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Kinetics

Mr Field
Using this slide show

 The slide show is here to provide structure to the lessons, but not
to limit them….go off-piste when you need to!

 Slide shows should be shared with students (preferably electronic to


save paper) and they should add their own notes as they go along.

 A good tip for students to improve understanding of the


calculations is to get them to highlight numbers in the question and
through the maths in different colours so they can see where
numbers are coming from and going to.

 The slide show is designed for my teaching style, and contains only
the bare minimum of explanation, which I will elaborate on as I
present it. Please adapt it to your teaching style, and add any notes
that you feel necessary.

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Menu:
 Lesson 1 –
 Lesson 2 –
 Lesson 3 –
 Lesson 4 –
 Lesson 5 –
 Lesson 6 –
 Lesson 8 –
 Lesson 9 –
 Lesson 10 –
 Lesson 11 –
 Lesson 12 –
 Lesson 13 –

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Lesson 1

The Rate of Reactions

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Reflecting on Kinetics
 Brainstorm everything you already know about the rates
of reactions.

 You have 3 minutes

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Overview
 Copy this onto an A4 page. You should add to it as a
regular review throughout the unit.

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Assessment

 This unit will be assessed by:

 An internal assessment on either this or energetics (0/24%) at


the end of the this unit.

 A test on this and equilibrium at the end of the equilibrium


unit (100/76%)

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We Are Here

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Lesson 1: Rates of Reaction

 Objectives:

 Understand the term ‘rate of reaction’

 Meet three possible approaches for measuring rates of


reaction

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The Rate of Reactions
 In simple terms, the rate of a reaction can be thought of
as its speed

 Some reactions are very fast

 Some reactions are very slow

Discuss:
 Think of examples of ‘fast’ and ‘slow’ reactions
 Why is ‘speed’ not a good word to use in this context?

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Defining the Rate of Reaction
 The rate of reaction is:  [ R] [ P]
Rate  
t t
 Where:
 ∆[R] is change in concentration of
reactants
 ∆[P] is change in concentration of
products
 ∆t is change in time

 Units: mol dm-3 s-1 (moles per


decimetre cubed per second)

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Measuring Reaction Rates
 We need to monitor something changing over time such as:
Technique Apparatus/Notes
Collecting gas Using a gas syringe or inverted measuring cylinder filled with
water
Mass loss Reaction conducted on a balance…if it produces a gas the mass
will decrease
Colour change Measured using a colorimeter
Obscured cross Useful if reaction produces a precipitate (for example sodium
thiosulphate and acid)
Iodine clock Produces a sudden colour change from colourless to
black….monitors any reaction producing iodine
pH Monitored using a pH probe
Temperature change Not ideal as difficult to prevent heat loss

 We then need to work out how the concentration has


changed, using our knowledge of stoichiometry
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Measuring Rates in Practice

 Complete the experiment here

 Any of these techniques could easily be modified for an


IA!

 Analysis should be completed for homework.

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Review

 [ R] [ P]
Rate  
t t

 Rates determined by monitoring a change

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Lesson 2

Collision Theory

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Practice

 What is the best definition of rate of reaction?

A. The time it takes to use up all the reactants


B. The rate at which all the reactants are used up
C. The time it takes for one of the reactants to be used up
D. The increase in concentration of a product per unit time

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We Are Here

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Lesson 2: Collision Theory

 Objectives:

 Understand the four main influences on the rate of a reaction

 Produce a learning resource to educate others about the


above.

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Reflect
 What are the four main influences on the rate of
chemical reactions?

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Collision Theory

 Reactions occur as the result of two particles colliding


with enough energy.
 ‘Enough energy’ is better know as the activation energy

 Anything that increases the number of collisions, or the


proportion of collisions that have enough energy will
increase the rate of reaction

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Simulation
 This should be downloaded and installed before the lesson!
 https://phet.colorado.edu/en/simulation/reactions-and-rates
 Complete the activity here.
 Once you have finished, you should attempt to develop an
analogy to describe your findings.

