Lesson 13

The State of Equilibrium for Reversible Reaction

Objectives:
The learners shall be able to:
1. describe reversible reaction;
2. explain chemical equilibrium in terms of the reaction rates of the forward and the
reverse reaction;
3. write the expression for the reaction quotient and equilibrium quotient; 4. explain the
significance of the value of the reaction quotient and equilibrium constant 5. calculate the
equilibrium constant and the pressure or concentration of reactant and products of a
system in equilibrium
6. state the Le Chatelier’s principle and apply it quantitatively to describe the effect of
changes in pressure, concentration, and temperature to a system in equilibrium

Concepts in a Box

Reversible Chemical Reaction

Chemical kinetics describes how fast or slow a chemical reaction occurs. Chemical
thermodynamics tells whether a reaction is spontaneous or not. But for all chemical reactions
described in these two disciplines, only two outcomes are possible: the reaction will either go to
completion, or it will reach a state of equilibrium.

Chemical reactions that can proceed in either direction (to the right or to the left) are
considered as reversible reactions. For example,

������(��) + ������(��) ����������(��) + ������(��)

The double-headed arrow signifies that the previous reaction is a reversible one. Both
forward (toward product formation) and backward reactions (toward the reactants) take place at
the same time, wherein reactants combine to form the products, and products react to yield the
reactants.

Chemical equilibrium refers to the state in a chemical reaction wherein the concentrations
of the reactants and the products remain constant. It is also called the dynamic equilibrium, in
which the rates of the forward and reverse reactions are the same.

Theoretically, all chemical reactions are reversible. Some are only perceived to be
irreversible because the forward reaction is too fast, while the reverse is too slow to be detected.
In such cases, although the reaction only attains "near" completion, it is practically assumed to
proceed in the forward direction. Other reactions are easily observed and described as reversible
because they have an appreciable rate of the reverse reaction. This type of reaction does not go to
completion; instead, both forward and reverse reactions occur at equally significant rates.

A good example of a reversible reaction is the decomposition of colorless dinitrogen

tetroxide (N2O4) gas into the brown nitrogen dioxide gas.

��������(��) ��������(��)

When pure (N2O4) gas is placed in a glass container at room temperature, a brown color will
be observed in the container after a few moments, indicating the formation of NO2. The brown
color will get darker as more NO2 is formed from N2O4 until the intensity of the brown color no
longer changes. At this point, the system has already reached equilibrium, a condition at which the
rate of formation of N2O4 from NO2 is equal to the rate of the decomposition of N2O4 to NO2.

Suppose pure NO2 gas is initially placed in a container instead of N2O4. After a few seconds,
the brown color of NO2 then will get lighter as it is converted to the colorless N2O4. The system has
again reached a state of equilibrium when no apparent change in color is observed. In both cases,
equilibrium is said to exist when there is no observable change in the system. Does this indicate
that the reaction actually goes to completion at equilibrium? What are the conditions at
equilibrium?

Recall from the rate law in chemical kinetics that the rate of a reaction increases at higher
concentrations of the reactants. In the context of a reversible reaction, this concept suggests that
as the forward reaction proceeds, more products are formed, which in turn serve as the reactants
for the reverse reaction. Thus, as the reaction proceeds, the rate of the forward reaction decreases
as the reactants are consumed. At the same time, the rate of the reverse reaction increases as
more products are formed. The system will eventually reach a point where the rate of the forward
reaction becomes equal to the rate of the reverse reaction. At this point, the system is said to have
reached a state of dynamic equilibrium. Hence, the reaction does not go to completion.

At equilibrium, no apparent change in the state of the system is observed. This is because
when the rates of the forward and reverse reactions become equal, the concentrations of the
reactants and products remain constant over time. This principle is known as the law of mass
action.
For the N2O4 – NO2 reaction at equilibrium, the rate of formation of NO2 is equal to the rate
of formation of N2O4 (whichever is the forward or reverse reaction). No change in color is observed
since the concentration of both species become constant

The Equilibrium Constant

The concentrations of the reactants and products remain constant at equilibrium. Thus, the
ratio of the equilibrium concentrations of these substances should also be constant.

