2.4.

Rate of Reaction and Equilibrium

• The study of chemical equilibrium gives information about how to control
reactions, including those that play key roles in life processes.

• Many reactions occur slowly. For example:

C6H12O6(s) + 6O2( g) → 6CO2(g) + 6H2O(l)
Glucose
This reaction is extremely slow, however. A sample of glucose exposed to O2 in
the air shows no measurable change even after many years.

Other reactions occur even faster. For example, if we add a solution of silver
nitrate to a solution of sodium chloride (NaCl), a precipitate of silver chloride
(AgCl) forms almost instantaneously.

Net ionic equation: Ag+(aq) + Cl-(aq) →AgCl(s)

Rate of reaction

The rate of a reaction is the change in

concentration of a reactant (or product) per unit
time.

Figure 22: Initial and Equilibrium Rate of Reaction

The rate of reaction is not constant over a long time.

At the beginning, in most reactions, the change in concentration is directly

proportional to time.

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Later, as the reactant is used up, the reaction rate decreases. The rate determined
later is less than the initial rate.

A and B must collide with each other for the reaction to start. If the energy of
the collision is large enough, bonds will break, and a reaction will take place. The
minimum energy necessary for a reaction to occur is called the activation
energy.

Figure 23: Energy Changes during the progress of the reaction

Factors affecting the rate of reaction and activation energy

A. Nature of the Reactants

In general, reactions that take place between ions in aqueous solution are
extremely rapid, and activation energies for these reactions are very low, whereas
reactions between covalent molecules, whether in aqueous solution or not, take
place much more slowly.

B. Concentration

In most cases, the reaction rate increases when we increase the concentration
of either or both reactants. If the concentration of A is doubled, there are twice as

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many molecules of A in the same volume, so the molecules of B in that volume
now collide with twice as many A molecules per second as before.
C. Temperature

When the temperature increases, molecules move more rapidly, which means
that they collide more frequently. More frequent collisions mean higher reaction
rates.
D. Presence of a Catalyst

Any substance that increases the rate of a reaction without itself being used up
is called a catalyst.

Catalysts work by allowing the reaction to take a different pathway, one with a
lower activation energy. A lower activation energy means a faster reaction rate.

Figure 24: Activation Energy for catalyzed and uncatalyzed reactions

2.5. Equilibrium Constant

• Chemical equations represent chemical reactions. These equations
typically have a unidirectional arrow (→) to represent irreversible
reactions.

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• Other chemical equations may have bidirectional arrows (⇌) that represent
reversible reactions.

• In reversible reactions (forward and backward), the chemical equilibrium occurs.

Chemical equilibrium is achieved when the rates of the forward and reverse
reactions are equal, and the concentrations of the reactants and products remain
constant.

This means that the reactant molecules continue to form product molecules
while product molecules react to yield reactant molecules

Before equilibrium, the rate of the forward reaction gradually decreases, and the
rate of the reverse reaction (which began at zero) gradually increases.

Eventually, the two rates become equal. At this point, the process is in dynamic
equilibrium (or just equilibrium).

Chemical equilibria can be described using a

straightforward mathematical expression.
The general equation for all reversible
reactions:

Figure 25: Concentration of Reactants and Products at

Equilibrium

The equilibrium constant (Keq):

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Practice: Calculate the equilibrium constant for the following reaction:

Practice:
1- Write the equilibrium expression for the following reactions:
i- SO3(g) + H2O(l) ↔ H2SO4(aq)
a. Keq = [H2SO4] / [SO3][H2O]
b. Keq = [SO3][H2O] / [H2SO4]
c. Keq = [H2SO4] / [SO3][H2O]2
d. Keq = [H2SO4]2 / [SO3][H2O]
ii- 2NH3(g) ↔ N2(g) + 3H2(g)
a. Keq = [H2][N2] / [NH3]
b. Keq = [H2]3[N2] / [NH3]2
c. Keq = [NH3] / [H2][N2]
d. Keq = [NH3]2 / [H2]3[N2]

2- What is the equilibrium constant value for the following reaction?

Equilibrium concentrations are given under the formula for each
component.

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Cl2 + PCl3 ↔ PCl5
1.66 M 1.66 M 1.66 M
a. 0.60
b. 1.66
c. 2.75
d. 4.57

2.6. Le Chatelier’s Principle

• If external stress is applied to a system in equilibrium, the system responds in a
manner that partially relieves that stress. Five types of stress can be put on
chemical equilibria:

A. Addition of a Reaction Component

• When more of any component is added to a system in equilibrium, that addition

constitutes stress. The system relieves this stress by increasing the concentrations
of the components on the other side of the equilibrium equation. We say that the
equilibrium shifts in the opposite direction.

B. Removal of a Reaction Component

• The removal of a component, or even a decrease in its concentration, lowers the

corresponding reaction rate and changes the position of the equilibrium.

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• If we remove a reactant, the reaction shifts to the left, toward the side from which
the reactant was removed.

• If we remove a product, the reaction shifts to the right, toward the side from
which the product was removed.

C. Change in Temperature

• The effect of a change in temperature on a reaction that has reached equilibrium

depends on whether the reaction is exothermic (gives off heat) or endothermic
(requires heat).
For an exothermic reaction:
• An increase in temperature drives an exothermic reaction toward the reactants (to
the left).
• A decrease in temperature drives an exothermic reaction toward the products (to
the right).
For an endothermic reaction, the opposite is true:
• An increase in temperature drives an endothermic reaction toward the products
(to the right).
• A decrease in temperature drives an endothermic reaction toward the reactants (to
the left).

D. Change in Pressure

• A change in pressure influences the equilibrium only if one or more components

of the reaction mixture are gases.

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• An increase in pressure shifts the reaction toward the side with fewer moles of
gas.
• A decrease in pressure shifts the reaction toward the side with more moles of gas.
• When the moles of gas are the same in a balanced reaction, an increase or
decrease in pressure results in no shift of the reaction.
• Le Châtelier’s principle does not apply to pressure increases caused by the
addition of a nonreactive (inert) gas to the reaction mixture. This addition does
not affect the equilibrium position.
E. The Effects of a Catalyst

• A catalyst increases the rate of reaction without itself being changed.

• For a reversible reaction, catalysts consistently increase the rates of both the
forward and reverse reactions to the same degree. Therefore, adding a catalyst
does not influence the position of the equilibrium.

• However, adding a catalyst to a system not yet at equilibrium causes it to

reach equilibrium faster than it would without the catalyst.

Practice:

1- What happens to the following equilibrium reaction when Br 2 gas is added

to the equilibrium mixture?

2NOBr(g) ↔ 2NO(g) + Br2(g)

a. The reaction shifts to the right

b. The reaction shifts to the left

c. The reaction will stop

d. There will be no change

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2- Consider the following equilibrium reaction for the decomposition of an
aqueous solution of hydrogen peroxide:

2H2O2(aq) ↔ 2H2O(l) + O2(g)

Hydrogen peroxide

Oxygen has limited solubility in water. What happens to the equilibrium after
the solution becomes saturated with oxygen?

a. The reaction shifts to the right

b. The reaction shifts to the left

c. The reaction will stop

d. There will be no change

3- Consider the following equilibrium reaction:

A↔B

Increasing the temperature results in an increase in the equilibrium

concentration of B. Is the conversion of A to B an exothermic reaction or an
endothermic reaction? Explain.

4- What happens to the following equilibrium reaction when the pressure

increases?

O2(g) + 4ClO2(g) ↔ 2Cl2O5(g)

a. The reaction shifts to the right

b. The reaction shifts to the left

c. The reaction will stop

d. There will be no change

CHEMISTRY FOR MEDICINE

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Life at High Altitudes and Hemoglobin Production
The human body needs to maintain numerous chemical
equilibria to guarantee physiological health. When
external conditions alter, the body must adjust to
maintain functionality.
The repercussions of an abrupt alteration in altitude
underscore this reality. Travelling from a location at
sea level to a city situated at a height of around 3 km
within two days may result in headaches, nausea, severe
exhaustion, and other ailments.
These characteristics are indicative of hypoxia, a
shortage in the oxygen supply to bodily tissues. In
severe instances, the victim may enter a coma and
succumb if not promptly treated.
The interaction of oxygen with the haemoglobin (Hb) molecule, responsible for
transporting oxygen in the blood, is a complex reaction; nevertheless, it can be
represented by a simplified equation for our purposes:
Hb(aq) + O2(aq) ⇌ HbO2(aq)
HbO2 refers to oxyhemoglobin, the combination of haemoglobin and oxygen
responsible for transporting oxygen to tissues.
The equilibrium constant for this reaction is:
Kc = [HbO2] / [Hb][O2]
At an elevation of 3 kilometres, the partial pressure of oxygen is around 0.14 atm,
in contrast to 0.2 atm at sea level. Le Châtelier’s principle posits that a reduction
in oxygen concentration will alter the equilibrium depicted in the aforementioned
equation from right to left. This alteration diminishes the availability of
oxyhemoglobin, resulting in hypoxia. With sufficient time, the body addresses the
issue of life at high altitudes and haemoglobin production by generating an
increased quantity of haemoglobin molecules. The balance will thereafter realign
towards the synthesis of oxyhemoglobin.

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