nA PA
[ A] = =
V RT
nB P
[ B] = = B
V RT
PA
Forward Reaction: Rate=k f
RT
PB
Reverse Reaction: Rate=kr
RT
Equilibrium is established when
the rate of the forward reaction
equals
the rate of the reverse reaction
PA PB
kf = kr
RT RT
PA k f
= =K
PB kr
PB kr 1
= = K' =
PA k f K
ZZX B
A YZZ
Law of Mass Action
ZZX cC + dD
aA + bB YZZ
[ C ]c [ D ]d
Q=
[ A] a [ B ] b
c d
[ Ceq ] [ Deq ]
Q( eq ) = K eq = a b
[ Aeq ] [ Beq ]
Pr oducts
K eq =
Re ac tan ts
Gaseous Equilibria
PCc PDd
K eq = a b
PA PB
Pi
Pi
Pr ef
Pr ef = 1atm
K eq is dimensionless
N 2O4 ( g ) U 2 NO2 ( g )
2
P
NO2
K eq =
PN2O4
Haber Process
N 2 ( g ) + 3H 2 ( g ) U 2 NH 3 ( g )
Magnitude of Keq
Characteristics of Equilibrium Constants
Given
H 2 ( g ) + I 2 ( g ) U 2 HI( g ) K eq =54.0
2 NH 3 ( g ) + 3I 2 ( g ) U 6 HI( g ) + N 2 ( g )
Calculating Equilibrium Constants
1. Given all concentrations
N 2 ( g ) + 3H 2 ( g ) U 2 NH 3 ( g )
2
PNH ( 0.166 )2 5
K eq = 3
= = 2 . 79 x10
PN 2 PH32 ( 2.46 )( 7.38 )3
0
PSO 3
= 0.500 atm ; PSO3 = 0.200atm
eq
2
P P
SO2 O2
K eq = 2
P SO3
Reaction Quotient
N 2 ( g ) + 3H 2 ( g ) U 2 NH 3 ( g )
Keq = 2.79x10-5
H 2 ( g ) + I 2 ( g ) U 2 HI( g ) K eq =50.5
Le Chateliers Principle
Add Product
H 2 ( g ) + I 2 ( g ) U 2 HI( g ) K eq =92.6
Effect of Changing the Volume
(Pressure)
2P2 ( g ) U P4 ( g )
CH 4 ( g ) + H 2O( g ) U CO( g ) + 3H 2 ( g )
Consider Haber Process for the synthesis
of NH3
N 2 ( g ) + 3H 2 ( g ) U 2 NH 3 ( g )
Effect of Temperature
N 2 ( g ) + O2 ( g ) U 2 NO( g ) ; endothermic
Heterogeneous Equilibria
Gas Solid
Gas Liquid
Liquid - Solid
Gas Solid
CO2 ( s ) U CO2 ( g )
PCO2
K eq = PCO2
[ CO2 ( s )]
[ CaO( s )] PCO2
K eq = PCO2
[ CaCO3 ( s )]
Generalize to any form of heterogeneous
equilibrium
1. Partial pressures of gases are
substituted into the equilibrium
expression
2. Pure solids, pure liquids, and solvents
are not included in the equilibrium
expression
3. Molar concentrations of dissolved
species are substituted in the equilibrium
expression
Sn( s ) + 2 H + ( aq ) U Sn +2 ( aq ) + H 2 ( g )
Consider the water gas reaction
C( s ) + H 2O( g ) U CO( g ) + H 2 ( g )
K eq = 14.1 at T=800 0 C