Notes 16(1)

& 16(2) (HL)

References
Oxford Chemistry Ch 16
Neuss p

16.1 Rate Expression & Reaction Mechanism (HL)

Essential idea: Rate expressions can only be determined empirically and
these limit possible reaction mechanisms. In particular cases, such as a linear
chain of elementary reactions, no equilibria and only one significant activation
barrier, the rate equation is equivalent to the slowest step of the reaction.

Rate Expression
aA

bB

cC

dD

Altering the concentration of A ([A]) or B ([B]) may affect the rate of

this reaction, but the effects may be different.
The mathematical way in which the concentration of A and B affects the
overall rate is given by the rate expression:

Rate

k [A]x [B]y

Where:
k is called the rate constant. Each reaction has its own rate constant
which is quoted at a given temperature, and which increases as the
temperature increases.
x is the order of reaction with respect to A and y is the order of reaction
with respect to B.
orders
zero
first

What this means

Rate remains constant when concentration is doubled
Rate doubles when concentration is doubled (ie rate is
proportional to concentration)
second
Rate quadruples when concentration is doubled (or rate x9
when conc triples etc)
The substances in the rate equation are the reactants/ catalysts in the
stoichiometric equation but the order numbers in the rate equation DO
NOT come from the stoichiometric equation.
The rate equation can only be determined experimentally.
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 The rate equation gives information regarding a possible reaction

mechanism
The order in the rate equation are the number of each reactant in the rate
determining step of a reaction mechanism (for reactions where there is a
linear chain of elementary reactions, no equilibria and only one
significant activation barrier)

Determining the Rate Expression

The effect of changing each concentration cannot be predicted from the
equation and can only be obtained by experiment.
E.g 1

A + 2B AB2

When [A] is doubled and [B] is kept constant, the initial rate of reaction
remains unchanged. What is the order wrt A?

When [B] is doubled and [A] kept constant, the initial rate also doubles.
What is the order wrt B?
Write the rate equation for this reaction using the above information

What is the overall order of this reaction?

E.g. 2

MN

In this reaction, [M] is trebled and [N] is kept the same, and this results in
the initial rate increasing nine times. What is the order wrt M?

When [N] is doubled and [M] kept constant the rate increases by eight
times. What is the order wrt N?

Write the overall rate equation for this reaction

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What is the overall order?

Determining the units for the Rate Constant (k)

The units of the rate constant (k) vary according to the overall order in
the rate expression.

First order reactions

Rate = k [A]
k = Rate / [A]

Rates are measured in mol dm-3 s-1 and concentrations in mol dm-3
k = mol dm-3 s-1 / mol dm-3
Therefore the units of a first order reaction (k)

s-1

Second order reactions Rate = k [A] [B]

k = mol dm-3 s-1 / mol2 dm-6
k = mol-1 dm3 s-1

Third order reactions

Rate = [A]2 [B]

k= mol dm-3 s-1 / mol3 dm-9
k= mol-2 dm6 s-1

Overall order

Units of k

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Experimental Methods to determine the order

Inspection Method
Several experiments are carried out where the concentration of each
substance is varied and the initial rate measured
The order is determined by comparing two experiments which differ only
in the concentration of ONE substance.
e.g.
For the reaction at 298K
A
+
B
+
C
D + E
Determine a) The order wrt each substance
b) The rate expression.
c) The overall order of reaction.
d) The value of the rate constant at 298K and its units.
Experiment
[A]

Concentrations(mol dm-3)
[B]
[C]

Initial Rate
(mol dm-3 s-1)

0.4

1.6

0.06

4.86

0.8

1.6

0.06

9.72

0.4

0.8

0.06

4.86

0.8

1.6

0.18

87.5

Use experiments 1 and 2 to find the order wrt A:

[A] doubles; [B] & [C] remain constant; rate doubles (ie 21), so first order

Use experiments 3 and 1 to find the order wrt B:

[B] doubles; [A] & [C] remain constant; rate remains constant (ie 20),
zero order wrt B

Use experiments 2 and 4 to find the order wrt C:

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so

[C] triples; [A] & [B] remain constant; rate increases nine times (ie 32)so
second order wrt C
b) Rate expression for this reaction:

Rate

k [A]1 [C]2

c) Overall order of reaction = 1 + 2 = 3

d) Value for rate constant:

(using experiment 1)

Rate /

[A]1 [C]2

4.86 /

(0.4) x

3375

Units for k =

mol dm-3 s-1 /

mol-2 dm6 s-1

Rate constant at 298K =

(0.06)2

mol3 dm-9

3375 mol-2 dm6 s-1

e.g.
Using the following results:
Run
Initial conc of
X / mol dm-3
1
0.10
2
0.10
3
0.05
4
0.10

Initial conc of
Y / mol dm-3
0.10
0.10
0.10
0.40

Initial conc of
Z / mol dm-3
0.10
0.30
0.10
0.10

Initial rate
/mol dm-3s-1
2.40 x 10-3
7.20 x 10-3
2.40 x 10-3
3.84 x 10-2

a) Find the order wrt each reactant. Explain how you reached your conclusions

b) Write the rate expression for the reaction

c) Determine the value of the rate constant and its units

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Graphical Methods to determine the order

1) Following a reaction

Follow the reaction by monitoring some changing quantity (eg colour;

volume of gas; mass etc) as the reaction progresses

Repeat the experiment with a different concentration

Draw a tangent to each line at time = 0; measure the gradient of the
tangent to determine the initial rate at each concentration
eg

vol

mass

time

time

NOTE: The rate of reaction at a particular concentration can be determined

from a concentration against time graph by drawing the tangent to the
curve at that point and taking the gradient of the tangent.

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2) Concentration vs time graphs

Plot the concentration of limiting reactant against time as a reaction
progresses
The order can be found from the shape of the graph
Zero order

First order

[A]

Second order

[A]

[A]

Time

time

time

In first order reactions, when the concentration decreases by ,the

gradient and therefore the rate also decreases by
so first order reactions have a constant half life( t1/2)
where

t1/2

0.693 / k

OR

t1/2

second order reactions have an increasing half life

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ln 2 / k

3) Rate vs concentration
Measure the initial rate at various concentrations of reactant
The initial rate can be found directly by measuring the time for a small
change to take place (eg time for 10cm3 gas to form) or from the gradient
of the tangent as in method 1
The order can be determined from the shape of the rate vs.
concentration graph

Zero order

rate

First order

rate

Second order

rate

[A]

[A]

In first order reactions the rate is directly proportional to the

concentration

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[A]

Reaction Mechanisms
NoS: (2.7) Principle of Occams razor states that newer theories need to
remain as simple as possible while maximizing explanatory power. The low
probability of three molecule collisions means stepwise reaction mechanisms
are more likely.
Many reactions are not a simple one step process.
They may occur with many steps.
The overall rate of a reaction is always dictated by the slowest step,
called the rate determining step (RDS)
E.g. For the reaction

2A

A2B

A possible mechanism is:

A

A-A

(step 1 = slow)

A-A +

A2B

(step 2 = fast)

In this case, the reaction rate will be mainly affected by the rate of the
first step, so this will be the rate determining step (RDS)
The rate expression for this reaction is rate = k [A]2[B]0
The rate expression does not tell you what the mechanism is but
indicates the number of particles involved in the slowest step allowing
scientists to suggest a possible mechanism
Steps involving 3 particles colliding simultaneously are unlikely and
should not be suggested in mechanisms
The number of particles taking part in an elementary step is called the
molecularity of the step

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E.g.1

(See SN1 in topic 10 : tertiary haloalkanes)

(CH3)3CBr +

OH-

(CH3)3COH

Rate =

k [(CH3)3CBr ]

Br-

The rate expression tells us all the particles involved in the rate determining
step. In this case it will be a unimolecular rate determining step. This usually
involved a particle breaking up forming a stabilised intermediate
This allows us to formulate a mechanism for the reaction.
Step 1

(CH3)3CBr

(CH3)3C+

Br-

(SLOW)

Unimolecular, slowest and rate determining step forming an intermediate ion.

Step 2

(CH3)3C+

OH-

(CH3)3COH

(FAST)

Bimolecular, but happens quickly and hence is not in the rate expression.

E.g. 2 (see SN2 in topic 10; primary halogenoalkanes)

CH3CH2Br +

OH-

CH3CH2OH

Rate = k [CH3CH2Br] [OH-]

What is the molecularity of the rate determining step?
Suggest a mechanism for the reaction.

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Br-

Rate Expressions from Mechanisms

The order of each substance in the rate expression gives the number of
particles of each substance in the rate determining step
Conversely, the rate determining step gives the order of each substance
in the rate expression.
Fractional orders can exist when there is more than one slow step in a
reaction but these mechanisms will not be considered here.
E.g. 3 Consider this reaction:

2 NO2 + F2

2 NO2F

The following mechanism is proposed.

Step 1

NO2 + F2

NO2F

Step 2

F + NO2

NO2F

SLOW

FAST

Which is the rate determining step and why?

