JW Kinetics IGCSE

Chemical Kinetics
Chemical Kinetics
Chemical kinetics is the study of:

• the rates of chemical reactions
• factors that affect these rates
• the mechanisms by which reactions occur
Calculating
Rates
Rates of Reaction
Change in concentration of a species per unit time
Example: rate of formation of product A  P
 [ P]   [ A]
Rate  Or … Rate 
t t
Appearance of product Disappearance of reactant
Units: moles per liter per (unit of) time

mol dm–3 s–1
2H2O2  2H2O + O2
1L
2.960 g O2 (0.09250 0.1850 mol H2O2/L

mole) produced in Rate =
60 s means … 60 s
… 0.1850 mol H2O2
reacted in 60 s.
= 0.00131 M H2O2 s–1
2H2O2  2H2O + O2
If the rate of consumption of H2O2 is 4.6 M/h, then …

… the rate of formation of H2O must also be 4.6 M/h, and …
… the rate of formation of O2 is 2.3 M/h
Average vs. Instantaneous Rate
Instantaneous rate is
the slope of the
tangent to the curve
at a particular time.
We often are interested

in the initial instantane-
ous rate; for the initial
concentrations of
reactants and products
are known at this time.
Gas Collection
Methods
Gas Collection Methods
4g mol-1
He
28g mol-1
Air
Density = mass 80% N2
volume
44g mol-1
All gases occupy 22.4L CO2
at 25°C and 1 atm.
Density is proportional
to molar mass
Measuring
Rates
Methods to measure the rate of reaction
If we want to How much product is formed

understand how fast a over a period of time?
reaction is happening
we have to investigate
the reaction as it is
happening How much reactant is used up
over time?
The choice of method depends on the reaction

State 3 methods to measure the rate of a reaction in which
a gas is evolved.
Explain how you would measure the rate of a reaction in
which a precipitate is produced
Directly measure the concentrations
of products or reactants by titration
• Take a sample of the reacting solution at
specific time intervals
• Stop or quench as quickly as possible
• Titrate with a suitable standard solution
Quenched by:
1. rapidly cooling in ice
2. removing the catalyst
3. removing one of the reactants
by another chemical reaction
4. diluting with a large vol. of
cold water
Coloured reactions can be
monitored using a spectrometer
Spectrometers measure the

amount of light absorbed or
transmitted by a sample at
selective wavelengths
Collision
Theory
Collision Theory
In order for reactions to occur particles must collide with each other in
1) The correct orientation
2) With sufficient energy
Is this a successful collision?

Collision Theory - Orientation
Not all collisions are successful
Collision Theory
An Analogy for Reaction Profiles and Activation
Energy
Collision Theory
The configuration of the atoms at the time of the collision
is called the transition state (activated complex)
Activation Energy
Heat (enthalpy)
of reaction (DH)
Collision Theory – Activation Energy
Even highly exothermic
reactions are not
Ea
guaranteed to be fast!
Why?
Activation Energy
If a reaction
is endothermic
you must keep supplying heat
If thereaction is exothermic it
Why does sugar in your sugar releases energy and this energy
bowl not spontaneously burst can provide the activation
into flames?
energy for following reactions
Collision Theory
To increase the rate of reaction requires...

• more frequent collisions
• increased particle speed (a higher temperature)
• more particles present (a higher concentration)
• more successful collisions
• particles with more energy (a higher temperature)
• a lower activation energy (use of a catalyst)
Factors affecting
rates of reaction
Factors affecting rates of reaction
• Concentrations of reactants:
↑Concentration = ↑Reaction rate concentration
• Solids = surface area
• Liquids = concentration pressure
• Gases = pressure
temperature
• Temperature:
↑Temperature = ↑Reaction rate surface area
• Catalysts: catalyst
Catalysts = ↑ Reaction rate
light
Inhibitors = ↓ Reaction rate
Light can be a catalyst in some reactions.
Concentration
Liquids
(concentration)
Factors affecting rates of reaction - Concentration
Increasing concentration = more frequent collisions
= increased rate of reaction
Low concentration Higher concentration

fewer collisions more collisions
However, increasing the concentration of some reactants

can have a greater effect than increasing others
Reactions are fastest at the start
Gradient = rate of reaction ..... why?
A + 2B  C
High concentration = more collisions
C
CONCENTRATION
A
B
Low concentration = few collisions
TIME
Expt. run 3 times:

(a) 2.0M HCl
(b) 1.0M HCl
(c) 0.5M HCl
Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)
Reaction rate: (a) > (b) > (c)

Concentration
Gases
(pressure)
Factors affecting rates of reaction - Pressure
• ↑ pressure = gas particles closer together = ↑ concentration
• ↑ frequency of collisions
• many industrial processes occur at high pressure to increase the rate...
but it can adversely affect the position of equilibrium and yield
pressure ∝ 1/volume
No effect on reaction with ONLY (s) and (l) because they are incompressible
Concentration
Solids
(surface area)
More particles are exposed with smaller pieces,
powdered solids react quicker than larger lumps.
Catalysts (e.g. in catalytic converters) are finely
divided for this reason
In many organic reactions there are two liquid

layers, one aqueous, the other non-aqueous.
Shaking the mixture increases the reaction rate
as an emulsion is often formed and the area of
the boundary layers is increased giving more
collisions.
1
CUT THE SHAPE INTO 1
1
SMALLER PIECES 1
3
3
SURFACE AREA SURFACE AREA

9+9+3+3+3+3 = 30 sq units 9 x (1+1+1+1+1+1) = 54 sq units
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
Reaction A is
faster than
reaction B
a
b
Temperature
Factors affecting rates of reaction - Temperature
1. ↑T  ↑kinetic energies (speed) of reactant particles
2. ↑kinetic energies (speed) of reactant particles

