g).

Q.22 IntheesterficationC2H5OH(l)+CH3COOH(l) l CH3COOC2H5 (l)+H2O(l)anequimolar

mixtureofalcoholandacidtakeninitiallyyieldsunderequilibrium,thewaterwithmolefraction=0.333.
Calculatetheequilibriumconstant.

Hetrogeneous equilibrium
Q.23 SolidAmmoniumcarbamatedissociatesas:NH2COONH4(s)l2NH3(g)+CO2(g).Inaclosed
vesselsolidammoniumcarbamateisinequilibriumwithitsdissociationproducts.Atequilibrium,ammonia
isaddedsuchthatthepartialpressureofNH3atnewequilibriumnowequalstheoriginaltotalpressure.
Calculatetheratiooftotalpressureatnewequilibriumtothatoforiginaltotalpressure.

Q.24 AsampleofCaCO3(s)isintroducedintoasealedcontainerofvolume0.821litre&heatedto1000K
untilequilibriumisreached.TheequilibriumconstantforthereactionCaCO3(s)lCaO(s)+CO2(g)is
4102atmatthistemperature.CalculatethemassofCaOpresentatequilibrium.

Q.25 Anhydrouscalciumchlorideisoftenusedasadessicant.InthepresenceofexcessofCaCl2,,the
amountofthewatertakenupisgovernedbyKp=6.41085forthefollowingreactionatroom
temperature,CaCl2(s)+6H2O(g)lCaCl2.6H2O(s).Whatistheequilibriumvapourpressureof
waterinaclosedvesselthatcontainsCaCl2(s)?

Q.26 20.0gramsofCaCO3(s)wereplacedinaclosedvessel,heated&maintainedat727 Cunder

equilibriumCaCO3(s)lCaO(s)+CO2(g)anditisfoundthat75 %ofCaCO3wasdecomposed.
WhatisthevalueofKp?Thevolumeofthecontainerwas15litres.

Changes in concentration at equilibrium Le Chatelier's principle

Q.27 Suggestfourwaysinwhichtheconcentrationofhydrazine,N2H4,couldbeincreasedinanequilibrium
describedbytheequation
N2(g)+2H2(g)lN2H4(g) H=95kJ

Q.28 Howwillanincreaseintemperatureaffecteachofthefollowingequilibria?Anincreaseinpressure?
(a) 2NH3(g)lN2(g)+3H2(g) H=92kJ
(b) N2(g)+O2(g)l2NO(g) H=181kJ
(c) 2O3(g)l3O2(g) H=285kJ
(d) CaO(s)+CO2(g)lCaCO3(s) H=176kJ

CHEMICAL EQUILIBRIUM [15]

Q.29(a)Methanol,aliquidfuelthatcouldpossiblyreplacegasoline,canbepreparedfromwatergasand
additionalhydrogenathightemperatureandpressureinthepresenceofasuitablecatalyst.Writethe
expressionfortheequilibriumconstantforthereversiblereaction.
2H2(g)+CO(g)lCH3OH(g) H=90.2kJ
(b) AssumethatequilibriumhasbeenestablishedandpredicthowtheconcentrationofH2,COandCH3OHwill
differatanewequilibriumif(1)moreH2isadded.(2)COisremoved.(3)CH3OHisadded.(4)thepressure
onthesystemisincreased.(5)thetemperatureofthesystemisincreased.(6)morecatalystisadded.

Q.30(a)Watergas,amixtureofH2andCO,isanimportantindustrialfuelproducedbythereactionofsteam
withred-hotcoke,essentiallypurecarbon.Writetheexpressionfortheequilibriumconstantforthe
reversiblereaction.
C(s)+H2O(g)lCO(g)+H2(g) H=131.30kJ
(b) Assumethatequilibriumhasbeenestablishedandpredicthowtheconcentrationofeachreactantand
productwilldifferatanewequilibriumif(1)moreCisadded.(2)H2Oisremoved.(3)COisadded.
(4)thepressureonthesystemisincreased.(5)thetemperatureofthesystemisincreased.

Q.31 Ammoniaisaweakbasethatreactswithwateraccordingtotheequation
NH3(aq)+H2O(l)lNH4++OH(aq)
Willanyofthefollowingincreasethepercentofammoniathatisconvertedtotheammoniumionin
water?
(a)AdditionofNaOH. (b)AdditionofHCl. (c)AdditionofNH4Cl.

Q.32 SuggesttwowaysinwhichtheequilibriumconcentrationofAg+canbereducedinasolutionofNa+,
Cl,Ag+andNO3,incontactwithsolidAgCl.
Na+(aq)+Cl(aq)+Ag+(aq)+NO3(aq)lAgCl(s)+Na+(aq)+NO3(aq)H=65.9kJ

Q.33 Additionalsolidsilversulfate,aslightlysolublesolid,isaddedtoasolutionofsilverionandsulfateionin
equilibriumwithsolidsilversulfate.Whichofthefollowingwilloccur?(a)TheAg+andSO42concentration
willnotchange.(b)Theaddedsilversulfatewilldissolve.(c)Additionalsilversulfatewillformand
precipitatefromsolutionasAg+ionsandSO42ionscombine.(d)TheAg+ionconcentrationwillincrease
andtheSO42ionconcentrationwilldecrease.

Kinetics and equilibrium constant

Q.34 Considerageneral,single-stepreactionofthetypeA+BlC.Showthattheequilibriumconstantis
equaltotheratiooftherateconstantfortheforwardandreversereaction,Kc=kf/kr.

Q.35 Whichofthefollowingrelativevaluesofkfandkrresultsinanequilibriummixturethatcontainslarge
amountsofreactantsandsmallamountsofproduct?
(a)kf>kr (b)kf=kr (c)kf<kr

Q.36 Considerthegas-phasehydrationofhexafluoroacetone,(CF3)2CO:
kf
(CF3)2CO(g)+H2O(g) (CF3)2C(OH)2(g)
kr

At76C,theforwardandreverserateconstantsarekf=0.13M1s1andkr=6.02104s1.What
isthevalueoftheequilibriumconstantKc?

CHEMICAL EQUILIBRIUM [16]

Q.37 ConsiderthereactionofchloromethanewithOHinaqueoussolution
kf
CH3Cl(aq)+OH(aq) CH3OH(aq)+Cl(aq)
kr
At25C,therateconstantfortheforwardreactionis6106M1s1,andtheequilibriumconstantKc
is11016.Calculatetherateconstantforthereversereactionat25C.

Q.38 Theprogressofthereaction
AlnBwithtime,ispresentedinfigure.Determine
(i) thevalueofn.
(ii) theequilibriumconstantK.
(iii) theinitialrateofconversionofA.

Temperature dependence of equilibrium constant

Q.39 Listedinthetableareforwardandreverserateconstantsforthereaction2NO(g)lN2(g)+O2(g)
Temperature (K) kf (M1s1) kr (M1s1)
1400 0.29 1.1106
1500 1.3 1.4105
Isthereactionendothermicorexothermic?Explainintermsofkinetics.

Q.40 ForwardandreverserateconstantforthereactionCO2(g)+N2(g)lCO(g)+N2O(g)exhibitthe
followingtemperaturedependence.
Temperature (K) kf (M1s1) kr (M1s1)
1200 9.11011 1.5105
1500 2.710 9 2.6105
Isthereactionendothermicorexothermic?Explainintermsofkinetics.

Q.41 TheequilibriumconstantKpforthereactionPCl5(g)lPCl3(g)+Cl2(g)is3.81102at600Kand
2.69103at700K.CalculaterH.

Temperature dependence of equilibrium constant

Q.42 RateofdisappearanceofthereactantAattwodifferenttemperatureisgivenbyAlB
d[A ]
=(2102S1)[A] 4103S1[B];300K
dt
d[A ]
=(4102S1)[A] 16104[B];400K
dt
Calculateheatofreactioninthegiventemperaturerange.Whenequilibriumissetup.

