General Chemistry 2 Page 1

Introduction to Chemical Equilibrium

INTRODUCTION TO CHEMICAL EQUILIBRIUM

CHEMICAL EQUILIBRIUM

A system is said to be in a state of chemical equilibrium if it satisfies the following conditions:

1. The amounts of the reactants and products are observed to be constant after some time, and

[𝑅] = 𝐾1 ; [𝑃] = 𝐾2

2. The rate of the product formed from the reactant is equal to the rate of the reverse reaction.

𝑅𝑎𝑡𝑒𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑅𝑎𝑡𝑒𝑏𝑎𝑐𝑘𝑤𝑎𝑟𝑑

The saturated solution of sodium chloride is an example of a system in chemical equilibrium. The
amount of table salt dissolved and suspended in water remains constant since it has reached its saturation
point. The rate of dissolution of NaCl is equal to the rate of recrystallization of sodium and chloride ions.

When you try to dissolve too much salt in a glass of water, notice that no observable changes can
be seen in a system even though constant formation and dissolution occur. This process can be described
as microscopically dynamic. No reactant or product must be removed for it to reach equilibrium.

How do we know if a system already achieved equilibrium? This can be done by observing if chemical
reactions are still proceeding. Color change, gas formation, precipitate formation, and change in the
temperature of the system indicate that chemical reactions are still proceeding.

REVERSIBLE REACTIONS

In a chemical reaction, chemical equilibrium is the state in which

both reactants and products are present in concentrations which have no
more tendency the change with time. In 1803, Claude Louis Berthollet, a
French chemist, noticed that reversible reactions occurred. With this in mind,
he developed the concept on chemical equilibrium.
Figure 1: Claude Louis Berthollet
Source: https://www.alamy.com/ To further understand chemical equilibrium let us discuss the
concept of reversibility.
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Introduction to Chemical Equilibrium

As mentioned earlier, the concept of reversible reaction was first discovered by Berthollet in late
1800s. He was recruited by Napoleon to accompany him as a scientific advisor in his expedition to Egypt in
1798. Berthollet observed deposits of sodium carbonate (Na 2CO3) around the edges of some salt lakes found
there. As a renowned scientist, he was aware of a reaction involving the formation sodium chloride and
calcium carbonate from sodium carbonate and calcium chloride.

𝑁𝑎2 𝐶𝑂3 + 𝐶𝑎𝐶𝑙2 → 𝐶𝑎𝐶𝑂3 + 2𝑁𝑎𝐶𝑙

He knew that the said reaction proceeds completely in the laboratory. He immediately realized that
the Na2CO3 must have been formed by the reverse of this process brought about by the very high
concentration of salt from the lake. Berthollet hypothesized that the reaction may proceed not only from a
single direction but from both ends. Thus, the concept of reversibility was born.

Consider the reaction studied by Berthollet,

𝑁𝑎2 𝐶𝑂3 + 𝐶𝑎𝐶𝑙2 ⇄ 𝐶𝑎𝐶𝑂3 + 2𝑁𝑎𝐶𝑙

Notice how we change the arrow from single headed to a double headed one. This is how a reversible
reaction is presented. The forward reaction, in this case the formation of CaCO 3 and NaCl, and the reverse
reaction, the formation of Na2CO3 and CaCl2, both proceed but not completely. The reaction is said to be
incomplete or reversible. The resulting equilibrium mixture is composed of finite amounts of all the
components.

A complete reaction therefore is a reaction where no reactants remain in the mixture and the
reverse reaction does not occur. All reactions are said to be reversible but restrictions such as low product
yield and kinetically inhibited (slow) reactions cause it not to be observable.

Chemical equilibrium results when the forward reaction proceeds at the same rate as the backward
reaction and only occur in a reversible reaction. A reversible reaction is a chemical reaction that results
when the products react to reform the original substances, the reactants.

EQUILIBRIUM CONSTANT EXPRESSION

Given the general reaction,

𝑎𝐴 + 𝑏𝐵 ⇄ 𝑐𝐶 + 𝑑𝐷

Where:
a, b, c, d = mole numbers of components
A, B, C, D = components
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Introduction to Chemical Equilibrium

Let us recall the rate law from chemical kinetics. One condition for an equilibrium system is that the
rate of the forward reaction equals the rate of the reverse reaction. Therefore, we can equate the rate law for
the forward and reverse reactions.

𝑅𝑎𝑡𝑒𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑅𝑎𝑡𝑒𝑏𝑎𝑐𝑘𝑤𝑎𝑟𝑑

𝑘𝑓 [𝐴]𝑎 [𝐵]𝑏 = 𝑘𝑏 [𝐶]𝑐 [𝐷]𝑑

Plots of rate versus time and concentration versus time will give us a better picture of what happens as
the reactions proceed.

The first paragraph shows the forward and reverse reactions achieve the same rate after some time. The
second graph shows the forward reaction while the third shows the reverse reaction. Both reactions achieve
the same equilibrium concentrations for each of the components. Therefore, equilibrium can be reached from
either direction.

