CHEMICAL REACTIONS

Recalling Physical Changes and Chemical Changes

Any change in the system that doesn’t change the particles themselves is a physical
change. Changes of state, dissolution and diffusion are physical changes. In these cases
what is changing form a microscopic point of view is the arrangement of the particles
Any change in which rearrangement of bonds (covalent, ionic or metallic) happens,
is called a chemical change. In this kind of change, the particles have changed and new
substances have been formed.

In the diagram above, the first and the third drawings show a chemical change. The
second drawing, the process itself in which this change happens is called the chemical
reaction.

Elements are represented by chemical symbols (Na, H, O, Fe) and substances by

chemical formulae (H2, NaOH, H2O, Fe2O3). Chemical reactions are represented by
means of chemical equation.

How do we know if a system suffered a physical or a chemical change if we cannot se

the particles? There are some signs generally accepted as distinctive between these two
types of change:

PHYSICAL CHANGE CHEMICAL CHANGE

Same substances before and after Different substances before and
change after change
Easy to reverse Not easily reversed if not impossible
Low to moderate energy exchange Generally strong energy exchange
with environment with environment

Recalling How to Write Word Equations:

In a chemical change the REACTANTS are the substances standing before the change
has happened and the PRODUCTS are the substances that remain after the reaction has
occurred.
• The first step is to decide which are which: find and label the reactants and the
products in the reaction. Most times it is rather simple, but sometimes some
information may be hidden
• Having identified the reactants and products, the next step is to write a word
equation. The reactants are written on the left side of the page, separated by “+”
signs. The products are written on the right side also separated by “+” signs.
 Between both reactants and products an arrow pointing in the direction of the
process, that is, from left to right will be written

Suppose that you are asked to write the word equation of the reaction between iron and
hydrochloric acid (aqueous hydrogen chloride) to form iron (II) chloride and hydrogen.
You have to analyse which are “befores” and which are “afters”. In this case, the
reactants (before) are iron and hydrochloric acid and the products (after) iron (II)
chloride and hydrogen. Writing both sets as previously explained:

iron + hydrochloric acid → iron (II) chloride + hydrogen

The essential rule to remember is the foundation of further development of chemical

science. It is called Lavoisier’s law on the conservation of mass and elements:

“The mass of a closed system and of each of the elements in it remains constant no
matter the changes that may happen.”

A very important observation was the conservation of the elements. If among the
products there is a copper salt, of course that some reactant must contain copper, and
vice versa, in case some element appears in the reactants’ list it should appear ion the
products’. This law knocks down the search of the philosopher’s stone, that magic
object that would turn vile metals into gold.

Recalling Symbol Equations: Writing Formulae of Compounds

The next step to complete a symbolic representation of a chemical reaction is to replace

the words by chemical symbols or formulae: this is called the symbol equation.
You will learn now how to write a formula for a compound or any element.
• The formula for a simple substance (element) is just the symbol for the atom
except for hydrogen, nitrogen, oxygen and the halogens (group VII
elements) that are represented as their molecules (X2). So, sulphur will be S
and sodium will be Na but hydrogen will be H2 and chlorine will be Cl2 . Ozone
is represented as O3
• The formulae of some compounds should be remembered: water H2O,
ammonia NH3, carbon dioxide CO2 and hydrogen peroxide H2O2.
• Although acids (both oxo and halo acids) are covalent, they ionise in solution
(we will see this in the next unit) so we will consider them as formed by
hydrogen cations and different anions. Remember that matter is essentially
neutral, that is, shows no net charge.
• All other substances that you will find during this course are ionic and we
will include here the acids. Writing and naming ionic compounds was recalled
in the corresponding chapter
The symbol equation will look this way:

Fe + HCl → FeCl2 + H2
Iron is just Fe, hydrochloric acid is worked out as if it were ionic as previously stated,
iron chloride has been dealt with in detail, and hydrogen is one of the seven simple
substances bearing a subscript.

