Chapter 12

Chemical Kinetics
Section 12.1

1. Know the definition of reaction rate and unit of reaction rate

How is the reaction rate of a chemical reaction defined? What are the units of the rate?
Reaction rate is the change in concentration of reactant or product per unit time.

Rate =

Units of reaction rate will be mol dm-3 time-1 OR M time-1 

2. Plot a curve of change of [reactants] and [products] versus time

Consider the following reaction: CO + ½ O2  CO2
Plot a curve of the concentration versus time for both the reactants and products of the above
reaction.

[CO2]

[]
(mol/dm3)

[O2]

[CO]

Time (sec)

According to the stochiometry of the reaction the:

Rate of decrease in [CO] = 2 × Rate of decrease in [O2] = Rate of increase in [CO2]

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 3. Know how to find the instantaneous reaction rate from a plot of [reactants]
or [products] versus time
How can you find the instantaneous rate from a plot of [reactants] versus time?
By computing the slope of a line tangent to the curve at that point.

Section 12.2

4. Determine the order of a reaction given the rate law

What is the overall order of the reaction shown by the rate law given below?
Rate = k [NO]2 [Br2]
Overall order is the sum of the exponents to which the concentration terms are raised.
Overall order = 2 + 1 = 3

Section 12.3

5. Know that the order and the rate law of a reaction are only determined
experimentally
Dibromoethane reacts with potassium iodide dissolved in methanol according to the equation:
C2H4Br2 + 2KI  C2H4 + 2KBr + I2
From the information given, we can deduce that the rate is:
[-A-] R = k[KI]2[C2H4Br2]
[-B-] R = k[KI]2
[-C-] R = k[C2H4Br2]
[-D-] not possible to deduce from this information
[-E-] R = k[KI][C2H4Br2]

6. Predict the change in the value of the reaction rate given the rate law and
the changes done to the [reactants]
For the reaction between sodium bromate and sodium bromide in acidic solution, the rate
equation is:
Rate = k[BrO3-][Br-][H+]2
When the concentrations of all three reactants are doubled, the rate will increase by a factor of:
[-A-] 4
[-B-] 6
[-C-] 8
[-D-] 16
[-E-] 32

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 7. Calculate and specify unit of k given the rate law, initial rate and [reactant]
The rate law for the reaction: 2I  I2 has been found to be r = k [I]2.
When the [I] was 2.0 x 10–4 M, the initial rate was 8.0 x 10-2 mol/L.s. Calculate the value of the
constant k, and specify its units.
.
k =   =  = 2.0 × 106 M-1 s-1 OR 2.0 × 106 dm3 mol-1 s-1
.

8. Calculate rate given the rate law, k and [reactant]

The rate law for the reaction: B2  2B has been found to be r = k [B2]. Given that the above
reaction has a constant of k = 3.0 x 10-2 min-1, find the initial rate when [B2] is 0.050 M.
Rate = k [B2] = (3.0 x 10-2 )(0.050) = 1.5 × 10-3 M min-1

Section 12.4

9. Write rate law for first order reaction and know unit of k
Write the rate law for a first order reaction. What are the units of k in such an expression?
Rate = k [A]
ln[A] = -kt + ln[A]
unit of k is time-1

10. For a first order reaction: know shape of [ ] versus time and ln [ ] versus time
The hydrolysis of sucrose is first order.
How will the graph of [sucrose] versus time look like?
How will the graph of ln [sucrose] versus time look like?
The graph of [sucrose] versus time is a curve
The graph of ln [sucrose] versus time is a straight line with a negative slope

11. Know the definition of the half–life of a reactant

Define the half–life of a reactant.
Half life is the time required for a reactant to reach half its original concentration.

12. Application on  = 

The decomposition of a chemical B is first order with a rate constant of 2.0 x 10-3 s–1.
Determine the half–life for B2.

 =   =  = 3.5 × 102 sec
.

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 13. Write rate law for second order reaction and know unit of k
Write the rate law for a second order reaction. What are the units of k in such an expression?
Rate = k [A]2
= kt +
°
units of k is M-1 time-1 OR dm3 mol-1 time-1

14. For a second order reaction: know shape of [ ] versus time and [ ] versus time
The decomposition of ozone is second order.
How will the graph of [O3] versus time look like?
How will the graph of   versus time look like?
The graph of [O3] versus time is a curve
The graph of   versus time is a straight line with a positive slope

15. Write rate law for zero order reaction and know unit of k
Write the rate law for a zero order reaction.
What are the units of k in such an expression?
Rate = k [A]o = k
[A] = -kt + [A]o
units of k is M time-1 OR mol dm-3 time-1

16. For a zero order reaction: know shape of [ ] versus time

The decomposition of N2O is zero order.
How will the graph of [N2O] versus time look like?
The graph of [N2O] versus time is a straight line with a negative slope.

