1

Aletta Wessels º Paarl 2015

Grade 11 and 12: Reaction rate

SUMMARY
Grade 11: Energy and chemical change Gr 11: p. 248 – 259
Study and Master

ENERGY CHANGES IN CHEMICAL REACTIONS

 For a reaction to take place bonds have to be broken and new bonds have to form. E.g. in the
reaction A2 + B2  2AB the bonds in A2 and B2 have to be broken and the new bonds in AB have
to form.
 To break the bonds in A2 and B2, energy is needed.
 To form the new bonds in AB, energy is released.

A2 B2 +EA –E 2AB
reactants activated complex products

 Activation energy (EA or Ea) = the minimum energy needed for a reaction to take place.

 An activated complex is the unstable transition state from reactants to products.

 All chemical systems have a total potential energy content - the total amount of energy a system
has at a given time.
 When energy is absorbed, the energy content increases.
 When energy is released, the energy content decreases.
–1
 The energy content is usually measured in kJ.mol .

 During a chemical reaction the energy content changes. The change in energy is called the heat
of reaction (ΔH).
(H is the symbol for enthalpy. H is total heat content of a
ΔH = Eproducts – Ereactants = Ef – Ei system. It is equal to the internal energy of the system plus
the product of pressure and volume.)

 Definition of heat of reaction (ΔH): the energy absorbed or released in a chemical reaction.

Example: For the reaction A2 + B2  2AB

Potential energy (kJ.mol )
–1

200

100

50

course of reaction
–1
Energy of the reactants: 100 kJ.mol
–1
Energy of activated complex: 200 kJ.mol
–1
Energy of the products: 50 kJ.mol
–1
Activation energy (energy absorbed): 100 kJ.mol
–1
Energy released: 150 kJ.mol (200 to 50)
–1
Heat of reaction (∆H ) = Hf – Hi = 50 – 100 = –50 kJ.mol
 2

EXOTHERMIC AND ENDOTHERMIC REACTIONS

 Exothermic reactions are defined as reactions that release energy.

 Endothermic reactions are defined as reactions that absorb energy.

EXOTHERMIC REACTION H = Hproducts – Hreactants

= E3 – E1
E2 < 0 (negative)
Potential energy

E1
H < 0
E3
time
For the reaction A2 + B2  2AB
E1 = energy of reactants (A2 + B2)
E2 = energy of activated complex
E3 = energy of products (2AB)
E2 – E1 = activation energy
In an EXOTHERMIC reaction:
 the energy absorbed to break the bonds in A2
and B2 < the energy released to form the new
bonds in AB.
 ∴ more energy is released than absorbed.
 ∴ the energy of the products is lower than that
of the reactants.
 ∴ H < 0
 In exothermic reactions the heat of reaction is
(H ) always negative.
 In such reactions the immediate surroundings
heat up as a result of the energy that is
released.

ENDOTHERMIC REACTION H = Hproducts – Hreactants

= E3 – E1
> 0 (positive)
Potential energy

E2

E3
H = Hprodukte – Hreagense
= E3 – E1
E1
< 0 (negatief)
For the reaction X2 + Y2  2XY
E1 = energy of reactants (X2 + Y2)
E2 = energy of activated complex
E3 = energy of products (2XY)
E2 – E1 = activation energy
In an ENODTHERMIC reaction:
 the energy absorbed to break the bonds in
X2 and Y2 > the energy released to form the
H > 0
new bonds in XY.
time  ∴ more energy is absorbed than released.
 ∴ the energy of the products is higher than
that of the reactants.
 ∴ H > 0
 In endothermic reactions the heat of
reaction (H ) always positive.
 In such reactions the immediate
surroundings cools down as a result of the
energy that is absorbed from the
surroundings.

CATALYST

 A catalyst functions by reacting with the reactants in such a way that the reaction takes an
alternative route of lower activation energy, ∴ Ea is lower.

