Higher Chemistry

Energy Matters
Reaction Rates
Rates
Reaction rates are dependant on
 the concentration of the reactants
 particle size
 temperature
Catalysts speed up reactions
The concentration of reactants in solution is measured in the units;
mol/litre or mol litre-1 or mol l-1.

How to find the rate of a reaction?

Usually found experimentally by measuring how fast a reactant is used up
or how fast a product is formed.
a) the rate of lass loss or increase in volume if a gas is a product.
b) a change in pH if, for example, and acid is being neutralised.
c) the rate at which a colour develops or disappears – this is gone using an
instrument called colorimeter.

Definition of rate: defined as the change in concentration of reactants or

products in unit time.

Experiment
reaction between marble chips (calcium carbonate) and dilute hydrochloric
acid.

CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g)

1. by measuring the mass loss of the flask as the carbon dioxide is

produced and escapes from the flask.
 2. by measuring the fall in concentration of the aci as the reaction
proceeds.

3. by collecting and measuring the volume of carbon dioxide produced.

Average Rate = loss of mass/time interval = ___ gs-1

Average Rate = decrease in acid concentration/time interval = ___

mol l-1 s-1
Effect of Concentration on Reaction Rate
• Persulphate Oxidation of Iodide Ions
• The Formation of Colloidal Sulphur from Thiosulphate ions.

For both of these reactions there is a straight line

through the origin showing that rate is directly
proportional to concentration.

Effect of Temperature on Reaction Rate

• Oxidation of oxalic acid by potassium permanganate at different
temperatures.
• Reaction between thiosulphate ions and dilute hydrochloric acid

These reactions show a marked increase in rate as the temperature is

increased.
 * Roughly the rate of a chemical reaction is doubles for every 10oC rise in
temperature *

Collision Theory
For a reaction to occur the reactant molecules have to collide. This is the
basis of the Collision Theory.

The collision provides energy to break the bonds in the reactant molecules
and for new bonds to be formed to make the product molecules.

Everything that we know about the effect of concentration, particle size and
temperature can be explained by the Collision Theory.

Concentration
The more concentrated the reactants the more collisions there are going to
be between the reactant molecules and hence the faster the reaction.
Particle Size
In a reaction with solids the smaller the particle size the larger the surface
area presented to the other reactant. This increases the chance of collision
and so increases the reaction rate.
Temperature
The temperature of a substance the measure of the average kinetic energy
of its molecules.
At low temperature, molecules are moving slowly so have a smaller kinetic
energy.
At a high temperature, molecules are moving quickly so have a high kinetic
energy.

If molecules are moving slowly they may collide but may not have enough
energy to react. If they were moving quickly they are more likely to react.
Meaning that there must be a minimum speed (kinetic energy) for the
reaction to take place, this is called the Activation Energy.

If the temperature of a reaction is raised it means that more molecules will

have successful collisions and will have the required Activation Energy. This
is why rate increases so much with temperature.

Light as a supplier of the Activation Energy

With some chemical reactions light can be used to increase the amount of
particles with energy greater than the activation energy, they are called
photochemical reactions.
Photography
Light hitting a photograph film provides the activation energy for this
reaction.
Ag+ + e-  Ag(s)
Hydrogen and Chlorine
When H and Cl are mixed together in the dark nothing happens. But when
an ultraviolet light is shone on them there is a explosive reaction forming
hydrogen chloride.
H2 + Cl2  2HCl
The light provides the activation energy for the dissociation of some chlorine
molecules.

Potential Energy Diagrams

During an exothermic reaction some of its chemical potential energy in the
reactant molecules is released as heat energy, meaning that the product
contains less potential energy than the reactant molecules.
During an endothermic reaction heat energy is absorbed from the
surroundings, so the products have more potential energy than the reactant
molecules.

Exothermic graph
the difference in the potential
energy is called the enthalpy
change for the reaction and has the
symbol ΔH. Exothermic reactions
have a negative ΔH.

Endothermic graph
Endothermic reactions have a
positive ΔH.

If the activation energy is low, many molecules have enough energy to over
comes the barrier and the reaction will be fast.
Energy Distribution and the Activated Complex

This shows that at 20oC only a few molecules have energy greater than Ea
(Activation Energy), whereas at 30oC many more molecules have greater
energy than Ea.

Activation Energy and the Activated Complex

When two molecules collide the first thing that happens is they join to form a
species called the activated complex. The activated complex is very
unstable so only exists for a short period of time. The activation energy
required energy for its formation because there may be bonds in the
reactants to be weakened or broken. This energy required comes from the
Ek of the colliding molecules and is stored as Ep in the bonds of the
activated complex. The energy needed to form the activated complex is the
activation energy.

*If the energy available from the collision is less than the Ea, the activated
complex cannot be formed so no reaction can occur *
The Effect of Catalysts on Reaction Rate
Definition of Catalyst: A catalyst is a substance that alters the rate of a
chemical reaction without itself undergoing any permanent chemical
change.

Because the catalyst is not used up the amount of catalyst is usually small
compared to the other reactants. Catalysts are normally used to speed up a
reaction, but can also be used to slow down a reaction.

When it is used to slow down a reaction it is called a inhibitor. Inhibitors are

used in rubber to increase its stability, in antifreeze to slow down rusting, to
stabilise monomers for polymerisation.

A catalyst provides an alternative pathway between the reactants and

products. To speed up a reaction the alternative route has a lower activation
energy than the route without the catalyst so the reaction is speeded up.

example with an exothermic

reaction.

* The ΔH for the reaction is the

same whether the catalyst is used
or not *

Types of Catalysts
Definition of Homogeneous Catalysts: Catalysts that are in the same
physical state as the reactants.
Definition of Heterogeneous Catalysts: Catalysts that are in a different
physical state from the reactants.
Examples of Heterogeneous Catalysts;
How do heterogeneous catalysts work?

Adsorption Reaction
Desorption
Molecules of the The molecules react
The products leave
reactants create on the surface of the
the catalyst and the
bonds with the catalyst.
empty active site can
catalyst. This
be used by another
weakens the bonds
molecule.
within the molecules.

Catalyst Poisoning
Definition of a Catalyst Poison: A substance which reacts with a catalyst
and prevents the catalyst from doing their job. This is done by preventing
the reactant molecules being absorbed and making the catalyst ineffective.

Even with precautions in place, impurities remain in the reactants mean that
catalysts must be regenerated or renewed from time to time.

Enzymes
Definition of an Enzyme: An enzyme is a catalyst that working in biological
systems. They catalyse the reactions that happen in the cells of plants and
animals.
Examples
1. yeast contains enzymes that convert carbohydrates into alcohol.
2. amylase is an enzyme that is used to hydrolyse starch.
3. catalase is an enzyme that helps with the decomposition of hydrogen
peroxide.

Enzymes are proteins which are complicated large molecules. Its 3D shape
is very important to its functions as an enzyme. If the enzyme changes in
temperature or pH the shape can be denatured, so this means that they
work best as certain temperatures and pHs.
One enzyme can only catalyse one reaction.

Enzymes in our bodies can be poisoned by arsenic, cyanide, and carbon

monoxide. This prevents the enzyme from doing its job which can lead to
death.
Chemical Reactions
Chemical Equilibrium
Reversible Reactions
Reactions where the products can form the reactants are called reversible
reactions.
A+B C+D
If we start with A and B and allow them to reaction, the rate of the forward
reactions (rf) will be high as the concentrations of A and B are high. The rate
of the reverse reactions is zero for a start as the concentrations of C and D
is zero. As the reactions proceed the concentrations of A and B decrease
while the concentrations of C and D increase. This means rf falls and rr
increases. This continues until the two rates become equal. At this point the
concentration of A, B, C and D do not change (unless the conditions are
altered) and is said to have reached equilibrium.

Definition of Dynamic equilibrium: At the molecular level the forward and

backward reactions are continuing but, because their rates are equal the
concentrations of the four substances remain constant.

Equilibrium is only reached in a closed system (no substances are added or

removed).