Consider a reversible reaction with the general equation:

���� + ���� ���� + ����

…where ��, ��, ��, and �� are the coefficients of the substances, and ���� and ����,
are the rate constants of theforward and the reverse reactions, respectively.

At equilibrium,

���������� = ����������

Using the rate law,

���� [��]��[��]�� = ����[��]��[��]��

The equilibrium constant (����) is expressed as

����=[��]��[��]��
���� [��]��

=����

[��]��

Based on the equation, a high ���� ���������� (>> ��) means that there are
relatively more products than reactants at equilibrium. This indicates that the formation of the
products (forward reaction) is highly favorable.

A low ���� ���������� (<< ��), on the other hand, places the equilibrium far to the
left, indicating that only a smaller portion of the reactants are being converted to products for
every portion of the products that are being converted back to reactants.

For the N2O4 – NO2 system whose equilibrium constant was experimentally determined to be
equal to 4.6 �� 10−3,
 ��������(��) ��������(��)

…the equilibrium constant expression at 25°�� is written as

���� =[����2]2

[��2��4]= 4.6 �� 10−3

The equilibrium constant K is usually expressed as a unitless value. In the thermodynamic
definition of an equilibrium constant, the concentrations are divided by the standard state value of
1 �� (or 1 ������ in case of pressures). Thus, the units cancel out, leaving K dimensionless.

Equilibrium constants are also temperature-dependent. Hence, the temperature must be

indicated for every given value of the equilibrium constant.

Since the equilibrium constant for a reaction is constant for a given temperature, it allows
for the determination of the equilibrium concentrations of reactants and products. For example, if
the equilibrium concentration NO2 of 0.025 M at 25°C, the equilibrium concentration of N2O4 can be
calculated.

���� =[����2]2
[��2��4]= 4.6 �� 10−3

���� =(0.025 ��)2

[��2��4]= 4.6 �� 10−3

[��2��4] =(0.025 ��)2

−3
4.6 �� 10 = 1.3 �� 10−1

Significance of ����

The magnitude of ���� describes the extent to which the reaction favors either the forward
reaction or the reverse reaction at equilibrium. Typically, when the reaction strongly favors a
forward reaction, ����is very large, equal to or greater than 1 000. The equilibrium position shifts
to the right. On the other hand, small values of ����that are equal to or less than 1 000 indicate
that a backward reaction is strongly favored. Here, the equilibrium position shifts to the left.
���� = 1 then the concentrations of the reactants and the products are the same at equilibrium.

Sample Problem:

Write the ���� expression for this reaction:

2������3(��) ��2(��) + 3����2(��_

 Suppose that at 588 K, the equilibrium concentrations are the following:

• [������3] = 0.10 ��
• [��2] = 0.20 ��
• [����2] = 0.30 ��

Calculate ���� of the reaction at this temperature. What does the ���� value at this
temperature suggests?
Homogeneous Equilibria

A homogeneous equilibrium involves reactants and products that are present in only one
phase. Examples are systems involving only gases, such as the system in the formation of ammonia
(NH3).

����(��) + ������(��) ��������(��)

The equilibrium constant of gaseous systems can be expressed in terms of the concentrations
and the partial pressures of the gases involved. To differentiate the two expressions for equilibrium
constant, the symbols ���� and ���� are used instead of ��. The symbol ���� is expressed in
partial pressures, while ����is based on molar concentrations.

��
[����] [����] ���� =����������
���� =[������]�� ����(����)����
�� ��
�� ���� ����
���� and ���� are related in the
equation,

���� =

…where �� is the universal gas constant (0.08206 �� · ������ / ������ · ��), �� is

the absolute temperature in ��, and ���� is the difference between the number of moles of
gaseous products and that of gaseous reactants.