Charges of ions to be used during the course

group charge group charge group charge

Hydrogen H +1 Copper(II) Cu +2 Bromide Br -1
Sodium Na +1 Zinc Zn +2 Iodide I -1
Potassium K +1 Iron(II) Fe +2 Nitrate NO3 -1
Silver Ag +1 Iron(III) Fe +3 Sulphate SO4 -2
Ammonium NH4+ +1 Aluminium Al +3 Carbonate CO3 -2
Calcium Ca +2 Hydroxide OH -1 Oxide O -2
Magnesium Mg +2 Chloride Cl -1 Sulphide S -2

Recalling How to Balance Symbol Equations

To write a balanced symbol equation, we must balance the number of chlorine and
hydrogen atoms on both sides. The law that we must take in account in this case is
related to Proust’s law of constant composition (or fixed proportion):

When elements combine to form a compound with definite properties, they do it

always in the same proportion

This law assigns a formula for each compound and this formula cannot be changed.
Once a formula is properly written it should never be changed. We cannot write
FeCl for iron (II) chloride because the proportion of iron to chlorine in it is 56 to 71 and
not any other. In case this “FeCl” could exist it would be a different substance with
different properties. What we can do is to add more HCl to the system, that is, to use a
higher proportion of it:

Fe + 2 HCl → FeCl2 + H2

This equation shows that two molecules of acid must be used for each iron atom in
order to cover the chemical requirements. The numbers that appear before a formula are
called coefficients and affect all atoms in the formula.
Sometimes balancing a chemical equation is not as simply as this example showed. A
general procedure follows using the reaction between sodium hydroxide and sulphuric
acid to form sodium sulphate and water:
• Check that the total number of atoms of an element is the same on both sides of
the equation. In our example all elements but sodium are balanced.
NaOH + H2SO4 → Na2SO4 + H2O
• Try a coefficient before NaOH that means, use twice as much of it.
2 NaOH + H2SO4 → Na2SO4 + H2O
 • Now check again every element. Sodium is now balanced but we have 4 H
atoms in the products side and just to in the reactants group! Re-try writing
another 2 coefficient but before the water formula:
2 NaOH + H2SO4 → Na2SO4 + 2 H2O
• Check once again. In our example the equation is balanced.

Some pupils find it easier to use diagrams as those shown below the equations of the
reaction between iron and hydrochloric acid. That is your choice and is an absolutely
valid approach

State Symbols

Whenever possible the physical state of each of the reactants and products should be
written in brackets after their formula respectively.

For a gas write (g) For a solid (s) For a liquid (l) For a dissolved substance (aq)

“aq” stands for aqueous. All reactions we will study will be carried out (if in solution) in
water that is in aqueous solution.
The equation between hydrochloric acid and iron will finally look this way:

Fe (s) + 2 HCl (aq) → FeCl2 (aq) + H2 (g)

The equation for the neutralisation of sodium hydroxide with sulphuric acid instead:

2 NaOH (aq) + H2SO4 (aq) → Na2SO4 (aq) + 2 H2O (l)

The Energetics of a Chemical Reaction

A chemical reaction involves bond breaking and bond formation. We have learned that
bonds are formed to stabilise the atoms: hence, bond breaking will always need energy
to be broken. This energy is usually taken from the environment as heat or light energy.
As new bonds are formed energy is given back to the surroundings, but seldom if ever
in the same amount. If result of these energy transfers is that the system is chemically
less energetic after the reaction happened (gives more than takes) it is called an
exothermic reaction (exergonic sometimes). The temperature of the system rises. On
the contrary, if chemical energy has been stored using the environment’s energy, the
system after the reaction gets colder. These reactions are called endothermic reactions
(endergonic)
Photosynthesis is an endothermic reaction. Burning kerosene is an exothermic reaction.

The Collision Theory of Reaction Rates

It is pretty obvious that if you have a situation involving two species they can only react
together if they come into contact with each other. According to the collision theory

• They have to collide but it isn't enough for the two species to collide
• They have to collide with the proper orientation
• They have to collide with enough energy for bonds to break.

The orientation of collision

Consider a simple reaction involving a collision between two species A2 and B2 to form
2 molecules of AB (actually the reaction between iodine and hydrogen to form
hydrogen iodide)

As a result of the collision between the two molecules the bonds between the A atoms
and the B atoms will loosen and break. In this particular example bond breaking is
simultaneous to bond formation

The reaction can only happen if the hydrogen molecules collide against the iodine
molecules not frontally but laterally. Any other collision between the two molecules
doesn't work. The two simply bounce off each other. Of the collisions shown in the
diagram, only collision 1 may possibly lead on to a reaction. You may wonder why
collision 2 won't work as well.

