RATE OF CHEMICAL REACTION

Rate of Chemical Reaction

Chemical reactions deal with reactants and products. As products are formed, reactants are used up.
The rate at which reactants are used up and products formed changes with time. The rate of chemical
reaction is the number of moles of reactants converted or products formed per unit time. In the reaction
below;

Calculations on Rate of Chemical Reaction:

Example 1
When 0.5g of calcium trioxocarbonate(iv) was added to excess dilute hydrochloric acid, carbon(iv)
oxide was evolved, the entire reaction took 5 minutes. What was the rate of the reaction?
CaCo3(s) + 2HCl(aq) → CaCl(aq) + H2O(l) + CO2(g)
Example 2
15g of Na2CO3 reacted with excess dilute of HCl to produce CO2. After 5 minutes, 5.3g of the
trioxocarbonate(iv) was left unused. What was the rate of reaction?

mass of Na2CO3 used up = mass given – mass unused

= 15g – 5.3g = 9.7g
Time taken = 5 minutes
= 9.7 / 5
=1.94g/min

Measuring the Rate of Chemical Reaction

Reaction rates are determined by measuring the rate at which the mass or volume or concentration of a
reactant decrease and the product increases.
For Example,

When dilute HCl is added to marble chips, effervescence is more vigorous at the start than at the end of
a reaction. The graph which shows the rate of reaction is known as the rate curve. The curve passes
through the origin because there is no loss in mass at the beginning of the reaction.

Rate curve graph of loss in mass against time

From the shape of the curve, the graph passes through the origin. The gradient of the curve becomes
steep as the rate of the reaction decreases. Finally, the curve becomes horizontal. Indicating the
endpoint of the reaction. A larger gradient indicates a faster reaction rate, while a smaller gradient
indicates a slower one.
Example: given the following values
Time in minutes 0 1 2 3 4 5 6 7 8
Volume of gas in cm3 0 5 10 15 20 25 30 30 30

From the graph of time against volume of oxygen, there is an increase in the volume of gas liberated as
time increases until the volume of gas becomes constant from the sixth minute.

Collision Theory
The collision theory states that for a chemical reaction to occur, the reacting particles must collide with
one another. Hence the rate of reaction is directly proportional to the frequency of collision between the
particles.
It is not all collisions between particles that will form a product. For a collision to be effective, the
particles must be properly oriented [aligned] and also possess minimum energy called ACTIVATION
ENERGY. Only a small fraction of the total number of collisions is effective.
Activation energy is the equivalent of the energy barrier that must be overcome before a reaction can
occur.
Reactions occur if the energy of the colliding particles is equal to or greater than the activation energy.
When the activation energy is acquired by the reactant particles, which could be ions, atoms, or
molecules, they form a complex particle of high energy content known as the activated complex. For its
high energy content, it is unstable and will readily decompose to give reactants and products.
Activation Energy and Chemical Reaction
Let us consider the two distinct types of reactions. Exothermic and Endothermic reaction. The energy
changes during endothermic and exothermic reactions can be illustrated graphically. This graphical
representation of the energy changes in the course of the reaction is known as a reaction profile.

A reaction profile is a sequence of steps shown graphically by which the reaction progresses from
reactants through activated complexes to product.
The figures below illustrate the energy profile diagram of an endothermic and exothermic reaction.

In an Endothermic reaction, the heat energy content of the product is greater than the heat energy of
the reactant.

In an Exothermic reaction, the heat energy content of the product is less than the heat energy of the
reactant.

The collision theory can be used to explain how changes in temperature, light concentration, nature of
reactant, pressure, and presence of catalysts affect the rate of a chemical reaction.
Factors Affecting Rate of Chemical Reaction
The rate of chemical reaction depends on
1. Nature of reactants.
2. Concentration of reactants.
3. Effect of temperature.
4. Surface area of reactants.
5. Presence of catalyst.
6. Pressure changes in gaseous reactants.
7. Effect of light.