Heterogeneous Equilibria

A heterogeneous equilibrium consists of reactants and products that exist in different phases.
An example is the decomposition of calcium carbonate into calcium oxide and carbon dioxide.

���������� ��������(��) + ������(��)

In a heterogeneous equilibrium, pure solid and liquid substances do not appear in the
equilibrium constant expression. The molar concentrations of these substances are always constant
(having a value equal to 1). The values are then not incorporated in the equilibrium constant
expression. For the calcium carbonate equilibrium reaction, the �� expression is therefore
simplified to include carbon dioxide only.

���� = [������] and ���� = ��������

Sample Problems

1. Write the equilibrium constant expression (���� and ����) for the following
reactions: a. 2����2(��) + ��2(��) 2����3(��)

b. 2������5(��) + ����2(��) 5��2(��)

c. 2������(��) + 3��2(��) 2������(��) + 2����2(��)
2. Consider the reaction below:

��2(��) + 3��2(��) 2����3(��)

If the partial pressures of ��2, ��2, and ����3 are 1.3 ������, 0.83 ������,
and 0.85 ����, respectively, what is the equilibrium constant of the reaction.

3. For the reaction below,

��������3(��) ������(��) + ����2(��)

What are the values of the equilibrium constants ���� and ����if the pressure of
����2 is 0.384 ������ at 500°��?

Predicting the Direction of the Reaction

Consider again the reversible reaction

���� + ���� ���� + ����

At non-equilibrium conditions (e.g., at the start of a reaction), the instantaneous ratio of the
concentrations of the products and reactants gives the reaction quotient (��) expressed as

�� ��
�� =[��] [��]
[��]��[��]��
 If only the reactants are present at the start of a reaction, the reaction will just proceed
forward. The same will be true for the reverse reaction if only the products (which are the
reactants of the reverse reaction) are present at the start of the reaction. For the N2O4 – NO2
system, if only N2O4 or NO2, is present at the start of the reaction, it is easy to predict where the
reaction is going.

But if all species of the reactants and products are present at the start of the reaction, three
possibilities may occur depending on the relative values of �� and ��. When �� is less than ��,
it means that there are more reactants than there should be at equilibrium. Thus, the forward
reaction will be favored, which will lessen the concentration of the reactants and raise the
concentration of the products. The opposite will occur when �� is greater than ��, which favors
the reverse reaction. When �� is equal to ��, the reaction is already in a state of equilibrium.

�� < ��, ������������ ��ℎ�� �������������� ����������������

�� > ��, ������������ ��ℎ�� �������������� ����������������

�� = ��, ��ℎ�� ���������������� ���� ����

����������������������

Sample Problem

A container initially contains N₂, H₂, and NH3, gases with concentrations of 0.82 M, 0.54 M,
and 0.31 M, respectively. The mixture was heated to 375°C and allowed to attain equilibrium. If K is
1.2 at this temperature, to which direction did the reaction proceed (forward or reverse) to reach
equilibrium?

��2(��) + 3��2(��) 2����3(��)

Solution:

To determine the direction in which the reaction proceeded, the reaction quotient (Q) is
calculated first from the initial concentrations.

�� ��
�� =[��] [��]
��
[��]��[��] =[0.31 ��]
2

3
[0.82 ��][0.54 ��] = 0.74

Since �� = ��, the reaction proceeded forward until it reached equilibrium.

Practice Exercises:

A 1.50 L reaction vessel contains a gaseous mixture of 2.1 mol NOCI, 0.52 mol NO, and 0.21
mol Cl₂. The vessel was heated to 400°C until the system attained equilibrium. If K, is 0.035 at this
temperature, to which direction did the reaction proceed to attain equilibrium?