 A catalyst is defined as a substance that increases the rate of a chemical reaction without itself
undergoing a permanent change.
EXOTHERMIC REACTION ENDOTHERMIC REACTION

without catalyst
with catalyst

 A positive catalyst increases reaction rate, a negative catalyst decreases reaction rate.
 3

SUMMARY
Grade 12: Reaction rate Gr 12: p. 185 – 204
Study and Master

p. 186
THE COLLISION THEORY

1. For a reaction between two particles of the reactants to take place:

1.1. the particles have to collide; and
1.2. the collision has to be effective.

2. For an effective collision between particles:

2.1. the particles have to be correctly orientated; and
2.2. the kinetic energy of the particles (Ek) has to be greater or equal to the activation energy
(EA) of the reaction  Ek (of particles)  EA (of reaction).

p. 186 REACTION RATE

 The rate of a reaction (reaction rate) = the change in concentration of reactants or products per
time unit.
△𝐜
Rate =
△𝐭 -3 -1
Unit is mol∙dm ∙s
–1 –1 –3 –1
 Examples of other units for reaction rate: mol.s ; g·min , mol·dm ·s , etc.

p. 187 FACTORS THAT INFLUENCE THE RATE OF REACTIONS

1 Nature of the reactants  Reactants in gas form lead to higher rates than solids.
 Ions in solution lead to higher rates than ionic solids.
 Smaller molecules lead to higher rates than bigger ones (e.g.
combustion of methane is quicker than that of octane).
2 Concentration* of reactants Increases the number of The higher the concentration,
particles that can collide the higher the rate.
effectively.
3 Temperature of reactants Increase the kinetic energy of The higher the temperature,
colliding particles. the higher the rate.
4 Presence of a catalyst Decreases the activation The rate increases in the
energy of the reaction. presence of a +catalyst.
5 Surface area of reactants Increases the number of The greater the surface area,
(State of sub–division of particles that can collide the higher the rate.
reactants) effectively.
𝐧
 * Concentration is mole per volume (c = ).
𝐕
 Increase concentration of solutions by greater mass of solute, or smaller volume of solvent
(water).
 Increase concentration of gases by decreasing volume, ∴ greater pressure on gas.

 From the nature of the reactants it can be determined what can be done to increase the reaction
rate:
 for a reactant in solution: → increase the concentration of the solution;
→ increase the temperature of the solution.
 for a solid reactant: → use in powdered form.
 for a reactant is the gas phase: → increase the concentration of the gas;
→ increase the temperature of the gas.

Zn(s) + 2HCℓ (aq)  ZnCℓ2(aq) + H2(g) H2 (g) + Cℓ2 (g) → 2HCℓ (g)

use increase c increase c increase c

powder increase T increase T increase T

 In all cases a positive catalyst can be added.

 4

EXPLANATION OF FACTORS IN TERMS OF COLLISION THEORY

 At a higher temperature the rate of a chemical reaction increases:

Explanation:
At a higher temperature:
- the particles move faster;
- ∴ the particles have higher kinetic energy;
- ∴ more particles have kinetic energy greater or equal to the activation energy;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

 At a higher concentration the rate of a chemical reaction increases:

Explanation:
At a higher concentration:
- more particles are present;
- ∴ more collisions take place;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

 With the addition of a catalyst the rate of a chemical reaction increases:

Explanation:
With the addition of a catalyst:
- the activation energy of the reaction decreases;
- ∴ more particles have kinetic energy greater or equal to the activation energy;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

 With the powdering of a solid reactant, the rate of a chemical reaction increases:

Explanation:
With the powdering of a solid reactant:
- the contact area of the solid reactant increases;
- ∴ more collisions takes place;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

Study this nota after p. 5:

Volume gas

Volume gas

time time
A B
 The graph of volume versus time is usually drawn as in graph A: The rate is at its highest right at
the start, because the concentrations of the reactants are at its highest.
 The graph can also be drawn as in B for an exothermic reaction: As the reaction progresses, the
temperature increases, which increases the reaction rate. The rate is then at its highest a short
while after the reaction started.
 5

p. 192 MEASUREMENT OF REACTION RATE

GAS FORMING REACTIONS

 For a reaction that liberates gas the rate of the reaction is determined by measuring the rate of
gas liberation.

