Topic 2.

3 – Kinetics I

 Factors affecting rate of reaction:

o Temperature: An increase in temperature increases the rate of reaction.
o Concentration: An increase in the concentration of a solution of reactants
increases the rate of reaction.
o Pressure: Increasing the pressure of a gas involved in a reaction increases the
rate of reaction. Increasing a gas pressure is like increasing the concentration
of the gas.
o Surface area of reactants: An increase in the surface area of a solid reactant
increases rate of reaction. The surface area of a solid is increased if it is
broken into smaller pieces.
o Catalyst: The use of a catalyst increases the rate of reaction.

 Changes in rate using collision theory:

o For a reaction to take place, particles must collide.
o However, they must do so in the correct orientation and with sufficient energy:
the activation energy. Activation energy is the minimum energy required for a
reaction to take place.
o The more frequently collisions take place, the faster the rate of reaction.
o Temperature:
 Increasing the temperature causes an increase of the rate of a chemical
reaction (exo- and endothermic).
 This is because particles have more kinetic energy, and more of them
have energy greater than the activation energy. Hence, there will be
more successful collisions, with the required energy for reaction.
o Concentration:
 Increasing the concentration of reactants causes an increase of the rate
of a chemical reaction.
 The particles are closer together and so there are more collisions.
 With acid, if we double the number of acid particles, we double the
number of collisions and therefore are likely to double the reaction rate.
o Pressure:
 Increasing the pressure of gases causes an increase of the rate of
reaction
 Again, due to the fact that molecules are close
o Surface area:
 Increasing the surface area of reactants causes an increase of the rate of
reaction.
 This is because a greater surface area allows for more frequent
collisions.
o Catalyst:
 Using a catalyst speeds up a reaction, without being used up.
 The catalyst provides an alternative route for the reaction, of lower
activation energy, so more particles at a certain temperature will be
able to react.

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  The Maxwell-Boltzmann Distribution.
o The Maxwell-Boltzmann Distribution is a plot of the number of particles
having each particular energy.
o The area under the curve is an indication of the number of particles present

 To speed up the reaction, you need to increase the number of the very energetic
particles - those with energies equal to or greater than the activation energy. Increasing
the temperature does this and changes the shape of the graph:

 The curve peak shifts to the right and lowers. The area under the higher temperature
curve to the right of the activation energy has doubled - therefore doubling the rate of
the reaction.
 A small increase in temperature gives a large increase in reaction rate.

 Catalysis.
o Catalysts alter the rate of a chemical reaction
without being consumed in the reaction. A
catalyst reduces the activation energy for a reaction
by providing an alternative path for the reaction.
o This can be illustrated on a Maxwell-Boltzmann
distribution:

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 o The effect of a catalyst can also be shown on a reaction profile:

o There are two types of catalysis

 Homogeneous catalysis: The catalyst in the same phase as the
reactants. Usually everything will be a gas or a liquid.
 Heterogeneous catalysis: This involves the use of a catalyst in a
different phase from the reactants. These involve a solid catalyst with
the reactants as either liquids or gases. Reaction examples include: the
Contact Process, catalytic converters, hydrogenation etc.
 Heterogeneous catalysis takes places in stages:
o One or more of the reactants are adsorbed on to the
surface of the catalyst at active sites. An active site is a
part of the surface, which is particularly good at
adsorbing things and helping them to react.

o The reaction happens.

o The product molecules are desorbed i.e. leave the active
site available for a new set of molecules to attach to and
react.

 A good catalyst does not absorb too strongly or too weakly.

 Thermodynamic and kinetic stability:

o One system is thermodynamically stable with respect to a second one if the
first one is lower than the second on an enthalpy level diagram. I.e. the reaction
must be exothermic  The products have a lower energy overall. Even if a
system is thermodynamically unstable and is expected to react to form a stable
one the system may not react. The system will not react if it is kinetically
stable.
o Kinetically stable means that the reaction proceeds too slowly for any reaction
to be seen. If kinetically unstable, a reaction is fast and observations can be
made.
o NOTE: When a system is thermodynamically unstable but kinetically stable,
the reaction is likely to be seen but only under favourable conditions.

