Reaction Mechanism and

Activation Energy
Kinetics Topic 16
1. 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
2. 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).

●What change in the experiment could

give line 2?
A. The same mass of magnesium in
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
3. Which quantities in the enthalpy level diagram are
altered by the use of a catalyst?
●A. I and II only
●B. I and III only
●C. II and III only
●D. I, II and III
 4. Which statement is true about using sulfuric acid as a catalyst
in the following reaction?

CH3–CO–CH3(aq) + I2(aq) CH3–CO–CH2–I(aq) + HI(aq)

I.The catalyst increases the rate of reaction.

II.The catalyst lowers the activation energy for the reaction.
III.The catalyst has been consumed at the end of the chemical
reaction.

A. I and III only

B. I and II only
C. II and III only
D. I, II and III
 Reaction Order

● Objectives:

● Understand the concept of reaction order

● Identify reaction order from appropriate graphs

 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
 Run # Initial [A] ([A]0) Initial [B] ([B]0) Initial Rate (v0)

For example:
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 0 order with respect to 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

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

▶Squared relationship
▶No effect ▶Direct proportion ▶Gradient positive and
▶Gradient 0 ▶Gradient positive and increasing
constant
 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

● 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 Rate / mol dm–3

[F2(g)] / mol 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
 Rate Equations

● Objectives:

● Build on our understanding of reaction order to construct rate

equations.

● Analyse experimental data in order to determine a rate

equation.
The Rate Expression
 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

 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
1o
2o
3o
 Experiment Initial [A] ([A]0) Initial [B] ([B]0) Initial Rate (v0)

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
 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
 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, substitute the rate and

concentration units into the above, and cancel units to
express in their lowest terms.
 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.
Most reactions involve a series of small steps
● Each step involves a small
number of particles colliding

● The sequence is called the

reaction mechanism

● Each step is an elementary

step
 Molecularity
● Indicates the number of
reactant particles in an
elementary step

● Unimolecular
A→B+C

● Bimolecular
A+B→C+D
 Intermediates
1) NO2 + NO2 →NO + NO3
2) NO3 + CO → NO2 + CO2

What are the intermediates?

What is the overall equation?

http://upload.wikimedia.org/wikipedia/commons/8/8b/NO2-N2O
4.jpg
 Sum of steps
● Must equal overall equation for reaction
● Intermediates on both sides cancel out
Step 1: NO2 + NO2 →NO + NO3

Step 2: NO3 + CO → NO2 + CO2

Overall: NO2 + CO → NO + CO2

● NO3 is a reaction intermediate
Rate determining step
 Rate determining step
● The overall rate of reaction is determined by the slowest step
in the sequence.

● The rate law or rate expression for the overall reaction depends on
the rate law for the rate determining step.

● The order of a reactant comes from its coefficient in the equation for
the rate determining step.
 The Rate Law and Molecularity

The equation for rate determining step:

A → products
Molecularity: Unimolecular
Rate = k[A]

Try 1) 2A → products 2) A + B → products

1) Molecularity: Bimolecular, Rate = k[A]2

2) Molecularity: Bimolecular, Rate = k[A][B]

 Finding the rate law using elementary steps

If rate determining step is first one

●Step 1: NO2Cl →NO2 + Cl slow

●Step 2: NO2Cl + Cl→ NO2 + Cl2 fast
●What is the overall equation?

●Overall: 2 NO2Cl → 2NO2 + Cl2

●Rate =k[NO2Cl ]
●First order reaction
What happens if the slow step is not the first step?
Then the rate may be affected by an intermediate.
Intermediates can not appear in the rate law.

Eg. Step 1: NO + NO →N2O2 fast

Step 2: N2O2 + O2→2NO2 slow

What is the overall equation?

Overall : 2NO + O2→2NO2

The rate for the slow step should be rate = k[N2O2] [O2] but since
intermediates are not included in the rate law:
Rate=k[NO]2[O2]
● The rate law is linked to reactants in the rate determining
step or reactants which affect the RDS.
 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 is slow so: Depending on RDS: Step 1 is the slowest

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

● From experimental data we find that the rate law is Rate = k[NO]2[O2].
● The only possibility that fits this is the second, with the second step as the
slow one.
 To Summarize
● The rate law can be found using the rate determining step.

● Reactants in the rate determining step appear in the rate law

unless they are intermediates. Then the reactants which made that
intermediate are put in the rate law.

● The order of a reactant comes from its coefficient in the equation

for the rate determining step.
 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
 Activation Energy

● Objectives:

● Understand the term activation energy

● Calculate activation energy from experimental data

Svante Arrhenius
● The effect of temperature on the rate constant for a reaction (k) is given
by the Arrhenius equation:

k = Ae-Ea/RT
● k is the rate constant
● Ea is the activation energy, in J/mol
● T is temperature in Kelvins
● e is Euler’s constant, 2.72
● R the gas constant (8.314 J K–1 mol–1)
● A is called the Arrhenius constant (frequency factor – frequency of
collisions and their orientation)
 -Ea/RT
K = Ae
● Take logs
● (If you don’t understand the maths behind it all, don’t worry, just trust the maths
people here and accept it!)

● ln k = ln A - Ea/RT
Rearranging in the form of an equation of a straight line we get

Remember y = mx + b?
y is ln k, –Ea/R is the gradient, m, and 1/T is x, b is ln A, (the intercept on the y-axis)
 (y = mx + b)

● A graph of ln k vs 1/T will be a straight line

● With a slope of –Ea/R (i.e. gradient)

● And the intercept on the y axis will be ln A

● If we know the gradient we can calculate Ea as the slope = –Ea/R
● This is known as an Arrhenius plot

● http://www.mathsisfun.com/equation_of_line.html
 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.

 Calculating Ea and T
● If we know the intercept we know ln A and can find A.
● If the values of the rate constant is known at two different
temperatures then Ea and A can be calculated.

Pearsons page 303 for an example.

http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Modeling_Reaction_Kinetics/Temperature_Dependence_
of_Reaction_Rates/The_Arrhenius_Law/Arrhenius_Equation
 What happens if you increase the temperature
by 10°C from, say, 20°C to 30°C (293 K to 303 K)?
●The frequency factor, A, in the equation is approximately
constant for a specific reaction.

●We need to look at how e-(Ea/ RT) changes - the fraction of

molecules with energies equal to or in excess of the activation
energy.

●Let's assume an activation energy of 50 kJ mol-1. In the

equation, we have to write that as 50000 J mol-1.

http://www.chemguide.co.uk/physical/basicrates/arrhenius.html
● At 20°C (293 K) the value of the fraction is:

● By raising the temperature just a little bit (to 303 K), this
increases:
● A catalyst will provide a route for the reaction with a lower
activation energy. Suppose in the presence of a catalyst
that the activation energy falls to 25 kJ mol-1. Redoing the
calculation at 293 K:

Without a catalyst: