EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015

KINETICS
The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1

 When a graph of concentration of reactant is

plotted vs time, the gradient of the curve is
the rate of reaction.
 The initial rate is the rate at the start of the
reaction where it is fastest
 Reaction rates can be calculated from graphs
of concentration of reactants or products

Experimental Methods for Following Reactions

The rate of a reaction can be determined by following some aspect of the materials which changes as the reaction proceeds.
When the effect of concentration on the rate of reaction is being investigated, it is important to keep other factors, such as the
temperature, constant during the process.
There are several different methods for measuring reactions rates. Some reactions can be measured in several ways

Measurement Of The Change in Volume Of A Gas

This works if there is a change in the number of moles of gas in the reaction. Using a gas syringe is a common way
of following this

Measurement Of Change Of Mass

This works if there is a gas produced which is allowed to escape. Works better with heavy gases such as CO 2
EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015

HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br- (aq) + CO2(g)

Titrating samples of reaction mixture with acid, alkali, sodium thiosulphate etc

Small samples are removed from the reaction mixture, quenched (which stops the reaction) and the titrated with a suitable
reagent.

HCOOCH3(aq) + NaOH(aq)  HCOONa(aq) + CH3OH(aq) The NaOH could be titrated with an acid

BrO3 –(aq) + 5Br –(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l) The H+ could be titrated with an alkali

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq) The I2 could be titrated with sodium
thiosuplate

Colorimetry

If one of the reactants or products is coloured

then colorimetry can be used to measure the H2O2(aq) + 2I- (aq) + 2H+(aq) 2H2O(l) + I2(aq)
change in colour of the reacting mixtures
The I2 produced is a brown solution

Measuring Change In Electrical Conductivity

Can be used if there is a change in the number of ions in the reaction mixture

HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)

Measurement Of Optical Activity.

If there is a change in the optical activity through the reaction this could be followed in a polarimeter

CH3CH2Br(l) + OH−(aq) CH3CH2OH(l) + Br−(aq)

Rate Equations
The rate equation relates mathematically the rate of reaction to the concentration of the reactants.

For the following reaction, aA + bB → products, the r is used as symbol for rate
generalised rate equation is:
The unit of r is usually moldm-3s-1
The square brackets [A] means the concentration of A (unit
mol dm-3)

k is called the rate constant

m, n are called reaction orders

Orders are usually integers 0,1,2 The total order for a reaction is worked out by adding all
the individual orders together (m+n)
0 means the reaction is zero order with respect to that
reactant 1 means first order 2 means second order

NOTE: the orders have nothing to do with the

stoichiometric coefficients in the balanced equation. They
are worked out experimentally
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Calculating orders from initial rate data

For zero order: the concentration of A has no effect
on the rate of reaction: r = k[A]0 = k

For first order: the rate of reaction is directly proportional to the

concentration of A
r = k[A]1

For second order: the rate of reaction is proportional to the

concentration of A squared
r = k[A]2

Graphs of initial rate against concentration show the different orders. The
initial rate may have been calculated from taking gradients from For a rate concentration graph to show
concentration /time graphs i.e the gradients of the following concentration the order of a particular reactant the
verses time graphs would be taken: concentration of that reactant must be
varied whilst the concentrations of the
other reactants should be kept constant.

Continuous rate experiments

Continuous rate data

This is data from one experiment where the concentration of

one substance is followed throughout the experiment.

Consecutive half-lives (t½) must be the same for the

For this method to work the concentrations of the reactants not beingreaction
followedtomust
be a 1best order
in large excess in the experiment so
reaction
their concentrations stay virtually constant and do not affect rate.

This data is processed by plotting the data and calculating successive half-lives

The half-life of a first-order reaction is independent of the concentration and is constant

EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015

This time the half-lives are NOT constant

The rate constant (k)

1. The units of k depend on the overall order of

reaction. It must be worked out from the rate For a 1st order overall reaction the unit of k is s -1
equation
2. The value of k is independent of For a 2nd order overall reaction the unit of k is mol-1dm3s -1
concentration and time. It is constant at a
fixed temperature. For a 3rd order overall reaction the unit of k is mol-2dm6s -1
3. The value of k refers to a specific temperature
and it increases if we increase temperature

Example (first order overall)

