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ChemWiki:TheDynamicChemistryEtextbook>PhysicalChemistry>Equilibria>ChemicalEquilibria>TheEquilibriumConstant

The Equilibrium Constant

Theequilibriumconstant,K,expressestherelationshipbetweenproductsandreactantsofareactionatequilibriumwithrespecttoaspecificunit.
Therearetwodifferenttypesofequilibriumreactions:(1)heterogeneousand(2)homogeneous.Thisarticleillustratesthedifferencebetweenthe
two, explains how to write equilibrium constants for both, and introduces the calculations involved with both the concentration and the partial
pressureequilibriumconstant.

Introduction
As mentioned above, there are two types of equilibrium reactions. It is important to understand the difference between the two, because their
equilibriumconstantsareexpresseddifferently.

Homogeneous
Thesimplerone,ahomogeneousreaction,isonewherethestatesofmatteroftheproductsandreactionsareallthesame(theword"homo"means
"same"). In most cases, the solvent determines the state of matter for the overall reaction. For example, the synthesis of methanol from a carbon
monoxidehydrogenmixtureisagaseoushomogeneousmixture,whichcontainstwoormoresubstances:
C O(g) + 2H2 (g) C H3 OH (g)

Atequilibrium,therateoftheforwardandreversereactionareequal,whichisdemonstratedbythearrows.Theequilibriumconstant,however,gives
theratiooftheunits(pressureorconcentration)oftheproductstothereactantswhenthereactionisatequilibrium.
Thesynthesisofammoniaisanotherexampleofagaseoushomogeneousmixture:
N 2 (g) + 3H2 (g) 2N H3 (g)

Heterogeneous
Aheterogeneousreactionisonewhereoneormorestateswithinthereactiondiffer(theGreekword"heteros"means"different").Forexample,the
formationofanaqueoussolutionoflead(II)iodidecreatesaheterogeneousmixturedealingwithmoleculesinboththesolidandaqueousstates:
P bI 2 (s) P b

+2

(aq) + 2I

(aq)

The decomposition of sodium hydrogen carbonate (baking soda) at high elevations is another example of a heterogeneous mixture, this reaction
dealswithmoleculesinboththesolidandgaseousstates:
2N aH C O3 (s) N a 2 C O3 (s) + H2 O(g) + C O2 (g)
C (s) + O2 (g) C O2 (g)

Once again, this difference is emphasized so that students remember that equilibrium constant calculations are different from heterogeneous
mixtures.

Writing Equilibrium Constants


An equilibrium constant is obtained by letting a single reaction proceed to equilibrium and then measuring the concentrations of each molecule
involvedinthatreactionandcreatingaratiooftheproductconcentrationstoreactantconcentrations.Becausetheconcentrationsaremeasuredat
equilibrium,theequilibriumconstantisremainthesameforagivenreactionindependentofinitialconcentrations,whichdeterminetherate(foran
idealreaction).Thisknowledgeallowedscientiststoderiveamodelexpressionthatcanserveasa"template"foranyreaction.Thisbasic"template"
formofahomogeneousequilibriumconstantisexaminedhere.
Thisdiscussionmakesuseofthefollowinghypotheticalreaction:
aA(g) + bB(g) gG(g) + hH (g)

*Thelowercaselettersrepresentthenumberofmolesofeachmolecule,theuppercaselettersrepresentthemoleculeitself,andthelettersinthe

parenthesisalwaysrepresentsthestateofmatterofthemolecule.

Equilibrium Constant of Concentration


Theequilibriumconstantofconcentrationgivestheratioofconcentrationsofproductsoverreactantsforareactionthatisatequilibrium.Thisis
usuallyusedwhenthestateofmatterforthereactionis(aq).TheequilibriumconstantexpressioniswrittenasKc,asintheexpressionbelow:
g

[G] [H ]
Kc =
[A]

[B]

IfK>1thenequilibriumfavorsproducts
IfK<1thenequilibriumfavorsthereactants
Here,thelettersinsidethebracketsrepresenttheconcentrationofeachmolecule.Noticethemathematicalproductofthechemicalproductsraisedto
thepowersoftheirrespectivecoefficientsisthenumeratoroftheratioandthemathematicalproductofthereactantsraisedtothepowersoftheir
respective coefficients is the denominator. This is the case for every equilibrium constant. Keep in mind that this expression was obtained by a
homogeneous equilibrium reaction. K represents an equilibrium constant and c represents concentration (K_c). This means that every molecule
showsupintheexpression,aslongasitisasolutionoragas.

Equilibrium Constant of Pressure


Gaseousreactionequilibriaarenotexpressedintermsofconcentration,butinsteadintermsofpartialpressures.Theequilibriumconstantofpressure
givestheratioofpressureofproductsoverreactantsforareactionthatisatequilibrium(again,theconcentrationsofallspeciesareraisedtothe
powersoftheirrespectiveconcentrations).TheequilibriumconstantiswrittenasKp,asshownbelow:
g

p
Kp =

Wherepcanhaveunitsofatmorbar.
Theprocedureforthisisthesameastheprocedurefortheconcentrationconstantabove.

