Chemical Equilibrium

Chapter 14

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Equilibrium is a state in which there are no observable
changes as time goes by.

Chemical equilibrium is achieved when:

• the rates of the forward and reverse reactions are equal and
• the concentrations of the reactants and products remain
constant

Physical equilibrium
H2O (l) H2O (g)

Chemical equilibrium
N2O4 (g) 2NO2 (g)
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 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

3
N2O4 (g) 2NO2 (g) constant

4
 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K= Law of Mass Action
[A]a[B]b

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 [C]c[D]d
K= aA + bB cC + dD
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

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 Homogenous Equilibria
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.
N2O4 (g) 2NO2 (g)

[NO2] 2 PNO
2
2
Kc = Kp =
[N2O4] PN O
2 4

In most cases
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)n
n = moles of gaseous products – moles of gaseous reactants
= (c + d) – (a + b) 7
 Homogeneous Equilibria

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
K‘c = [H2O] = constant
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc = = K‘c [H2O]
[CH3COOH]

General practice not to include units for the

equilibrium constant.

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 The equilibrium concentrations for the reaction between
carbon monoxide and molecular chlorine to form COCl2 (g)
at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)n

n = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

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The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if
the PNO 2= 0.400 atm and PNO = 0.270 atm?

2
PNO PO 2
Kp = 2
PNO 2

2
PNO
PO2 = Kp 2
2
PNO

PO2 = 158 x (0.400)2/(0.270)2 = 347 atm

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 Heterogeneous Equilibria
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

K‘c =
[CaCO3] [CaO] = constant

[CaCO3]
Kc = [CO2] = K‘c x Kp = PCO2
[CaO]

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
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 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

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Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm. Calculate
Kp and Kc for the reaction?

Kp = PNH PH S = 0.265 x 0.265 = 0.0702

3 2

Kp = Kc(RT)n

Kc = Kp(RT)-n
n = 2 – 0 = 2 T = 295 K

Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

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 Multiple Equilibria
[C][D] [E][F]
A+B C+D K‘c K‘c = K‘‘c =
[A][B] [C][D]
C+D E+F K‘c‘
[E][F]
A+B E+F Kc Kc =
[A][B]

Kc = K‘c x K‘c‘

If a reaction can be expressed as the sum

of two or more reactions, the equilibrium
constant for the overall reaction is given by
the product of the equilibrium constants of
the individual reactions.

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N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10 -3
K‘ = = = 216
[N2O4] [NO2] 2 K

When the equation for a reversible reaction

is written in the opposite direction, the
equilibrium constant becomes the
reciprocal of the original equilibrium
constant.

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 Writing Equilibrium Constant Expressions
1. The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
2. The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
3. The equilibrium constant is a dimensionless quantity.
4. In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
5. If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of the
individual reactions.

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Chemical Kinetics and Chemical Equilibrium

kf ratef = kf [A][B]2
A + 2B AB2
kr rater = kr [AB2]

Equilibrium
ratef = rater

kf [A][B]2 = kr [AB2]

kf [AB2]
= Kc =
kr [A][B]2

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 The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
IF
• Qc < Kc system proceeds from left to right to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc > Kc system proceeds from right to left to reach equilibrium

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 Calculating Equilibrium Concentrations

1. Express the equilibrium concentrations of all species in

terms of the initial concentrations and a single unknown x,
which represents the change in concentration.
2. Write the equilibrium constant expression in terms of the
equilibrium concentrations. Knowing the value of the
equilibrium constant, solve for x.
3. Having solved for x, calculate the equilibrium
concentrations of all species.

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 At 12800C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g)

Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M

and [Br] = 0.012 M, calculate the concentrations of these
species at equilibrium.
Let x be the change in concentration of Br2
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2 Solve for x

Kc = Kc = = 1.1 x 10-3
[Br2] 0.063 - x
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 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
x=
-b ±  b 2
– 4ac
ax2 + bx + c =0
2a
x = -0.0105 x = -0.00178
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.0648 M
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 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.

 Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium
Add
shifts left to
NH3
offset stress

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 Le Châtelier’s Principle

 Changes in Concentration continued

Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
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 Le Châtelier’s Principle

 Changes in Volume and Pressure

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

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 Le Châtelier’s Principle

 Changes in Temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

colder hotter 25
 Le Châtelier’s Principle
 Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.
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 Chemistry In Action
Life at High Altitudes and Hemoglobin Production

Hb (aq) + O2 (aq) HbO2 (aq)

[HbO2]
Kc =
[Hb][O2]

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Chemistry In Action: The Haber Process

N2 (g) + 3H2 (g) 2NH3 (g) H0 = -92.6 kJ/mol

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 Le Châtelier’s Principle

N2(g) + 3H2(g) 2NH3(g) H0 = −92.6 kJ/mol

Change Equilibrium
Change Shift Equilibrium Constant
Concentration Yes No
Pressure Yes No
Volume Yes No
Temperature Yes Yes
Catalyst No No

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