Chemical Equilibrium
Dynamic equilibrium in chemical systems
Chemical reactions carried out in a closed vessel
generally achieve an equilibrium state
At equilibrium the reaction may look “finished”, but the
forward and reverse reactions actually continue to
happen at the same rate
A forward reaction is when reaction proceeds from
left to right and a reverse reaction proceeds form
right to left
Consider the equilibrium process:
At equilibrium, the rate of the forward reaction is equal
to the rate of reverse as shown in the following figure:
1
Expression of equilibrium constants
Consider the equilibrium reaction:
aA + bB cC + dD
The general form of the equilibrium constant expression
for the reaction is
[C]c [D]d
K=
[A]a [B]b
where, K is the equilibrium constant (the constant is
dependent on temperature)
[x] symbolizes the molar concentrations of the
products and reactants
Examples of equilibrium constant expressions:
[CO]2 [O 2 ]
2CO2(g) 2CO(g) + O2(g) K =
[CO 2 ]2
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)
[CS 2 ][H2 ]4
K=
[CH4 ][H2S]2
2
The equilibrium constant expression can be written in
terms of concentration or pressure
[CS 2 ][H2 ] 4 (PCS 2 )(PH42 )
eg: Kc = or Kp =
[CH4 ][H2S]2 (PCH4 )(PH22S )
Kc is the equilibrium constant expression in terms of
concentrations
Kp is the equilibrium constant expression in terms of
pressure
Calculating equilibrium constant values from
experimental data
Consider the reaction: H2(g) + I2(g) 2HI(g)
At 425oC, H2 and I2 gases are placed in a sealed
container, each with a partial pressure of 5.73 atm. At
equilibrium the partial pressure of HI is 9.00 atm.
Calculate Kp.
H2(g) + I2(g) 2HI(g)
P(Initial): (5.73) (5.73) 0
Change: -x -x +2x
Equilibrium: 5.73-x 5.73-x 2x
3
Given: PHI = 9.00 atm = 2x x = 4.50 atm
At equilibrium: P(H2) = P(I2) = 5.73 - 4.50 = 1.23 atm
PHI2 (900)2
Kp = 53.5
PH 2 (PI2 ) (1.23)(1.23)
Homogenous and heterogenous equilibria
An equilibrium reaction involving similar states of
matter is called a homogenous equilibrium
An equilibrium reaction involving different states of
matter is called a heterogenous equilibrium
[Solids (s) and liquids (l) which have constant
concentrations, do not appear in the equilibrium
constant expression]
Consider the following equilibrium reactions:
[H2O]
H2(g) + FeO(s) H2O(g) + Fe(s) Kc =
[H2 ]
Ag+(aq) + Fe2+(aq) Fe3+(aq) + Ag(s)
[Fe 3 ]
Kc = 3
[Ag ][Fe ]
4
Equilibrium position and stoichiometry
The value of K is related to the equilibrium
position (the conversion of reactants to products or
the reverse)
For reactions in which K = 1 (in general 10-2<K< 102),
the conversion of reactants to products is almost
equal
For reactions in which K << 1 (generally lower than
10-2), the conversion of reactants to products is
negligible (substances remain mostly as reactants)
The ratio of products formed to reactants used is low
The equilibrium position is to the left
Consider the following reactions:
COCl2(g) CO(g) + Cl2(g)
[CO][Cl2 ]
Kc = 2.19 1010
[COCl2 ]
The symbol ( ) is preferably used in the equation
and the equation is written as
COCl2(g) CO(g) + Cl2(g)
5
For reactions in which K >> 1 (generally higher than
102), the conversion of reactants to products is high
The ratio of products formed to reactants used is high
The equilibrium position is to the right
2NO(g) N2(g) + O2(g) Kc = 1.00 1030
The symbol ( ) is preferable in the equation and the
equation is written as
2NO(g) N2(g) + O2(g)
The value of K is related to the stoichiometry and
the direction of the reaction
If a reaction is reversed, then the new K = K-1
Consider the reaction: 2NO(g) N2(g) + O2(g)
[N2 ][O 2 ] 30
Kc = 1.00 10
[NO] 2
For the reverse reaction: N2(g) + O2(g) 2NO(g)
[NO]2
K’c = = (Kc)-1 = 1.00x10-30
[N2 ][O 2 ]
6
If the stoichiometry is multiplied by n, then the new
K = Kn
Consider the reaction: 4NO(g) 2N2(g) + 2O2(g)
The reaction can be rewritten as
2[2NO(g) N2(g) + O2(g)]
[N2 ]2 [O 2 ]2
K’’c = = (K c )2 = 1.00x1060
[NO]4
Sample problems
(a) A one liter vessel contains a mixture of 1.75 moles
of HI, 1.125 moles of H2 and 0.125 moles of I2 in
equilibrium at 20oC.