The energy of the collision: Activation Energy

Even if the species are orientated properly, you still won't get a reaction unless the
particles collide with a certain minimum energy called the activation energy of the
reaction. Activation energy is the minimum energy required for a collision to be
effective. You can show this on an energy profile for the reaction. It looks like this:
The state of maximum energy of the system is called the activated complex or its
transition state. For an exothermic reaction (the products are less energetic than
the reactants), energy is released as heat or eventually light. The only difference if
the reaction were endothermic would be the relative positions of the reactants and
products lines: the products would have a higher energy than the reactants, and so
the green arrow would be pointing upwards. Compare this diagram to the roller
coaster’s photograph
If the particles collide with less energy than the activation energy, nothing important
happens. They bounce apart. You can think of the activation energy as a barrier to the
reaction. Only those collisions which have energies equal to or greater than the
activation energy result in a reaction. (Otherwise cart goes backwards)

Factors Affecting the Rate of Reaction

What makes a reaction to go faster or more slowly than others? Why does it take years
for a piece of iron to rust completely (it reacts with atmospheric oxygen) and the same
mass of kerosene burns in a few minutes? (It also reacts with atmospheric oxygen).

There are factors that we cannot control as

• The energetics of the reaction (the bonding energy between different atoms)
• The orientation of the collisions

But there are other factors that allow us to have some control on reaction rates, namely

• The frequency of collisions

• The energy of the colliding particles
• The possibility of offering a different path to the reaction

Controlling Reaction Rates

The effect of surface area on reaction rates

The more finely divided the solid is, the faster the reaction happens. A powdered
solid will normally produce a faster reaction than if the same mass is present as a single
lump. The powdered solid has a greater surface area than the single lump. In the
diagram below the green particles in the liquid or gaseous states must collide with the
green ones in the solid
Notice the number of collisions in both halves of the diagram. In which part do you find
more collisions? (The number of particles is the same

Increasing the surface area of the solid increases the chances of collision taking
place. Increasing the number of collisions per second increases the rate of reaction.

The highest degree of division of a substance is its molecule (or ions). In a solution the
molecules (or ions) are all available for collisions. That is why reactions are always
carried out in solution.

The Effect of Concentration on Reaction Rates

In reactions involving liquids or gases, increasing the

concentration of the reactants increases the rate of
reaction. Don't assume that if you double the
concentration of one of the reactants that you will
double the rate of the reaction. It may happen like
that, but the relationship may well be more
complicated.

In order for any reaction to happen, particles must first collide. If the concentration is
higher, the chances of collision are greater.

The Effect of Temperature on Reaction Rates

As you increase the temperature the rate of reaction increases. As a rough

approximation, for many reactions happening at around room temperature, the
rate of reaction doubles for every 10°C rise in temperature. You have to be careful
not to take this too literally.

Particles can only react when they collide. If you heat a substance, the particles move
faster and so collide more frequently. That will speed up the rate of reaction. However,
the effect of increasing collision frequency on the rate of the reaction is very minor. The
important effect is quite different.

Collisions only result in a reaction if the particles collide with enough energy to get the
reaction started (the activation energy for the reaction). Generally only the very fast
(energetic) particles will get to the transition state. A vast majority of collisions are not
fruitful. If temperature is raised, the number of particles having the minimum energy
needed to react increases substantially. In this case then, it is not the number of
collisions what determines the increase in rate but the number of effective
collisions.
The Effect of Offering a Different Path to Reaction Rates: Catalysts

A catalyst is a substance which speeds up a reaction, but is chemically unchanged

at the end of the reaction. When the reaction has finished, you would have exactly the
same mass of catalyst as you had at the beginning.

To increase the rate of a reaction you need to increase the number of successful
collisions. One possible way of doing this is to provide an alternative way for the
reaction to happen which has a lower activation energy.

In other words, to lower the activation energy this way:

Adding a catalyst has exactly this effect on activation energy. A catalyst provides an
alternative route for the reaction. That alternative route has lower activation energy.
You must recall that a catalyst is not used up, will not change the reaction’s
energetics (the heat evolved or absorbed will be the same) and will not change the
yield., that is, the amount of products will be the same as if there is no catalyst
being added.

How Can Reaction Rates Be Measured?

Reaction rates are measured measuring the rate of

appearance of a product or the rate of disappearance
of a reactant. For instance, in the reaction between
iron and hydrochloric acid, the rate of hydrogen
formation can be followed in time measuring the gas
produced in a gas syringe.