Which step has the highest activation energy?
What is the rate expression?
Another proposed mechanism for this reaction is:
Step 1

NO2 + F2

Step 2

NO2F2 + NO2

NO2F2

2NO2F

FAST
SLOW

Which is the rate determining step this time?

What is the rate expression for the reaction if this mechanism is correct?
Explain how you reach your answer

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Complete Question Sheet : Rate Equations from Mechanisms

Mechanisms from Rate Expression (harder to do!)

When suggesting a mechanism, three criteria must be followed:

1) the rate determining step must fit with the order in the rate expression
2) No more than two reactants should be suggested in any step
3) the steps must add up to give the overall equation for the reaction.
E.g. 4 Consider the reaction:

2ICl(g) + H2(g)

Rate equation is:

2HCl(g) + I2 (g)

rate = k[ICl(g)][H2(g) ]

Suggest a possible mechanism for the reaction.

Solution
From the rate expression, the RDS involves one ICl and one H2 in a collision
(ie it is bimolecular)
ICl(g) + H2(g)

products

(SLOW)

Suggest products the easiest thing to suggest is a combined intermediate.

ICl(g) + H2(g)

IClH2

(SLOW)

As there are 3 reactant molecules in the overall equation, there must be at least
one more step involving another ICl molecule. This could react with the
intermediate
ICl(g] + IClH2

2HCl(g) + I2(g)

Check the steps add to give the overall equation.

Suggest another possible mechanism for this reaction:

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(FAST)

Complete Question Sheet : Mechanisms from Rates Equations

Energy Level Profiles

Each step in a mechanism will have its own activation energy (Ea)
The rate determining step is the one with the largest Ea value
e.g. Energy Profile for a two step mechanism where the RDS is step 1

Energy

Reaction proceeding
A catalyst works by providing an alternative mechanism with lower
activation energy in the rate determining step.
e.g.

Cancer research is all about identifying mechanisms; for carcinogens as

well as cancer killing agents and inhibitors

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ToK: Reaction mechanism can be supported by indirect evidence. What is the

role of empirical evidence (information that is acquired by observation or
experimentation) in scientific theories? Can we ever be certain in science?

16.2 Activation Energy (HL)

Essential idea: The activation energy of a reaction can be determined from the
effect of temperature on reaction rate.
NoS: (2.5) Theories can be supported or falsified and replaced by new theories
changing the temperature of a reaction has a much greater effect on the rate
of reaction than can be explained by its effect on collision rates. This resulted
in the development of the Arrhenius equation which proposes a quantitative
model to explain the effect of temperature change on reaction rate.
The rate and the rate constant (k) for a reaction both increase as the
absolute temperature (T) increases.
This is due to the increase in energy of the reactant particles so that a larger
proportion has the activation energy (Ea) to react.
The relationship between the rate constant, temperature and activation energy
is given by the Arrhenius equation.
The Arrhenius Equation (see Data Booklet p1)

A e -Ea / RT

OR

ln k = ln A - Ea/RT

k is the rate constant

R is the gas constant (8.31 J mol-1 K-1 ; given in data booklet)
A is the Arrhenius constant or frequency factor and takes into account the
frequency of collisions with proper orientations.

The logarithmic form of the equation fits the equation for a straight line

ln k

ln A

- Ea. 1
R T
- 14 -

m x

Plot a graph of ln k on the y-axis against 1/T on the x-axis

This will give a straight line of negative gradient

1/T

/ K-1

ln A

ln k

Measure the gradient and since gradient = - Ea/R from the Arrhenius
equation then
Ea = gradient x (-R)
What are the units of Activation Energy?

The intercept (when graph starts at 0,0) gives the value of ln A.

How can A be obtained from this value?

Finding the Activation Energy by experiment

The initial rate is used instead of the rate constant since the initial rate is
proportional to the rate constant if concentrations of reactants are kept
constant

The reaction is carried out at different temperatures and the initial rate is
measured (by measuring the time taken to produce a small quantity of
product or for a limiting reactant to disappear or by drawing the tangent to a
curve)
Temp
(C)

Temp
(K)

1/T
(K-1)

time, t
(s)

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rate = 1/t
( s-1)

ln rate (no
units)

A graph of ln rate vs 1/T would be plotted.

If only two temperatures are investigated then the equation can be used in
the following form. However, this is not as good as investigating several
temperatures and plotting a graph as any errors in the points are not taken
into account

ln(k1/k2) = EA/R (1/T1 - 1/T2)

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