Zn(s) + 2HCℓ(aq)  ZnCℓ2(aq) + H2(g) CaCO3(s) + 2HCℓ (aq)  CaCℓ2(aq) + H2O(ℓ) + CO2(g)

METHOD 1 METHOD 2

Close the reaction The reaction takes place in

container with a rubber
stopper and collect the
gas in a syringe. Measure
the volume of gas that is
collected in the syringe
regularly.
an open container, on a
scale. Measure the mass
of the reaction mixture
regularly.

Explanation of change in rate

The volume of gas that from t1 to t2: The mass of the beaker and the
collects in the syringe contents decrease as the gas
 t1: [acid] initially is high and
increases. escapes from the beaker.
contact area of solid reactant
still great
Volume gas (dm3)

slow
∴ high rate initially

and contens (g)

 t2: [acid] decreases and Mass of beaker
fast contact area of solid reactant
fast
decreases
time(s)
t0 t1 t2 t3
∴ rate decreases slow

Rate of reaction = gradient
 t1 rate is high;
 t2  rate is lower;
 t3  rate = 0
Explanation of “flattening”
after t3:
The limiting reactant is used up;
no more gas is produced and
the reaction stops.
t0 t1 t2 t3 time (min)
Rate of reaction = gradient
 t1 rate is high;
 t2  rate is lower;
 t3  rate = 0

is obtained when the rate

Each curve represents
is increased: Each curve represents
another experiment.
 higher temperature; another experiment.
 higher concentration reactant;
Mass of beaker
and contents

 pulverize solid reactant;

Volume gas

 add a catalyst.

is obtained when the rate

time is decreased.
time

CALCULATION OF REACTION RATE

 Determine the rate of the reaction for a time interval (e.g. the average rate between t1 and t2):
y value at t2 − y value at t1
Reaction rate = gradient =
t2 − t1
 The unit of the rate is derived from the axes:
3 –1 –1
e.g. method 1: dm .s and method 2: g.min
 The magnitude of the answer shows the magnitude of the rate. A “great” number in both
methods indicates a high rate, although the rate in method 1 is positive and in method 2
negative.
 6

 Determine the rate of the reaction at a specific time (e.g. at time t1): Draw a tangent to the curve
at t1 and determine the gradient of the tangent.

VARIABLES

 You must be able to identify the variables in these experimental investigations:

Investigation between Independent variable Dependent variable Control variables

Reaction rate; or  Temperature of reactants
Concentration and Concentration (of a (Method 1: volume gas)  State of sub–division of the
reaction rate reactant) (Method 2: mass of container solid reactant
and contents)  Absence of a catalyst
Reaction rate; or  Concentration of reactants
Temperature and Temperature of reactants (Method 1: volume gas)  State of sub–division of the
reaction rate (Method 2: mass of container solid reactant
and contents)  Absence of a catalyst
State of sub-division of
Reaction rate; or  Concentration of reactants
a solid reactant and
State of sub–division of a (Method 1: volume gas)  Temperature of reactants
reaction rate
solid reactant (Method 2: mass of container  Absence of a catalyst
and contents)
Reaction rate; or  Concentration of reactants
Presence of a catalyst
and reaction rate
Catalyst (Method 1: volume gas)  Temperature of reactants
(Method 2: mass of container  State of sub–division of the
and contents) solid reactant

PRECIPITATION REACTIONS

 In a reaction where a precipitate forms, the rate of the reaction is determined by the rate at which
the precipitate forms, e.g.:
Die precipitate is
fine, yellow sulphur.
p. 195 Na2S2O3(aq) + 2HCℓ(aq)  2NaCℓ + H2O(ℓ) + SO2(g) + S(s)

 INVESTIGATION 1: Determine the relationship between concentration and reaction rate:

 Place the beaker in which the reaction takes place (and the precipitate forms) on a piece of
paper with a mark (e.g. a cross). Take the time it takes for the cross to “disappear”.

cross disappears
as precipitate forms

 Repeat the experiment at a higher concentration HCℓ (or Na2S2O3). The rate is higher at a
higher concentration; ∴ time is shorter at a higher concentration.
 Independent variable: [HCl] (or [Na2S2O3]);
 Dependent variable: time for cross to disappear / reaction rate;
 Control variables: temperature of solutions; volume of Na2S2O3 and HCℓ.
Reaction rate (s )
–1

Time Each point represents

(s) another experiment at a
higher concentration.

