Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 1

Rates of Combustion Reactions

The combustion reactions we use in everyday life proceed at very different rates. We
have:
• slow combustion as in slow combustion stoves where large lumps of fuel (coal,
coke or wood) take many hours to burn
• fast combustion such as burning methane, LPG, kerosene and heating oil in
stoves or heating appliances or of powdered coal in power stations, and
• explosive combustion as in the cylinders of petrol and diesel engine vehicles.

All of the chemical reactions involved in these combustion processes are spontaneous
reactions. This means that once started (ignited) they proceed without further assistance
and continue going until all of the fuel is used up.

Slow combustion occurs when we use big lumps of fuel and limit the supply of air. This
means that burning occurs only on the surface of the big lumps and its speed is controlled
by the limited supply of air.

For fast combustion in power stations, coal is ground into very small particles that are
sprayed into a plentiful supply of air: there is a large surface area of fuel exposed to an
excess of oxygen and there is good mixing to stop oxygen concentrations becoming
depleted near the surface of the particles. In other fast combustion appliances, gaseous
fuel or vaporised liquid fuel is mixed with excess air: the gaseous nature of the mixture and
the high temperature ensure that fuel is always in contact with oxygen and so combustion
proceeds rapidly.

In petrol engines a spark is used to ignite a heated mixture of petrol and air. In diesel
engines liquid fuel is injected and vaporised into an excess amount of heated air. In both
cases the conditions used are such as to promote very rapid reaction. An explosion is just
an extremely rapid reaction – one that goes to completion within a few microseconds.

Collision Theory
The chemical equation for a reaction indicates the nature of the reactants and products but
provides no information about the way in which the reactants are converted to products.
For example, the decomposition of hydrogen iodide is represented by the following
equation:

2HI(g) → H2(g) + I2(g)

This equation indicates that for every two molecules of HI(g) which decompose, one
molecule of H2(g) and one molecule of I2(g) are produced. However, the equation does not
indicate how HI molecules are converted to H2 and I2. The first step in a chemical reaction
is thought to involve a collision between the reactant particles. This idea is part of the
collision theory of reaction rates. The collision theory assumes that if particles are to react
they must first undergo an appropriate collision.

From the kinetic theory, the particles in a gas are in continuous state of random straight-
line motion. While most of the particles have energies that are close to the average for all
the particles in the system, a small fraction have energies much lower or much higher than
the average. Because of this range of kinetic energies, collisions between HI molecules
will occur with differing energies. A collision between reactant molecules does not
necessarily mean that a reaction will take place. In fact, most collisions do not bring about
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 2

a reaction. The collision theory requires that for a collision between reactant molecules to
lead to a chemical reaction the following conditions must be fulfilled:
1. The molecules must collide with sufficient energy to disrupt the bonds of the
reactant molecules.
2. The molecules must collide with an orientation that is suitable for the breaking of
some bonds and the formation of others.

For a reaction to occur between reactant molecules they must collide with a certain
minimum energy. Unless this minimum energy is exceeded, the colliding molecules will
simply rebound and move away from each other. The minimum energy that is required for
a collision to result in a reaction is known as the activation energy for the particular
reaction. Some reactions have relatively low activation energies and so react at a
significant rate at room temperature. For these reactions, a noticeable reaction occurs as
soon as the reactants are mixed. For example, a piece of sodium metal is added to water
at room temperature produces a violent reaction almost instantaneously. Other reactions
occur at an almost insignificant extent at room temperature. In such reactions the
activation energy is so high that it is very unlikely that reactant molecules will undergo
reaction. For example, methane will not react with oxygen unless the mixture is ignited.
There is a relatively high activation energy for the reaction between methane and oxygen.
Despite the fact that under standard conditions there would be in the order of 1010
collisions per second between reactant molecules, virtually none of these would have
sufficient energy for a reaction to take place.

As well as needing a minimum amount of energy, successful collisions also often have an
orientational requirement. The relative orientations of the reactant molecules during a
collision must be favourable for the breaking of particular bonds in the reactants and the
formation of new bonds in the products. This factor also contributes to the fact that many
collisions between reactants are unsuccessful in producing a reaction.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 3

Energy Profile Diagrams

An energy profile diagram is a way of representing the energy changes that occur during a
chemical reaction. A typical example of an energy profile diagram is shown below.

