Chapter 5

Chemical Equilibrium
5.1 Dynamic Equilibrium

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Dr. Asyilla
 Learning Outcomes

i. Explain the concept of dynamic equilibrium,

ii. Explain the equilibrium constant.
iii.Describe the calculation value of Kp.
iv. Explain the calculation of Kc and Kp for
heterogenous equilibria.
v. Explain the relationship of Kp with Kc for
homogenous and heterogenous system.
vi. Explain the degree of dissociation () and
reaction quotient (Q).
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 Concept of Equilibrium
• All reactions are reversible and under suitable
conditions will reach a state of equilibrium
• Chemical equilibrium is the point at which the
rate of the forward reaction is equal to the rate
of the reverse reaction
• At equilibrium, the concentrations of products
and reactants no longer change because the
rates of the forward and reverse reactions are
equal
At equilibrium: rateforward = ratereverse
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• Chemical equilibrium is a dynamic state
because reactions continue to occur, but
because they occur at the same rate, no net
change is observed on the macroscopic level.
• The state where the concentrations of all
reactants and products remain constant with
time
• Equilibrium only occurs in a closed system at
constant temperature

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 Condition for Chemical Equilibria

• Constant observable macroscopic properties

– Temperature, pressure, concentration
• A closed system
• Reversibility
• Rates of opposing changes are equal

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 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

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Reaching equilibrium on the macroscopic and molecular levels.

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• As the reaction progresses
o [A] decreases to a constant,
o [B] increases from zero to a constant.
• When [A] and [B] are constant, equilibrium is
achieved.
– The double arrow implies the process is dynamic
& reversible

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 The Equilibrium Constant, K
• The concentrations of products and reactants
are related in an equation called the
equilibrium constant expression, K
• Types of K:
• describes the equilibrium of a reaction
Kc where the concentrations of the materials
is known (c = concentration)

• describes the equilibrium of a gaseous

Kp reaction using partial pressures instead of
concentrations (p = pressure)
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• No matter the starting composition of
reactants and products, the same ratio of
concentrations is achieved at equilibrium.
• For a general reaction:

• The equilibrium constant expression is:

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Consider the reaction N2O4(g) 2NO2(g)
At equilibrium ratefwd = raterev
2
so kfwd[N2O4] = krev[NO2]

The ratio of constants gives a new constant, the

equilibrium constant:

kfwd [NO2]2
Kc = =
krev [N2O4]

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The Equilibrium Constant in Terms of Pressure
• If Kp is the equilibrium constant for reactions
involving gases, we can write:

• Kp is based on partial pressures measured in

atmospheres.
• Eg:

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• K is constant despite different initial and
equilibrium concentrations of reactants and
products
• Eg:

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 The Magnitude of Equilibrium Constants
• The equilibrium constant, K, is the ratio of
products to reactants.
• Therefore, the larger K the more products are
present at equilibrium.
• Conversely, the smaller K the more reactants are
present at equilibrium.

If K >> 1, then products dominate at equilibrium

and equilibrium lies to the right.

If K << 1, then reactants dominate at equilibrium

and the equilibrium lies to the left.
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• An equilibrium can be approached from any
direction.
• Example:

• The equilibrium constant for a reaction in one

direction is the reciprocal of the equilibrium
constant of the reaction in the opposite direction.
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 Homogeneous Equilibrium
• Applies to reactions in which all reacting
species are in the same phase

• In most cases, Kc ≠ Kp

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 Heterogeneous Equilibrium

• An equilibrium involving reactants and/or

products in more than one phase.

• Experimentally, the amount of CO2 does not seem

to depend on the amounts of CaO and CaCO3.

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• Neither density nor molar mass is a variable,
the concentrations of solids and pure liquids
are constant.
• The concentrations of pure liquids and pure
solids in equilibrium constant expressions are
ignored
• The amount of CO2 formed will not depend
greatly on the amounts of CaO and CaCO3
present.

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• The concentrations of solids and liquids are
essentially constant
• Therefore, the concentrations of solids and
liquids do not appear in the equilibrium
expression
• Eg:

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 Sample Problem 1
The following concentrations were measured for an
equilibrium mixture at 472 °C.
[N2] = 4.02 x 10-2 M
[H2] = 1.21 x 10-1 M
[NH3] = 2.72 x 10-3 M
Calculate the equilibrium constant at 472 °C for the
reaction
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Solution:

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 Sample Problem 2

Two moles of ammonia and oxygen and three moles of

water are placed in a 1L flask at room temperature.
Pressure is monitored and observed to reach a constant
P. At this point, there are 1.6 moles of ammonia.
Calculate the concentrations of all substances.

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 Solution
This means that [NH3] decreased by 0.4 moles. So
by coefficients, what must have happened to the
other quantities?

Things reacted in ratios according to the coefficients of

the balanced reaction. Make sure understand + and - and
why each substance has a different #

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 Sample Problem 3

• 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.

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Solution

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 Degree of Dissociation, α

• Dissociation involves breaking of molecules

into smaller molecules, atoms or ions
• Degree of dissociation, α
o The fraction of a molecule dissociated
• Complete dissociation, α = 1 or 100%

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• Eg:
The concentration of H+ ion measured for
HCOOH 0.5 M is 8.9 x 10-3 M. What is the degree
of dissociation of the compound?

HCOOH H+ + HCOO-

Degree of dissociation, α = 8.9 x 10-3 M

0.5 M
= 0.02

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 Reaction Quotient, Q

• The equilibrium constant, K for a reaction has

a particular numerical value when the
reactants & products are at equilibrium.
• When the reactants & products in a reaction
are NOT at equilibrium, it is convenient to
calculate the reaction quotient, Q
Q = product concentrations
reactant concentrations
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 Predicting the Direction of Reaction

• We can determine the direction in which a

reaction has to shift by calculating the
reaction quotient, Q
• Q gives the same ratio the equilibrium
expression gives but for a system that is not at
equilibrium

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If Q < K then the forward reaction must occur to reach
equilibrium (go right)

If Q = K, then system is at equilibrium

If Q > K then the reverse reaction must occur to reach

equilibrium (go left)

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 Sample Problem

For the reaction N2(g) + 3H2(g) 2NH3(g)

Kc = 1.7 x 102 at 500 K
[N2] = 2.0 x 10-2 M
[H2] = 3.5 x 10-2 M
[NH3] = 2.0 x 10-2 M

Is the reaction at equilibrium, if not in which

direction will the reaction proceed?

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 Solution

• Qc is larger than Kc, therefore the reaction will

move to the left (making more reactants)

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Thank You

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