Factor Effect Chemical Explanation Analogy


Explanation
Concentration
(pressure in
gases)
Temperature

Particle size

Catalyst

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Review
 Reaction rates increase if you increase:
 The number of collisions
 The energy of those collisions

 Increasing temperature, concentration and surface area


will increase the number of collisions

 Increasing temperature increases the energy of collisions.

 Using a catalysts decreases the energy needed.

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Lesson 3

Hess’ Law

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Recap
 Excess magnesium, was added to a
beaker of aqueous hydrochloric acid.
A graph of the mass of the beaker
and contents was plotted against
time (line 1). Mass 1

 What change in the experiment


could give line 2? 2
A. The same mass of magnesium in Time
smaller pieces
B. The same volume of a more
concentrated solution of
hydrochloric acid
C. A lower temperature
D. A more accurate instrument to
measure the time

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We Are Here

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Lesson 3: Catalysts

 Objectives:

 Understand what catalysts are and how they work.

 Complete an experiment to see how catalysts work.

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What are catalysts?

 Catalysts are substances that speed up reactions without


taking part.

 Correct? Discuss.

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So then, what are catalysts?

 Catalysts are substances that increase the rate of


chemical reactions without being used up.

 How do they work?


 They DO take part in the reaction!
 They provide an alternative pathway for the reaction with a
lower activation energy – which increases the proportion of
particles with enough energy to react during collisions.
 Catalysts are often changed during the course of a reaction,
but will always be re-formed by the end of it.

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Enthalpy Level Diagrams
 Sketch an enthalpy level diagram for a reaction with and
without a catalyst.

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Catalysts in Practice

 Complete the experiment here to investigate the effect of


a Co2+ catalyst on the oxidation of tartrate ions by
hydrogen peroxide.

C4H4O62-(aq) + 5H2O2(aq)  2OH-(aq) + 4CO2(g) + 6H2O(l)

 You will need to adapt the given method to give you a


quantitative measure of the rate.
 Review lesson 1 if you need to

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Review

 Catalysts increase the rate of reactions without being


used up.

 They DO take part in reactions, they are just left as they


started at the end.

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Lesson 4

The Maxwell Boltzmann Distribution

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Recap
 Which quantities in the enthalpy level
diagram are altered by the use of a catalyst?
I II
Enthalpy
 A. I and II only
 B. I and III only III
 C. II and III only
 D. I, II and III Time

 Which statement is true about using sulfuric acid as a catalyst


in the following reaction? A. I and II only
CH3–CO–CH3(aq) + I2(aq) CH3–CO–CH2–I(aq) + HI(aq) B. I and III only
I. The catalyst increases the rate of reaction.
C. II and III only
II. The catalyst lowers the activation energy for the reaction. D. I, II and III
III. The catalyst has been consumed at the end of the chemical
reaction.

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We Are Here

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Lesson 4: The Maxwell-Boltzmann
Distribution

 Objectives:

 Use a simulation to explore the Maxwell-Boltzmann


Distribution

 Practice past exam questions on the SL Kinetics material

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A Glass of Water
DISCUSS:
 What is the relationship between
the temperature of this water and
the movement of its molecules?

 In a glass of room temperature


water, are all the molecules moving
at the same speed?

 Bonus: Where is there more heat


energy, a glass of room temperature
water or a red-hot needle?

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The Maxwell-Boltzmann Distribution
 Describes how energy is distributed in a collection of
particles:

 x-axis: Energy of particles  Emp: most-populated energy level


 y-axis: Number of particles with a  Ē: the average energy, i.e the
given energy temperature

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Simulating the Maxwell-Boltzmann
Distribution
 As with much physical chemistry, computer-based simulations are one of
the best ways to get to grips with this.

 Follow the instructions here


 This will require you to have installed Java

 Technical Note:
 Java’s security settings sometimes prevent the simulation from working. To fix:
 Go to Java Control Panel (sometimes called ‘javacpl’)
 Se

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Practice Questions

 Attempt the practice questions here

 Complete them for homework

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The Boltzmann Graphs

Red: 100K

Green: 300K

Blue: 500K

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Review

 The particles in a body possess a range of energies.