1. Nature of Reactant:
The rate of reaction is affected by the nature of reactants taking part in the reaction. For example, when
iron, zinc, and gold react with hydrochloric acid. The reaction is slow, but with a piece of gold, there is
no evidence of reaction. This is because of the position of these metals in the activity series. Gold is
lower than hydrogen in the activity series, it cannot displace hydrogen from the solution of its salt.
Zn[s] + 2HCl[aq] → ZnCl2[aq] + H2[g]
Fe[s] + 2HCl[aq] → FeCl2[aq] + H2[g]
Thus the rate of reaction is determined by the chemical nature of different substances.

2. Concentration of Reactants:
Concentration is a measure of the number of reactant particles in the solution. An increase in
concentration of the reactant will result in a corresponding increase in the effective collision of the
reactants and hence an increase in the reactant rate.
Example: Mg[s] + HCl[aq] → MgCl2[aq] + H2[g]
When magnesium wire is dropped into a beaker of dilute hydrochloric acid, the metal dissolves with
effervescence. The reaction rate is obtained by measuring the duration of effervescence. The
concentration of the acid is varied while the mass of the metal is kept constant.
Experiment: To study the rate curve for different concentrations of hydrochloric acid in the reaction
between HCl and Mg.
The rate curve below shows the time taken when excess hydrochloric acid of different concentrations
reacted separately with the same mass of magnesium at the same temperature. The concentration 0.5m,
1.0m, 1.5m and 2.0m.
 Graph of the effect of concentration of a reactant on reaction rate.

From the graph, the rate of reaction is faster at the beginning of the reaction where the acid is more in
concentration. Generally, an increase in the concentration of reactants increases the frequency of
collision and hence increases the reaction rate. A decrease in the concentration of reactants decreases
the chances of collision and hence decrease the rate of reaction.

3. Temperature Effect:
The rate of most reactions increases as temperature rises. This effect is observed for most Exothermic
and Endothermic Reactions. Increasing the temperature of a system leads to an increase in the rate of
reaction. This is because molecules gain more energy at higher temperatures. This increases their
kinetic energy resulting in a more effective collision and the reaction proceeds at a faster rate.

The figure below illustrates the effect of temperature on the kinetic energies of particles. At lower
temperature T1, the shaded area under the curve represents the number of particles that possess the
minimum energy EA [activation energy]. As the temperature increases to T2, more reactants acquire
more energy greater than activation energy, EA, hence the rate of reaction increases.
T1 = Lower temperature
T2 = higher temperature
We store food in a refrigerator because of this effect of temperature on reaction rates. The rates of the
reactions that lead to food spoilage are decreased considerably by cooling the food from room
temperature to that in a refrigerator. The rates of these reactions are decreased even further by storing
food in a freezer.

4. Effect of Surface Area of Reactant:

The rate of chemical reaction can be increased by the area of contact of the reacting substances. The
greater the surface area of the reactant, the higher the rate of reaction. To increase the surface area of
the solid is to break it into smaller pieces. This will make room for greater contact between the reacting
particles. The powdered substance offers a greater surface area than the lump substance.

For example, dilute hydrochloric acid reacts more vigorously with powdered marble [CaCO3] than
marble chips. This is because the powdered marble offers a greater area of contact than marble chips.
Charcoal burns more easily when it is broken into small pieces than when it is in lump form.

5. Effect of Catalyst:
A catalyst is a substance that alters the rate of a chemical reaction without being used up in the reaction.
Eg platinum, Nickel, Manganese[iv]oxide, Iron, Vanadium(V)oxide. A catalyst operates by providing an
alternate path/route for the reaction.

If the alternative route has lower activation energy, the catalyst is said to be a positive catalyst or
promoter. But the one which has higher activation energy is known as a negative catalyst or inhibitor.

A positive catalyst lowers the energy barrier of a chemical reaction, more reactant particles are able to
react when they collide, which increases the rate of chemical reaction while a negative catalyst slows
down the rate of chemical reaction.
The effect of the activation energy with the catalyst and without the catalyst is illustrated in the energy
profile diagrams below;

Exothermic Reaction.

Endothermic Reaction.
Characteristics of Catalyst:
1. It alters the rate of a chemical reaction.
2. Remain unchanged after the reaction.
3. A catalyst cannot start a reaction
4. A catalyst has no effect on the equilibrium of a relevant reaction.
5. A catalyst is specific in action.
6. A catalyst does not affect the type of product formed.

