Reactivity 2.2.

1
Reactivity 2.2.1—The rate of reaction is expressed as the change in concentration of a
particular reactant/product per unit time.
● Determine rates of reaction.
Guide:
Calculation of reaction rates from tangents of graphs of concentration, volume or mass
against time should be covered.
Tool 1, 3, Inquiry 2—Concentration changes in reactions are not usually measured
directly. What methods are used to provide data to determine the rate of reactions?
Tool 1—What experiments measuring reaction rates might use time as i) a dependent
variable ii) an independent variable?
The rate of reaction (Reactivity 2.2.1)
Chemical reactions proceed at different speeds. Fast reactions, such as
explosions, occur within milliseconds.
Slow reactions, such as the formation of fossil fuels, take millions of years
The rate of reaction, ν, as the change in concentration, Δc, of a reactant or
product per unit time, Δt:

The reaction rates are measured in mol dm-3 s-1, although other units, such
as mmol dm-3 min-1 or mol m-3 h-1, can also be used.
Measuring Rates of Reaction
● Change in mass
● Change in volume (gas production)
● Change in pressure
● Change in color
● Change in conductivity
● Rate of formation of precipitate
Measuring the change in volume:
Gas is one of the products
Measuring the change in volume:
Gas is one of the products
Measuring the change in mass:
Many reactions in which
gases are produced will show
a decrease in mass if the gas
is removed from the reaction
mixture.
Measuring the changes in color:
Spectrophotometer or
Colorimetry
➢ Absorbance or
➢ Transmittance
As the concentration of some
solutions increases, they become
darker and absorb proportionally
more light. This means less light is
transmitted.
Measuring the changes in
conductivity:
Changes in ion concentration
when reactants change into
products, can be monitored by
taking conductivity
measurements
Measuring the rate of formation
of precipitate:
➢ measuring the time taken for
the solution to turn opaque,
so that a cross viewed
through the solution is no
longer visible
Measuring the rate of clock
reactions:
➢ series of chemical reactions
where an additional reaction
can only occur after the
reaction(s) under study is/are
complete
Example

Consider the following reaction:

2N2O(g) → 2N2(g) + O2(g)
Under certain conditions, the concentration of nitrogen(I) oxide
in the reaction mixture decreases by 0.20 mol dm-3 over 10
seconds, producing 0.20 mol dm-3 of nitrogen and 0.10 mol dm
-3
of oxygen over the same period of time. Calculate:
a. the rate of reaction, in mol dm-3 s-1, with respect to each of the
three species involved in the reaction
b. the overall rate of reaction, in the same units as above.
Solve
Under certain conditions, ammonia can be oxidized to
nitrogen(II) oxide:
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
Over a period of 5 s, the concentration of nitrogen(II) oxide in
the reaction mixture increased from 0 to 6.0 × 10-3 mol dm-3.
Calculate:
a. the rate of reaction, in mol dm-3 s-1, with respect to NO(g) and
O2(g)
b. the overall rate of reaction, in the same units as above.
Answer

a. ν(NO) = 1.2 × 10−3 mol dm−3 s−1

ν(O2) = 1.5 × 10−3 mol dm−3 s−1

−4 −3 −1
b. V(overall) = 3.0 × 10 mol dm s
Note: Vm(SATP) = 24.8 dm3 mol-1
Determine the initial rate, in mol dm-3 s-1, and the instantaneous rate, in the
same unit, at t=55s for the reaction of hydrochloric acid with magnesium.
Reactivity 2.2.2—Species react as a result of collisions
of sufficient energy and proper orientation.
Explain the relationship between the kinetic energy of the particles and
the temperature in kelvin, and the role of collision geometry
The collision theory (Reactivity 2.2.2) Definition of Terms
◆Collision theory: A simple model which considers particles to be hard spheres
that react with each other when they collide with sufficient kinetic energy.
◆Unsuccessful collision: A collision between two reactant particles without the
correct orientation and/or sufficient kinetic energy to overcome the activation
energy.
◆Successful collision: A collision between two reactant particles with the correct
orientation and with sufficient kinetic energy for the reaction to occur.
◆Steric effect: An effect in which the rate or path of a chemical reaction depends
on the size or arrangement of groups in a molecule.
Activation energy

The minimum amount of combined total kinetic energy

required by a colliding pair of ions, atoms or molecules for a
chemical reaction to occur; the energy barrier that has to be
overcome to form the transition state.
Transition state

The partially bonded, short lived chemical species of

highest potential energy located at the top of the activation
energy barrier as a reaction proceeds from reactants to
products.
Reactivity 2.2.3

Reactivity 2.2.3—Factors that influence the rate of a reaction

include pressure, concentration, surface area, temperature
and the presence of a catalyst.