Q.43 TheKPforreactionA+BlC+Dis1.34at60Cand6.64at100C.Determinethefreeenergy
changeofthisreactionateachtemperatureandHforthereactionoverthisrangeoftemperature?

Equilibrium expressions and equilibrium constants

Q.44 IfKc=7.5109at1000KforthereactionN2(g)+O2(g)l2NO(g),whatisKcat1000Kforthe
reaction2NO(g)lN2(g)+O2(g)?

CHEMICAL EQUILIBRIUM [17]

Q.45 AnequilibriummixtureofPCl5,PCl3andCl2atacertaintemperaturecontains8.3103MPCl5,
1.5102MPCl3,and3.2102MCl2.CalculatetheequilibriumconstantKcforthereaction
PCl5(g)lPCl3(g)+Cl2(g).

Q.46 AsampleofHI(9.30103mol)wasplacedinanempty2.00Lcontainerat1000K.Afterequilibrium
wasreached,theconcentrationofI2was6.29104M.CalculatethevalueofKcat1000Kforthe
reactionH2(g)+I2(g)l2HI(g).

Q.47 Thevapourpressureofwaterat25Cis0.0313atm.CalculatethevaluesofKpandKcat25Cforthe
equilibriumH2O(l)lH2O(g).

Thermodynamic and equilibrium constant

Q.48 -D-Glucoseundergoesmutarotationto-D-Glucoseinaqueoussolution.Ifat298Kthereis60%
conversion.CalculateGofthereaction.
-D-Glucosel -D-Glucose

Q.49 Forthereactionat298K
A(g)+B(g)lC(g)+D(g)
H=29.8kcal;S=0.1kcal/K
CalculateGandK.

Q.50 Theequilibriumconstantofthereaction2C3H6(g)lC2H4(g)+C4H8(g)isfoundtofittheexpression
1088 K
lnK=1.04
T
Calculatethestandardreactionenthalpyandentropyat400K.

CHEMICAL EQUILIBRIUM [18]

 PROFICIENCY TEST
Q.1 Fill in the blanks with appropriate items :

1. Kforthereaction2A+Bl2Cis1.51012.Thisindicatesthatatequilibriumtheconcentrationof
______wouldbemaximum.

2. ThereactionN2+O2 l2NOHeat,wouldbefavouredby_______temperature.
1 1
3. KforthereactionX2+Y2 l2XYis100K.ForreactionXYl X2+ Y2wouldbe_________.
2 2

4. ComparedtoKforthedissociation,2H2Sl2H++2HS,thenK'fortheH++HS lH2Swouldhave
_______.

5. Theequilibriumconstantforareactiondecreaseswith increaseintemperature,thereactionmustbe
______.

6. Forthereaction,PCl5(g)l PCl3(g)+Cl2(g),KPandKCarerelatedas______.

7. Forthereactions,N2O4(g)l2NO2(g),atequilibrium,increaseinpressureshiftstheequilibriumin
_______direction.

8. GisrelatedtoKbytherelation__________.

9. VantHoff'sequationis_________.

10. Whenthereactionisatequilibrium,thevalueofGis_______.

11. Dimensionsofequilibriumconstant,Kcforthereaction2NH3 lN2+3H2,are_______.

12. ThevalueofKforareactioncanbechangedbychanging_______.

13. Thelawofmassactionwasproposedby________.

14. ThedegreeofdissociationofPCl5[PCl5(g)lPCl3(g)+Cl2(g)],_________withincreaseinpressure
atequilibrium.

15. Ifconcentrationquotient,QisgreaterthanKC,thenetreactionintakingplacein_____direction.

16. Thereaction,N2+3H2 l2NH3wouldbefavouredby____pressure.

17. KPisrelatedtoKCas_______.

18. Solubilityofagasinwater___withincreaseintemperature.

19. Introductionofinertgasatconstantvolumetoagaseousreactionatequilibriumresultsinformationof
______product.

20. Theproductismorestablethanreactantsinreactionhaving______K.

CHEMICAL EQUILIBRIUM [19]

Q.2 True or False Statements :

21. Van'tHoff'sequationgivesthequantitativerelationbetweenchangeinvalueofKwithchangein
temperature.

22. ThelargervalueofKindicatesthattheproductismorestablerelativetoreactants.

23. Thevalueofequilibriumconstantchangeswithchangeintheinitialconcentrationofthereactants.

24. Extentofareactioncanalwaysbeincreasedbyincreasingthetemperature.

25. KPisrelatedtoKCasKP=KC(RT)n.

26. Introductionofinertgasatagaseousreaction(ng 0)atequilibriumkeepingpressureconstanthasno

effectonequilibriumstate.

27. Forthereaction,N2O4(g)l2NO2(g),KP=KC(RT).

28. ForareactionthevalueofQgreaterthanKindicatesthatthenetreactionisproceedinginbackward
direction.

29. Solubilitiesofallsolidsinwaterincreasewithincreaseintemperature.

30. Dissolutionofgasesinwaterishighatlowtemperature.
[ NH 3 ]2
31. Forthereaction,N2+3H2l2NH3,theequilibriumexpressionmaybewrittenasK= .
[ N 2 ][H 2 ]3

32. Forthereaction,CaCO3(s)lCaO(s)+CO2(g),KP= p CO2 .

33. Acatalystincreasesthevalueoftheequilibriumconstantforareaction.

34. IfconcentrationquotientofreactionislessthanK,thenetreactionisproceedinginthebackward
direction.

35. Incaseofendothermicreactions,theequilibriumshiftsinbackwarddirectiononincreasingthetemperature.

36. ThevalueofKincreaseswithincreaseinpressure.

37. Forthereaction,H2+I2 l2HI,theequilibriumconstant,Kisdimensionless.

38. Thereaction2SO2(g)+O2(g)l2SO3(g),H=XkJ,isfavouredbyhighpressureandhightemperature.

39. AveryhighvalueofKindicatesthatatequilibriummostofthereactantsareconvertedintoproducts.

40. ThevalueofKforthereaction,N2+2H2 l2NH3,canbeincreasedbyapplyinghighpressureorby

usingacatalyst.

CHEMICAL EQUILIBRIUM [20]

 EXERCISE II
Q.1 2molesofA&3molesofBaremixedin1litrevesselandthereactioniscarriedat400Caccording
totheequation;A+Bl2 C.Theequilibriumconstantofthereactionis4.Findthenumberofmoles
ofCatequilibrium.

Q.2 2NOBr (g)l2NO (g)+Br2(g).Ifnitrosylbromide(NOBr)is33.33%dissociatedat25C&

atotalpressureof0.28atm .CalculateKpforthedissociationatthistemperature.

Q.3 At90C,thefollowingequilibriumisestablished:
H2(g)+S(s)lH2S(g)Kp=6.8102
If0.2molofhydrogenand1.0molofsulphurareheatedto90Cina1.0litrevessel,
whatwillbethepartialpressureofH2Satequilibrium?

Q.4 Theequilibriumconstantforthereactionis9.40at900CS2(g)+C(s)lCS2(g).Calculatethe
pressureoftwogasesatequilibrium,when1.42atmofS2andexcessofC(s)cometoequilibrium.

Q.5 Amixtureof2molesofCH4&34gmsofH2Swasplacedinanevacuatedcontainer,whichwasthen
heated to &maintained at 727 C. When equilibrium was established in the gaseous reaction
CH4+2H2SlCS2+4H2thetotalpressureinthecontainerwas0.92atm&thepartialpressureof
hydrogenwas0.2atm.Whatwasthevolumeofthecontainer?