 This range is described by the Maxwell-Boltzmann


Distribution

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Lesson 5
HL Only
Reaction Order

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Recap
 On the same axes, sketch the Maxwell-Boltzmann
distribution for a lower and a higher temperature, and
use this to explain why increasing the temperature
increases the rate of reaction.

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We Are Here

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Lesson 5: Reaction Order

 Objectives:

 Understand the concept of reaction order

 Identify reaction order from appropriate graphs

 Complete an experiment to determine the order of a reaction


with respect to the concentration of acid.

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What is reaction order?
 Reaction order describes how changes to the
concentration of reactants affect the rate of a reaction
 Assuming temperature and pressure are fixed

0th Order (0o) 1st Order (1o) 2nd Order (2o)

Changing the
concentration does not
affect the rate

Doubling the Doubling the


Doubling the
concentration of a concentration of a
concentration of a
reactant would double the reactant would quadruple
reactant would have no
rate, tripling it would the rate, tripling it would
effect on rate
triple the rate increase rate nine-fold

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For example:
Run # Initial [A] Initial [B] Initial Rate (v0)
([A]0) ([B]0)
1 1.00 M 1.00 M 1.25 x 10-2 M/s
2 1.00 M 2.00 M 2.5 x 10-2 M/s
3 2.00 M 2.00 M 2.5 x 10-2 M/s

 The reaction is 0th order w.r.t reactant A


 Comparing Runs 2 and 3:
 [A] doubles but [B] remains fixed
 Rate unchanged

 The reaction is 1st order w.r.t reactant B


 Comparing Runs 1 and 2:
 [B] doubles but [A] remains fixed
 Rate doubles

 Overall the reaction is 1st order

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Another example:
Experiment Initial [NO] / Initial [H2] / Initial rate /
mol dm–3 mol dm–3 mol (N2) dm–3 s–1
1 0.100 0.100 2.53×10–6
2 0.100 0.200 5.05×10–6
3 0.200 0.100 1.01×10–5
4 0.300 0.100 2.28×10–5
 The reaction is 1st order w.r.t reactant H2
 Comparing Runs 1 and 2:
 [H2] doubles but [NO] remains fixed
 Rate doubles

 The reaction is 2nd order w.r.t reactant NO


 Comparing Runs 1 and 3:
 [NO] doubles but [H2] remains fixed
 Rate quadruples

 Overall the reaction is 3rd order (1st order + 2nd order = 3rd order)

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Rate-Concentration Graphs
0th Order 1st Order 2nd Order

No effect Directproportion Squared relationship


Gradient 0 Gradient positive and Gradient positive and
constant increasing

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Concentration-Time Graphs
0th Order 1st Order 2nd Order

t1/2 t1/2 t1/2 t1/2 t1/2 t1/2

Half-life decreases Half-life constant Half-life increases

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Rate Graphs in Practice

 In the experiment you will follow the progress of a


reaction using a data logger with pH probe

 Follow the instructions here.

 This will collect so much data that the only realistic way
to analyse it will be by spreadsheet. There is an example
here.

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Review

 The order of a reaction tells us the effect on the rate of


changing the concentration of the reactants.

 Order can be determined by:


 Directly comparing experimental data
 The gradient of a rate-concentration graph
 The shape of a concentration-time graph

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Lesson 6
HL Only
Rate Equations

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Recap
 What is the order of reaction with respect to NO2(g)
and F2(g) given the following rate data at a certain
temperature?
[NO2(g)] / mol [F2(g)] / mol Rate / mol dm–3
dm–3 dm–3 min–1
0.1 0.2 0.1
0.2 0.2 0.4
0.1 0.4 0.2

Order with respect to NO2(g) Order with respect to F2(g)


A. first first
B. first second
C. second first
D. second second

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We Are Here

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Lesson 6: Rate Equations

 Objectives:

 Build on our understanding of reaction order to construct rate


equations.

 Analyse experimental data in order to determine a rate


equation.