The volume of gas is measured at different times

and the data are plotted in a volume-time graph
(see left). The plot shows how steep (fast) the
reaction is when reactants are just mixed, and
how it slows down with time (less particles
colliding as concentration falls because of their
being used up). When there is no more gas produced the reaction comes to an end
(Vf ,Tf)

You can also measure the rate at which the mass of the
system decreases as the gas evolves. In this case the shape of
the curve will be different because “something is
disappearing”.

The same as in the previous experiment, the curve

will be steeper when reaction starts getting to a
limiting value when it is finished. Of course both
methods will give the same results provided that
all variables are kept the same.

PROBLEMS

1- Decide whether the following are physical or chemical changes:

a- Ice melting
b- Petrol burning
c- Iron rusting
d- Salt dissolving
e- Obtaining copper from copper (II) oxide
f- A paper being torn into pieces
g- A paper burning

2- Using the combining numbers table write the formula of the following
substances
a- sulphuric acid (hydrogen sulphate)
b- Sodium oxide
c- Potassium hydroxide
d- Magnesium chloride
e- Calcium nitrate
f- Iron(II) carbonate
g- Lead (II) chloride
h- Ammonium nitrate

3- Using the same chart find the name of the following substances:
a- CuSO4
b- NH4Cl
c- FeS
d- Al(OH)3
e- H3PO4
 f- Fe2O3
g- Mg(NO3)2

4- Write a word and a balanced equation for the following reactions. Use physical
state symbols when possible:
a- Liquid water is formed when hydrogen combines with oxygen
b- Magnesium metal burns fiercely in air to form magnesium oxide
c- Methane (natural gas) burns to form carbon dioxide and water vapour
d- Magnesium oxide and carbon black are formed if a stream of carbon
dioxide is blown over red hot magnesium turnings.
e- To detect sulphates e.g. sodium sulphate in solution, some drops barium
chloride solution are added. An insoluble white precipitate (barium
sulphate) is formed
f- Mercury (II) oxide breaks when heated into oxygen and mercury

5- Define the following terms:

Chemical change endothermic reactant transition state catalyst

6- State Lavoisier’s and Proust’s laws.

7- The graph shows three curves for the thermal self decomposition of hydrogen
peroxide.
a- Write a word and a
balanced equation for this
reaction.
b- Why are transition metal
oxides added?
c- Which oxide seems to be
most effective?
d- When did the reaction
finished?
e- How should the curve for
manganese (IV) oxide look
if the temperature were
raised?
f- Sketch the three curves if instead of measuring the volume of oxygen
formed, the mass of the system was continuously recorded by setting the
open flask on a top balance.
g- This is an exothermic reaction. Sketch an energy-reaction course
diagram for the three experiments using the same pair of axes.

8- A similar experiment to the one with manganese (IV) oxide was carried out but
at a higher temperature. The data are shown in the table below.
Time (min) 1 2 3 4 5 6 7 8
0
Vol. of gas (cm3) 4 6 9 10 11 12 12 120
0 0 5 2 7 5 0 0

a- Plot the data.

b- Which point doesn’t fit properly with the rest of the set?
 c- Which could be a reasonable value for it?
d- How would you check your answer to c?
e- What will be the reading at time 9 minutes? Why?
f- How long did it take to 50 cm3 of oxygen to be produced?
g- Explain how and why the rate of reaction changed as it proceeded.

9- The figure shows diagrams for two

different reactions. One is a one-
step and the other a two-step
reaction
a- Are the reactions endo or
exothermic?
b- Is there any endothermic
process in the diagrams?
c- Name all labels from 1 through 8
d- Show the activation energies.
e- Mark the energy exchanged with the environment.

10- The reaction between hydrochloric acid and marble (calcium carbonate
Experiment Acid Size of marble Temperature
concentr.
A 5% Chips 20°C
B 10% Powder 60°C
C 10% Chips 20°C
D 5% Powder 60°C
essentially) was studied under different conditions.

a- Write the balanced equation for this reaction

b- Sketch two different apparatus, suitable for carrying out this experiment
c- Sketch the curves you would expect for each of the two apparatuses
d- Decide in which the reaction was the fastest and in which the slowest. Give
reasons for your answer
e- Which would you expect to be the third one? Are you 100% sure about your
choice?