Section 12.5

17. Know what is the rate determining step

What is the rate determining step of a reaction mechanism?
The rate determining step of a reaction mechanism is the slowest step in the mechanism, it
is the one that determines the overall rate.

18. Know what is an elementary step

What is an elementary step in a reaction mechanism?
An elementary step is a reaction whose rate law can be written from its molecularity.
(Molecularity is defined as the number of species that must collide to produce the reaction
indicated by that step.)

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 19. Know that for elementary steps, the rate law can be deduced for the stoichiometry
Write the rate law for each of the following elementary steps in the given mechanism:
NO2 + NO2  NO3 + NO
NO3 + CO  NO2 + CO2
For NO2 + NO2  NO3 + NO rate = k[NO2]2
For NO3 + CO  NO2 + CO2 rate = k[NO3][CO]

Section 12.6
20. Know how to draw and label the energy profile for an endothermic reaction
Draw a labelled sketch of the energy profile for an endothermic reaction.
        Activated complex

Potential
Energy
Products
Ea

∆
reactants

Reaction Coordinates OR Reaction Progress

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 21. Know how to draw and label the energy profile for an exothermic reaction
Draw a labeled sketch of the energy profile for an exothermic reaction.
Activated complex

Potential
Energy

Ea
reactants

Hreaction
Products

Hreactants Hproducts

Reaction Coordinates OR Reaction Progress

22. Know how to draw the Boltzman distribution curve at two different temperatures on
same graph
Sketch the Boltzman distribution curve at a temperature T1.
Sketch, on the same graph, the Boltzman distribution curve at a temperature T2 > T1.

Number T1
Of
collisions

T2

Energy

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 23. Be able to explain the effect of an increase in temperature on reaction rate using the
Boltzman distribution curve
An increase in temperature increases rates of reactions. Explain this observation using the
Boltzman distribution curve.

Number T1
Of
collisions

T2

Ea

Energy

Area under the graph represents the number of effective collisions.

At a higher temperature, the area increases, an increase in the number of effective
collisions, increases the reaction rate.

24. Know that for a collision to produce a reaction, it must occur at minimum amount of
energy AND proper orientation
What are the two factors that determine whether a collision is successful or not?
Minimum amount of energy AND proper orientation

25. Application on ln = ln  = ‐ 

For a particular reaction the values of its rate constant k at 200K and 400K were 1 x 10-6 and 1 x
10–4 s–1. Use the equation ln  = ‐    to calculate the activation energy of the
reaction. R = 8.31 J/K
.
ln  = ‐     ln  = ‐   
. .

Ea = 1.53 × 104 J = 15.3 kJ/mol

Section 12.7
26. Know the definition of a catalyst
Define a catalyst.
A substance that speeds up a reaction without being consumed.

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 27. Know the difference between homogenous and heterogeneous catalysts
What is the difference between homogenous and heterogeneous catalysts?
A homogeneous catalyst is one that is present in the same phase as the reacting molecules.
A heterogeneous catalyst is one that is present in a different phase than the reacting
molecules.

28. Be able to explain the effect of a catalyst on reaction rate using the Boltzman
distribution curve
The addition of a catalyst increases the rate of a reaction. Explain this observation using the
Boltzman distribution curve.

Number T1
Of
collisions

Ea’ Ea

Energy
Ea = activation energy of the reaction without using a catalyst
Ea’ = activation energy of the reaction using a catalyst
Area under the graph represents the number of effective collisions.
Using a catalyst, a route with a lower activation energy becomes available to the reactants.
The area under the curve increases which means that the number of effective collisions
increases thus, the reaction rate incraeses.