Q.6 PCl5dissociatesaccordingtothereactionPCl5 lPCl3(g)+Cl2(g).At523K,Kp=1.78atm.Find

thedensityoftheequilibriummixtureatatotalpressureof1atm.

Q.7 Thefollowingdatafortheequilibriumcompositionofthereaction
2Na(g)lNa2(g)
at1.013MPapressureand1482.53Khavebeenobtained.
mass%Na(monomergas)=71.3
mass%Na2(dimergas)=28.7
CalculatetheequiliriumconstantKp.

Q.8 ThedegreeofdissociationofHIataparticulartemperatureis0.8.Findthevolumeof1.5Msodium
thiosulphatesolutionrequiredtoreactcompletelywiththeiodinepresentatequilibriuminacidicconditions,
when0.135moleachofH2andI2areheatedat440Kinaclosedvesselofcapacity2.0L.

Q.9 Areactionsysteminequilibriumaccordingtotheequation2SO2+O2 l2 SO3in1litrereactionvessel

atagiventemperaturewasfoundtocontain0.11molofSO2,0.12molofSO3and0.05molofO2.
Another1litrereactionvesselcontains64gofSO2atthesametemperature.WhatmassofO2mustbe
addedtothisvesselinorderthatatequilibriumhalfofSO2isoxidisedtoSO3?

Q.10 Amixtureofhydrogen&iodineinthemoleratio1.5:1ismaintainedat450C.Aftertheattainmentof
equilibriumH2(g)+I2(g)l2 HI(g),itisfoundonanalysisthatthemoleratioofI2toHIis1:18.
Calculatetheequilibriumconstant&thenumberofmolesofeachspeciespresentunderequilibrium,if
initially,127gramsofiodineweretaken.

Q.11 Inaclosedcontainernitrogenandhydrogenmixtureinitiallyinamoleratioof1:4reachedequilibrium.It
isfoundthatthehalfhydrogenisconvertedtoammonia.Iftheoriginalpressurewas180atm,whatwill
bethepartialpressureofammoniaatequilibrium.(Thereisnochangeintemperature)

CHEMICAL EQUILIBRIUM [21]

Q.12 TheequilibriumconstantforthereactionCO(g)+H2O(g)lCO2(g)+H2(g)is7.3at450C&1atm
pressure.Theinitialconcentrationofwatergas[CO&H2inequimolarratio]&steamare2moles&
5molesrespectively.FindthenumberofmolesofCO,H2,CO2&H2O(vapour)atequilibrium.

Q.13 At1200C,thefollowingequilibriumisestablishedbetweenchlorineatoms&molecule:
Cl2(g)l 2Cl(g)
Thecompositionoftheequilibriummixturemaybedeterminedbymeasuringtherateofeffusionofthe
mixturethroughapinhole.Itisfoundthatat1200Cand1atmpressurethemixtureeffuses1.16times
asfastaskryptoneffusesunderthesamecondition.CalculatetheequilibriumconstantKc.

Q.14 SO3decomposesatatemperatureof1000Kandatatotalpressureof1.642atm.Atequilibrium,the
densityofmixtureisfoundtobe1.28g/linavesselof90literes.FindthedegreeofdissociationofSO3
forSO3 lSO2+1/2O2.

Q.15 Considertheequilibrium:P(g)+2Q(g)lR(g).Whenthereactioniscarriedoutatacertaintemperature,
theequilibriumconcentrationofPandQare3Mand4Mrespectively.Whenthevolumeofthevesselis
doubledandtheequilibriumisallowedtobereestablished,theconcentrationofQisfoundtobe3M.
Find(A)Kc(B)concentrationofRattwoequilibriumstages.

Q.16 Asaturatedsolutionofiodineinwatercontains0.33gI2/L.MorethanthiscandissolveinaKIsolution
becauseofthefollowingequilibrium:I2(aq)+I aq)l I3 aq.A0.10MKIsolution(0.10M I)
actuallydissolves12.5gofiodine/L,mostofwhichisconvertedtoI3.Assumingthattheconcentration
ofI2inallsaturatedsolutionsisthesame,calculatetheequilibriumconstantfortheabovereaction.
WhatistheeffectofaddingwatertoaclearsaturatedofI2intheKIsolution?

Q.17 TheequilibriumpXyloquinone+methylenewhitelpXylohydroquinone+methylenebluemaybe
studiedconvinentlybyobservingthedifferenceincolormethylenewhiteandmethyleneblue.Onemmol
ofmethylenebluewasaddedto1Lofsolutionthatwas0.24MinpXylohydroquinoneand0.012Min
pXyloquinone.Itwasthenfoundthat4%oftheaddedmethylenebluewasreducedtomethylene
white.Whatistheequilibriumconstantoftheabovereaction?Theequationisbalancedwithonemole
eachof4substances.

Q.18 AcertaingasApolymerizestoasmallextentatagiventemperature&pressure,nAlAn.Showthat

thegasobeystheapprox.equation PV 1 (n 1)K c where K c A n & V isthevolume ofthe

n 1 n
RT V A
conatiner.AssumethatinitiallyonemoleofAwastakeninthecontainer.

Q.19 103molofCuSO4.5H2Oisintroducedina1.9Lvesselmaintainedataconstanttemperatureof27Ccontaining
moist air at relative humidity of 12.5%. What is the final molar composition of solid mixture?
ForCuSO4.5H2O(s)lCuSO4(s)+5H2O(g),Kp(atm)=1010.Takevaporpressureofwaterat27Cas28torrs.

Q.20 TwosolidsXandYdisssociateintogaseousproductsatacertaintemperatureasfollows:
X(s)lA(g)+C(g),andY(s)lB(g)+C(g).Atagiventemperature,pressureoverexcess
solidXis40mmandtotalpressureoversolidYis60mm.Calculate:
(a) thevaluesofKpfortworeactions(inmm)
(b) theratioofmolesofAandBinthevapourstateoveramixtureofXandY.
(c) thetotalpressureofgasesoveramixtureofXandY.

CHEMICAL EQUILIBRIUM [22]

Q.21 When1moleofA(g)isintroducedinaclosedrigid1litrevesselmaintainedatconstanttemperaturethe
followingequilibriaareestablished.
A(g) l B(g) + C(g) : KC
1

C(g) l D(g) + B(g) : KC

2

KC [ C]eq 1
2
Thepressureatequilibriumistwicetheinitialpressure.Calculatethevalueof if =
KC [ B]eq 5
1

Q.22 Solid NH4I on rapid heating in a closed vessel at 357C develops a constant pressure of
275mmHgowingtopartialdecompositionofNH4IintoNH3andHIbutthepressuregraduallyincreases
further(whentheexcesssolidresidueremainsinthevessel)owingtothedissociationofHI.Calculate
thefinalpressuredevelopedatequilibrium.
NH4I(s) l NH3(g)+HI(g)
2HI(g) l H2(g)+I2(g),Kc=0.065at357C

Q.23 G(298K)forthereaction1/2N2+3/2H2 NH3is16.5kJmol1.Findtheequilibrium

constant(K1)at25C.WhatwillbetheequilibriumconstantsK2andK3forthefollowingreactions:
N2+3H2 2NH3

NH3 1/2N2+3/2H2

Q.24 ForthereactionSO2(g)+1/2O2(g)lSO3(g)H298=98.32kJ/mole,
S298= 95.0J/K/mole.FindtheKpforthisreactionat298K.

Q.25 Givenarethefollowingstandardfreeenergiesofformationat298K.
CO(g) CO2(g) H2O(g) H2O(l)
fG/kJmol1137.17 394.36 228.57 237.13
(a)FindrGandthestandardequilibriumconstantKp0at298Kforthereaction
CO(g)+H2O(g)lCO2(g)+H2(g)
(b)IfCO,CO2andH2aremixedsothatthepartialpressureofeachis101.325kPaandthemixtureis
broughtintocontactwithexcessofliquidwater,whatwillbethepartialpressureofeachgaswhen
equilibriumisattainedat298K.Thevolumeavailabletothegasesisconstant.

