CHAPTER 15

CHEMICAL EQUILIBRIUM

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 Reaction Dynamics
• When a reaction starts, the reactants are consumed
and products are made.
– The reactant concentrations decrease and the product
concentrations increase.
– As reactant concentration decreases, the forward
reaction rate decreases.

• Eventually, the products can react to re-form some of

the reactants, assuming that the products are not
allowed to escape.
– As product concentration increases, the reverse reaction
rate increases.

• Processes that proceed in both the forward and reverse

directions are said to be reversible.
– reactants products
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 Arrow Conventions
• Chemists commonly use two kinds of arrows in
reactions to indicate the degree of completion of the
reactions.

• A single arrow indicates that all the reactant molecules

are converted to product molecules at the end.

• A double arrow ( ) indicates that the reaction is in

equilibrium.

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 15.2 Dynamic Equilibrium
• Dynamic equilibrium is the condition wherein the rates of the
forward and reverse reactions are equal.
– Because the forward reaction slows and the reverse reaction
accelerates, eventually they reach the same rate.
• Once the reaction reaches equilibrium, the concentrations of all
the chemicals remain constant because the chemicals are
being consumed and made at the same rate.

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 Dynamic Equilibrium
• As the concentration of product increases, the
reactants’ concentrations decrease.

• Therefore, the rate of forward reaction decreases

and the rate of the reverse reaction increases.

• Dynamic equilibrium: Rate of forward reaction =

rate of reverse reaction.

• Concentrations of reactant(s) and product(s) no

longer change.

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 NOTE: Equilibrium Does NOT Mean Equal
Amounts of Reactants and Products Exist
• The rates of the forward and reverse reactions are equal at
equilibrium.
• But that does not mean the concentrations of reactants and
products are equal.
• Some reactions reach equilibrium only after almost all the
reactant molecules are consumed: We say the position of
equilibrium favors the products.
• Other reactions reach equilibrium when only a small
percentage of the reactant molecules are consumed: We
say the position of equilibrium favors the reactants.

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 15.3 Equilibrium Constant: K
• The relationship between the chemical equation and the concentrations
of reactants and products is called the law of mass action.

• For the general equation aA + bB cC + dD, the law of mass action

gives the relationship below.
– The lowercase letters represent the coefficients of the balanced chemical
equation.
– Always products over reactants

• K is called the equilibrium constant.

– K value does not have units.

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 Writing Equilibrium Constant Expressions

•So, for the reaction

2 N2O5(g) 4 NO2(g) + O2(g)

the expression for the equilibrium constant, K,

is as follows:

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 What Does the Value of K Imply When Its
Value Is Greater Than 1?
• When the value of
K >> 1, when the reaction
reaches equilibrium there
will be many more
product molecules
present than reactant
molecules.

• When K > 1, the

position of equilibrium
favors products.
– The reaction is product
favored. K = 1.9 × 1019
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 What Does the Value of K Imply If Its Value
Is Less Than 1?
• When the value of
K << 1, when the
reaction reaches
equilibrium there will be
many more reactant
molecules present than
product molecules.

• When K < 1, the

position of equilibrium
favors reactants.
– Say the reaction is
reactant favored. K = 4.1 × 10–31
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 What Does the Value of K Imply If Its Value
Is equal to 1
When K =1,
neither direction is favored, forward reaction
proceeds about halfway.

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 Relationships Between K and Chemical
Equations
• When the reaction is written in reverse (i.e., backward), the equilibrium
constant, K, is inverted.

• The equilibrium constant expression for the reaction

aA + bB cC + dD (forward)

[C]c × [D]d
Kforward =
[A]a × [B]b
• The equilibrium constant expression for the reaction
cC + dD aA + bB (reverse)

[A]a × [B]b
Kreverse =
[C]c × [D]d
Therefore, Kforward = 1/Kreverse
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 Relationships Between K and Chemical
Equations
• When the coefficients of an equation are multiplied by a
factor, the equilibrium constant is raised to that factor.

• The equilibrium constant expression for the reaction:

aA + bB cC [C]c
K1 =
[A]a × [B]b
– For the reaction:
2 aA + 2 bB 2 cC
[C]2c or [C]c 2
K2 = K2 =
[A] × [B]
2a 2b
[A]a × [B]b

– Therefore, K1 = K2n
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 Relationships Between K and Chemical
Equations
• When you add equations to get a new equation, the equilibrium
constant of the new equation is the product of the equilibrium
constants of the old equations.

• For the reactions (1) aA bB and (2) bB cC, the equilibrium

constant expressions are as follows:

[B]b [C]c
K1 = K2 =
[A]a [B]b
• For the reaction aA cC, the equilibrium constant expression is
as follows:
[B]or
b
[C]c [C]c
K1 = × K3 =
[A] a
[B] b
[A]a
‒ Therefore, K3 = K1 × K2
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 15.4 Equilibrium Constants for Reactions
Involving Gases
• The concentration of a gas in a mixture is proportional to
its partial pressure.
– Therefore, the equilibrium constant can be expressed
as the ratio of the partial pressures of the gases.

• For aA(g) + bB(g) cC(g) + dD(g), the equilibrium

constant expressions are as follows:

[C]c × [D]d Pcc × Pdd

Kc = or Kp =
[A] × [B]
a b
Paa × Pbb

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 Kc and Kp Connection
• In calculating Kp, the partial pressures are always
in atm.

• The values of Kp and Kc are not necessarily the

same because of the difference in units.
– Kp = Kc when Δn = 0

• The relationship between them is as follows:

Kp = Kc × (RT)Δn

– Where Δn is the difference between the number of moles of

gaseous reactants and the number of moles of gaseous
products
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 15.5 Heterogeneous Equilibria
• The concentrations of pure solids and pure liquids do not
change during the course of a reaction.

• Because their concentration doesn’t change, solids and

liquids are not included in the equilibrium constant
expression.

• For the reaction

CO2(g) + H2O(l) H+(aq) + HCO3–(aq)

the equilibrium constant expression is as follows:

[H+][HCO3–]
Kc =
[CO2]

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 Heterogeneous Equilibria
The amount of C is different, but the amounts of CO and CO 2
remain the same. Therefore, the amount of C has no effect on
the position of equilibrium.

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