Unit: Chemical Kinetics MYP5

Unit- Organic Chemistry

Key Concept - Change

Related Concept – Energy

Global context - Scientific and technical innovation

Statement of Inquiry: Scientific and technological advances can enable functional energy
transformations within, and between, systems.

Learning Targets:

1. Word and chemical reactions and formula, balancing the reactions

2. Reaction kinetics – catalyst and their role
3. Factors affecting rates/ collision theory
Unit: Chemical Kinetics MYP5

Table of Contents
COLLISION THEORY ..................................................................................................................... 3
FACTORS THAT AFFECT THE RATE OF A REACTION ............................................................. 3
SURFACE AREA ......................................................................................................................... 4
CATALYSTS................................................................................................................................ 5
TEMPERATURE .......................................................................................................................... 5
CONCENTRATION ..................................................................................................................... 6
TYPES OF SYSTEM ........................................................................................................................ 8
WHAT IS THE ROLE OF ENERGY IN CHEMICAL REACTIONS? .............................................. 8
ENERGY CHANGE ....................................................................................................................... 10
BOND ENERGIES...................................................................................................................... 11
CALCULATING THE ENERGY CHANGES IN REACTIONS ..................................................... 12
RATE OF REACTION ................................................................................................................... 14
DYNAMIC EQUILIBRIUM ........................................................................................................... 15
AMMONIA – AN IMPORTANT NITROGEN CONTAINING CHEMICAL .................................. 16
HABER’S PROCESS ...................................................................................................................... 18
CONCENTRATION OF REACTANTS OR PRODUCTS ........................................................... 18
PRESSURE ................................................................................................................................. 19
TEMPERATURE ........................................................................................................................ 19
ARTIFICIAL FERTILIZERS .......................................................................................................... 20
PROBLEMS WITH FERTILIZERS ............................................................................................ 20
NITROGEN CYCLE....................................................................................................................... 20
EXTENDED READING ................................................................................................................. 21
REFERENCES................................................................................................................................ 21
Unit: Chemical Kinetics MYP5

Chemical kinetics is the branch of chemistry that involves the study of the rate of a chemical
reaction under changing conditions. It is useful for us to know what is happening at the
atomic level when the reaction takes place, and if the chemical reaction will occur at a useful
rate for a given set of conditions (temperature/pressure/ concentration).

COLLISION THEORY
The collision theory is a model helping us understand what is happening at the atomic level
when reacting particles collide. For a reaction to occur:
 the reacting particles must collide with each other
 the colliding particles must have the correct orientation at the time of collision
 the particles must have the minimum kinetic energy required to initiate a reaction
The net movement of matter occurs constantly. Particles all around us are involved in
collisions at every moment of the day, but only a small proportion of these collisions are
successful in causing a chemical reaction. In most collisions, particles will simply bounce off
each other, resulting in a change in direction. For a collision to be successful, the three
conditions that form the basis of the collision theory need to be met.

Figure 1 The collision theory explains why some collisions are successful while some are not

FACTORS THAT AFFECT THE RATE OF A

REACTION
● Concentration of the reactants and gas
pressure.
● Temperature at which the reaction is carried
out.
● Surface area.
● Use of a catalyst, including enzymes.
Unit: Chemical Kinetics MYP5

SURFACE AREA
Collisions take place at the surface of solids. With a larger surface area collision are more
frequent, and there is a greater chance of a ‘successful’ collision. In reactions involving
solids, powders react much faster than lumps or granules, which react faster than lumps (all
other variables kept constant).

Figure 2 Collision theory and effect of surface area

Figure 3 compares the effect of surface area on the reaction between two equal masses of
calcium carbonate and hydrochloric acid. Notice how initial reaction rate is very much faster
for the powdered solid because the acid can attack the surface of the carbonate more easily.
However, the outcome of the experiment is identical for both conditions; the same amount of
carbon dioxide, CO2 is eventually produced.

Figure 3 The effect of surface area on the reaction rate between HCl and two equal
masses of CaCO3
Unit: Chemical Kinetics MYP5

CATALYSTS
A catalyst works by providing an alternative reaction pathway or lower activation needed for
the transition state. This may be due to a steric effect (e.g. some enzymes hold the substrate in
the correct orientation for reaction), but it could also be because the presence of the catalyst
leads to a different reaction mechanism. Catalysts can also initiate reactions which would
normally happen extremely slowly. The alternative pathway increases the rate at which
products are formed. However, Figure 4 shows that the presence of the catalyst does not
change the total amount of product formed, nor does it affect the overall energy (enthalpy)
change of a reaction

Figure 4 A catalyst lowers the energy barrier and thus lowers the energy required to initiate
a chemical reaction.

Enzymes function the same way. They lower the energy of the transition state. However,
because they are proteins, these very large molecules are also affected by intermolecular
attractions. Most enzymes are adapted to function best in particular, narrow conditions, for
example at a particular temperature or within narrow ranges of pH.

TEMPERATURE
When the temperature of the reaction mixture is increased, the reacting particles (molecules,
ions or atoms) move around at higher average speeds and hence have higher average values
of kinetic energy. This results in an increased rate of successful collisions and therefore an
increased rate of reaction plots the initial rate of a chemical reaction with temperature. The
rate indicates the frequency of successful collisions. Figure 6 shows that the proportion of
collisions whose combined kinetic energy is greater than the activation energy increases
exponentially with temperature. For every 10 °C rise in temperature, the rate of reaction is
approximately doubled. Figure 6(b) presents the same information, but the data has been
transformed mathematically. The x-axis shows the temperature as a reciprocal. The y-axis
plots the natural log (In) of the initial reaction rate.
Unit: Chemical Kinetics MYP5

Figure 5 Collision theory and effect of temperature

Figure 6 Effect of temperature on the rate of reaction

CONCENTRATION
As the concentration of a substance increases, the particles (usually ions or molecules) are
closer together. The number per unit volume increases. Concentration is usually measured in
moles per cubic decimeter (mol dm−3). The word ‘concentration’ is usually used to describe
a solution. In gases, increasing the pressure has the same effect of pushing more particles
together per unit volume. This produces an increased number of collisions and so the reaction
rate increases. A gas at high pressure is more concentrated than a gas at low pressure.
Increasing the concentration affects the reaction rate because it increases the probability that
a collision will occur (Figure 7). This principle is applied in petrol engines, when the mixture
of petrol vapor and air is compressed before it is ignited by a sparking plug, to help it react
very quickly – explosively.
Unit: Chemical Kinetics MYP5

Figure 7 Collision theory and the effect of concentration (On solution and gases)
Figure 8 compares the effect of concentration on the decomposition of two different
concentrations of hydrogen peroxide to water and oxygen. The graph shows that the initial
rate for this reaction, as well as the volume of oxygen gas produced, is exactly proportional to
the concentration of the reactants.

Figure 8The amount of oxygen gas produced from the decomposition of hydrogen peroxide at
two different concentrations
Unit: Chemical Kinetics MYP5

TYPES OF SYSTEM

When we understand the characteristics of each type of system it enables us to use the system
in more efficient ways. Industrial processes may take place in open, closed and isolated
systems. Chemists and chemical engineers working within industry are constantly refining
industrial processes to use finite resources more efficiently. Industrial processes that produce
fewer by-products and have reduced consequences for the environment are increasingly being
recognized as the way of the future.

WHAT IS THE ROLE OF ENERGY IN CHEMICAL REACTIONS?

All chemical reactions involve an energy change. Energy may be released into the
surroundings or it may be absorbed from the surroundings. Most commonly the energy is in
the form of heat, but it may also be as sound or light. Reactions that release energy are
referred to as exothermic, while reactions that absorb energy are endothermic.
In other words, when a chemical reaction happens, energy is transferred to or from the
surroundings. When energy is transferred to the surroundings, this is called an exothermic
reaction.
These reactions can be described as:
Reactants  products + energy
Other examples of exothermic reactions
All these are exothermic:

 The neutralization of acids by alkalis.