Rate = k[A][B]0 m = 1 and n = 0

Remember: the values of the reaction orders must be
 reaction is first order in A and determined from experiment; they cannot be found by
looking at the balanced reaction equation
zero order in B
 overall order = 1 + 0 = 1
 usually written: Rate = k[A]

Calculating units of k

1. Rearrange rate 2. Insert units and

equation to give k as cancel
subject
k = mol dm-3s -1
k = Rate [A] mol dm-3
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Example: Write rate equation for reaction between A and B where A is 1st order and B is 2nd order.

r = k[A][B]2 overall order is 3

Calculate the unit of k

2. Insert units and cancel 3. Simplify fraction

1. Rearrange rate
equation to give k as k = s-1
k = mol dm-3s -1
subject mol2dm-6
mol dm-3.(moldm-3)2
k = Rate [A][B]2
Unit of k = mol-2dm6s -1

Working Out Orders From Experimental Initial Rate Data

The initial rate is the rate at the start of the reaction, where it is
fastest. It is often obtained by taking the gradient of the conc vs time
graph.

Normally to work out the rate equation we do a series of experiments

where the initial concentrations of reactants are changed (one at a
time) and measure the initial rate each time. This data is normally
presented in a table.

Example: work out the rate equation for the following reaction, A+ B+ 2C D + 2E, using the
initial rate data in the table
In order to calculate the order for a particular
reactant it is easiest to compare two experiments
where only that reactant is being changed

If conc is doubled and rate stays the

same: order= 0

If conc is doubled and rate doubles:

order= 1

If conc is doubled and rate quadruples :

order= 2
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For reactant A compare between experiments 1 and 2

For reactant A as the concentration doubles (B and C staying constant) so does the
rate. Therefore the order with respect to reactant A is first order

For reactant B compare between experiments 1 and 3 : As the concentration of B

doubles (A and C staying constant) the rate quadruples. Therefore the order with
respect to B is 2nd order

For reactant C compare between experiments 1 and 4 :

As the concentration of C doubles (A and B staying constant) the rate stays the
same

Therefore the order with respect to C is zero order

The overall rate equation is r = k [A] [B]2 The reaction is 3rd order overall and the
unit of the rate constant =mol-2dm6s -1

Working Out Orders When Two Reactant Concentrations Are Changed

Simultaneously
In most questions it is possible to compare between two experiments where only one reactant has its initial concentration
changed. If, however, both reactants are changed then the effect of both individual changes on concentration are multiplied
together to give the effect on rate.

In a reaction where the rate equation is r = k [A] [B] 2

If the [A] is x2 that rate would x2

If the [B] is x3 that rate would x32= x9

If these changes happened at the same time then the rate would x2x9= x 18

Example work out the rate equation for the reaction, between X and Y, using the initial rate data in the table

For reactant X compare between experiments 1 and 2

For reactant X as the concentration doubles (Y staying constant) so does the rate.

Therefore the order with respect to reactant X is first order

EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015

Comparing between experiments 2 and 3 :

Both X and Y double and the rate goes up by 8

We know X is first order so that will have

doubled rate The overall rate equation is r = k [X][Y]2

The effect of Y, therefore, on rate is to have The reaction is 3rd order overall and the unit of the
quadrupled it.
rate constant =mol-2dm6s -1
Y must be second order

Calculating A Value For k Using Initial Rate Data

Using the above example, choose any one of the experiments and put the values into the rate equation that has been rearranged
to give k. Using experiment 3:

Remember k is the same for all experiments done at the same temperature.

Increasing the temperature increases the value of the rate constant k

Effect of Temperature On Rate Constant

Increasing the temperature increases the

value of the rate constant k

Increasing temperature increases the rate constant k. The

relationship is given by the Arrhenius equation k =
Ae-Ea/RT where A is a constant R is gas constant and Ea is
activation energy.
The Arrhenius equation can be rearranged

ln k = constant – Ea/(RT)

k is proportional to the rate of reaction so ln k can be replaced

by ln(rate)

From plotting a graph of ln(rate) or ln k against 1/T the

activation energy can be calculated from measuring the
gradient of the line
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Rate Equations And Mechanisms

A mechanism is a series of steps through which the Each step can have a different rate of reaction. The
reaction progresses, often forming intermediate slowest step will control the overall rate of reaction.
compounds. If all the steps are added together they will The slowest step is called the rate-determining
add up to the overall equation for the reaction step.