The potential energies of the reactants (a) and products (c) are identified in the figure. The
energy difference between the reactants and products represents the heat of reaction.
Between the reactant and product states is a very high energy state (b) known as the
transition state or activated complex. The transition state represents the highest energy
state for the reacting system and corresponds to some stage in the reaction at which
bond-breaking and bond-formation are taking place. The transition state is an unstable
state and cannot have any more than a very temporary existence. Once formed it will
quickly convert to products or return to reactants. The activation energy (Ea) for the
reaction is the difference in the potential energies of the reactants and the transition state.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 4

The energy profile diagrams for exothermic and endothermic reactions are shown in fig
21.9. These also indicate that an activation energy exists for both exothermic and
endothermic reactions.

Collision Theory and Reaction Rate

In general, if other factors affecting reaction rates are equal, slower reactions will have
higher activation energies than faster reactions. The different activation energies for
different reactions are related to the ease with which bond-breaking and reforming
processes occur. High activation energies are often associated with reactions in which
strong bonds have to be broken. For example, the low reactivity of nitrogen gas (N2) is
related to the large amount of energy needed to break the N≡N triple bond.

One of the fundamental assumptions of the collision theory is that molecules must collide
before they react. The effect of increasing the concentration of a reactant in solution is to
increase the rate at which reactant molecules collide with one another. If a greater number
of collisions occur per unit of time, the reaction rate will increase. Although the same
proportion of these collisions will be successful collisions, the greater rate of collisions
results in a greater number of successful collisions. The same argument can be applied to
reactions involving gases. Increasing the pressure of reactant gases increases the rate of
collisions between the molecules and hence the rate of reaction.

The extent of the increase in reaction rate which occurs when the concentration of
reactants is increased depends on the reaction involved. Often the relationship is a fairly
simple one. For example, in the reaction

H2(g) + I2(g) → 2HI(g)

doubling the pressure of H2 (g) doubles the rate of reaction. For the reaction

2HI(g) → H2(g) + I2(g)

doubling the pressure of HI (g) quadruples the rate.

Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 5

If the surface area of a solid or liquid reactant is increased, more of the reactant
molecules are exposed to collision. Fig 21.11 indicates how subdividing a piece of solid
reactant increases the surface area. Since molecules must collide before they react,
increasing the surface area can lead to an increased rate of reaction. Solid reactants are
often powdered to increase the rate of reaction. When liquid reactants are used, the liquids
are frequently used as sprays or subjected to vigorous agitation to ensure that a large
surface area is available for reaction.

The temperature of the reacting system has a significant effect on the rate of reaction. At
room temperature, an increase of 10°C can lead to a two or three-fold increase in the rate
of solution reactions. In gaseous systems, there is often an even greater increase in
reaction rate. An increase in temperature increases the average kinetic energy of the
reacting molecules and, more importantly, changes the distribution of molecular kinetic
energies.

The increased velocities of the molecules lead to a greater rate of collision and hence a
greater rate of reaction. However, the increase in reaction rate due to the increased rate of
collisions is fairly small.

The main reason that temperature increases reaction rate is because of its effect on the
distribution of molecular kinetic energies as shown in fig 21.12. As the temperature is
raised, a greater proportion of reactant molecules have sufficient kinetic energy to supply
the activation energy needed for the reaction. This means that a greater proportion of
molecular collisions will be successful collisions. As a result, the rate of the reaction is
increased.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 6

A catalyst acts to provide an alternative reaction pathway to that available when the
reactants alone are used. This different pathway has a lower activation energy as shown in
fig 21.13. The catalyst allows the reaction to occur in such a way that less collision energy
is required for reactions to take place. As a result, a greater proportion of reactant
collisions will be successful and the reaction rate will be greater than without a catalyst. Fig
21.14 illustrates how a greater proportion of reactant molecules have sufficient energy to
overcome the activation energy barrier in a catalysed reaction.

