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CHAPTER 15

CHEMICAL EQUILIBRIA
 Learning Outcomes

• Understand the concept of chemical equilibrium

• Apply the chemical equilibrium concept to account for the
equilibrium composition of chemical reactions.
• Gas phase reactions are first used to explore how equilibrium
responds to changes in the conditions.
• Apply the concept of equilibrium to account for the pH’s of
solutions and extent of chemical reactions.

Faculty/Department name here 18pt Arial

 The Concept of Equilibrium

Chemical equilibrium occurs when a reaction and its

reverse reaction proceed at the same rate.
The Concept of Equilibrium

• As a system approaches
equilibrium, both the forward
and reverse reactions are
occurring.
• At equilibrium, the forward
and reverse reactions are
proceeding at the same rate.
 A System at Equilibrium

• Once equilibrium is achieved, the amount of each

reactant and product remains constant.
 Depicting Equilibrium

• In a system at equilibrium, both the forward and reverse

reactions are being carried out; as a result, we write its
equation with a double arrow:

N2O4 (g) 2 NO2 (g)

 The Equilibrium Constant

• Forward reaction:
N2O4 (g)  2 NO2 (g)

• Rate law:
Rate = kf [N2O4]
• Reverse reaction:
2 NO2 (g)  N2O4 (g)

• Rate law:
Rate = kr [NO2]2
 The Equilibrium Constant

• Therefore, at equilibrium

Ratef = Rater

kf [N2O4] = kr [NO2]2

• Rewriting this, it becomes

kf [NO2]2
kr = [N2O4]
 The Equilibrium Constant

• The ratio of the rate constants is a constant at that

temperature, and the expression becomes
kf [NO2]2
Keq = =
kr [N2O4]
• To generalize this expression, consider the reaction

aA + bB cC + dD
• The equilibrium expression for this reaction would be

Kc = [C]c[D]d
[A]a[B]b
 The Equilibrium Constant

• Because pressure is proportional to concentration for gases

in a closed system, the equilibrium expression can also be
written (PC)c (PD)d
Kp =
(PA)a (PB)b

Relationship between Kc and Kp

• From the ideal gas law we know that
PV = nRT
• Rearranging it, we get

P= n RT
V
 Relationship between Kc and Kp

Plugging this into the expression for Kp for each substance,

the relationship between Kc and Kp becomes

Kp = Kc (RT)n
Where
n = (moles of gaseous product) − (moles of gaseous reactant)
 Equilibrium Can Be Reached from Either Direction

• As you can see, the ratio of [NO2]2 to [N2O4] remains

constant at this temperature no matter what the initial
concentrations of NO2 and N2O4 are.
Equilibrium Can Be Reached from Either Direction

This is the data from the

last two trials from the
table on the previous
slide.
 Equilibrium Can Be Reached from Either Direction

• It does not matter whether we start with N2 and H2 or

whether we start with NH3. We will have the same

proportions of all three substances at equilibrium.
What Does the Value of K Mean?

• If K >> 1, the reaction is product-

favored; product predominates at
equilibrium.

• If K << 1, the reaction is reactant-

favored; reactant predominates at
equilibrium.
 Manipulating Equilibrium Constants

• The equilibrium constant of a reaction in the reverse reaction

is the reciprocal of the equilibrium constant of the forward
reaction.

[NO2]2
N2O4 (g) 2 NO2 (g) Kc = = 0.212 at 100C
[N2O4]
[N2O4]
2 NO2 (g) N2O4 (g)
[NO2]2
Kc = 4.72 at 100C
 Manipulating Equilibrium Constants

• The equilibrium constant of a reaction that has been multiplied

by a number is the equilibrium constant raised to a power that
is equal to that number.

[NO2]2
N2O4 (g) 2 NO2 (g) Kc = = 0.212 at 100C
[N2O4]

[NO2]4
2 N2O4 (g) 4 NO2 (g) Kc = = (0.212)2 at 100C
[N2O4]2
 Manipulating Equilibrium Constants

• The equilibrium constant for a net reaction made up of two

or more steps is the product of the equilibrium constants for
the individual steps.
 Heterogeneous Equilibrium

• The concentrations of solids and liquids are essentially

constant
• Both can be obtained by dividing the density of the
substance by its molar mass—and both of these are
constants at constant temperature.
• Therefore, the concentrations of solids and liquids do not
appear in the equilibrium expression
PbCl2 (s) Pb2+ (aq) + 2 Cl−(aq)

Kc = [Pb2+] [Cl−]2
 CaCO3 (s) CO2 (g) + CaO(s)

• As long as some CaCO3 or CaO remain in the system, the

amount of CO2 above the solid will remain the same.

 Equilibrium Calculations

A closed system initially containing 1.000 x 10−3 M H2 and

2.000 x 10−3 M I2. At 448C is allowed to reach equilibrium.

Analysis of the equilibrium mixture shows that the
concentration of HI is 1.87 x 10−3 M. Calculate Kc at 448C
for the reaction taking place, which is
H2 (g) + I2 (g) 2 HI (g)
 What Do We Know?

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At 1.87 x 10-3
equilibrium
We can now calculate the equilibrium concentrations of all three
compounds…

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

equilibrium
…and, therefore, the equilibrium constant

Kc = [HI]2
[H2] [I2]

= (1.87 x 10-3)2
(6.5 x 10-5)(1.065 x 10-3)

= 51
 The Reaction Quotient (Q)

• To calculate Q, one substitutes the initial concentrations on

reactants and products into the equilibrium expression.
• Q gives the same ratio the equilibrium expression gives,
but for a system that is not at equilibrium.
If Q = K, the system is at equilibrium.
If Q > K, there is too much product and the equilibrium shifts to
the left.
If Q < K, there is too much reactant, and the equilibrium shifts to
the right.
 Le Châtelier’s Principle

“If a system at equilibrium is disturbed by a change in

temperature, pressure, or the concentration of one of the
components, the system will shift its equilibrium position so as
to counteract the effect of the disturbance.”
Le Chatelier's Principle Part 1 The Chemistry Journey The Fuse School (1).mp4
 The Haber Process

• The transformation of nitrogen and hydrogen into ammonia

(NH3) is of tremendous significance in agriculture, where
ammonia-based fertilizers are of utmost importance.
The Haber Process

If H2 is added to the

system, N2 will be
consumed and the two
reagents will form more
NH3.
The Haber Process

This apparatus helps

push the equilibrium to
the right by removing
the ammonia (NH3) from
the system as a liquid.
 The Effect of Changes in Temperature

When CoCl2 is dissolved in aqueous HCl, the ΔH > 0. The colour

of the product is pink.
When the product is heated it turns blue.
Co(H2O)62+(aq) + 4 Cl-(aq) CoCl4 (aq) + 6 H2O (l)
pink blue
 The Effect of A Catalyst

Catalysts increase the rate of both the forward and reverse

reactions.
Equilibrium is achieved faster, but the equilibrium composition
remains unaltered.
END