CHEMICAL EQUILIBRIUM [23]

 EXERCISE III
Only one is correct
Q.1 Forthereactionequilibrium;
N2O4(g) l 2NO2(g) ; the concentration of N2O4 and NO2 at equilibrium are 4.8 102 and
1.2102mol/Lrespectively.ThevalueofKcforthereactionis:
(A)3103M (B)3103M (C)3.3102M (D)3101M

Q.2 Whatistheequilibriumconstantforthereaction
P4(s)+5O2(g) P4O10(s):
1 P4O10 P4O10
(A)Kc= 5 (B)Kc= 5 (C)Kc=[O2]5 (D)Kc=
O2 5[P4 ][O 2 ] [P4 ][O 2 ]5

Q.3 Theequilibriumconstantforthereaction;
N2(g)+O2(g)l2NO(g)attemperature
Tis4104.ThevalueofKcforthereaction.
1 1
NO(g)l N2(g)+ O2(g)atthesametemperatureis:
2 2
(A)0.02 (B)50 (C)4104 (D)2.5102

Q.4 Theequilibriumconstantforthegivenreaction:
1
SO3(g)lSO2(g)+ O (g);Kc=4.9102
2 2
ThevalueofKcforthereaction:
2SO2(g)+O2(g)l2SO3(g),willbe
(A)416 (B)2.40103 (C)9.8102 (D)4.9102

Q.5 Forthefollowingthreereactions1,2and3,equilibriumconstantsaregiven:
(1)CO(g)+H2O(g)lCO2(g)+H2(g) ;K1
(2)CH4(g)+H2O(g)lCO(g)+3H2(g) ;K2
(3)CH4(g)+2H2O(g)lCO2(g)+4H2(g) ;K3
Whichofthefollowingrelationsiscorrect?
(A)K1 K 2 =K3 (B)K2K3=K1 (C)K3=K1K2 (D)K3K23K12

Q.6 Considerfollowingreactionsinequilibriumwithequilibriumconcentration0.01Mofeveryspecies
(I)PCl5(g)lPCl3(g)+Cl2(g) (II)2HI(g)lH2(g)+I2(g)
(III)N2(g)+3H2(g)l2NH3(g)
Extentofthereactionstakingplaceis:
(A)I>II>III (B)I<II<III (C)II<III<I (D)III<I<II

Q.7 AdefiniteamountofsolidNH4HSisplacedinaflaskalreadycontainingammoniagasatacertain
temperatureand0.50atmpressure.NH4HSdecomposestogiveNH3andH2Sandatequilibriumtotal
pressureinflaskis0.84atm.Theequilibriumconstantforthereactionis:
(A)0.30 (B)0.18 (C)0.17 (D)0.11

CHEMICAL EQUILIBRIUM [24]

Q.8 Forthereaction3A (g)+B (g)l2C (g)atagiventemperature,Kc=9.0.Whatmustbethe
volumeoftheflask,ifamixtureof2.0moleachofA,BandCexistinequilibrium?
(A)6L (B)9L (C)36L (D)Noneofthese

Q.9 Sulfideioninalkalinesolutionreactswithsolidsulfurtoformpolysulfideionshavingformulas
S22,S32,S42 andsoon.TheequilibriumconstantfortheformationofS22is12(K1)&forthe
formationofS32is132(K2),bothfromSandS2.Whatistheequilibriumconstantfortheformation
ofS32fromS22 andS?
(A)11 (B)12 (C)132 (D)Noneofthese

Q.10 1moleN2and3molH2areplacedinaclosedcontaineratapressureof4atm.Thepressurefallsto3
atmatthesametemperaturewhenthefollowingequilibriumisattained.
N2(g)+3H2(g)l2NH3(g).TheequilibriumconstantKPfordissociationofNH3is:
1
(A) (1.5)3atm2 (B)0.5(1.5)3atm2
0 .5
0.5 (1.5) 3 3 3
(C) atm2 (D) atm2
3 3 0.5 (1.5) 3

Q.11 OnemoleofN2O4(g)at300Kisleftinaclosedcontainerunderoneatm.Itisheatedto600K
when20%bymassofN2O4(g)decomposestoNO2(g).Theresultantpressureis:
(A)1.2atm (B)2.4atm (C)2.0atm (D)1.0atm

Q.12 Forthefollowinggasesequilibrium. N2O4 (g)l 2NO2 (g)

KpisfoundtobeequaltoKc.Thisisattainedwhentemperatureis
(A)0C (B)273K (C)1K (D)12.19K

1
Q.13 Forthereaction:CO(g)+ O2(g)lCO2(g),Kp/Kcis:
2
(A)RT (B)(RT)1 (C)(RT)1/2 (D)(RT)1/2

Q.14 Forthereaction;2NO2(g)l2NO(g)+O2(g)
Kc=1.8106at184CandR=0.083JK1mol1.WhenKpandKcarecomparedat184C,itis
foundthat:
(A)Kp>Kc (B)Kp<Kc
(C)Kp=Kc (D)Kp Kcdependsuponpressureofgases

Q.15 PCl5dissociationaclosedcontaineras:
PCl5(g)lPCl3(g)+Cl2(g)
IftotalpressureatequilibriumofthereactionmixtureisPanddegreeofdissociationofPCl5is,the
partialpressureofPCl3willbe:
2
(A)P (B)P (C)P (D)P
1 1 1 1

CHEMICAL EQUILIBRIUM [25]

Q.16 Forthereaction:2Hl(g)lH2(g)+I2(g),thedegreeofdissociated()ofHl(g)isrelatedtoequilibrium
constantKPbytheexpression

1 2 Kp 1 2K p 2K p 2 Kp
(A) (B) (C) 1 2K (D) 1 2 K
2 2 p p

Q.17 Theequilibriumconstantforthereaction
A(g)+2B(g)lC(g)
is0.25dm6mol2.Inavolumeof5dm3,whatamountofAmustbemixedwith4molofBtoyield1mol
ofCatequilibrium.
(A)3moles (B)24moles (C)26moles (D)Noneofthese

Q.18 ForthereactionA(g)+2B(g)lC(g)+D(g); Kc=1012.

IftheinitialmolesofA,B,CandDare0.5,1,0.5and3.5molesrespectivelyinaonelitrevessel.What
istheequilibriumconcentrationofB?
(A)104 (B)2104 (C)4104 (D)8104

Q.19 TheequilibriumconstantKCforthereaction,
A(g)+2B(g)l3C(g)is2103
WhatwouldbetheequilibriumpartialpressureofgasCifinitialpressureofgasA&Bare1&2atm
respectively.
(A)0.0625atm (B)0.1875atm (C)0.21atm (D)Noneofthese

Q.20 A20.0litrevesselinitiallycontains0.50moleeachofH2andI2gases.Thesesubstancesreactandfinally
reachanequilibriumcondition.CalculatetheequilibriumconcentrationofHIifKeq=49forthereaction
H2 +I2 l 2HI.
(A)0.78M (B)0.039M (C)0.033M (D)0.021M

Q.21 Avesselof250litrewasfilledwith0.01moleofSb2S3and0.01moleofH2toattaintheequilibriumat
440CasSb2S3(s)+3H2(g)l2Sb(s)+3H2S(g).
AfterequilibriumtheH2SformedwasanalysedbydissolvingitinwaterandtreatingwithexcessofPb2+
togive1.195gofPbS(Molecularweight=239)precipitate.
WhatisvalueofKcofthereactionat440C?
(A)1 (B)2 (C)4 (D)Noneofthese