It is important to note that the activation energies for both the forward and reverse
reactions are decreased by the action of a catalyst. The rates of both the forward and
reverse reactions are therefore increased by the use of a catalyst.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 7

Catalysts are extremely important industrially because they help make reactions possible
that would normally be slow or expensive to achieve. The use of catalysts often allows
reactions to be carried out at much lower temperatures, thereby using less energy than
would otherwise be required. The Haber process is used to produce industrial quantities of
ammonia; iron/iron oxide is used as the catalyst. Catalytic cracking is used in the
petroleum industry to break up long hydrocarbon chains into smaller, more useful,
hydrocarbons. Zeolites are used to catalyse this catalytic cracking.

Catalysts generally operate by forming intermediate compounds in which the bond-

breaking and rearrangement processes require less energy than if the reactants alone
were involved. For example, with metal catalysts reactant molecules that collide with the
metal surface may become attached to the metal. The molecular rearrangements that
occur during this process make it more likely that subsequent reactant collisions will be
successful. For example, in the manufacture of ammonia using an iron catalyst it appears
that the N2 and H2 reactants are bound to the surface as separate atoms. These atoms are
reactive and combine to form NH3 molecules as shown in fig 21.15.

Increasingly catalysts are controlling the emission of pollutants, both from cars and power
plants. An example is the use of catalytic converters in cars sold in Australia since 1986.
The catalytic converter is located between the engine and the exhaust pipe. Its function is
to catalyse reactions between which remove pollutants leaving the engine: unburnt petrol
(mainly octane), carbon monoxide and nitrogen oxides. Typically catalytic converters
contain platinum and rhodium.

Another important group of catalysts are the biological catalysts called enzymes. Enzymes
are proteins which catalyse the thousands of chemical reactions involved in sustaining life.

Plants and animals are only able to survive within a limited temperature range. All
chemical reactions which occur in them must take place within this temperature range.
However, many of these reactions involve large and complex molecules which would
normally react very slowly. The rates of these reactions are increased by enzymes which
help the complex bond-breaking and molecular rearrangements to occur more readily.
These natural catalysts are highly specific in their activity. Each enzyme catalyses a
particular type of reaction.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 8

?First-hand investigation: Reaction Rates 5.3.1

• solve problems, identify data, perform first-hand investigations and gather first-
hand data where appropriate, to observe the impact on reaction rates of:
- changing temperature
- changing concentration
- size of solid particles
- adding catalysts

Combustion reactions and explosions: Energy and Rate Factors

Combustion reactions are those in which a substance reacts with oxygen releasing heat
and light energy and is usually accompanied by a flame. Commonly we think of
combustion reactions involving hydrocarbon fuels such as methane, petrol or coal but
other examples are the reactions of oxygen with ethanol, metals such as magnesium and
iron, and non-metals such as phosphorus, sulfur and carbon (in the form of coke).

Combustion reactions are always exothermic. The decrease in enthalpy of the reacting
system is accompanied by the release of heat and light energy to the surroundings. The
actual rate at which combustion reactions take place depends on the many factors that
influence reaction rates. These include the nature of the reactants (affects activation
energy); the surface area, concentration and pressure of the reactants; temperature, and
the use of catalysts.

Some combustion reactions are spontaneous under normal conditions. For example, white
phosphorus reacts spontaneously with oxygen in the air to form phosphorus(V) oxide.

P4(s) + 5O2(g) → P4O10(s)

Because of the spontaneous nature of this reaction, white phosphorus is stored under
water to prevent it coming into contact with air. Phosphorus has been responsible for many
fires when its storage under water has not been carefully controlled or monitored.

Hydrocarbon fuels do not undergo spontaneous combustion at normal temperatures. This

is due to the high activation energy of these reactions. However, at temperatures above
their ignition temperature, hydrocarbons and other fuels will undergo spontaneous
combustion. Fortunately the ignition temperatures for most fuels are reasonably high. As a
result they do not spontaneously react with oxygen in the air unless heated to high
temperatures or a flame or spark is present which can initiate the reaction. The presence
of a flame or spark can provide the activation energy required for some molecules to react.
The release of heat energy that accompanies the reaction of these molecules is then
sufficient to maintain a high enough temperature so that the reaction continues. This is
why the flash point for fuels is much lower than the ignition temperature. This is clearly
illustrated by the burning of wood, coal, natural gas, sulfur and magnesium. Once a flame
has provided the activation energy for some of the molecules to react these reactions
become self-sustaining.