Conversion of K c to K p
ToconvertKctoKp,thefollowingequationisused:
Kp = Kc (RT )

n gas

where:
1K1or8.31447Jmol
1K1
R=0.0820575Latmmol
T=TemperatureinKelvin
ngas=Molesofgas(product)MolesofGas(Reactant)

Reaction Quotient
Anotherquantityofinterestisthereactionquotient,Qc,whichisthesameratioconstantatanypointinthereactionatwhichthereactionisnotat
equilibrium. The reaction quotient is calculated the same way as is Kc, but is not necessarily equal to Kc. It is used to determine which way the
reactionwillproceedatanygivenpointintime.
g

[G] [H ]
Qc =
[A]

[B]

IfQc>Kc,thenthereactionsshiftstotheleft
Qc<Kc,thenthereactionsshiftstotheright
Qc=Kcthenthereactionisstillatequilibrium
*ThesameprocessisemployedwhencalculatingQp

Heterogeneous Mixture
Themostimportantconsiderationforaheterogeneousmixtureisthatsolidsandpureliquidsarealwaysexcludedfromtheequilibriumconstant.
Inamathematicalperspective,theactivitiesofsolidsandliquidseachequalone,whichdoesnotaffecttheoverallKvalue.Solventsalsoequalone.
The molarity of solids, liquids, and solvents remain constant throughout the reaction, which means their value can be denoted as 1. This rule is
extremelyimportanttoremember,especiallyindealingwithheterogeneoussolutions.

Example1
Inahypotheticalreaction:
aA(s) + bB(l) gG(aq) + hH (aq)

Theequilibriumconstantexpressioniswrittenasfollows:
[G
c

[H

= [G

[H

[G] [H ]
Kc =

h
g

= [G] [H ]

1 1

Inthiscase,sincesolidsandliquidsdonotaffecttheequilibriumconstantexpression,theexpressionisindependentfromtheconcentrationofthe
reactants. Thus, A and B are omitted the final expression. When the product of the reaction is a solvent, the numerator equals one, which is
illustratedinthefollowingreaction:
H

(aq) + OH

(aq) H2 O(l)

Theequilibriumconstantexpressionwouldbe:
1
Kc =
[H

][OH

whichistheinverseoftheautoionizationconstantofwater.
1
Kc =

= 1 10

Kw

Manipulation of Constants
Theequilibriumconstantexpressionmustbemanipulatedifareactionisreversedorsplitintoelementarysteps.Whenthereactionisreversed,the
equilibriumconstantexpressionisinverted.Thenewexpressionwouldbewrittenas:

[A]

[G] [H ]
[A]

[B]

[B]

[G] [H ]

Whentherearemultiplestepsinthereaction,eachwithitsownK(inascenariosimilartoHess'slawproblems),thenthesuccessiveKvaluesfor
eachsteparemultipliedtogethertocalculatetheoverallK.

Activity Series
Because the concentration of reactants and products are not dimensionless (i.e. they have units) in a reaction, the actual quantities used in an
equilibriumconstantexpressionareactivities.Activityisexpressedbythedimensionlessratio
andcisthechosenreferencestate:

[X]
c

where[X]signifiesthemolarityofthemolecule

[B]
ab =

Forgasesthatdonotfollowtheidealgaslaws,usingactivitieswillaccuratelydeterminetheequilibriumconstantthatchangeswhenconcentrationor
pressurevaries.Thus,theunitsarecanceledandKbecomesunitless.

Practice Problems
Writetheequilibriumconstantexpressionforeachreaction.
1. 2SO2 (g) + O2 (g) 2SO3 (g)
1
2. N 2 O(g) + 2 O2 (g) 2N O(g)
3. C u(s) + 2Ag + (aq) C u +2 (aq) + 2Ag(s)
4. C aC O3 (g) C aC O(s) + C O2 (g)
5. 2N aH C O3 (s) N a 2 C O3 (s) + C O2 (g) + H2 O(g)
WhatistheKc ofthefollowingreaction?
2SO2 (g) + O2 (g) 2SO3 (g)

withconcentrationSO2 (g) = 0.2M O2 (g) = 0.5M SO3 (g)


Also,WhatistheKp ofthisreaction?Atroomtemperature
2.Forthesamereaction,thedifferingconcentrations:SO2 (g)
Wouldthisgotowardstoproductorreactant?
WritethePartialPressureEquilibrium.
1.

= 0.7M

= 0.1M O2 (g) = 0.3M SO3 (g) = 0.5M

C (s) + O2 (g) C O2 (g)

WritethereactionforthisPartialPressure:

2
p

2.Kp

HI

=
PH

PI2

*Answersmaybefoundatbottomofpage(undercontributors).

References
1. Petrucci,RalphH.GeneralChemistry:PrinciplesandModernApplications9thEd.NewJersey:PearsonEducationInc.2007.
2. http://dwb.unl.edu/Teacher/NSF/C14/C14Links/learn.chem.vt.edu/tutorials/equilibrium/eqexpression.html

Outside Links
Formoreinformationonequilibriumconstantexpressionspleasevisitthewikipedia
site:http://en.wikipedia.org/wiki/Equilibrium_constant
Theimagebelowcanbefoundhere:http://image.tutorvista.com/content/chemicalequilibrium/reactionratetimegraph.gif

Answers to Practice Problems


1. Kc

[SO3 ]

=
[O2 ][SO2 ]

2. K c

[N O]
=
[ O2 ]

3. K c

[C u

0.5

+2

=
[Ag

[N 2 O]

[C O2 ]

4. K c

5. Kc

= [H2 O][C O2 ]

[C aC O3 ]

WhatisKc fortheReaction
1)Kc:24.5
Kp:1.002Atm
2)Qc=83.33>Kcthereforethereactionshiftstotheleft
1. Kp

PCO
=
PO

2. H2 (g) + I 2 (g)

2H I (g)

Contributors
HeatherVoigt
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