6. Effect of Pressure:
A change in pressure affects a chemical reaction in which one or more of the reactants or products are
gases. An increase in pressure in gases leads to more effective collision and increases the rate of
reaction. But a decrease in pressure leads to less effective collision and a decrease in the rate of
reaction.

7. Effect of Light:
Some reactions only occur in the presence of sunlight. Such reactions will not occur in the dark. In these
reactions, sunlight provides the energy required to promote frequent collisions between the particles of
the reactants. A reaction that occurs in the presence of light is a photochemical reaction. Other examples
of photochemical reactions include….
i. Photosynthesis in plants
ii. Substitution reaction between methane and chlorine
iii. Decomposition of hydrogen peroxide
In the above reactions, the reactant particles absorb energy and react rapidly.
Evaluation Questions
Question 1:
(a) What is meant by the rate of chemical reaction?

(b) Excess dilute hydrochloric acid was added to 1.5g of magnesium trioxocarbonate[IV], and
carbon[IV]oxide gas was evolved. If the reaction was completed after 3 minutes, what was the rate of
the reaction?

Question 2:
(a) Draw the energy profile diagram for the reaction
H2(g) + I2(g) → 2HI(g) ∆H = -13KJmol -1

(b) If the concentration of the HI increases from 0 to 0.001moldm-3 in 50seconds, what is the rate of
reaction?

(c) Collision theory suggests that for two particles to react, they must collide. What five factors
determine whether or not the collision would lead to formation of product.

(d) Explain the observations on adding dilute H2SO4 separately to Zinc dust and Zinc granules of the
same mass. The dust produced more vigorous efferverscence than granules?

Question 3:
(a) Explain in terms of the collision theory
i. The effect of temperature increases on a reaction rate.
ii. How the rate of a gaseous reaction is affected by an increase in pressure.

(b) consider the reaction represented by the equation:

Mg[s] + 2HCl[aq] → MgCl2[aq] + H2[g]
i. Name the type of reaction involved
ii. Give two ways by which the reaction could be made faster

(c) What volume of hydrogen gas would be produced from 6.0g of the magnesium? [H = 1, Mg = 24, 1
mole of a gas occupies 22.4dm3 at s.t.p ]
Question 4:
Draw an energy profile diagram to illustrate a catalysed exothermic reaction and label parts of the curve
representing the following.
i. Activated complex [without catalyst]
ii. Activation energy [with catalyst]
iii. Enthalpy change

(a) State two conditions that can lead to ineffective collisions during chemical reaction.

(b)The photocatalytic reaction between hydrogen and chlorine, when carried out in a dimly lit room, is
represented by the following equation.
H2[g] + Cl2[g] → 2HCl[g] △H = -XKJmol-1
Explain what happens when the reaction is carried out in sunlight.

(c) i. Define the term catalyst

ii. Give two characteristics of a catalyst
iii. Using energy profile diagrams, show catalysed and uncatalyzed reactions.

Question 5:
a. The volume of carbon(IV)oxide produced from calcium trioxocarbonate(IV) and excess hydrochloric
acid was measured at selected intervals until two successive readings agree as shown in table
i. Plot the volume of CO2 gas collected against time taken.
ii. State the time taken for the reaction to reach completion
iii. What was the volume of CO2 collected after 20 seconds?
iv. Why did the reader stop taking readings at 6-second intervals after 36 seconds?
v. Why must the readings continue until three successive readings agree?
Table 2
Time [secs] 6 12 18 24 30 36 50 60 100 150 250
vol. of CO2 collected [cm3] 40 60 75 85 93 100 105 112 115 115 115

a. Two different samples of calcium trioxocarbonate(IV( of the same mass were put in two separate
beakers as shown as in fig5 (diagrams are labelled X and Y). Bench hydrochloric acid were added to
each in excess and effervescence colourless gas evolved.
Fig 5

Fig 5: beakers bearing calcium trixocarbonate[iv] of the same mass.

i. Which of the setups in X and Y will be the first to stop producing effervescence.
ii. Explain your answer in [i] above
iii. Identify the colourless gas evolved
iv. Write a balanced equation for this reaction.