2HI(g) H2(g) + I2(g)
(i) Write the equilibrium constant expression and
calculate the equilibrium constant of the forward and
reverse reaction
(ii) For the forward reaction, predict the equilibrium
position and formation of products
7
Solution
8
What are the values of Kp for the reactions given?
(i) 2SO2(g) + O2(g) 2SO3(g)
(ii) SO2(g) + 1/2O2(g) SO3(g)
Solution
9
The relationship between Kc and Kp
In general, Kp = Kc(RT)n
Where, n = (Total moles of gaseous products) –
(Total moles of gaseous reactants)
Consider the following reaction at 480oC:
2Cl2(g) + 2H2O(g) 4HCl(g) + O2(g) Kp = 0.0752
4
(PHCl )(PO 2 )
Kp = = 0.0752
(PCl2 2 )(PH 2 O )
[HCl] 4 [O 2 ]
Kc = =?
[Cl2 ]2 [H2O]2
From the ideal gas equation: PV = nRT
Px = MxRT = [x]RT
Substitute ([x]RT) into the Kp expression
[HCl] 4 (RT) 4 [O 2 ]RT
Kp =
[Cl2 ]2 (RT) 2 [H2O]2 (RT)2
[HCl] 4 [O 2 ]
= 2 2
RT = Kc(RT)
[Cl2 ] [H2O]
For the given reaction: n = (4+1) – (2+2) = + 1
n Kp
Kp = Kc(RT) Kc =
(RT) Δn
10
0.0752
Kc =
[(0.0821L atm mol 1 K 1 )(273 480)K]1
= 1.22x10-3
11
Predicting the direction of a reaction
The direction in which a reaction will initially move to
achieve equilibrium can be predicted by comparing the
Qc and Kc values
Qc known as the reaction quotient, is the equilibrium
constant expression with the initial values substituted in
the equilibrium expression
Direction of reaction shifts:
When Qc > Kc : The system has too much product, thus
the equilibrium will shift to the left until
Kc is achieved (get back the original Kc
ratio)
When Qc < Kc : The system has too much reactants,
thus the equilibrium will shift to the right
until Kc is achieved
When Qc = Kc: The system is at equilibrium, thus there
is no equilibrium shift
12
Consider the reaction:
COCl2(g) CO(g) + Cl2(g) Kc = 2.19x10-10
The initial concentrations are given as follows:
[COCl2]o = 3.50x10-3 M
[CO]o = 1.10x10-5 M
[Cl2]o = 3.25x10-6 M
Is the reaction at equilibrium? If not to which direction
will it shift?
[CO]o [Cl2 ]o
Qc =
[COCl2 ]o
[1.1 10 5 ][3.25x10 6 ]
=
[3.5 10 3 ]
= 1.02x10-8 > Kc
The initial system is not at equilibrium because
Qc Kc or
Qc > Kc
The system has too much product, therefore it will shift
to the left until Kc is achieved
COCl2(g) CO(g) + Cl2(g)
13
Calculations of equilibrium concentrations
Sample problem 1
Consider the equilibrium reaction:
Br2(g) + Cl2(g) 2BrCl(g) Kc = 7.0 at 400K
If 0.50 moles of Br2 and 0.50 moles of Cl2 are introduced
into a one liter container, what will be the equilibrium
concentration of all the species?
Solution
14
Sample problem 2
The following equilibrium exists for HBr gas. What will be
the equilibrium concentrations of all species if a
container initially containing 1.00 M HBr is allowed to
reach equilibrium ?