Q.22 TheequilibriumconstantforthereactionCO(g)+H2O(g)lCO2(g)+H2(g)is3at500K.Ina2litre
vessel60gmofwatergas[equimolarmixtureofCO(g)andH2(g)]and90gmofsteamisinitiallytaken.
WhatistheequilibriumconcentrationofH2(g)atequilibrium(mole/L)?
(A)1.75 (B)3.5 (C)1.5 (D)0.75

Q.23 At87C,thefollowingequilibriumisestablished
H2(g)+S(s)lH2S(g) Kp=7102
If0.50moleofhydrogenand1.0moleofsulfurareheatedto87Cin1.0Lvessel,whatwillbethe
partialpressureofH2Satequilibrium?
(A)0.966atm (B)1.38atm (C)0.0327atm (D)9.66atm

CHEMICAL EQUILIBRIUM [26]

Q.24 Atcertaintemperature(T)forthegasphasereaction
2H2O(g)+2Cl2(g)l4HCl(g)+O2(g) Kp=12108atm
IfCl2,HCl&O2aremixedinsuchamannerthatthepartialpressureofeachis2atmandthemixtureis
broughintocontactwithexcessofliquidwater.WhatwouldbeapproximatepartialpressureofCl2
whenequilibriumisattainedattemperature(T)?
[Given : Vapour pressure of water is 380 mm Hg at temperature (T)]
(A)3.6105atm (B)104atm (C)3.6103atm (D)0.01atm

Q.25 At675K,H2(g)andCO2(g)reacttoformCO(g)andH2O(g),Kpforthereactionis0.16.
Ifamixtureof0.25moleofH2(g)and0.25molofCO2isheatedat675K,mole%ofCO(g)in
equilibriummixtureis:
(A)7.14 (B)14.28 (C)28.57 (D)33.33

Q.26 Inwhichofthefollowingreactions,increaseinthepressureatconstanttemperaturedoesnotaffectthe
molesatequliibrium:
1
(A)2NH3(g)lN2(g)+3H2(g) (B)C(g)+ O2(g)lCO(g)
2
1
(C)H2(g)+ O2(g)lH2O(g) (D)H2(g)+I2(g)l2HI(g)
2

Q.27 Changeinvolumeofthesystemdoesnotalterthenumberofmolesinwhichofthefollowingequilibrium
(A)N2(g)+O2(g)l2NO(g) (B)PCl5(g)lPCl3(g)+Cl2(g)
(C)N2(g)+3H2(g)l2NH3(g) (D)SO2Cl2(g)lSO2(g)+Cl2(g)

Q.28 Theconditionsfavourableforthereaction:
2SO2(g)+O2(g)l2SO3(g);H=198kJ
are:
(A)lowtemperature,highpressure (B)anyvalueofTandP
(C)lowtemperatureandlowpressure (D)hightemperatureandhighpressure

Q.29 TheexothermicformationofClF3isrepresentedbytheequation:
Cl2(g)+3F2(g) l2ClF3(g) H=329kJ
WhichofthefollowingwillincreasethequantityofClF3inanequilibriummixtureofCl2,F2andClF3:
(A)Increasingthetemperature (B)RemovingCl2
(C)Increasingthevolumeofcontainer (D)AddingF2

Q.30 Densitiesofdiamondandgraphiteare3.5and2.3gm/mL.
C(diamond)lC(graphite) rH=1.9kJ/mole
favourableconditionsforformationofdiamondare
(A)highpressureandlowtemperature (B)lowpressureandhightemperature
(C)highpressureandhightemperature (D)lowpressureandlowtemperature

Q.31 TheequilibriumSO2Cl2(g)lSO2(g)+Cl2(g)isattainedat25Cinaclosedrigidcontainerandaninert
gas,heliumisintroduced.Whichofthefollowingstatementsis/arecorrect.
(A)concentrationsofSO2,Cl2andSO2Cl2donotchange
(B)morechlorineisformed
(C)concentrationofSO2isreduced
(D)moreSO2Cl2isformed
CHEMICAL EQUILIBRIUM [27]
Q.32 Followingtwoequilibriumissimultaneouslyestablishedinacontainer
PCl5(g) PCl3(g)+Cl2(g)
CO(g)+Cl2(g) COCl2(g)
IfsomeNi(s)isintroducedinthecontainerformingNi(CO)4(g)thenatnewequilibrium
(A)PCl3concentrationwillincrease (B)PCl3concentrationwilldecrease
(C)Cl2concentrationwillremainsame (D)COconcentrationwillremainsame

Q.33 Theyieldofproductinthereaction
2A(g)+B(g) 2C(g)+QkJ
wouldbelowerat:
(A)lowtemperatureandlowpressure (B)hightemperature&highpressure
(C)lowtemperatureandtohighpressure (D)hightemperature&lowpressure

Q.34 What is the effect of the reduction of thevolume of the system for the equilibrium 2C(s) + O2(g)l2CO(g)?
(A)Theequilibriumwillbeshiftedtotheleftbytheincreasedpressurecausedbythereductionin
volume.
(B)Theequilibriumwillbeshiftedtotherightbythedecreasedpressurecausedbythereductionin
volume.
(C)Theequilibriumwillbeshiftedtotheleftbytheincreasedpressurecausedbytheincreaseinvolume.
(D)Theequilibriumwillbeshiftedtotherightbytheincreasedpressurecausedbythereductionin
volume.

Q.35 ThevapourdensityofN2O4atacertaintemperatureis30.Whatisthe%dissociationofN2O4atthis
temperature?
(A)53.3% (B)106.6% (C)26.7% (D)None

Q.36 TheequilibriumconstantKP(inatm)forthereactionis9at7atmand300K.
A2(g)lB2(g)+C2(g)
Calculatetheaveragemolarmass(ingm/mol)ofanequilibriummixture.
Given :MolarmassofA2,B2andC2are70,49&21gm/molrespectively.
(A)50 (B)45 (C)40 (D)37.5

Q.37 Vapourdensityoftheequilibriummixtureofthereaction
2NH3(g)lN2(g)+3H2(g)is6.0
Percentdissociationofammoniagasis:
(A)13.88 (B)58.82 (C)41.66 (D)Noneofthese

Q.38 EquimolarmixtureoftwogasesA2andB2istakeninarigidvesselattemperature300K.Thegases
reactsaccordingtogivenequations:
A2(g)l2A(g) K P1 ?
B2(g)l2B(g) K P2 ?
A2(g)+B2(g)l2AB(g) K P3 2
Iftheinitialpressureinthecontainerwas2atmandfinalpressuredevelopedatequilibriumis2.75atm
K P2
inwhichequilibriumpartialpressureofgasABwas0.5atm,calculatetheratioof K .
P1
[Given : Degree of dissociation of B2 is greater than A2].
(A)8 (B)9 (C)1/8 (D)Noneofthese
CHEMICAL EQUILIBRIUM [28]
Q.39 Theequilibriumconstants K P and K P forthereactions
1 2

Xl2YandZlP+Q,respectivelyareintheratioof1:9.IfthedegreeofdissociationofXand
Zbeequalthentheratiooftotalpressuresattheseequilibriais:
(A)1:36 (B)1:1 (C)1:3 (D)1:9

Q.40 WhenN2O5isheatedattemp.T,itdissociatesas N 2 O 5 l N 2O 3 O 2 ,Kc=2.5.Atthesametime

N2O3alsodecomposesas:N2O3 lN2O+O2.Ifinitially4.0molesofN2O5aretakenin1.0litreflask
andallowedtoattainequilibrium,concentrationofO2wasformedtobe2.5M.Equilibriumconcentration
ofN2Ois
(A)1.0 (B)1.5 (C)2.166 (D)0.334

Q.41 Anexothermicreactionisrepresentedbythegraph:

(A) (B) (C) (D)

Q.42 Thecorrectrelationshipbetweenfreeenergychangeinareactionandthecorrespondingequilibrium
constantKis
(A)G=RTlnK (B)G=RTlnK (C)G=RTlnK (D)G=RTlnK

o
Q.43 Thevalueof G f ofgaseousmercuryis31KJ/mole.Atwhattotalexternalpressuremercurystart
boilingat25C.[R=8.3J/Kmole]
(A)105.44 (B)1012.5 (C)106.52 (D)103.12

Q.44 WhatisrG(KJ/mole)forsynthesisofammoniaat298Katfollowingsetsofpartialpressure:
N2(g)+3H2(g)l2NH3(g);rG=33KJ/mole.[TakeR=8.3J/Kmole,log2=0.3;log3=0.48]
Gas N2 H2 NH3
Pressure(atm) 1 3 0.02
(A)+6.5 (B)6.5 (C)+60.5 (D)60.5

Q.45 Gforthedissociationofthedimer(A2 l2A)inbenzenesolutionat27Cis6.909kcal/mol.