Predict and explain the effects of changing conditions on the

rate of a reaction.
Factors affecting the rate of reaction
Concentration
● an increase in concentration
often causes an increase in the
reaction rate.
● if the concentration is
increased, then the frequency
of collisions between reacting
particles in solution also
increases because the particles
are closer together and there
are more per unit volume
Pressure
For reactions in which molecules collide and react in the gas phase, an increase
in pressure will cause an increase in the rate of reaction. The increase in
pressure forces the particles closer together, so there are more particles per unit
volume (equivalent to an increase in concentration). This causes an increase in
the number of collisions per unit time and hence the rate of reaction.
Temperature
When temperature increases, the
average speed and kinetic energy
of particles also increase.
As particles move faster, they
collide with one another more
often. At the same time, a higher
percentage of these collisions
become successful, as a greater
number of particles have sufficient
kinetic energy for the reaction to
occur.
Particle size
The surface area of a solid is greatly increased if it is broken up into smaller
pieces or particles.

The greater the surface area of a solid reactant, the greater the rate of reaction;
there are more particles on the surface that can react and so there are more
successful collisions per unit time.
Catalysts
A catalyst is a substance that increases the rate of a chemical reaction but remains
chemically unchanged at the end of the reaction.
The rate is often directly proportional to the concentration of the catalyst.
A catalyst works by providing a reaction pathway with a lower activation energy. This
means that a greater proportion of the sample particles have sufficient kinetic energy to
react when they collide
 Copy figure 10 and, on
the same graph, sketch
and label three curves
for the following
changes in
experimental
conditions:
• increased initial
concentration of
hydrogen peroxide
• lowered temperature
of the reaction mixture
• increased
atmospheric pressure.
Answer
Reactivity 2.2.4
Reactivity 2.2.4—Activation energy, Ea, is the minimum energy that colliding
particles need for a successful collision leading to a reaction.

● Construct Maxwell–Boltzmann energy distribution

curves to explain the effect of temperature on the
probability of successful collisions
● Sketch and explain energy profiles with and without
catalysts for endothermic and exothermic reactions.
Maxwell Boltzmann energy distribution

● Maxwell Boltzmann energy distribution curves, show the

probability of finding a particle with a certain kinetic energy
against that energy.
● Theoretical calculations and experimental measurements show
that kinetic energies of molecules in an ideal gas are distributed
over a wide range known as a Maxwell–Boltzmann distribution
The total area under the curve is
directly proportional to the total
number of molecules and the
area under any portion of the
curve is directly proportional to
the number of molecules with
kinetic energies in that range.
Activation energy (Reactivity 2.2.4)

The minimum kinetic energy, Ek, of colliding particles required for the
reaction to occur is known as the activation energy, Ea
The activation energy,
Ea , is equal to the
difference in energy
between the
reactants and the
transition state.
Reactivity 2.2.5
Reactivity 2.2.5—Catalysts increase the rate of reaction by providing an
alternative reaction pathway with lower Ea.

Construct Maxwell–Boltzmann energy distribution curves to explain the effect of

different values for Ea on the probability of successful collisions
Definition of Terms

◆ Homogeneous catalyst:
A catalyst in the same phase as the reactants.
◆ Heterogeneous catalyst:
A catalyst that is in a different phase from the reactants and
provides a surface on which the reaction can occur.
Enzymes

◆Enzymes are biological catalysts that work in aqueous solution.

They are protein molecules that enable biochemical reactions in
living organisms to occur at a fast rate at relatively low
temperatures.
◆ Active site: The region on the surface of an enzyme molecule
that binds the substrate molecule.
◆ Substrate: A substance acted upon by an enzyme at its active
site.
 a. Your sketch should be very similar to that
shown in figure on the left. The height of the
Ea barrier should be approximately twice as
large as the drop in enthalpy between the
reactants and products.

b. Ea' = Ea– ∆Hr = 30kJ mol–1

Answer
Calculating reaction rates
Practice
During a reaction, 0.040 mol of a substance is produced in a 2.5dm3 vessel in
20 seconds. Calculate the average rate of reaction in units of mol dm–3 s–1.

concentration = 0.016 mol dm–3

rate = 8.0 × 10–4 mol dm–3 s–1
Solve

1. A reaction produces 44.02 g of carbon dioxide in 15.00 s in a

vessel of volume 4.00 dm3. Calculate the average rate of
reaction in units of mol dm–3 s–1 .

2. Acidified hydrogen peroxide and aqueous potassium iodide

react to form iodine. It was found that the concentration of
iodine was 0.06 mol dm–3 after allowing the reactants to react
for 30 s. Calculate the average rate of formation of iodine
during this time, in units of mol dm–3 s–1