2HBr(g) H2(g) + Br2(g)
Kc = 6.25x10-6 at 1024 K
Solution
15
Factors that affect equilibrium and Le Chatelier’s
principle
The factors that affect chemical equilibrium are as
follows:
Change in concentrations by adding or removing
reactants or products
Change in the temperature of the system
Change in the pressure of the system (affects only
gases and depends on how the change is
accomplished)
The presence of a catalyst
Le Chatelier’s Principle states that when a system at
equilibrium is stressed (disturbed) the system shifts so
as to counteract the effect of the disturbance
The Le Chatelier’s principle summarizes the affect of the
above factors on the position of equilibrium
1
Consider the equilibrium:
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
H = + 2816 kJ
The effect of concentration on equilibrium
When [CO2] is increased by adding more CO2,
equilibrium moves to the right to reduce the stress
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
More products are formed to maintain Kc
When [O2] is increased by adding more O2,
equilibrium shifts to the left to reduce the stress
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
More reactants are re-formed until Kc is maintained
When [H2O] is decreased by removing H2O,
equilibrium moves to the left
More reactants are re-formed to maintain Kc
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
When some C6H12O6(s) is removed, there is no
equilibrium shift because K does not depend on the
amount of solids or liquids (provided some still
remains in the system)
2
The effect of pressure on equilibrium (depends on
the method of applying pressure)
Adding pressure by reducing volume results in a shift
in the direction which occupies the smallest volume
(to the side with fewest # of moles of gas)
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
Reducing volume by introducing an inert gas (eg N2 or
He) does not result in any shifts because the partial
pressures do not change
The effect of temperature on equilibrium
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
H = + 2816 kJ
energy + 6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
For an endothermic system, increasing temperature
(adding heat):
- shifts the reaction away from the side which contains
heat energy
- increases the value of K
Heat the system (right shift):
6CO2(g) + 6H2O(g) C6H12O6(s) + 6O2(g)
3
For an exothermic system, increasing temperature:
- shifts the reaction away from the side which contains
heat energy
- decreases the value of K
N2(g) + 3H2(g) 2NH3(g) H = -42.6 kJ
N2(g) + 3H2(g) 2NH3(g) + energy
Heat the system (left shift):
N2(g) + 3H2(g) 2NH3(g)
The effect of a catalyst on equilibrium
Addition of a catalyst lowers Ea for both the forward
and reverse reaction by the some amount
There is no shift of reaction
The catalyst changes the reaction rate (form products
faster but not more) and the rate constant
4
Solubility equilibrium
Solubility equilibrium and solubility product
Solubility equilibrium is the equilibrium between a
slightly soluble solid and its dissolved ions in
solution
Solubility is the amount of substance that dissolves
in a given amount of solvent to make a saturated
solution
Molar solubility is given in units of moles per liter (M)
and solubility is given in grams per liter (g L-1)
The solubility product constant, Ksp is the
equilibrium expression related to ion concentration in
a solution
For the generalized equilibrium:
MaXb(s) + H2O aMb+(aq) + bXa-(aq)
the equilibrium constant expression is written as:
Ksp = [Mb+]a [Xa-]b
where, [Mb+] and [Xa-] are the concentrations or
molar solubility (M) of the dissolved ions
Ksp is the solubility product constant
5
Examples of equilibrium constant expressions:
AgCl(s) Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-] = 1.6x10-10 M2
Ca(OH)2(s) Ca2+(aq) + 2(OH)-(aq)
Ksp = [Ca2+][OH-]2 = 6.5x10-6 M3
Fe(OH)3(s) Fe3+(aq) + 3(OH)-(aq)
Ksp = [Fe3+][OH-]3 = 1.1x10-36 M4
Sample problems
(a) The Ksp for solid PbCl2 is 1.7x10-4 M3.
Determine (i) the molar solubility (mol dm-3) and (ii)
the solubility (g dm-3) of PbCl2
(b) The solubility of Ag2S at 25oC is 1.24x10-14 g L-1.
Determine the Ksp of Ag2S
Solution
6
The common ion effect
Common ions are ions from an external source that are
similar to the ions in equilibrium
Adding common ions into an equilibrium solution
causes:
a decrease in solubility
an increase in precipitation
Consider the following solubility equilibrium:
Ag2SO4 (s) 2Ag+(aq) + SO42-(aq)
Ksp = [Ag+]2[SO42-]
The common ions in this equilibrium are Ag+ and SO42-
Adding a very soluble solution containing Ag+ to the
equilibrium, for instance AgNO3 solution:
AgNO3 Ag+(aq) + NO3-(aq)
would cause the reaction to shift to the left:
Ag2SO4 (s) 2Ag+(aq) + SO42-(aq)
Thus, solubility decreases and Ag2SO4 precipitates
1
Sample problem
If 0.10 L of 0.003 M Pb(NO3)2 is added to 0.40 L of 0.005
M Na2SO4, will PbSO4 precipitate?
Ksp(PbSO4) = 1.6 10-8
Solution