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What is a rate equation?
 A rate equation allows us to calculate the rate we would expect for
any concentration of reactants.

 For example in the reaction:

A+B+CD+E

 The rate equation is:

Rate = k[A]x[B]y[C]z

 Where:
 [A], [B] an [C] are the concentrations of each reactant
 x, y, and z are the order of reaction with respect to each reactant
 k is the ‘rate constant’

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The rate constant, k
 The rate constant k is essentially a measure of how
readily a reaction will take place:
 Higher k  faster reaction
 Lower k  slower reaction

 k is dependent on temperature
 As temperature increases, so does k
 As temperature decreases, so does k

 k is independent of concentration:
 Provided the temperature is fixed, k is always the same

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Units of k
 K has specific units, dependent on the overall order of reaction.

 Units are determined by recognising that:


k = rate / concentration
Reaction Equation for k Units for k
Order
0o 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏
𝒌=
(𝒎𝒐𝒍 𝒅𝒎−𝟑 )𝟎
1o 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏 𝒔−𝟏
𝒌=
(𝒎𝒐𝒍 𝒅𝒎−𝟑 )𝟏
2o 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏 𝒎𝒐𝒍−𝟏 𝒅𝒎𝟑 𝒔−𝟏
𝒌=
(𝒎𝒐𝒍 𝒅𝒎−𝟑 )𝟐
3o 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏 𝒎𝒐𝒍−𝟐 𝒅𝒎𝟔 𝒔−𝟏
𝒌=
(𝒎𝒐𝒍 𝒅𝒎−𝟑 )𝟑

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For example (from last lesson):
Experiment Initial [A] Initial [B] Initial Rate (v0)
([A]0) ([B]0)
1 1.00 M 1.00 M 1.25 x 10-2 M/s
2 1.00 M 2.00 M 2.5 x 10-2 M/s
3 2.00 M 2.00 M 2.5 x 10-2 M/s

 The reaction is 0th order w.r.t reactant A, and 1st order w.r.t reactant
B

 Therefore, the rate equation is:


 Rate = k[B]

 The value of k is given by (using values for Experiment 1):


k = Rate / [B]
k = 1.25x10-2 / 1.00 = 1.25x10-2 s-1

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Another example (from last lesson):
Experiment Initial [NO] / Initial [H2] / Initial rate /
mol dm–3 mol dm–3 mol (N2) dm–3 s–1
1 0.100 0.100 2.53×10–6
2 0.100 0.200 5.05×10–6
3 0.200 0.100 1.01×10–5
4 0.300 0.100 2.28×10–5
 The reaction is 1st order w.r.t [H2], and second order w.r.t [NO]

 Therefore, the rate equation is:


 Rate = k[H2][NO]2

 The value of k is given by (using values for Experiment 2):


k = Rate / [H2][NO]2
k = 5.05x10-6 / (0.200x0.1002) = 2.53x10-3 mol-2 dm6 s-1

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Rate Equations in Practice
 In this activity you will need to determine the rate equation
for the following reaction

 You will use real-life data collected from the lab, which will be
messy and lumpy in way that the data in exams won’t be.

 Follow the instructions here

 You will need to download the spreadsheet ‘Iodination of


Propanone’ from the blog
(http://mrjdfield.edublogs.org/2014/02/14/topic-6-kinetics/)

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Review

Rate = k[A]x[B]y[C]z

 To determine k, divide the rate by the concentration of


reactants.

 To determine the units of k, sub the rate and


concentration units into the above, and cancel units to
express in their lowest terms.

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Lesson 7
HL Only
The Reaction Mechanism

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Recap
 What is the order of reaction with respect to NO2(g)
and F2(g) given the following rate data at a certain
temperature?
[NO2(g)] / mol [F2(g)] / mol Rate / mol dm–3
dm–3 dm–3 min–1
0.1 0.2 0.1
0.2 0.2 0.4
0.1 0.4 0.2

Order with respect to NO2(g) Order with respect to F2(g)


A. first first
B. first second
C. second first
D. second second

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We Are Here

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Lesson 7: The Reaction Mechanism

 Objectives:

 Understand what a reaction mechanism is

 Understand the relationship between rate equations and


reaction mechanisms
 This will explain how things can be ‘zero’ order

 Learn to identify possible reaction mechanisms from suitable


rate data.