Position of Equilibrium
Equilibrium does not imply 50% reactants and 50% products. Sometimes
equilibrium is established when the forward reaction is nearly complete – so
we would say that equilibrium lies to the right. In other cases equilibrium is
reached when the forward reaction is barely started – equilibrium lies to the
left.
Factors Which Affect the Position of Equilibrium
Equilibrium is reached when the rates of two opposing reactions become
equal.
The rate is affected by;
a) catalysts
b) concentration
c) pressure (of gases)
d) temperature

Catalysts
A catalyst has the effect of lowering the energy barrier between reactants
and products by providing an alternative reaction path. The net effect is that
a catalyst does not alter the position of equilibrium. However, a catalyst
speeds up both the forward and reverse reaction, so the same equilibrium is
reached more quickly.

Position
A + B (reversible reaction) C + D
Increasing the concentration of A + B will speed up the forward reactions so
producing more C and D until a new equilibrium position further to the right
is established. Decreasing the concentration of C or D will slow down the
reverse reaction which converts C and D into A and B. This means the
concentration will increase again moving the equilibrium to the right.

* The intensity of the colour indicates the position of equilibrium *

Pressure
A change of pressure can only affect equilibria in which gasses are
involved.
The pressure exerted by a gas I caused by the freely moving gas molecules
colliding with the walls of the containing vessel. An increase in the number
of molecules in the vessel will cause an increase in pressure; so long the
container size is kept constant. Increasing the pressure favours whichever
reaction brings about a reduction in the total number of gas molecules.
Decreasing the pressure favours the reaction that increases the total
number of gas molecules.

If an equilibrium system has the same number of gas molecules on both

sides of the arrow, a change in pressure will have no effect on the position
of equilibrium. However an increase in pressure will increase both forward
and reverse reactions and so reduce the time for equilibrium to be
established.

Temperature
In a system at equilibrium, if the forward reaction is exothermic the reverse
reaction must be endothermic, and vice versa.

If the temperature is raised, then the rate of both reactions increases but not
equally. A rise in temperature favours the reaction that needs to have heat
supplied (the endothermic reaction). A decrease in temperature has the
opposite effect and favours the exothermic reaction.

Le Chatelier’s Principle
The effect of changes in concentration, pressure and temperature on an
equilibrium can be predicted using Le Chatelier’s principle.

“If a system at equilibrium is subjected to a change, the system will

adjust to oppose the effect of the change”

The Haber Process for Ammonia

N2(g) + 3H 2NH3(g) ΔH = -92kJ mol-1

Catalyst
In the absence of a catalyst the nitrogen and the hydrogen hardly combine.
The high temperature needed to make thee nitrogen and hydrogen combine
would forc the equilibrium to the left so little ammonia would be formed. An
iron catalyst is used in the Haber Process; this allows a fast reaction rate at
a lower temperature and gives a reasonable yield of ammonia.

Pressure
The formation of ammonia gives a decrease in the number of molecules of
gas, so a high pressure favours the ammonia production. However plants
that operate at high pressure and costly to build and require expensive
compressors.

Temperature
A low temperate would give a high equlibirium yield of ammonia. However a
low temperature means a slow rate and a long time to come to equilibrium.
A higher temperature increases the rate but gives a reduced yield of
ammonia.

Raw materials for the Haber process

Nitrogen comes from the air. The Hydrogen comes from the syngas
manufactured from natural gas and steam.
Marketability of Ammonia
This is clearly important for any industrial product. There is a large market
for ammonia because it is further converted into fertilisers, nitric acid and
nylon.

Equilibrium in aqueous solutions

Pure water conducts electricity slightly, due to the slight dissociation of
water molecules..
H2O(l) H+(aq) + OH-(aq)
Equilibrium lies to the left; only 1 in every 555 million water molecules
dissociates.

The pH Scale
Dilution of 1 mol l-1 HCl
With a pH meter we can see that 1 mol l-1 HCl hada pH of 0. We took 10ml
of this acid solution and made the volume up to 100ml with distilled water –
this is a ten fold dilution and left us with 0.1 mol l-1 HCl with a pH of 1. This
dilution was repeated several times.