If8molesofAisdissolvedin10dm3ofbenzeneat27C.Whatistheratioofequilibriumconcentration
ofmonomertodimer [A] [A 2 ] ?Given:R=2Cal/mol.K
(A)1:200 (B)1:100 (C)200:1 (D)800:1

Q.46 ForthereactiontakesplaceatcertaintemperatureNH4HS(s)lNH3(g)+H2S(g),
ifequilibriumpressureisXbar,thenrGwouldbe
(A)2RTlnX (B)RTln(Xln2)
(C)2RT(lnXln2) (D)Noneofthese

CHEMICAL EQUILIBRIUM [29]

Q.47 Calculate log10 {[C]eq [A]eq } where[C]and[A]areequilibriummolarconcentrationofrespective
species,when2moleeachofAandBwereallowedtocometoequilibriumat900K.
A+B C+D ; G=460.6Calorie
Take: lnX 2.303 log X
R 2 Cal / K mole
(A)5.561002 (B)5.571003
(C)1.1102 (D)1.1103

More than one may be correct

Q.48 ForthereactionPCl5(g)lPCl3(g)+Cl2(g),theforwardreactionatconstanttemperatureisfavouredby
(A)introducinganinertgasatconstantvolume
(B)introducingchlorinegasatconstantvolume
(C)introducinganinertgasatconstantpressure
(D)introducingPCl5atconstantvolume.

Q.49 WhenNaNO3isheatedinaclosedvessel,oxygenisliberatedandNaNO2isleftbehind.Atequilibrium
(A)additionofNaNO2favoursreversereaction
(B)additionofNaNO3favoursforwardreaction
(C)increasingtemperaturefavoursforwardreaction
(D)increasingpressurefavoursreversereaction

Q.50 Forthegasphasereaction,C2H4+H2 lC2H6(H=32.7kcal),carriedoutinaclosedvessel,the

equilibriummolesofC2H4canbeincreasedby
(A)increasingthetemperature (B)decreasingthepressure
(C)removingsomeH2 (D)addingsomeC2H6

Q.51 PhasediagramofCO2isshownasfollowing

73
Solid Liquid
67
P(atm)
5

1 Gas

195 217 298 304

T(K)
Basedonabovefindthecorrectstatement(s)
(A)298KisthenormalboilingpointofliquidCO2
(B)At1atm&190KCO2willexistasgas.
(C)CO2(s)willsublimeabove195Kundernormalatmosphericpressure
(D)Meltingpoint&boilingpointofCO2willincreaseonincreasingpressure

CHEMICAL EQUILIBRIUM [30]

Q.52 Theequilibriumbetween,gaseousisomersA,BandCcanberepresentedas
Reaction Equilibrium constant
A(g)lB(g) : K1=?
B(g)lC(g) : K2=0.4
C(g)lA(g) : K3=0.6
IfonemoleofAistakeninaclosedvesselofvolume1litre,then
(A)[A]+[B]+[C]=1Matanytimeofthereactions
(B)ConcentrationofCis4.1Mattheattainmentequilibriuminallthereactions
1
(C)ThevalueofK1is
0.24
(D)Isomer[A]isleaststableasperthermodynamics.

Q.53 Forthegasphaseexothermicreaction,A2+B2 lC2,carriedoutinaclosedvessel,theequilibrium

molesofA2canbeincreasedby
(A)increasingthetemperature (B)decreasingthepressure
(C)addinginertgasatconstantpressure (D)removingsomeC2

Q.54 ConsidertheequilibriumHgO(s)+4I(aq)+H2O(l)lHgI42(aq)+2OH(aq),whichchangeswill
decreasetheequilibriumconcentrationofHgI42
(A)Additionof0.1MHI(aq) (B)AdditionofHgO(s)
(C)AdditionofH2O(l) (D)AdditionofKOH(aq)

Q.55 Inthelaboratorytheequilibriumconstantforaparticularreactioncanbemeasuredatdifferent
temperatures.Plottingthedatayieldsthegraphshown.Whichofthefollowingstatementsisfalse?
(Note:Thenotation4.40e4isequivalentto4.40104)

(A)Scanbeobtainedfromthey-intercept
(B)Theslopeofthelineisequalto+(H/R)
(C)Thereactionisendothermic
(D)Thestandardfreeenergychangeofthereactionispositive.

Q.56 Decreaseinthepressureforthefollowingequilibria:H2O(s)lH2O(l)resultinthe:
(A)formationofmoreH2O(s) (B)formationofmoreH2O(l)
(C)increaseinmeltingpointofH2O(s) (D)decreaseinmeltingpointofH2O(s)

CHEMICAL EQUILIBRIUM [31]

Assertion Reason

Q.57 Statement -1 : Totalnumberofmolesinaclosedsystematnewequilibriumislessthantheoldequilibrium

ifsomeamountofasubstanceisremovedfromasystem
(considerareactionA(g) B(g) )atequilibrium.
Statement -2 : Thenumberofmolesofthesubstancewhichisremoved,ispartiallycompensatedasthe
systemreachedtonewequilibrium.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.

Q.58 Statement-1 : Anexothermicreaction,non-spontaneousathightemperature,maybecome

spontaneousatlowtemperature.
Statement-2 : Entropyofanexothermicreactionalwaysdecreaseswithdecreasein
temperature.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.

Q.59 Statement-1 : Ammoniaatapressureof10atmandCO2atapressureof20atmareintroduced

intoanevacuatedchamber.IfKpforthereaction
NH2COONH4(s)l2NH3 (g)+CO2(g)is2020atm3,thetotalpressure
afteralongtimeislessthan30atm.
Statement-2 : Equilibriumcanbeattainedfrombothdirections.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.