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BASIC QUESTIONS

Basic Question 1
12.1 Find the rate of the reaction in terms each chemical given initial and final
number of moles and time
Consider the following reaction: N2 + 3H2  2NH3
The rate of the reaction was studied by introducing 6 moles of H2 and 4 moles of N2. After
30mins, the following number of moles was found to exist: 5.1 moles of H2, 3.7 moles of N2 an
0.6 moles of NH3.
Calculate the rate of the reaction in terms of the variation of concentration of each chemical with
time.
N2 + 3H2  2NH3
Initially 4mol 6mol
After 30 min
3.7mol 5.1mol 0.6mol

4  3.7
Rate with respect to N2 =  0.010 mole / min
30
6  5.1
Rate with respect to H2 =  0.030 mole / min
30
0.6
Rate with respect to NH3 =  0.020 mole / min
30

Basic Question 2
12.3 Find the rate law of a give reaction using the initial rate method T, G

For the reaction: 2X +Y Z, the following results were obtained:

__________________________________________________________________
Experiment [Xo] [Yo] Initial Rate
__________________________________________________________________
1 0.3 0.8 2.4
2 0.3 1.6 9.6
3 0.1 1.6 3.2
__________________________________________________________________
a) What is the rate law for this reaction?
Consider experiments 1+2: [X]=same
As [Y] doubles, rate quadruples  rate  [Y] 2

Consider experiments 2+3: [Y]=same

As [X] decreases by 3 times, rate decreases by 3 times  rate  [X]

Rate = k[Y] 2 [X]

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 12.3 Find the rate law constant of a give reaction using the initial rate method T, G

b) Calculate the rate constant of the reaction.

Given: Rate = k[Y] 2 [X]
RTF: k
Rate = k[Y] 2 [X] choose any experiment, let us say experiment 1
2.4 = k (0.8)2(0.3)
k = 12.5

Basic question 3
The rate of the reaction: 2X X2, was studied. The following results on the
concentration of X were obtained:

[X] 1 0.8 0.6 0.4 0.2

Time (s) 0 10 23 41 72
Ln[X] 0 -0.223 -0.51 -0.916 -1.609

a) Show that the reaction is first order with respect to X.

Plot ln[X] vs time
time vs ln[X]
0
0 10 20 30 40 50 60 70 80
‐0.2

‐0.4

‐0.6

‐0.8

‐1

‐1.2

‐1.4

‐1.6

‐1.8

Straight line with a negative slope

 the reaction is a first order reaction
ln[X] = -kt + ln[X]o
b) What are the value and units of the specific rate constant?
slope = -k
 k = 0.223 / 10 = 0.0223 s-1

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Basic Question 4
12.3 Find the rate law of a give reaction using the initial rate method T, G

For the reaction: 2X + Y  2Z, the initial rate was studied and the following results were
obtained:
__________________________________________________________________
Experiment [Xo] [Yo] Initial Rate
1 0.2 0.2 2.4
2 0.2 0.3 2.4
3 0.4 0.1 9.6
__________________________________________________________________
What is the rate law for this reaction?

Consider experiments 1 and 2: [X] = same

As [Y] changes the rate remains the same  [Y] does not affect the rate

Rate = k[X]n
Consider experiments 1 and 3:
Rate3 = k
Rate1 = k
Divide the two equations:
. .
4 = 2n 22 = 2 n  n=2 Rate = k[X]2
. .

Basic Question 5
The decomposition of a certain chemical, X2O, is first order with a constant of 1.4 x 10-2s–1.

12.4 Find half life of a first order reaction given rate constant T, G

a) Determine the half–life for the decomposition of X2O.

Given: k=1.4  10-2 s-1 , first order reaction
RTF: half-life
ln2 0.693
t1 = = = 49.5sec
2
k 1.4×10-2

12.4 Application on lnPf = -Kt + lnP to find time T, G

b) The initial pressure of a sample of X2O was 6atm. How long will it take the sample to
decompose and reach a pressure of 0.75atm?
Given: Pinitial = 6atm, Pfinal = 0.75atm
RTF: time

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 1
m = m 0 ( )n
2
0.75 1 n 1
= ( ) = 0.125 = ( )3  n = 3
6 2 2
t = 3(49.5) = 148.5sec
OR
lnPf = -kt + lnP
ln0.75 = (-1.4  10-2)t + ln 6 t = 148.5 sec

Basic Question 6
12.4 Calculate the time needed for a sample to change mass from given mi to mf using T
value of half life
The half–life of a radioactive chemical is 10 hours. A sample of the chemical with a mass of 10g
was left in the lab. How long will it take the sample to decay to a mass of 1.25g?
Given: minitial = 10g, mfinal = 1.25g, t1/2 = 10hrs
RTP: time needed for m change

m = m( 1.25 = 10 n=3

required time = 3 × 10 = 30 hours
OR
/ / /
10 5 2.5 1.25 3 half-lives
Required time = 3 × 10 = 30 hours

Basic Question 7
The radioactivity of a radioactive material was measured at different time intervals and
found to be as in the table below.
Time (h) 0 3 6 9 12
Activity (cpm) 8000 6681 5580 4661 3892
ln activity 8.99 8.80 8.63 8.45 8.27
a) Plot a graph of ln activity versus time and find the value of k.