 The combustion of fuels. We burn fuels to obtain heat for cooking, heating homes,
and so on. The more energy they give out, the better!
 Respiration in your body cells. It provides the energy to keep your heart and lungs
working, and for warmth and movement
Unit: Chemical Kinetics MYP5

Figure 9 Examples of exothermic reaction

When energy is taken in from the surroundings, this is called an endothermic reaction and the
temperature of the surroundings decreases. This includes reactions such as citric acid and
sodium hydrogen carbonate.
These reactions can be described as:
reactants + energy  products

Figure 10 Examples of endothermic reaction

Other examples of endothermic reactions
Reactions D and E above are spontaneous. They start off on their own. But many
endothermic reactions are like F, where energy must be put in start the reaction and keep it
going. For example:

 Reactions that take place in cooking.

Unit: Chemical Kinetics MYP5

 Photosynthesis. This is the process in which plants convert carbon dioxide and water
to glucose. It depends on the energy from sunlight.

ENERGY CHANGE
Making and breaking bonds
In a chemical reaction, bonds must first be broken. Then new bonds form. Breaking bonds
takes in energy. Making bonds releases energy.
Example 1: an exothermic reaction
Hydrogen reacts with chlorine in sunshine, to form hydrogen chloride

Figure 11 HCl formation

But the energy taken in for step 1 is less than the energy given out in step 2. So this reaction
gives out energy, overall. It is exothermic. If the energy taken in to break bonds is less than
the energy released in making bonds, the reaction is exothermic.
Example 2: an endothermic reaction
If you heat ammonia strongly, it breaks down to nitrogen and hydrogen. Here we use lines to
show the bonds. (Note the triple bond in nitrogen.)
Unit: Chemical Kinetics MYP5

Figure 12 Nitrogen and hydrogen from ammonia

This time, the energy taken in for step 1 is greater than the energy given out in step 2. So the
reaction takes in energy, overall. It is endothermic. If the energy taken in to break bonds is
greater than the energy released in making bonds, the reaction is endothermic.
BOND ENERGIES
The energy needed to make or break bonds is called the bond energy Look at Figure 13. 242
kJ must be supplied to break the bonds in a mole of chlorine molecules, to give chlorine
atoms. If these atoms join again to form molecules, 242 kJ of energy are given out. The bond
energy is the energy needed to break bonds, or released when these bonds form. It is given in
kJ / mole.

Figure 13 Bond energies

Unit: Chemical Kinetics MYP5

CALCULATING THE ENERGY CHANGES IN REACTIONS

The calculation is always: energy in – energy out

The minus sign shows the energy is given out and the plus sign shows the energy is taken in.
Unit: Chemical Kinetics MYP5
Unit: Chemical Kinetics MYP5

RATE OF REACTION
Often, the reactants involved in industrial chemical processes are natural resources, which are
finite. It is therefore important to use these resources effectively. One area of scientific
research focuses on redesigning chemical processes to minimize waste.
When considering how a chemical reaction will proceed from the start of the reaction to
completion, there are a number of things we need to consider
What is occurring when the reactants collide?

 What proportions of the starting materials have successfully reacted to form new
products?
 How quickly has the reaction occurred?
 What is happening to the distribution of energy during the reaction?
 Does the reaction require energy to be transferred from the surroundings into the
system? If so, this is called an endothermic reaction.
 Does the reaction produce energy to be transferred into the surroundings from the
system? If so, this is called an exothermic reaction.
 Is the reaction spontaneous or non-spontaneous for a given set of conditions?

Observations can provide us with important information about reactions that are taking place.
What are some observations you can make to infer a chemical reaction is taking place?
For example, cooking an egg in a fry pan. The observations tell us how well the egg is
cooked.
Quantitative data or numerical data is collected and analyzed to monitor the progress or rate
of a chemical reaction. Sometimes you will hear the term “empirical data” being used. This is
any type of data that is collected under experimental conditions in a laboratory.
The rate of reaction is defined as the change in amount of either reactants or products per unit
of time:

Reversible reaction: A chemical reaction which can go both ways. This means that once
some of the products have been formed they will undergo a chemical change once more to re-
form the reactants. The reaction from left to right, as the equation for the reaction is written,
is known as the forward reaction and the from right to left is known as the back reaction.
You are probably very familiar with the reversibility of physical changes. For example, when
water is cooled below 0 °C at STP, it freezes to form ice. When the ice is warmed to a
temperature above 0 °C, it melts to form water. These two changes may be represented by a
single equation:
Unit: Chemical Kinetics MYP5

In this equation, the symbol means that the change is reversible. A reversible change can go
in either direction depending upon the conditions. Many chemical changes are also reversible.
If steam is passed through a heated tube containing iron filings, iron oxide with the formula
Fe3O4 is formed. If hydrogen is then passed over this iron oxide, the reverse process takes
place. These two chemical changes may be represented by a single chemical equation:
Thermal dissociation refers to the reversible splitting up of a compound by heat to form
products, which can recombine on cooling. Usually the mechanism involved is quite simple,
in which a single bond is broken and hence thermal dissociation is a reversible reaction. Two
examples of thermal dissociation are:

Thermal decomposition refers to the splitting up of a compound by heat to form products

which do not recombine on cooling. Compared to thermal dissociation, more bonds are
broken and/or rearranged and therefore these reactions are not so easily reversible. An
example is:

In a closed system, a reversible chemical change involves a mixture of products and

reactants, both being converted to one another simultaneously. Compare the example of
calcium carbonate (chalk or marble) being heated in an open container such as a crucible,
with the same reaction occurring in a closed container.

DYNAMIC EQUILIBRIUM
In the open container, the calcium carbonate decomposes and the product formed, carbon
dioxide, escapes as a gas into the air. The reaction continues until all the calcium carbonate is
converted to calcium oxide. In other words, the reaction goes completely to the right of the
equation. It is said to go to completion. In the closed container, the carbon dioxide
recombines with the calcium oxide to form calcium carbonate. In this situation both forward
and backward reactions occur together under the same conditions:

However, overall, the reaction to the right-hand side is faster than the backward reaction. As
the calcium carbonate is used up, the forward reaction becomes slower. Eventually the rate of
the forward reaction equals the rate of the backward reaction. At this point of balance, the
reaction is said to be in dynamic equilibrium. Dynamic equilibrium is reached when the rate
of the forward reaction equals the rate of the backward reaction.
Unit: Chemical Kinetics MYP5

Figure 14 Graph for a reaction that reaches equilibrium rather than going to completion (i.e.
the concentrations of the reactants do not drop to zero)

AMMONIA – AN IMPORTANT NITROGEN CONTAINING CHEMICAL

Nitrogen from the air is used to manufacture ammonia, a very important bulk chemical. A
bulk chemical is one that, because of its large usage across a range of uses, is produced in
very large quantities. The major process used for making ammonia is the Haber process.
This process was developed by the German scientist Fritz Haber in 1913. He was awarded a
Nobel Prize in 1918 for his work. The process involves reacting nitrogen and hydrogen. It
was first developed to satisfy the need for explosives during World War I, as explosives can
be made from ammonia. We now have many more uses for this important gas including the
manufacture of nitric acid and of fertilizers such as ammonium nitrate.

Obtaining nitrogen
The nitrogen needed in the Haber process is obtained from the atmosphere by fractional
distillation of liquid air

Obtaining hydrogen
The hydrogen needed in the Haber process is obtained from the reaction between methane
and steam.

Making ammonia
In the Haber process, nitrogen and hydrogen in the correct proportions (1: 3) are pressurized
to approximately 200 atmospheres and passed over a catalyst of freshly produced, finely
divided iron at a temperature of between 350 °C and 500 °C. The reaction in the Haber
process is:

The reaction is exothermic. The industrial conditions employed ensure that sufficient
ammonia is produced at a fast-enough rate.
Unit: Chemical Kinetics MYP5

The principles which underpin equilibrium processes such as this are discussed below
Under these conditions the gas mixture leaving the reaction vessel contains about 15%
ammonia, which is removed by cooling and condensing it as a liquid. The unreacted nitrogen
and hydrogen are re-circulated into the reaction vessel to react together once more to produce
further quantities of ammonia.