The molecularity (number of moles of each substance) of the molecules in the slowest step will be the same as the
order of reaction for each substance. e.g. 0 moles of A in slow step would mean A is zero order. 1 mole of A in the
slow step would mean A is first order

Example 1 Example 2

overall reaction A + 2B + C  D + E overall reaction

Mechanism A + 2B + C  D + E

Step 1 A + B  X + D slow Mechanism

Step 2 X + C  Y fast Step 1 A + B  X + D fast

Step 3 Y + B  E fast Step 2 X + C  Y slow

r = k [A]1 [B]1 [C]o Step 3 Y + B  E fast

C is zero order as it appears in the r = k [X]1 [C]1

mechanism in a fast step after the slow The intermediate X is not one of the reactants so
step must be replaced with the substances that make up
the intermediate in a previous step

A+BX+D

r = k[A]1 [B]1 [C]1

Investigating The Rate of Reaction Between Iodine And Propanone

Propanone reacts with iodine in acidic solution (the acid is a catalyst) as shown in the equation below.

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)

This reaction can be followed by removing small samples from the reaction mixture with a volumetric pipette.
The sample is then quenched by adding excess sodium hydrogencarbonate to neutralize acid catalyst which
stops the reaction. Then the sample can be titrated with sodium thiosulphate using a starch catalyst

2S2O32-(aq) + I2 (aq)  2I- (aq) + S4O62-(aq)

yellow/brown sol colourless sol
This reaction is zero order with respect to I2 but
1st order with respect to the propanone and acid
catalyst

The rate equation for the reaction is

Rate = k[CH3COCH3(aq)][H+(aq)]

If there is a zero order reactant there must be

at least two steps in the mechanism because the
rate determining step will not involve the zero
order reactant
EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015

The rate determining step of this reaction must therefore contain one propanone
molecule and one H+ ion forming an intermediate. The iodine will be involved in a
subsequent faster step.

Example 3: SN1 or SN2?

Remember the nucleophilic substitution reaction of halogenoalkanes and hydroxide ions. This is a one step
mechanism

CH3CH2Br + OH- CH3CH2OH + Br- slow step

The rate equation is This is called SN2.

Primary halogenalkanes tend to
Substitution,
r = k [CH3CH2Br] [OH-] react via the SN2 mechanism
Nucleophilic, 2 molecules
in rate determining step
SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes
Tertiary halogenoalkanes
undergo this mechanism as the
tertiary carbocation is made
stabilised by the electron
releasing methyl groups around
The Br first The hydroxide it. (see alkenes topic for
breaks away from nucleophile then another example of this). Also
the haloalkane to attacks the positive the bulky methyl groups prevent
form a carbocation carbon
intermediate the hydroxide ion from
attacking the halogenoalkane in
the same way as the mechanism
above
Overall Reaction
(CH3)3CBr + OH–  (CH3)3COH + Br– This is called SN1.
The rate equation is
Substitution, Nucleophilic, 1
Mechanism:
r = k [(CH3)3CBr] molecule in rate determining
(CH3)3CBr  (CH3)3C+ + Br slow
– step

(CH3 )3C+ + OH– (CH3)3COH fast

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Primary halogenoalkanes don’t do the SN1 mechanism

because they would only form an unstable primary
carbocation.

Example 4 Example 5

Overall Reaction Using the rate equation rate = k[NO]2 [H2] and the
overall equation 2NO(g) + 2H2 (g)  N2 (g) + 2H2O(g), the
NO2 (g) + CO(g) → NO(g) + CO2 (g) following three-step mechanism for the reaction was
Mechanism: suggested. X and Y are intermediate species

Step 1 NO2 + NO2→ NO + NO3 slow Step 1 NO + NO  X

Step 2 NO3 + CO → NO2 + CO2 fast Step 2 X + H2 Y

• NO3 is a reaction intermediate Step 3 Y + H2  N2 + 2H2O

NO2 appears twice in the slow steps so it is Which one of the three steps is the rate-determining
second order. CO does not appear in the slow step?
step so is zero order. Step 2 – as H2 appears in rate equation and combination
r = k [NO2] 2 of step 1 and 2 is the ratio that appears in the rate
equation

SUMMARY NOTES
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EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015
EDEXCEL KINETICS NOTES UNIT 4 MISS CHOHAN 12/21/2015
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