Final Review Session

Chemical Equilibrium
ExpressionforEquilibriumConstant

Considerthefollowingequilibriumsystem:
wA+xByC+zD
[C] y [D] z
Kc= [A] w [B] x

ThenumericalvalueofKciscalculatedusingthe
concentrationsofreactantsandproductsthatexistat
equilibrium.
Productsoverreactants
ExpressionsforEquilibriumConstants

Examples: [NH 3 ] 2
N2(g)+3H2(g)2NH3(g);Kc= [N 2 ][H 2 ]3

PCl5(g)PCl3(g)+Cl2(g); Kc= [PCl 3 ][Cl 2 ]

[PCl 5 ]
3
CH4(g)+H2(g)CO(g)+3H2(g);Kc= [CO][H 2 ]
[CH 4 ][H 2 O]
Relationshipsbetweenchemicalequationsandtheexpressions
ofequilibriumconstants
The expression of equilibrium constant depends on how the
equilibrium equation is written. For example, for the following
equilibrium: 2
[HI]
H2(g) + I2(g) 2 HI(g); Kc
[H 2 ][I 2 ]
For the reverse reaction:
[H 2 ][I 2 ]
2HI(g) H2(g) + I2(g); Kc ' 2
1/K c
[HI]
And for the reaction: HI(g) H2(g) + I2(g);
[H 2 ][ I 2 ]
Kc " 2
Kc ' 1
[HI] Kc
ExpressionandValuesof
EquilibriumConstantUsingPartialPressures

Considerthefollowingreactioninvolvinggases:
2SO2(g)+O2(g)2SO3(g)
2
(PSO3 )
Kp= (PSO2 ) 2 (PO2 )
RelationshipbetweenKcandKp
In general, for reactions involving gases such that,

aA + bB cC + dD
where A, B, C, and D are all gases, and a, b, c,
and d are their respective coefficients,
Kp = Kc(RT)n
and n = (c + d) (a + b)
n = (moles of gaseous product) (moles of gaseous reactant)
The Concentrations of Solids and
Liquids Are Essentially Constant
Therefore, the concentrations of solids
and liquids do not appear in the
equilibrium expression2+
PbCl2 (s) Pb (aq) + 2 Cl

(aq)

Kc = [Pb2+] [Cl]2
Homogeneous&HeterogeneousEquilibria

Homogeneousequilibria:
CH4(g)+H2O(g)CO(g)+3H2(g);
CO(g)+H2O(g)CO2(g)+H2(g);

Heterogeneousequilibria:
CaCO3(s)CaO(s)+CO2(g);
HF(aq)+H2O(l)H3O+(aq)+F(aq);
PbCl2(s)Pb2+(aq)+2Cl(aq);
Equilibrium constant is used to predict the direction of net
reaction
For a reaction of known Kc value, the direction of net reaction can be predicted by
calculating the reaction quotient, Qc.
Qc is called the reaction quotient, where for a reaction such as:
[C]c [ D] d
aA + bB cC + dD; Qc
[A] a [ B] b

Qc has the same expression as Kc , but

Qc is calculated using concentrations that are not necessarily at equilibrium.
ApplicationsofEquilibriumConstant

Foranysystemorreaction:
1. Knowingtheequilibriumconstant,wecanpredictwhetherornotareaction
mixtureisatequilibrium,andwecanpredictthedirectionofnetreaction.
Qc=Kcequilibrium(nonetreaction)
Qc<Kcanetforwardreaction;
Qc>Kcanetreversereaction
2. ThevalueofKtellsuswhetherareactionfavorstheproductsorthe
reactants.
Using the ICE table to calculate equilibrium
concentrations
Equation: H2(g) + I2(g) 2 HI(g),

Initial [ ], M 0.1000 0.1000 0.0000

Change [ ], M -x -x +2x
Equilibrium [ ], M (0.1000 - x) (0.1000 - x) 2x
2 2
[HI] (2 x )
Kc

55.6
[H 2 ][ I 2 ] (0.100 - x ) 2
Le Chteliers Principle
The Le Chtelier's principle states that:
when factors that influence an equilibrium are altered, the equilibrium will
shift to a new position that tends to minimize those changes.

Factors that influence equilibrium:

Concentration, temperature, and pressure (for gases only)
 Concentration
Changes
Add more reactant Shift to
products
Remove reactants Shift to
reactants
Add more product Shift to
reactants
Remove products Shift to
products
Temperature Changes
Exothermic Reactions

Consider heat as a product in

exothermic reactions.
A + B = AB +
Heat
Add heat
Shift to reactants
Remove heat
Shift to products
Temperature Changes
Endothermic Reactions

Consider heat as a reactant

in endothermic reactions.
A + B + heat
Add heat = AB

Shift to products
Remove heat
Shift to reactants
Pressure Changes

Only affects equilibrium

systems with unequal
moles of gaseous
reactants and products.
Presence of an Inert Substance
An inert substance is a substance that is
not- reactive with any species in the
equilibrium system.
These will not affect the equilibrium
system.
If the substance does react with a
species at equilibrium, then there will be
a shift!
Presence of a Catalyst
A Catalyst lowers the activation energy
and increases the reaction rate.
It will lower the forward and reverse
reaction rates,
Therefore, a catalyst has NO EFFECT on
a system at equilibrium!
It just gets you to equilibrium faster!
Catalysts increase the rate of both the
forward and reverse reactions.
Equilibrium is achieved faster, but the
equilibrium composition remains unaltered.