The 15% of ammonia produced does not seem a great deal. The reason for this is the
reversible nature of the reaction. Once the ammonia is made from nitrogen and hydrogen, it
decomposes to produce nitrogen and hydrogen. There comes a point when the rate at which
the nitrogen and hydrogen react to produce ammonia is equal to the rate at which the
ammonia decomposes. This situation is called a chemical equilibrium.

Because the processes continue to happen, the equilibrium is said to be dynamic. The
conditions used ensure that the ammonia is made economically. Figure below shows
how the percentage of ammonia produced varies with the use of different temperatures and
pressures.

You will notice that the higher the pressure and the lower the temperature used, the more
ammonia is produced. Relationships such as this were initially observed by Henri Le
Chatelier, a French scientist, in 1888 He noticed that if the pressure was increased in
reactions involving gases, the reaction which produced the fewest molecules of gas was
favored.

If you look at the reaction for the Haber process you will see that, going from left to right, the
number of molecules of gas goes from four to two. This is why the Haber process is carried
out at high pressures. Le Chatelier also noticed that reactions which were exothermic
produced more products if the temperature was low. Indeed, if the Haber
process is carried out at room temperature you get a higher percentage of ammonia. However,
in practice the rate of the reaction is lowered too much and the ammonia is not produced
quickly enough for the process to be economical.

An optimum temperature is used to produce enough ammonia at an acceptable rate. It should

be noted, however, that the increased pressure used is very expensive in capital terms and so
alternative, less expensive routes involving biotechnology are being sought at the present
time.
Unit: Chemical Kinetics MYP5

A number of very significant industrial processes, including the production of ethanol and
ammonia, are reversible reactions and can be explained by the application of Le Chatelier’s
principle. This principle states that if a system in equilibrium is disturbed by changes in
temperature, pressure or concentration of the components, the system acts to oppose the
change and rebalance the system.
This principle is named after Henry Louis Le Chatelier, a French chemist whose pioneering
work opened the door to a better understanding of how equilibrium reactions behave. As we
will see, this principle has critical implications for the production of ammonia (once
considered a finite resource) and its use in large-scale agricultural applications.
According to Le Chatelier’s principle, when a change is made to the conditions of a chemical
equilibrium, the position of the equilibrium will readjust to minimize the change made. The
balance between the forward and reverse reactions will shift to offset the change and return
the system to equilibrium.

HABER’S PROCESS
Factors affecting the production of ammonia
CONCENTRATION OF REACTANTS OR PRODUCTS
According to Le Chatelier’s principle, at a given temperature, the position of the equilibrium
will change in response to a change in concentration of reactants or products. When industry
collects ammonia by changing the pressure, thereby decreasing the concentration of ammonia
present in the reaction vessel, the equilibrium will change to counteract this change. When
the concentration of one or more reactants is increased, the forward reaction will be favored
to minimize this change. Effectively, the reaction will try to use up the additional reactants.
By decreasing the concentration of a product, the forward reaction will also be favored to
replenish the missing products. Both of these changes in concentration help to force the
reaction in the forward direction and manufacture more ammonia. Chemists and chemical
engineers who work at ammonia production facilities understand the principles of the Haber
process and adjust reaction conditions to maximize yield and in turn profits.
Unit: Chemical Kinetics MYP5

PRESSURE
The Haber process is an equilibrium system that involves only substances in the gaseous
state. This means that the system will be affected by changes in applied pressure. In this
reaction, the number of moles of gas on the reactant and product side is unequal. How many
moles of gas are on the reactant side and how many are on the product side?
A change in pressure applied to the system will result in a shift in the equilibrium position,
either favoring the forward or reverse reactions. Consider the fact that 1 mol of a gas under
standard conditions (temperature of 273 K and pressure of 1 atm) occupies 22.7 dm3 of
volume. According to Le Chatelier’s principle, an increase in pressure applied to the system
will favor the side of the reaction with the least number of moles of a gas. For example, in the
case of nitrogen gas reacting with hydrogen gas, the forward reaction is favored and the yield
increases:

TEMPERATURE
The production of ammonia is an exothermic process, where energy is released as heat into
the surroundings during the reaction. The reverse reaction, which produces hydrogen and
nitrogen gas, is therefore endothermic, and takes in energy from the surroundings. When the
system is at equilibrium, the forward and reverse reactions occur at equal rates and there is no
change in energy. Increasing the temperature of a reaction effectively adds additional reactant
for an endothermic reaction, or product for an exothermic reaction. Therefore in the Haber
process, increasing the temperature is adding to the ammonia side, so the reverse reaction is
favored to balance the equilibrium.