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Topic 2.4 – Chemical equilibrium I
 Dynamic equilibrium:
o A reversible reaction is one that can be made to go in either direction
depending on the conditions.
o A closed system is one in which no substances are either added to the system
or lost from it. Energy can, however, be transferred in or out at will.
o A dynamic equilibrium means that the rates of the forward and reverse
reactions are equal and so the concentration of each species remains constant.
o Homogeneous equilibrium: reactants and products are all in the same phase.

 Le Chatelier’s principle:
o If a system in a state of dynamic equilibrium is disturbed, the equilibrium
position shifts in the direction which reduces the disturbance and restores the
equilibrium (i.e. oppose the change).

 Changes in a system in equilibrium:

Factor Effect
 Increasing the temperature favours the endothermic reaction
Temperature  Decreasing the temperature favours the exothermic reaction
 Increasing pressure causes eq. to shift in direction of fewer moles
of gas.
Pressure  Decreasing pressure causes eq. to shift in direction of more moles
of gas.
 Increasing concentration of reactants or decreasing conc. of
products shifts equilibrium to the right (towards the products)
Concentration  Increasing concentration of products or decreasing con. of reactants
shifts eq. to the left (towards the reactants).

 A catalyst does not alter the position of equilibrium or yield. It helps to establish
the equilibrium position at a faster rate.

 An example of the importance of temperature control in industrial processes involving

equilibrium (e.g. the Haber Process, the Contact process) is: in the Haber process a
moderately high temperature of around 500oC is used to speed the rate at which
equilibrium is reached. This temperature is chosen in spite of the fact that a lower
temperature gives a higher yield.

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Topic 2.5 – Industrial inorganic chemistry
 The Haber Process:
o The Haber Process combines nitrogen from the air with hydrogen derived
mainly from natural gas (methane) into ammonia. The reaction is reversible
and the production of ammonia is exothermic.

o KOH is a promoter used to make the surface of the iron more effective.
o NOTE: Very high pressures are very expensive to produce. Extremely strong
pipes and containment vessels are needed to withstand the very high pressure.
That increases your initial costs when the plant is built. High pressures cost a
lot to produce and maintain. That means that the running costs of a plant are
also very high.
o Ammonia is used for making fertilisers (ammonium nitrate), nylon and
nitric acid, soaps.

 Producing Nitric acid- the Oswald process:

o This is another equilibrium process, which starts with the reaction of ammonia
and oxygen.
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g) H= -900 kJmol-1
o The optimum (best) conditions for this process which give the greatest yield
are:
 a pressure of 10 atmospheres
 a temperature of about 900oC
 a catalyst of platinum and rhodium (gauze for surface area)
o The nitrogen monoxide is then mixed with oxygen and flows up a column
down which water flows. The result is a solution of 65% nitric acid.
4NO(g) + 3O2(g) +2H2O(l)  4HNO3(aq)
o Nitric acid is used for fertilisers, dyes, plastics and explosives.

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  The Contact Process:
o makes sulphur dioxide;
o converts the sulphur dioxide into sulphur trioxide
o converts the sulphur trioxide into concentrated sulphuric acid.

o STAGE 1:

 Sulphur is burnt in excess oxygen to make sulphur dioxide.
o STAGE 2:

 The sulphur dioxide is converted to sulphur trioxide 
o STAGE 3:
 Water cannot be just added to the SO3 because the reaction is
uncontrollable and very vigorous.
 Instead, the sulphur trioxide is dissolved in sulphuric acid to
form oleum.

 This can then be diluted by adding water to sulphuric acid.

o Sulphuric acid is used for fertilisers, fibres, paints and detergents.