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Reaction Mechanisms Explained…with ping
pong balls
 The task:
 As a class seated in a big circle, you need to see how quickly
you can pass 10 ping pong balls around the circle.
 Most of you can use your hands
 One of you must use THE SPATULA OF DOOM

 The rules:
 If the person you are trying to pass to already has a ball, hold
on to it until they have given it away
 Each person can only have one ball at a time

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Reflecting on the silly ping-pong balls thing
 What were the main factors that influenced how fast the balls
could be passed around?

 Was each step in the reaction the same speed?


 This is a polite way of asking if someone found this activity
‘challenging’

 Picture a million ping-pong balls being passed around the circle,


which person would have the biggest impact on how long it
took to pass them all around.

 How much can the people present after the slow one
influence the rate?

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Eating Elephants…
 How do you eat an
elephant?

 One mouthful at a time!

 Chemical reactions are


similar.

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Reaction Mechanisms
Example 1
 Most reactions happen by a series of small steps, and this series is called the
‘reaction mechanism’

 The individual steps can take place at very different rates.

 For example:
NO2(g) + CO(g)  NO(g) + CO2(g)

 The steps in the mechanism are:

 Step 1: 2NO2(g)  NO3(g) + NO(g) (slow)

 Step 2: NO3(g) + CO(g)  NO2(g) + CO2(g) (fast)

 Note:
 NO3 is an intermediate something that is made in one step and used up in another
 The left at right sides of the mechanism cancel out to give you the overall equation.

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A note on molecularity…
 Molecularity describes the number of particles involved
in a single step:

 Unimolecular: one molecule involved:


A  B +C

 Bimolecular: two molecules involved


A+A  C
A+B  C

 Termolecular: three molecules involved (extremely


rare, you will not encounter these at IB level).

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Mechanisms and Rates
Example 1
 Looking at our previous example
 NO2(g) + CO(g)  NO(g) + CO2(g)

 Step 1: 2NO2(g)  NO3(g) + NO(g) (slow)

 Step 2: NO3(g) + CO(g)  NO2(g) + CO2(g) (fast)

 If you think about it….


 Changing the concentration of CO will not affect the rate
 Because it is involved in a fast step after the RDS, and so the only thing
relevant to this step is how quickly the NO3 can be made, and this is
made by a step which is very slow.
 Changing the concentration of NO2 will affect the rate
 Due to it being involved in the slow step
 Since it appears twice in the slow step, changing it’s concentration will
have double the impact

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Mechanisms and Rates
Example 2
 2NO(g) + O2(g)  2NO2(g)

 Step 1: 2NO(g)  N2O2(g) (fast)

 Step 2: N2O2(g) +O2(g)  2NO2(g) (slow)

 In this reaction:
 Changing the concentration of O2 will affect the rate
 Because it is involved in the slow step.
 Changing the concentration of NO will affect the rate
 Because it will affect the rate at which N2O2 is made, and this is needed in the slow
step.

 In summary:
 Rate is affected by everything up to and including the slow step
 Rate is not affect by anything after the slow step
 For this reason, the slow step is called the rate determining step.

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How can we determine the reaction mechanism?
Example 1: NO2(g) + CO(g)  NO(g) + CO2(g)
 First we identify a series of possible reaction mechanisms:
Possibility 1: Possibility 2:

2NO2(g)  NO3(g) + NO(g) NO2  NO + O

NO3(g) + CO(g)  NO(g) + CO2(g) CO + O  CO2

Depending on which is RDS either: Depending on RDS either:


•Rate = k[NO2]2 •Rate = k[NO2]
•Rate = k[NO2]2[CO] •Rate = k[NO2][CO]

RDS most likely to be step 1. RDS most likely to be step 1.