𝟏
Rate of reaction =
𝐭𝐢𝐦𝐞
[HCl] or [Na2S2O3] [HCl] (or [Na2S2O3])
 7

 INVESTIGATION 2: Determine the relationship between temperature and reaction rate:

 Place the beaker in which the reaction takes place (and the precipitate forms) on a piece of
paper with a mark (e.g. a cross). Take the time it takes for the cross to “disappear”.
 Repeat the experiment at a higher temperature. The rate is higher at a higher temperature;
∴ time is shorter at a higher temperature.
 Independent variable: temperature;
 Dependent variable: time for cross to disappear / reaction rate;
 Control variables: [HCl]; [Na2S2O3]; volume of Na2S2O3 and HCℓ.

Each point represents

Reaction rate (s )
–1
another experiment at a
Time higher temperature.
(s)
𝟏
Rate of reaction =
𝐭𝐢𝐦𝐞

temperature (°C) temperature (°C)

p. 202 MAXWELL-BOLTZMANN GRAPHS

 Ek  T: The average kinetic energy of the particles in a substance is directly proportional to the
temperature or the substance, ∴ the higher the temperature, the greater the average kinetic
energy of the particles.

 A Maxwell-Boltzmann graph shows the distribution of kinetic energy of the particles in a system.

Fraction of
particles with Fraction of particles
given Ek with Ek = EA

Particles with
enough Ek for a reaction
Ek  EA

0
EA Kinetic energy
average kinetic energy

 The curve is drawn through the origin, because no particles have kinetic energy equal to 0 J.
 The curve is asymptotically to the x-axis: theoretically, all kinetic energies are possible.
 The area under the graph = the total number of particles in the system.
 The peak of the curve = the average kinetic energy of the particles. That is the most probable
kinetic energy of the particles.
 The shaded area represents the fraction of particles which has kinetic energy equal or greater
than the activation energy (∴ Ek ≥ EA). This fraction of particles can therefore perform effective
collisions if the orientation is correct, since they have enough kinetic energy.

At a higher temperature the curve changes:

 The average kinetic energy of the particles increases as the

temperature increases ∴ the peak is more to the right.
 The number of particles remains the same,
Fraction of particles

∴ the area under the graph remains the same.

Low Temp
with given Ek

 ∴ the peak is lower and broader.

High Temp

EK of particles
EA
 8

 At a higher temperature the rate of a chemical reaction increases:

Explanation: At a higher temperature:
- the particles move faster;
- ∴ the particles have more kinetic energy;
- ∴ more particles have kinetic energy greater or equal to the activation energy;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

∴ the area under the graph to the right of the EA-broken line increases.

At a higher concentration the curve changes:

 The number of particles increases,

∴ the area under the graph increases.

Fraction of particles
low concentration


with given Ek
The peak is higher, but at the same place.
high concentration

EK of particles
EA
 At a higher concentration the rate of a chemical reaction increases:
Explanation: At a higher concentration:
- more particles are present;
- ∴ more collisions take place;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases.

∴ the area under the graph to the right of the EA-broken line increases.

With the addition of a catalyst:

 The curve does not shift.

Fraction of particles

 The activation energy of the reaction

with given Ek

EA with catalyst
now has a lower value.
EA without catalyst

EK of particles

 With the addition of a catalyst the rate of a chemical reaction increases:

Explanation: With the addition of a catalyst:
- the activation energy of the reaction decreases;
- ∴ more particles have kinetic energy greater or equal to the activation energy;
- ∴ more collisions take place between particles with kinetic energy greater or equal to the
activation energy;
- ∴ more effective collisions per time unit takes place;
- ∴ the rate of the reaction increases;

∴ the area under the graph to the right of the EA-broken line increases.

With the powdering of a solid reactant:

 This factor does NOT show on the Maxwell-Boltzmann graphs.