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ln[activity] = -kt + ln[activity]o
at t= 3 ; 8.80 = (-k)(3) + 8.99
k = 0.063 hr-1
OR
k = -slope
b) Use the value of k to find the half–life of the decay process.
ln2 ln2
for first order: t 1 = 
2
k 0.063
t1/2 = 11 hours.

Basic question 8
The rate of the reaction: 2X X2, was studied. The following results on the
concentration of X were obtained:
Time (s) 0 10 20 30 40
[X] 80 48.8 35.2 27.2 22.4
1 0.0125 0.02 0.028 0.036 0.044
[X ]

Show that the reaction is second order with respect to X.

1
Plot a graph  vs time 
[X ]
it shows a straight line with a positive slope = k
1 1
 = kt +
[X ] [ X ]0

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Basic question 9
For the reaction: 2P + Q R, the initial rate was studied and the following results
were obtained:

Experiment [Po] [Qo] Initial Rate

1 1 1 3
2 1 2 3
3 2 1 12
Show that the reaction is zero–order with respect to Q.
Consider experiment 1 and 2: [P]o does not change and as [Q]o is doubled the rate remains
unchanged, thus the reaction is zero order with respect to Q.

Basic Question 10
12.6 Predict if a mechanism of a given reaction is plausible given the rate law T

The rate law for the reaction: 2H2 + 2NO  N2 + 2H2O is r = k [ H2 ] x [ NO ]2.
The following mechanism has been proposed:
H2 + 2NO  N2O + H2O ( slow )

H2 + N2O  N2 + H2O ( fast )

Is this an acceptable mechanism?

Yes.
1. The sum of the elementary steps of the mechanism equal the overall reaction.
2. The rate law of the slowest reaction, the rate determining step, matches the rate
law.

Basic Question 11 T

The following mechanism has been proposed for the reaction of methane gas with
bromine gas. All species are in the gas phase.
Step 1 Br2 ⇄ 2Br fast equilibrium
Step 2 CH4 + Br → CH3 + HBr slow
Step 3 CH3 + Br2 → CH3Br + Br fast
Step 4 CH3Br+ Br → CH2Br2 + H fast
Step 5 H + Br → HBr fast

12.7 Predict whether a chemical is a catalyst or intermediate from reaction mechanism

a) In the mechanism, is CH3Br a catalyst, or is it an intermediate? Justify your answer.

CH3Br is an intermediate because it is produced in step 3 and consumed in step 4 of
the reaction mechanism.

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 12.7 Identify the order of the reaction with respect to named chemicals according to given
mechanism
b) Identify the order of the reaction with respect to each of the following according to the
mechanism. In each case, justify your answer.
i. CH4 (g)
All steps in a reaction mechanism are elementary steps. The rate laws of
elementary steps can be predicted from the reaction stoichiometry. The rate
law of the rate determining step is the rate law of the overall reaction.
Rate = k[CH4][Br]
But the first step is a quick equilibrium relating the [ ] as follows:
∙
Keq = [Br] = (Keq[Br2])1/2 
1/2
Rate = k(Keq[Br2]) [CH4]
The order of the reaction with respect to CH4 is 1.

ii. Br2(g)
The order of the reaction with respect to Br2 is 1/2

Basic question 12
Consider the following reaction:
H2(g) + Br2(g) → 2HBr(g)

The table below gives data for a reaction rate study of the reaction above.
Initial [H2] Initial [Br2] Initial Rate of formation of HBr
Experiment
(mol.L−1) (mol.L−1) (mol.L−1.s−1)
1 0.00100 0.000500 3.64 × 10−12
2 0.00200 0.000500 7.28 × 10−12
3 0.00200 0.000250 3.64 × 10−12
a) Determine the order of the reaction with respect to H2 and justify your answer.
Consider experiments 1 and 2:
Initial [Br2] is unchanged,
and as initial [H2] is doubled the rate is doubled
 the reaction is first order with respect to [H2]
b) Determine the order of the reaction with respect to Br2 and justify your answer.
Consider experiments 2 and 3:
Initial [H2] is unchanged,
and as initial [Br2] is halved the rate is halved
 the reaction is first order with respect to [Br2]
c) Write the overall rate law for the reaction.
R = k[H2][Br2]
d) Write the units of the rate constant.
Ms-1 = k (M)(M)
 k unit is M-1s-1 OR Lmol-1s-1
e) Predict the initial rate of the reaction if the initial concentration of H2 is 0.00300 mol.L−1 and
the initial concentration of Br2 is 0.000500 mol.L−1.