 From experimental data we find that the rate law is Rate = k[NO2]2
 This tells us that the reactions at/before the RDS involve two NO2 or things that can
be made from it.
 The only possibility that fits this is the first, with the first step as the RDS.

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Key Point

 The order of reaction with respect to a reactant tells you


the number of molecules of the reactant involved up to
and including the rate determining step.

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How can we determine the reaction mechanism?
Example 2: 2NO(g) + O2(g)  2NO2(g)
 First we identify a series of possible reaction mechanisms:
Possibility 1: Possibility 2: Possibility 3:

NO + O2  NO2 + O 2NO  N2O2 NO  N + O


NO + O  NO2 N2O2 + O2  2NO2 NO + O  NO2
N + O2  NO2

Step 1 would be slow so: Depending on RDS: Step 1 likely to be


•Rate = k[NO][O2] •Rate = k[NO]2 slowest so:
•Rate = k[NO]2[O2] •Rate = k[NO]

 From experimental data we find that the rate law is Rate = k[NO]2[O2]
 This tells us that the reactions at/before the RDS only at least two NO and one
O2.
 The only possibility that fits this is the second, with the second step as the slow
one

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Time to Practice
 Complete the worksheets here:
 http://wcmiller.borderland.ca/TFSScience/Chemistry%2040S/Do
cuments/Reaction%20Mechanisms%20worksheet.pdf
 http://butane.chem.illinois.edu/cyerkes/104_s_12/worksheets/
Worksheet-Reaction%20Mechanism.pdf

 In a few lessons time you will be doing an IA on either


Energetics or Kinetics, you may wish to start planning
now.

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Review

 Rate equations are determined by the mechanism of a


reaction

 We can use the rate equation to help us choose from


possible candidate mechanisms

 The order of the reaction with respect to each reactant


tells you the number of times they are involved in the
mechanism up to and including the RDS.

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Lesson 8
HL Only
Activation Energy

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Recap
1. Two species, P and Q, react together according to the following equation.
P+Q→R
The accepted mechanism for this reaction is
P + P P2 fast
P2 + Q → R + P slow
What is the order with respect to P and Q?

P Q
A. 1 1
B. 1 2
C. 2 1
D. 2 2

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We Are Here

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Lesson 8: Activation Energy

 Objectives:

 Understand the term activation energy

 Calculate activation energy from experimental data

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Activation Energy
 Activation energy is the minimum energy to colliding
particles need in order to react

 You can think of it as:


 The energy required to begin breaking bonds
 The energy that particles need to overcome the mutual
repulsion of their electron shells.

 Can you think of an analogy?

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The Arrhenius Equation

 We met the rate constant, k, a couple of lessons ago

 The Arrhenius Equation tells us how k is related to a


variety of factors:

Where:
•k is the rate constant
•Ea is the activation energy
•T is the temperature measured in Kelvins
•R is the gas constant, 8.314 J mol-1 K-1.
•e is Euler’s number
•A is the ‘frequency factor’

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Rearranging Arrhenius

 If we take logs of both sides, we can re-express the Arrhenius


equation as follows:

 This may not look like it, but is actually an equation in the form
y = mx + c
Where:
•‘y’ is ln k
•‘m’ is -Ea/R
•‘x’ is 1/T
•‘c’ is ln A
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To determine Ea Experimentally:
(Assuming we know the rate equation)
 Measure the rate of reaction at
various different temperatures.
 Keeping all concentrations the same

 Calculate the rate constant, k, at


each temperature.

 Plot a graph of ln k (y-axis) vs 1/T


(x-axis)

 The gradient of this graph is


equal to ‘-Ea/R’, this can be
rearranged to calculate Ea.

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In practice…
 You will be using the method described previously to
determine the activation energy for:

S2O32-(aq) + 2H+(aq)  SO2(aq) + S(s) + H2O(l)

 Follow the instructions here

 You may wish to use the spreadsheet template here for


your calculations:
http://mrjdfield.edublogs.org/2014/02/14/topic-6-kinetics/

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Recap
 Activation energy can be determined by the gradient of a
graph of ln k vs 1/T

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Lesson 9
HL Only
Independent Practice

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