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Chapter 5

Chemical Equilibrium
The Equilibrium State

Learning objectives:
 Define chemical equilibrium
 State examples of chemical equilibrium
 Write a balanced chemical equation for any reversible
reaction.
 Interpret how equilibrium state is achieved from a
reaction.

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The Equilibrium State
• What does equilibrium mean to you?
• Chemical Equilibrium: A state achieved when the rates of the
forward and reverse reactions are equal and the concentrations of the
reactants and products remain constant.
– Examples are . . .
• Saturated solutions
• Phase equilibrium
• Many reactions
• Human body
 equilibria involving O2 molecules and the protein Hb play a
crucial role in the transport and delivery of O2 from our
lungs to cells throughout our body. 3
The Equilibrium State
•Equilibrium
Chemists arebetween
interested inphases is known
these reversible as
reactions.
One example is the following:
physical equilibrium.

The decomposition of the colorless gas dinitrogen tetroxide (N2O4)


to the dark brown gas nitrogen dioxide (NO2).
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The Equilibrium State

N2O4 (s) N2O4 (g) 2NO2 (g) N2O4 (g) 2NO2 (g)
Frozen N2O4 As N2O4 is warmed Eventually the color stops changing
is nearly colorless above its boiling point, as N2O4 (g) and NO2 9g) reach
it starts to dissociate concentration at which they are
into brown NO2 gas interconverting at the same rate.
The wo gases are in equilibrium.5
The Equilibrium State
N2O4(g) 2NO2(g)
Change in the concentrations of N2O4 and NO2 with time in two experiments at 25°C

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The Equilibrium State
The Equilibrium State
Important lesson about equilibrium…

A mixture if reactants and products is formed in which


concentrations no longer change with time indicates
that the reaction has reached a state of equilibrium.

For equilibrium to occur, neither reactants nor products


can escape from the system.

At equilibrium, the particular ratio of concentration


terms equals to constant.

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The Equilibrium Constant

Learning objectives:
 Write equilibrium constant expression.
 Calculate the equilibrium constant Kc from the
equilibrium concentrations of products and reactants.

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The Equilibrium Constant Kc
• Equilibrium expression for determining the equilibrium
constant, Kc, for the general reversible reaction
aA + bB cC +dD.

In this expression:
 Product concentrations always appear in the numerator
 Reactant concentrations always appear in the denominator
 Each concentration is always raised to the power of its stoichiometric
coefficient in the balance equation
 Kc is independent of concentration changes, but dependent on the
temperature. 10
The Equilibrium Constant Kc
Kc for a chemical reaction is very useful because it indicates whether a
reaction is product or reactant favored, and it can be used to calculate
the quantity of reactant or product present at equilibrium

Experiment 1 Experiment 5
[NO2]2 (0.0125)2 (0.0141)2
Kc = = 4.64 x 10-3 = 4.63 x 10-3
[N2O4] 0.0337 0.0429
Homogeneous &
Heterogeneous Equilibria
Learning objectives:
 Distinguish between homogenous and heterogeneous
equilibrium.

 Write the equilibrium equation for any balanced


chemical equation representing a homogenous or
heterogeneous equilibrium.

 Calculate the equilibrium constant Kp from the


equilibrium partial pressures of reactants and products.

 Interconvert between Kc and Kp using a balanced


equation.
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Homogeneous Equilibria
• Homogeneous Equilibrium: When all reacting species
are in the same phase, all reactants and products are
included in the expression.
• Eg.

Ag+ (aq) + 2NH3 (aq) Ag(NH3)2+ (aq)


diamminesilver(I) cation

Co (g) + Cl2 (g) COCl2 (g)


phosgene

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Homogeneous Equilibria
• Kc is obtained when equilibrium concentrations
expressed in molarity are substituted into equilibrium –
constant expression.
• Kp is obtained equilibrium partial pressures expressed in
atm are substituted into equilibrium –constant
expression.
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NO2 2 PNO2
Kc   Kp
N2O4  PN2O4

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Homogeneous Equilibria
• We can convert between Kc and Kp using an equation
derived from PV = nRT:
For aA bB

Kp = Kc (RT) ∆n
∆n = moles gas products – moles of gas reactants
∆n = b – a
R = 0.08206 (L.atm)/K.mol)

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Heterogeneous Equilibria
• Heterogeneous Equilibrium:
– When reacting species are in different phases
– Solution and gas phases are included, solid and liquid
phases are excluded from the equilibrium equation
because their concentrations “do not change.”

CaCO3(s)  CaO(s) + CO2(g)

Kc = [CO2] because CaCO3 and CaO are solids.

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Heterogeneous Equilibria
Thermal decomposition of calcium carbonate:
CaCO3(s) <=> CaO(s) +CO2(g)

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Using Equilibrium Constants
Learning objectives:
 State generalizations concerning the composition of
equilibrium mixtures

 Define reaction quotients. Relate reaction quotient to


equilibrium constant.

 Determine whether or not a system is at equilibrium for


a given mixture of reactants and products. If it is not,
determine the direction in which the reaction must go
to achieve equilibrium.

 Calculate the final concentrations of reactants and/or


products from Kc and initial concentrations of reactants
and/or products. 18
Using Equilibrium Constants
• The magnitude of equilibrium constant provides us with important
information about the composition of an equilibrium
mixture.

• We can make the following generalizations concerning the


composition of equilibrium mixtures:

If Kc > 103, products predominate over reactants. If Kc is very large,


the reaction is said to proceed to completion.