Comprehension :
Paragraph for Question Nos. 60 to 63
Ina7.0Levacuatedchamber ,0.50molH2and0.50molI2reactat427C.
H2(g)+I2(g)l 2HI(g).Atthegiventemperature,KC=49forthereaction.
Q.60 WhatisthevalueofKp?
(A)7 (B)49 (C)24.5 (D)None

Q.61 Whatisthetotalpressure(atm)inthechamber?
(A)83.14 (B)831.4 (C)8.21 (D)None

Q.62 Howmanymolesoftheiodineremainunreactedatequilibrium?
(A)0.388 (B)0.112 (C)0.25 (D)0.125

Q.63 Whatisthepartialpressure(atm)ofHIintheequilibriummixture?
(A)6.385 (B)12.77 (C)40.768 (D)646.58

CHEMICAL EQUILIBRIUM [32]

 Paragraph for Question Nos. 64 to 66
Equilibriumconstantsaregiven(inatm)forthefollowingreactionsat0C:
SrCl26H2O(s)lSrCl22H2O(s)+4H2O(g) Kp=51012
Na2HPO412H2O(s)lNa2HPO47H2O(s)+5H2O(g) Kp=2.431013
Na2SO4 10H2O(s)lNa2SO4(s)+10H2O(g) Kp=1.0241027
Thevaporpressureofwaterat0Cis4.56torr.
Q.64 Whichisthemosteffectivedryingagentat0C?
(A)SrCl2 2H2O (B)Na2HPO47H2O (C)Na2SO4 (D)allequally

Q.65 AtwhatrelativehumiditieswillNa2SO4 10H2Obeefflorescent(releasemoisture)whenexposedto

airat0C?
(A)above33.33% (B)below33.33% (C)above66.66% (D)below66.66%

Q.66 AtwhatrelativehumiditieswillNa2SO4bedeliquescent(i.e.absorbmoisture)whenexposedtotheair
at0C?
(A)above33.33% (B)below33.33% (C)above66.66% (D)below66.66%

Paragraph for Question Nos. 67 to 69

Ifweknowtheequilibriumconstantforaparticularreaction,wecancalculatetheconcentrationsinthe
equilibriummixturefromtheinitialconcentrations.Commonlyonlytheinitialconcentrationofreactants
aregiven.
Q.67 Inastudyofequilibrium
H2(g)+I2(g)l2HI(g)
1molofH2and3molofI2gaveriseatequilibriumtoxmolofHI.
Additionofafurther2molofH2gaveanadditionalxmolofHI.Whatisx?
(A)0.5 (B)1 (C)1.5 (D)Noneofthese

Q.68 Inaboveproblem,whatisKpatthetemperatureoftheexperiment.
(A)1 (B)2 (C)4 (D)Noneofthese

Q.69 Inastudyofequilibrium
2SO2(g)+O2(g)l 2SO3(g).
Startingwith2moleSO2and1.5moleO2in5litreflask.Equilibriummixturerequired0.4moleKMnO4
inacidicmedium.HenceKCis:
(A)0.2 (B)5.0 (C)675.0 (D)Noneofthese

Match the column :

Q.70 Column I Column II

(A) KP<KC (P) N2 + 3H2 l 2NH3

(B) Introductionofinertgasat (Q) PCl5(g)lPCl3(g)+Cl2(g)

constantpressurewilldecrease
theconcentrationofreactants

(C) K oP isdimensionless (R) 2NO2 (g)l N2O4 (g)

(D) Temperatureincreasewillshift (S) NH3(g)+HI(g)lNH4I(s)

thereactiononproductside.
CHEMICAL EQUILIBRIUM [33]
 EXERCISE IV

Q.1 The degree of dissociation is 0.4 at 400K & 1.0 atm for the gasoeus reaction
PCl5 lPCl3+Cl2(g).Assumingidealbehaviourofallgases.Calculatethedensityofequilibrium
mixtureat400K&1.0atmpressure. [JEE 1999]

Q.2 When3.06gofsolidNH4HSisintroducedintoatwolitreevacuatedflaskat27C,30%ofthesolid
decomposesintogaseousammoniaandhydrogensulphide.
(i) CalculateKC&KPforthereactionat27C.
(ii) WhatwouldhappentotheequilibriumwhenmoresolidNH4HSisintroducedintotheflask?
[JEE 2000]

Q.3 WhentworeactantsAandBaremixedtogiveproductsCandD,thereactionquotientQ,attheinitial
stagesofthereaction: [JEE 2000]
(A)iszero (B)decreasewithtime
(C)independentoftime (D)increaseswithtime

Q.4 Forthereversiblereaction: [JEE 2000]

N2(g)+3H2(g)l 2NH3(g)at500C.ThevalueofKpis1.44105,whenpartialpressureis
measuredinatmospheres.ThecorrespondingvalueofKcwithconcentrationinmolL1is:
(A)1.44105/(0.082500)2 (B)1.44105/(8.314773)2
5
(C)1.4410 /(0.082500) 2 (D)1.44105/(0.082773)2

Q.5 Atconstanttemperature,theequilibriumconstant(KP)forthedecompositionreaction.N2O4 l 2NO2

isexpressedbyKP=4x2P/(1x2)wherePispressure,xisextentofdecomposition.Whichofthe
followingstatementistrue? [JEE 2001]
(A)KPincreaseswithincreaseofP
(B)KPincreaseswithincreaseofx
(C)KPincreaseswithdecreaseofx
(D)KPremainsconstantwithchangeinPorx

Q.6 When1-pentyne(A)istreatedwith4NalcoholicKOHat175C,itisconvertedslowlyintoanequilibrium
mixtureof1.3%1-pentyne(A),95.2%2pentyne(B)&3.5%of1,2,pentadiene(C).Theequilibrium
wasmaintainedat1750C.CalculateGforthefollowingequilibria.
B=A G10=?
B=C G20=?
FromthecalculatedvalueofG10&G20indicatetheorderofstabilityofA,B&C.Writeareasonable
reactionmechanismsharingallintermediateleadingtoA,B&C. [JEE 2001]

Q.7 Considerthefollowingequilibriuminaclosedcontainer:N2O4(g)l2NO2(g).
Atafixedtemperature,thevolumeofthereactioncontainerishalved.Forthischange,whichofthe
followingstatementsholdstrueregardingtheequilibriumconstant(KP)anddegreeofdissociation():
(A)NeitherKPnorchanges [JEE 2002]
(B)BothKPandchange
(C)KPchanges,butdoesnotchange
(D)KPdoesnotchange,butchanges

CHEMICAL EQUILIBRIUM [34]

Q.8 N2O4(g) l 2NO2(g)
Thisreactioniscarriedoutat298Kand20bar.5moleachofN2O4andNO2aretakeninitially.
Given: G oN 2O 4 =100kJmol1; G oNO2 =50kJmol1
(i) FindGforreactionat298Kundergivencondition.
(ii) Findthedirectioninwhichthereactionproceedstoachieveequilibrium. [JEE 2004]

Q.9 IfAg++NH3 l[Ag(NH3)]+ ; K1=1.6103and [JEE 2006]

+
[Ag(NH3)] +NH3 l[Ag(NH3)2] +
; K2=6.8103 .
Theformationconstantof[Ag(NH3)2]+is:
(A)6.08106 (B)6.8106 (C)1.6103 (D)1.088107

Q.10 N2 + 3H2 l 2NH3

WhichiscorrectstatementifN2isaddedatequilibriumcondition?
(A)TheequilibriumwillshifttoforwarddirectionbecauseaccordingtoIIlawofthermodynamicsthe
entropymustincreasesinthedirectionofspontaneousreaction.
(B)Theconditionforequilibriumis G N 2 3G H 2 2G NH 3 whereGisGibbsfreeenergypermoleofthe
gaseousspeciesmeasuredatthatpartialpressure.Theconditionofequilibriumisunaffectedbythe
useofcatalyst,whichincreasestherateofboththeforwardandbackwardreactionstothesame
extent.
(C)Thecatalystwillincreasetherateofforwardreactionbyandthatofbackwardreactionby.
(D)Catalystwillnotaltertherateofeitherofthereaction. [JEE 2006]

Q.11 STATEMENT-1: Foreverychemicalreactionatequilibrium,standardGibbsenergyofreaction

iszero
and
STATEMENT-2: Atconstanttemperatureandpressure,chemicalreactionsarespontaneousin
thedirectionofdecreasingGibbsenergy.
(A)STATEMENT-1isTrue,STATEMENT-2isTrue;STATEMENT-2isacorrectexplanationfor
STATEMENT-1
(B)STATEMENT-1isTrue,STATEMENT-2isTrue;STATEMENT-2isNOTacorrectexplanation
forSTATEMENT-1
(C)STATEMENT-1isTrue,STATEMENT-2isFalse
(D)STATEMENT-1isFalse,STATEMENT-2isTrue [JEE 2008]