 Uses of ammonia, nitric acid and sulphuric acid:

o All three substances are used to make nitrogen containing fertilisers e.g.
o Ammonium nitrate NH3(g) + HNO3(aq)  NH4NO3(aq)
o Ammonium sulphate H2SO4(aq) + 2NH4OH(aq) (NH4)2SO4(aq) + H2O(l)

 Extraction of aluminium:
o Bauxite contains: Al2O3 , SiO2 , Fe2O3
o The ore is purified by
 (a) Dissolving amphoteric (both acidic and basic) Al2O3 in hot aqueous
NaOH under pressure.
 Iron oxide is not soluble.
 Silicon (IV) oxide is acidic but is not soluble because of strong
bonds in giant structure.
 (b) The solid impurities are filtered.
 (c) Aluminium hydroxide is precipitated and filtered.
 (d) Al(OH)3 is heated to produce Aluminium oxide

o Aluminium is manufactured by the electrolysis of pure aluminium oxide

dissolved in molten cryolite (Na3AlF6) to lower melting point from 2000º to
1000º, which saves money.
o This mixture is heated and the molten liquid used as the electrolyte.
o Both electrodes are made of graphite (carbon).

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 o CATHODE  Al3+ (l) + 3e-  Al(l)
o ANODE  2O2-(l) -----> O2(g) + 2e-

o The oxygen produced at the anode reacts with the graphite electrodes,
producing CO2 and therefore the anodes have to replaced regularly.

 Uses of aluminium:
o Aluminium is common but expensive because a lot of electricity is needed for
the electrolysis.

Use Property
Overhead power cables Good electrical conductor, low density
Drink cans Does not react with water
Aircraft parts High strength and low density
Window frames Does not corrode due to oxide layer protection
Saucepans Good thermal conductivity
o Because Aluminium is expensive to produce, it is good economically to
recycle it. This is why aluminium is often used for disposable containers.
However it may lose in quality during recycling.

 Electrolysis of Sodium Chloride solution:

o The chlor-alkali industry:
Sodium hydroxide,
chlorine and hydrogen are
produced from natural
deposits of sodium chloride
(rocksalt).
o There are many different
processes used in the
electrolysis of brine. An
aqueous solution contains
the following ions: Na+, Cl-,
H+ and OH-
o The electrolysis takes place
in a membrane cell:

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 o Cathode  2H+(aq) + 2e-  H2(g)
o Anode  2Cl-(aq)  Cl2(g) + 2e-

o In the remaining solution H2O(l)  H+(aq) + OH-(aq)

o H+ ions are removed at the cathode so there are OH- ions left which react with
the Na+ ions present to form NaOH.

o How the membrane cell works:

 Saturated brine is pumped into the anode compartment.
 The brine level in the anode compartment is kept higher than the level
in the cathode compartment so that brine seeps through the membrane,
but hydroxide ions do not seep in the opposite direction. (The mixing of
hydroxide ions and chlorine would produce unwanted sodium
chlorate(I)).
 The resulting solution leaving the cell, is evaporated and crystallised
leaving a solution containing 50% sodium hydroxide and less than 1%
sodium chloride.

o To make Sodium chlorate (I):

 Cl2(g) + 2NaOH(aq)  NaCl(aq) + NaClO(aq) + H2O(l)

 Uses of chlorine and sodium chlorate (I):

 CHLORINE:
o as a cheap industrial oxidant in the manufacture of bromine because chlorine
is a stronger oxidising agent than bromine
o as a bleach because it oxidises coloured dyes to colourless compounds
o as a germicide in the treatment of household water supplies and in swimming
baths because it oxidises materials in the cell walls of bacteria hence killing
them
o to produce HCl in a reaction with hydrogen
o to manufacture Chloroethene.

 SODIUM CHLORATE (I):

o As a bleach
o As a disinfectant and in sewage treatment
o As a germicide because it is a strong oxidising agent.

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