* For dilutions such as this, C1V1 = C2V2*

Square brackets are used in chemistry to denote the concentration. [H+]

means “the concentration of H+ ions” and is normally measured in mol l-1.

0.1 mol l-1 HCl [H+] = 10-1 mol l-1

0.01 mol l-1 HCl [H+] = 10-2 mol l-1
0.001 mol l-1 HCl [H+] = 10-3 mol l-1

Results
Dilution of 1 mol l-1 NaOH
Doing a similar experiment we got these results;

Ionic Product for Water

H2O(l) H+(aq) + OH-(aq)
When pure water dissociates one H+ ion is produced for every OH- ion, so
[H+] = [OH-]
For water to have a pH 7
[H+] = [OH-] = 10-7mol l-1
The ionic product of water, Kw = [H+] [OH-] = 10-7 x 10-7 mol2 l-2
= 10-14 mol2 l-2

* This is true at all pH values. *

[H+] [OH-] = 10-14 mol2 l-2 must be true at all times in aqueous solutions.

Calculating the pH of solutions

Example 1;
What is the pH of a 0.01 mol l-1 solution of hydrochloric acid?
HCl(g)  H+(aq) + Cl-(aq)
1 mole 1 mole .
+ -1
[H ] = 0.01mol l
= 10-2 mol l-1
So the pH = 2
Example 2;
What is the pH of a 0.001 mol l-1 solution of sodium hydroxide?
NaOH  Na+(aq) + OH-(aq)
1 mole 1 mole
[OH ] = 0.001 mol l-1
-
 = 10-3 mol l-1
In any aqueous solution:
[H+][OH-] = 10-14 mol2 l-2
So [H+] = 10-14/[OH-]
= 10-14/10-3
= 10-11 mol l-1
So the pH = 11

Strong and Weak acids

The pH of a 0.1 mol l-1 solution of hydrochloric acid is 1. Hydrochloric acid is
a strong acid and is fully dissociated into ions in aqueous solution.
HCl(g)  H+(aq) + Cl-(aq)
1 mole 1 mole .
So if the HCl concentration is 0.1mol l then [H+] is also 0.1 mol l-1
-1

Ie [H+] 0.1 = 10-1 mol l-1

So the pH = 1
-1
When the pH of 0.1 mol l ethanoic acid is measured it is found to be 3. this
indicates a lower hydrogen ion concentration. Ethanoic acid is a weak acid
because it is not fully dissociated into ions in aqueous solution.
CH3COOH(aq) CH3CO|O-(aq) + H+(aq)
Comparison of Strong and Weak Acids
Equimolar (0.1 mol l-1) solution of hydrochloric and ethanoic acids were
compared in a number of experiments. The results were:

The higher concentration of [H+](aq) ions in hydrochloric acid accounts for the
lower pH, the high conductivity and the faster reaction rates.

Those experiments can be used to distinguish strong and weak acids

Amount of Alkali Neutralised by Strong and Weak Acids

Neutralisation is the joining of H+ and OH- ions to form water.
H+(aq) + OH-(aq)  H2O(l)
It would be expected that weak acids with the lower concentration of H+ ions
would neutralise a small amount of alkali than a strong acid, however 0.1
mol l-1 ethanoic acid neutralises exactly the same volume of sodium
hydroxide as 0.1 mol l-1 hydrochloric acid.
CH3COOH(aq)   CH3COO-(aq) + H+(aq)

removed by OH-(aq) to form water.

The amound of alkali neutralised cannot be used to distinguish strong and

weak acids.

Examples of Strong Acids

Hydrochloric Acid – HCl  H+(aq) + Cl-(aq)
Nitric Acid – HNO3  H+(aq) + NO3-(aq)
Sulphuric Acid – H2SO4  2H+(aq) + SO42-(aq)

Examples of Weak Acids

Carboxylic Acids

Carbonic Acid
CO2 + H2O(l)  H2SO3(aq)   2H+(aq) + CO32-(aq)