 ↑ no. of effective collisions per unit time
(↑ collision frequency & ↑proportion of high energy collisions)
Factors affecting rates of reaction - Temperature
Na2S2O3(aq) + 2HCl(aq) 2NaCl(aq) + SO2(g) + H2O(l) + S(s)
t = time taken for the

disappearance of the cross
rate  1/t
Time t2 < t1
Rate 2 > 1
Light
Factors affecting rates of reaction - Light
Consider the following reaction:
C6H14 + Br2  C6H13Br  ………

light (substitution reactions)
UV
Br2 2Br·
Reddish brown Colourless
Light provides energy to split up Br2 molecules into Br.
radicals which are highly reactive.
Factors affecting rates of reaction - Light
• shining a suitable light source onto some reactants increases the rate of reaction
• the light - often U.V. - provides energy to break bonds and initiate a reaction
• the greater the intensity of the light, the greater the effect
Examples a) the reaction between methane and chlorine - see alkanes

b) the darkening of silver salts - as used in photography
c) the reaction between hydrogen and chlorine
Equation H2(g) + Cl2(g)  2HCl(g)
Bond enthalpies H-H 436 kJ mol-1 Cl-Cl 242 kJ mol-1
Mechanism Cl2  2Cl• ----- INITIATION

H2 + Cl•  HCl + H• - - - - - PROPAGATION H• + Cl2 
HCl + Cl•
2Cl•  Cl2 ----- TERMINATION
2H•  H2
H• + Cl•  HCl
Catalysts
INTRODUCTION
• Catalyst = substance that speeds up reaction without

undergoing any permanent change.
• Often the catalyst is consumed in one step of the
mechanism, but is regenerated in another step.
• They provide an alternative mechanism with lower activation

energy.
© www.chemsheets.co.uk A2 044 12-Jul-12

INTRODUCTION
Types of catalysts
Heterogeneous Homogeneous
different state to the reactants same state as the reactants
Adsorb Absorb
(Surface) (Body)
HETEROGENEOUS CATALYSTS
Hydrogen is adsorbed
onto the surface of a
nickel catalyst. A C=C
approaches …
… and is adsorbed.
Hydrogen atoms attach

to the carbon atoms,
and the molecule is
desorbed.
Nature of catalyst
• Large surface area.

• Spread thinly over ceramic
honeycomb.
Nature of catalyst – Catalytic Converter
• Large surface area.

• Spread thinly over ceramic
honeycomb.
HOMOGENEOUS CATALYSTS
1) Catalyst reacts with a reactant to form intermediate.

2) Intermediate reacts to form product faster than original
reactant (and regenerates catalyst).
e.g. acid catalyst
X + Y  products
1) X + H+ → HX+
2) HX+ + Y → products + H+

HOMOGENEOUS CATALYSTS
e.g. transition metal catalyst
works by metal varying oxidation state
Fe2+ or Fe3+
e.g. 2 I- + S2O82- → I2 + 2 SO42-
Slow because both –ve ions so repel.
1) 2 Fe2+ + S2O82- → 2 Fe3+ + 2 SO42-
2) 2 Fe3+ + 2 I- → 2 Fe2+ + I2

Graphs
Summary
Which graph is which?
2g of Mg turnings + 50cm3 1M HCl (excess) at 25°C X

2g of Mg ribbon + 50cm3 1M HCl (excess) at 25°C C
2g of Mg powder + 50cm3 1M HCl (excess) at 25°C B
2.5g of Mg turnings + 50cm3 1M HCl (excess) at 25°C A

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Chemical Kinetics

Chemical kinetics is the study of:

Units: moles per liter per (unit of) time

2.960 g O2 (0.09250 0.1850 mol H2O2/L

If the rate of consumption of H2O2 is 4.6 M/h, then …

We often are interested

If we want to How much product is formed

The choice of method depends on the reaction

Spectrometers measure the

Is this a successful collision?

To increase the rate of reaction requires...

Low concentration Higher concentration

However, increasing the concentration of some reactants

Expt. run 3 times:

Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)

Reaction rate: (a) > (b) > (c)

In many organic reactions there are two liquid

SURFACE AREA SURFACE AREA

1. ↑T  ↑kinetic energies (speed) of reactant particles

2. ↑kinetic energies (speed) of reactant particles

Na2S2O3(aq) + 2HCl(aq) 2NaCl(aq) + SO2(g) + H2O(l) + S(s)

t = time taken for the

Consider the following reaction:

C6H14 + Br2  C6H13Br  ………

Examples a) the reaction between methane and chlorine - see alkanes

Equation H2(g) + Cl2(g)  2HCl(g)

Bond enthalpies H-H 436 kJ mol-1 Cl-Cl 242 kJ mol-1

Mechanism Cl2  2Cl• ----- INITIATION

• Catalyst = substance that speeds up reaction without

• They provide an alternative mechanism with lower activation

© www.chemsheets.co.uk A2 044 12-Jul-12

Hydrogen atoms attach

• Large surface area.

• Large surface area.

1) Catalyst reacts with a reactant to form intermediate.

e.g. acid catalyst

© www.chemsheets.co.uk A2 044 12-Jul-12

e.g. transition metal catalyst

works by metal varying oxidation state

e.g. 2 I- + S2O82- → I2 + 2 SO42-

Slow because both –ve ions so repel.

1) 2 Fe2+ + S2O82- → 2 Fe3+ + 2 SO42-

© www.chemsheets.co.uk A2 044 12-Jul-12

2g of Mg turnings + 50cm3 1M HCl (excess) at 25°C X

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