CHEMICAL EQUILIBRIUM [35]

 ANSWER KEY
EXERCISE I
Q.1 (a)25,shiftsleft,(b)0.22,shiftsright,(c),shiftsleft,(d)1,shiftsright,(e)0,shiftright

Q.2 (a)K=[Ag+][Cl]islessthan1.AgClisinsolublethustheconcentrationofionsaremuchlessthan1M
(b)K=1/[Pb2+][Cl]2isgreaterthanonebecausePbCl2isinsolubleandformationofthesolidwill
reducetheconcentrationofionstoalowlevel

Q.4 Kabout10 Q.6(a)incomplete(b)almostcomplete

Q.7 c Q.8 ~91032mol/L

Q.9 ThereactionisnotanequilibriumbecauseQc>Kc.Thereactionwillproceedfromrighttolefttoreach
equilibrium

Q.11 5.9103M Q.12 [NO]=0.056M,[N2]=[O2]=1.37M

Q.13 [PCl3]=[Cl2]=0.071M,[PCl5]=0.089

Q.14 PCIF= PF2 =0.389atm, PClF3 =1.08atm

Q.15 KP=0.4,a~0.1 Q.16 50%

Q.17 (a) 6.667 10 3 mol L 1 ; (b) n (N 2 O 4 ) = 0.374 mol; n (NO 2 ) = 0.052 mol ;
(c)10.49atm(d)6.44%

Q.18 0.97atm Q.19 KP=1.310 3 atm 2

Q.20 Kp=2.5atm,P=15atm Q.21 53.33%

Q.22 K=4 Q.23 31/27 Q.24 22.4mg

Q.25 PH 2O =51015atm Q.26 0.821atm

Q.27 addN2,addH2,increasethepressure,heatthereaction

Q.28 (a)shiftright,shiftleft,(b)shiftright,noeffect,(c)shiftleft,shiftleft,(d)shiftleft,shiftright

Q.29 (a)K=[CH3OH]/[H2]2[CO],
(b)1.[H2]increase,[CO]decrease,[CH3OH]increase;2.[H2]increase,[CO]decrease,[CH3OH]
decrease;3.[H2]increase,[CO]increase,[CH3OH]increase;4.[H2]increase,[CO]increase,
[CH3OH]increase;5.[H2]increase,[CO]increase,[CH3OH]decrease;6.nochange
Q.30 (a)K=[CO][H2]/[H2O];
(b)ineachofthefollowingcasesthemassofcarbonwillchange,butitsconcentration(activity)willnot
change.1.[H2O]nochange,[CO]nochange,[H2]nochange;2.[H2O]decrease,[CO]decrease,
[H2]decrease;3.[H2O]increase,[CO]increase,[H2]decrease;4.[H2O]increase,[CO]increase,
[H2]increase;5.[H2O]decrease,[CO]increase,[H2]increase
CHEMICAL EQUILIBRIUM [36]
Q.31 b

Q.32 AddNaClorsomeothersaltthatproducesClinthesolution.Coolthesolution.

Q.33 a

kf [C]
Q.34 kf[A][B]=kr[C]; k [A][B] =kc Q.36 216
r

Q.38 (i)2;(ii)1.2mol/L;(iii)0.1moles/hr

Q.39 krincreasemorethankf,thismeansthatEa(reverse)isgreaterthanEa(forward).Thereactionis
exothermicwhenEa(reverse)>Ea(forward).

Q.42 16.06kJ Q.43 810J/mol;5872J/moland41.3kJ/mol

Q.44 1.3108 Q.45 0.058

Q.46 29.0 Q.47 Kp=0.0313atm,Kc=1.28103

Q.48 1.005kJ/mol Q.49 G=0;K=1

Q.50 H=9.04kJ/mol;S=8.64J/mol1K1

PROFICIENCY TEST

1 1
1. C 2. high 3. 4.
10 K

5. exothermic 6. KP=KC(RT) 7. backward 8. G=RTlnK

K2 H T2 T1
9. log K = 10. zero 11. mol2L2
1 2.303 R T2 T1

12. temperature 13. GuldbergandWaage 14. decreases

15. backward 16. high 17. KP=KC(RT)n

18. decreases 19. sameamountof 20. largervalueof

21. T 22. T 23. F 24. F

25. T 26. F 27. T 28. T

29. F 30. T 31. T 32. T

CHEMICAL EQUILIBRIUM [37]

33. F 34. F 35. F 36. F

37. T 38. F 39. T 40. F

EXERCISE II

Q.1 2.4mole Q.2 Kp=0.01atm Q.3 0.379atm

Q.4 PCS =1.284atm,PS2=0.1365atm Q.5 300L

2

Q.6 2.7g/lit Q.7 p Na =0.843MPa;p Na =0.170MPa; k p =0.239

2

Q.8 V=144mL Q.9 9.34g

Q.10 Kc=54,nHI=0.9mol,nI2 =0.05mol,nH2=0.3mol

Q.11 48atm Q.12 nCO2 =0.938,nH2 =1.938,nCO=0.062,nH2Og=4.062

Q.13 6.7110 4

Q.14 =0.5 Q.15 Kc=1/12,[R]=4(initial),=1.5(final)

Q.16 K=707.2,backwardreactionisfavoured Q.17 Kc=480

Q.18 Tobeproved Q.19 CuSO4 .5H2 O=9.2104 mol,CuSO4 =810 5 moles

Q.20 (a)400mm2,900mm2 (b)4:9,(c)72.15mmHg

Q.21 4 Q.22 337mmHg

Q.23 KA=779.4,KB=6.07410 5 ;Kc=1.28310 3

Q.24 Kp=1.86210 12 atm1/2

Q.25 p CO 2 =202.65kPa; p H2 O =3.16kPa;p CO=0.124kPa

CHEMICAL EQUILIBRIUM [38]

 EXERCISE III

Q.1 A Q.2 A Q.3 B Q.4 A Q.5 C Q.6 B Q.7 D

Q.8 A Q.9 A Q.10 B Q.11 B Q.12 D Q.13 C Q.14 A

Q.15 A Q.16 D Q.17 C Q.18 B Q.19 B Q.20 B Q.21 A

Q.22 A Q.23 A Q.24 C Q.25 B Q.26 D Q.27 A Q.28 A

Q.29 D Q.30 C Q.31 A Q.32 B Q.33 D Q.34 A Q.35 A

Q.36 C Q.37 C Q.38 A Q.39 A Q.40 D Q.41 A Q.42 A

Q.43 A Q.44 D Q.45 Q.46 C Q.47 A Q.48 C,D Q.49 C,D

Q.50 A,B,C,D Q.51 C,D Q.52 A,C,D Q.53 A,B,C

Q.54 C,D Q.55 B,D Q.56 A,C Q.57 B Q.58 C Q.59 D

Q.60 B Q.61 C Q.62 B Q.63 A Q.64 A Q.65 B Q.66 A

Q.67 C Q.68 C Q.69 B

Q.70 (A)P,R,S(B)P,Q,R,S(C)P,Q,R,S(D)Q

EXERCISE IV
Q.1 4.54gdm3

Q.2 (i)Kc=8.1105mol2L2;Kp=4.91102atm2(ii)Noeffect;

Q.3 D Q.4 D Q.5 D

Q.6 15991Jmol1,12304Jmol1;B>C>A Q.7 D

Q.8 (i)5.705103Jmol1
(ii)SinceinitialGibbsfreeenergychangeofthereactionispositive,sothereversereactionwilltake
place

Q.9 D Q.10 B Q.11 D

CHEMICAL EQUILIBRIUM [39]