If Kc is in the range 10–3 to 103, appreciable concentrations of both


reactants and products are present.

If Kc < 10–3, reactants predominate over products. If Kc is very small,


the reaction proceeds hardly at all.
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Using the Equilibrium Constant
2H2O(g) 2H2(g) + O2(g)

(at 500 K) Kc = 4.2 x 10-48

H2(g) + I2(g) 2HI(g)


2H2(g) + O2(g) 2H2O(g)
(at 500 K) Kc = 57.0
(at 500 K) Kc = 2.4 x 1047
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Using the Equilibrium Constant
aA + bB cC + dD

[C]tc[D]td
Reaction quotient: Qc =
[A]ta[B]tb

The reaction quotient, Qc, is defined in the same way as


the equilibrium constant, Kc, except that the concentrations
in Qc are not necessarily equilibrium values.

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Using the Equilibrium Constant
• To determine the direction in which the reaction will
proceed to achieve equilibrium, we compare the values
of Qc and Kc:

net reaction goes from left to right


• If Qc < Kc (reactants to products).

• If Qc > Kc net reaction goes from right to left


(products to reactants).

• If Qc = Kc no net reaction occurs.

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Using Equilibrium Constants
Using the reaction quotient

• Predicting the direction of reaction. The direction of


reaction depends on the relative values of Qc and Kc.
• If Qc < Kc, the reaction goes from left to right If Qc = Kc,
the reaction is at equilibrium If Qc > Kc, the reaction goes
from right to left 23
Steps to follow
in calculating
equilibrium
concentrations
from initial
concentrations.

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Using the Equilibrium Constant
Set up a table:
H2(g) + I2(g) 2HI(g)

I 0 0 0.250
C +x +x -2x
E x x 0.250 - 2x

Substitute values into the equilibrium expression:


[HI]2 (0.250 - 2x)2
Kc = 57.0 =
[H2][I2] x2
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Using the Equilibrium Constant
Solve for “x”:

(0.250 - 2x)2
57.0 = x = 0.0262
x2

Determine the equilibrium concentrations:

H2: 0.0262 M

I2: 0.0262 M

HI: 0.250 - 2(0.0262) = 0.198 M


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Le Châtelier’s Principle
Learning objectives:
 State Le Chateliers’s Principle.

 State the factors that alter the composition of an


equilibrium mixture based on Le Chateliers’s Principle.

 Explain the effect of the changes on reactant or


product when a stress is applied to a system.

 Determine the reaction direction when a system at


equilibrium reacts to a stress applied to the system,
including changes in concentrations, pressure and
volume, or temperature.

 Describe the effect of adding a catalyst to a system at 27


equilibrium.
Le Châtelier’s Principle
Le Châtelier’s Principle: If a stress is applied to a
reaction mixture at equilibrium, net reaction occurs in
the direction that relieves the stress.

• The concentration of reactants or products can


be changed.

• The pressure and volume can be changed.

• The temperature can be changed.

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Le Châtelier’s Principle
Changes in Concentration
Haber process for synthesis of ammonia.

N2(g) + 3 H2(g) 2 NH3(g) Kc = 0.291 at 700 K

Given an equilibrium mixture of 0.50 M N2, 3.00 M H2,


and 1.98 M NH3 at 700 K, what happens when the
concentration of N2 is increased to 1.50 M?

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Altering an Equilibrium Mixture: Concentration
N2(g) + 3H2(g) 2NH3(g)
Le Châtelier’s Principle
In general, when an equilibrium is disturbed by the addition
or removal of any reactant or product, Le Châtelier’s
principle predicts that

– The concentration stress of an added reactant or


product is relieved by reaction in the direction that
consumes the added substance.

– The concentration stress of a removed reactant


or product is relieved by reaction in the direction
that replenishes the removed substance.
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Le Châtelier’s Principle
Changes in Pressure and Volume
In general Le Châtelier’s principle predicts that

An increase in pressure by reducing the volume will


bring about net reaction in the direction that decreases
the number of moles of gas.

A decrease in pressure by enlarging the volume will


bring about net reaction in the direction that increases
the number of moles of gas.
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Effect of pressure and volume
N2(g) + 3 H2(g) 2 NH3(g) Kc = 0.291 at 700 K

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Le Châtelier’s Principle
Changes in Temperature
In general, when an equilibrium is disturbed by a change in
temperature, Le Châtelier’s principle predicts that
• the equilibrium constant for an exothermic reaction
(negative H°) decreases as the temperature
increases. Equilibrium shifts to form more reactants
(reverse reaction).

• the equilibrium constant for an endothermic reaction


(positive H°) increases as the temperature increases.
Equilibrium shifts to form more product (forward
reaction). 34
Altering an Equilibrium Mixture: Temperature
N2(g) + 3H2(g) 2NH3(g) H° = -2043 kJ

As the temperature increases, the equilibrium shifts from


products to reactants.
Effect of a catalyst on equilibrium
Potential energy profiles for a
reaction whose activation energy
is lowered by the presence of a
catalyst.

The activation energy for the


catalyzed pathway (red curve) is
lower than that for the
uncatalyzed pathway (blue curve)
by an amount ΔEa.

The catalyst lowers the activation


energy barrier for the forward and
reverse reactions by exactly the
same amount.

The catalyst therefore accelerates the forward and reverse reactions


by the same factor, and the composition of the equilibrium mixture is
unchanged. 36