15
initial [Br2] is not changed with respect to experiment 1, but Initial [H2] is increased by
three times, and since the rate is 1st order with respect to [H2] so it will increase by three
times as well
Rate = 3(Rate of experiment 1) = 3 × 3.64 × 10-12 = 1.092 × 10-11 mol.L−1.s−1

Basic Question 13 T

The gas-phase decomposition of nitrous oxide has the following two-step mechanism.

Step 1: N2O → N2 + O
Step 2: O + N2O → N2 + O2

12.8 Write the overall reaction given the reaction mechanism

(a) Write the balanced equation for the overall reaction.

2N2O → 2N2 + O2

12.8 Predict whether a chemical is a catalyst or intermediate from reaction mechanism

(b) Is the oxygen atom, O, a catalyst for the reaction or is it an intermediate? Explain.
The O atom is an intermediate because it is formed and then consumed during the
course of the reaction.(Had it been a catalyst, it would have been present both at the
beginning and the end of the reaction.)

12.8 Determine the rate determining step given reaction mechanism and reaction rate law

(c) Identify the slower step in the mechanism if the rate law for the reaction was determined
to be rate = k [N2O]. Justify your answer.
Step 1 is slower because N2O appears in Step 1 as the single reactant, which is
consistent with the given rate law.

Basic Question 14 T

Fill in the blanks:

When the following reaction takes place in an isothermal sealed container:

H2+ I2 → 2HI rate= k [H2] [ I2]

The rate of the reaction ….increases…while the rate constant is …unchanged…when some
hydrogen gas is added to the container.

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Multiple Choice
12.2 Know that the reaction order depends on the reaction mechanism

1. Which of the following is true about the order of the reaction.

[-A-] must be a positive integer

[-B-] A second order reaction involves two reactants
[-C-] can be predicted from the net ionic equation.
[-D-] Catalyst changes the order
[-E-] Depends on the mechanism.

12.4 Calculate starting m needed for given m to reach destination given sample half life

2. The half – life of 55Cr is 2.0 hours. The delivery of a sample of this isotope from the reactor
to a certain laboratory requires 14 hours. About what mass of such material should be
shipped in order that 1.0 mg of 55Cr is delivered to the laboratory?

[-A-] 128 mg
[-B-] 64 mg
[-C-] 32 mg
[-D-] 11 mg
[-E-] 1.0 mg

Either: n = number of half-lives = = 7.0 hrs

.
.
m = m i( ) n  m i = = = 128mg
.

OR 1.0 2.0 4.0 8 16 32 64 128 mg

12.4 Find time needed for given % of sample to decay from its half life

3. Sr-90 has t1/2 = 29 years. How long does it take 80% of a sample of Sr to decay?

[-A-] 9.3 years

[-B-] 21 years
[-C-] 38 years
[-D-] 67 years
[-E-] 96 years

80% decay means that if we started with 100 we end with 20, this means we have 2 full
half lives plus a little more (100  50  25). Two half lives is 29 × 2 = 58 years. The
actual answer must be a little more  best choice is D.

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 12.7 Know the function of the spark plug in an automobile engine

4. Which of the following best describes the role of the spark plug in an automobile engine?

[-A-] The spark decreases the energy of activation for the slow step
[-B-] The spark increases the concentration of the volatile reactant
[-C-] The spark supplies some of the energy of activation for the combustion reaction
[-D-] The spark provides a more favourable activated complex for the combustion
reaction
[-E-] The spark provides the heat of vaporization for the volatile hydrocarbon.

12.5 Identify the intermediate species in a given reaction mechanism

5. Consider the following reaction mechanism:

X +YZ
Y+ZP+E

Which of the following is an intermediate in the above mechanism?

[-A-] X
[-B-] Y
[-C-] Z
[-D-] P
[-E-] E

12.6 Know that addition of a catalyst does not affect the enthalpy change of a reaction.

6. The energy diagram for the reaction X + Y → Z is shown below. The addition of a catalyst to
this reaction would cause a change in which of the indicated energy differences?

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[-A-] I only
[-B-] II only
[-C-] III only
[-D-] I and II only
[-E-] I, II and III.

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