If a combustion reaction has a low activation energy or is initiated by a flame or spark the
rate of the reaction is mainly dependent on the availability of fuel molecules for collision
with oxygen molecules. This is often a function of the state of subdivision or surface area
of the fuel. In coal and wood fires the solid fuels is usually present in ‘limps’ and has a
relatively small surface area. The combustion is slow as a result. The reaction rate can be
increased by increasing the surface area of the fuel, by chopping the wood or breaking the
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 9

coal into smaller pieces. If the fuel is very finely divided, as in coal dust, the collision rate of
fuel and oxygen molecules is much greater. This can increase the rate of reaction to such
an extent that an explosion may occur. In liquids, too, the rate of combustion depends on
the state of subdivision of the fuel. To increase the rate of combustion in some furnaces,
liquid fuels are injected as a spray. Where the rate of combustion needs to be controlled
the supply of fuel is often limited. For gases this is achieved by varying the rate of inflow of
gas, as in a stove or oven. In liquids a wick is sometimes used to provide a steady supply
of fuel. Explosive chemical reactions are those that result in a rapid increase in pressure,
often in a confined space. These are always exothermic reactions and often involve the
release of large volumes of gas. Many hydrocarbons have the ability to react explosively
under certain conditions. For example the combustion reaction of propane is exothermic
and releases large quantities of gas.

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

Hydrogen, nitroglycerine (C3H5(NO3)3), TNT (C7H5(NO3)3) and ammonium nitrate

(NH4NO3) also have the capacity to react explosively.

2H2(g) + O2(g) → 2H2O(g)

2C3H5(NO3)3(s) → 3N2(g) + 6CO2(g) + 5H2O(g) + ½ O2(g)

Nitroglycerine reacts so rapidly it is usually mixed with a clay material to reduce the rate of
decomposition and make the material easier to handle. This mixture, dynamite, is often
about 75:25 mix of nitroglycerine and clay material.

In explosive chemical reactions the reaction must occur at a very rapid rate so that the
heat and gas products are released over a short period of time. Explosive reactions may
have high activation energies. However, once a reaction has commenced, initiated by a
flame or spark, the exothermic nature of the process maintains a rapid reaction rate. Other
important factors that can affect the rate of those that influence the rate of the pressure of
oxygen. In most explosive reactions the reactants are finely divided, existing as vapour,
powder or dust, which increases that rate of collision between reactant particles and
therefore favours a rapid reaction rate.

From a safety point of view it is important to control or eliminate those conditions that
favours explosive combustion. Naked flames and sparks can initiate chemical reactions
must be avoided in high risk environments such as oil refineries and petrol stations. In
other situations such as homes, boats and caravans, as well as high risk locations, care
must be exercised to maintain equipment so that accumulations of vapour, finely divided
coal and cereal dust are avoided.
Preliminary CHEMISTRY ENERGY PART 5: REACTION DYNAMICS page 10

! Exercises
1. Describe the different types of combustion (slow, spontaneous, explosive) and
explain the conditions under which they occur.
2. What factors determine whether a particular collision between reactant molecules
will lead to a reaction?
3. Explain the relationship between temperature and kinetic energy of particles.
4. What is the activation energy for a reaction?
5. A piece of white phosphorus left in the open air at room temperature spontaneously
ignites and burns to form P4O10. In contrast, a piece of iron rusts very slowly when
exposed to the atmosphere. What does this information suggest about the
activation energies for these reactions?
6. The ignition temperature for the combustion of kerosene is 220°C while that of
natural gas is 540°C. What does this suggest about the relative activation energies
for the combustion reactions of natural gas and kerosene?
7. Describe the role of a catalyst. Identify a catalyst required for a particular industrial
process.
8. Why are many liquid fuels vaporised before being used in combustion chambers?
9. Glucose is quite stable in aqueous solution but in the human body is fairly rapidly
converted to CO2 and H2O by the catalytic effect of certain enzymes. Explain how a
catalyst can increase the fraction of successful collisions between reactant
molecules.
10. (a) Under what conditions do explosions occur? Relate your answer to collision
theory.
(b) State the safety precautions required so explosions do not occur in work
environments.