(a)

(b)

Figure 2: (a) Rate versus time of both reactants and products,

(b) Concentration versus time of both reactants and products

The law of mass action by Cato Maximilian Guldberg and Peter Waage expresses the relationship
between the amounts of the reactants and products present at equilibrium. The law state that “the
composition of a reaction mixture can vary according to the quantities of components that are present”. This
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Introduction to Chemical Equilibrium

will tend to change in a direction that brings it closer to its equilibrium composition. The equilibrium expression
can be expressed in two ways. The first is the gaseous substance while the second is for solution.

(𝑃𝐶 )𝑐 𝑒𝑞 (𝑃𝐷 )𝑐 𝑒𝑞
𝐾𝑒𝑞 = 𝐾𝑃 =
(𝑃𝐴 )𝑎 𝑒𝑞 (𝑃𝐵 )𝑏 𝑒𝑞

(𝐶)𝑐 𝑒𝑞 (𝐷)𝑐 𝑒𝑞
𝐾𝑒𝑞 = 𝐾𝐶 =
(𝐴)𝑎 𝑒𝑞 (𝐵)𝑏 𝑒𝑞

These equations are called equilibrium constant expressions. Keq is called an equilibrium
constant. The expression varies according to the given reaction which may be decomposition, formation,
complexation, neutralization, or solid formation. These reactions may be categorized into two in terms of
number of phases present. The first type is called homogenous reaction. If you look at the reaction below,
you can see that all the substance involved are in gas phase. All components are in the same place.
Therefore, the system is a homogenous reaction.

2𝐻𝐼(𝑔) ⇄ 𝐻2 (𝑔) + 𝐼2 (𝑔)

Equilibrium reactions involving components in more than one phase are called heterogenous
reactions. An example of the said reaction can be seen in the reaction.

𝐻2 (𝑔) + 𝑆(𝑠) ⇄ 𝐻2 𝑆(𝑔)

Certain rules are needed to be considered in writing the equilibrium expression.

1. [A], [B], [C], and [D] are molar concentrations (M) in the equilibrium. PA’, PB’, PC’, and PD’ are
equilibrium pressures in terms of atmosphere.

2. The products are always in the numerator, and the reactants are always in the denominator.

3. The coefficient of the reactants and the products in the balanced chemical equations correspond to
their exponents for the expression.

4. Compounds or molecules in a solid or liquid phase are ignored. They are not included in the
expression.

5. Keq does not have a unit since it is an expression for a ratio.

6. Only substance in a gas phase are expressed in the KP expression.

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Introduction to Chemical Equilibrium

The following equilibrium expression for the given gas are as follows:

[𝐼2 ][𝐻2 ] [𝐻2 𝑆]

𝐾𝑒𝑞 = and 𝐾𝑒𝑞 =
[𝐻𝐼]2 [𝐻2 ]

Using these rules to write expressions for homogenous reactions may produce different expression
for KP and KC’.

Illustrative Examples

1. Given the reaction, 2HCl (g) ⇄ H2 (g) + Cl2 (g), determine the equilibrium constant expression.

Solution: Since all the substance are in gaseous form, Keq shall be

[𝐻2 ][𝐶𝑙2 ]
𝐾𝑒𝑞 =
[𝐻𝐶𝑙]2

2. In the problem above, assuming that the hydrogen chloride is in the form of liquid or aqueous, what
is the equilibrium constant expression?
2HCl (l) ⇄ H2 (g) + Cl2 (g)

Solution: Since the reactant is in the form of liquid, Keq shall be

𝐾𝑒𝑞 = [𝐻2 ][𝐶𝑙2 ]

3. Using the reaction, H2 (g) + Cl2 (g) ⇄ 2HCl (aq)

Solution: Since hydrogen chloride is a product and in liquid form, Keq is

1
𝐾𝑒𝑞 =
[𝐻2 ][𝐶𝑙2 ]

4. Determine the value of the equilibrium constant, Kc, for the chemical reaction given below, if 0.108
moles of CO2, 0.098 moles of H2, 0.0082 moles of CO, and 0.0082 moles of H2O vapor were
present in a 2.00 L container and at equilibrium.

CO2 (g) + H2 (g) ⇄ CO (g) + H2O (g)

Given: 0.108, 0.098, 0.0082, 0.0082 (all values in moles)

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Introduction to Chemical Equilibrium

Solution:

[𝐻2 𝑂][𝐶𝑂]
𝐾𝑒𝑞 = [𝐻2 ][𝐶𝑂2 ]
and the substituting the values, we shall have

𝑚𝑜𝑙𝑒𝑠
Since all the gases are in a 2.00 L container, molarity = 𝑉𝑜𝑙 (𝐿)

[𝐻2 𝑂][𝐶𝑂]
𝐾𝑒𝑞 = [𝐻2 ][𝐶𝑂2 ]
= 6.35 x 10-3