����������(��) ������(��) + ������(��)

Le Chatelier’s Principle

Le Chatelier's principle states that when stress is introduced into a system in equilibrium, the
system will adjust to relieve the stress and regain equilibrium. The stress is relieved as the reaction
shifts either to the left (reverse) or the right (forward) of the reversible reaction.

One factor that can affect systems in equilibrium is the change in the amount of either the
reactants or the products. Adding more reactants to a reaction that is already in equilibrium will
cause it to shift to the right (since �� will become smaller than ��).

Adding more of the products will favor the reverse reaction (since �� will become greater
than ��). The opposite effect results when either a reactant or a product is removed from the
reaction. In any case, the system adjusts by favoring the reaction direction that consumes the
excess (reactant or product) to attain a new equilibrium.

Action Shift in Equilibrium

Adding more reactants Favors the forward reaction

Adding more products Favors the reverse reaction

Removing a reactant Favors the reverse reaction

Removing a product Favors the forward reaction

Figure 1: Lever-and-function analogy of equilibrium shift with (a) addition or (b)

removal of a reactant

Another factor that facilitates shifts in equilibrium is the change in the temperature of the
reaction system. Recall in thermochemistry that if a forward reaction is endothermic, its reverse
reaction is exothermic, and vice versa.

Increasing the temperature is equivalent to adding energy to the action, which favors the
direction of the endothermic reaction. Decreasing the temperature favors the direction of the
exothermic reaction. Using the N2O4 – NO2 system again as an example,

��������(��) ��������(��) ���������� = 57.2

����/������

The reaction may also be written as,

��������(��) + ���������� ��������(��)

Since the reaction is endothermic, an increase in temperature will shift the reaction towards
the production of brown NO2 gas (forward), while a decrease in temperature will favor the
formation of the colorless N2O4 gas (reverse).

Changes in pressure can also induce a shift in equilibrium but only affect systems that involve
gases. To understand this concept, recall the inverse relationship between P and V as reflected in
Boyle's law. For a system in equilibrium, increasing the pressure (decreasing volume) will favor the
direction that will produce less total number of moles of gas. On the other hand, decreasing the
pressure (increasing volume) will favor the direction that will produce more total number of moles
of gas.

��������(��) ��������(��)

1 mole 2 mole

For the N2O4 – NO2 system, the forward reaction produces two moles of gas, while the reverse
reaction forms one mole of gas. An increase in pressure will cause a shift in the equilibrium to the
left, favoring the formation of N₂O. A decrease in pressure will favor the formation of the brown
NO2 gas.

Another factor that can affect systems in equilibrium is catalysts. Catalysts can increase the
rate of a chemical reaction, but they have no net effect on a system in equilibrium. If a catalyst can
speed up the forward reaction, it can also speed up the reverse reaction. The only effect it will
have been that the system will reach equilibrium faster.

Sample Problem:

The Haber process for the synthesis of ammonia from nitrogen and hydrogen gases in an
exothermic process.

����(��) + ������(��) ��������(��)

How will the following conditions affect the equilibrium of the system?
 a. Adding more N2
b. Removing H2
c. Removing NH3
d. Increasing the pressure in the reaction vessel
e. Decreasing the temperature of the system

Answer:

a. Adding more N₂ will favor the forward reaction.

b. Removing H₂ will favor the reverse reaction.
c. Removing NH3, which is the only product of the reaction, will push the reaction
forward.
d. A total of 4 moles of gas react to produce 2 moles of NH3. An increase in pressure (or
decrease in volume) will favor the formation of NH3.
e. Since the production of NH3, is an exothermic process, a decrease in temperature will
favor the forward reaction.

Practice Exercises:

The oxidation of ammonia into nitric oxide is an exothermic process.

4����3(��) + 5��2 4����(��) + 6��2��(��) ���������� = −904.4 ����

a. Adding more O2
b. Adding H2O
c. Removing NH3
d. Increasing the temperature of the system
e. Decreasing the pressure in the vessel