Figure 15 A summary of different changes on the position of equilibrium

Unit: Chemical Kinetics MYP5

ARTIFICIAL FERTILIZERS
Some of the ammonia produced by the Haber process is used to produce nitric acid. If
ammonia is then reacted with the nitric acid, we have the basic reaction for the production of
many artificial fertilizers. The use of artificial fertilizers is essential if farmers are to produce
sufficient crops to feed the ever-increasing world population. Crops remove nutrients from
the soil as they grow; these include nitrogen, phosphorus and potassium. Artificial fertilisers
are added to the soil to replace these nutrients and others, such as calcium, magnesium,
sodium, sulfur, copper and iron.
PROBLEMS WITH FERTILIZERS
If artificial fertilizers of all kinds are not used correctly, problems can arise. If too much
fertilizer is applied to the land, rain washes the fertilizer off the land and into rivers and
streams. This leaching leads to eutrophication by encouraging the growth of algae and marine
plants. As the algae die and decay, oxygen is removed from the water, leaving insufficient
amounts for fish and other organisms to survive.
In extreme cases, no normal aquatic life can survive. There are also worries about the effect
of agricultural fertilizers, especially nitrates, on the public water supply.
There is evidence that the fertilizer sodium nitrate is implicated in infant brain damage, and it
is also suspected of being carcinogenic.

NITROGEN CYCLE
The vital importance of nitrogen to both plants and animals can be summarized by the
nitrogen cycle.
If farm crops are harvested from the land rather than left to decay, the soil becomes deficient
in this important element. The nitrogen is removed in the harvested crops rather than
remaining as the plants decay. In addition, nitrates can be washed from the soil by the action
of rain (leaching). For the soil to remain fertile for the next crop, the nitrates need to be
replaced. The natural process is by decay or by the action of lightning on atmospheric
nitrogen. Without the decay, however, the latter process is not efficient enough to produce
nitrates on the scale required.
Farmers often need to add substances containing these nitrates. Such substances include
farmyard manure and artificial fertilizers. One of the most commonly used artificial fertilizers
is ammonium nitrate, which as you saw earlier is made from ammonia gas and nitric acid,
both nitrogen containing compounds
Unit: Chemical Kinetics MYP5

Figure 16 Nitrogen Cycle

EXTENDED READING
http://www.chemguide.co.uk/physical/equilibria/lechatelier.html#top

http://www.chemguide.co.uk/physical/equilibria/haber.html

https://www.compoundchem.com/wp-content/uploads/2017/05/Reversible-Reactions-Equilibrium-
and-Le-Chateliers-Principle.pdf

https://chem.libretexts.org/Bookshelves/General_Chemistry/Book%3A_CLUE_(Cooper_and_Klymko
wsky)/8%3A_How_Far_How_Fast/8.1%3A_What_Factors_Control_Reactions

REFERENCES
Annie, Termaat and Talbot Christopher. Chemistry - MYP 4 and 5 . Hodder Education, 2018.

Bryan, Earl and Doug Wilford. Cambridge IGCSE Chemistry. Hodder Education, 2014.

Gary, Horner. MYP Chemistry : A Concept based approach. Oxford Education, 2018.

https://www.bbc.co.uk/bitesize/guides/z3nbqhv/revision/1. n.d. 25 2 2022.

Rosemarie, Gallagher and Ingram Paul. Complete chemistry for cambridge IGCSE. Oxford Education,
2011.
Unit: Chemical Kinetics MYP5

Young, Lucy Bell-. https://www.chemicals.co.uk/blog/rate-and-extent-of-chemical-change. n.d. 25 2

2022.