Explaining and Applying

6.5 Chemical Kinetics

When pyrotechnists design fireworks they mix the chosen chemicals together very care-
fully, and assemble the various parts so that explosive chemical reactions will happen in
the right sequence and at the expected rates. How can we explain the rates at which
reactions happen? In Sections 6.2 and 6.4, you learned how factors such as temperature
and initial concentration affect rate of reaction. Can we apply collision theory to explain
the effects of these factors?
As you know, the rate at which a reaction occurs depends on two criteria:
• the frequency of collisions, and
(a)
• the fraction of those collisions that are effective.
In this section we will explore how the frequency of collisions and the fraction of effec-
tive collisions depend on factors such as temperature and chemical nature of reactant.

Theoretical Effect of Chemical Nature of Reactant

When nickel metal is added to hydrochloric acid, the reaction is slow. However, magnesium
reacts quickly in the same acid (Figure 1). To explain these empirical observations, we
need to consider factors such as the atomic structure of the reactants and the nature of
their bonds, as well as the type of reaction occurring.
Think about the molecules in the air about you. There are billions and billions of
(b) them moving rapidly and colliding in every cubic centimetre. However, the molecules
are not all moving at the same speed: Some are moving quickly and some slowly, but most
Figure 1 are in some mid-range of kinetic energy. This distribution of kinetic energies is called
The different rates of reaction of
a Maxwell-Boltzmann distribution, and has been experimentally found to fit the pattern
(a) magnesium and (b) nickel with
hydrochloric acid in Figure 2. Note the axes: the vertical axis represents the number of molecules with a
particular kinetic energy, and the horizontal axis represents the different energies. An
analogy might be a distribution of heights of students on a Grade 8 field trip to an
amusement park (Figure 3): Most students are in the mid-range, with fewer students at
high and low heights.
In a chemical reaction, an effective collision requires a minimum energy—energy of
collision—which is converted into potential energy (the activation energy) as the acti-
vated complex is formed. This minimum energy is called the threshold energy.

threshold energy the minimum

kinetic energy required to convert Maxwell-Boltzmann Distribution
kinetic energy to activation energy
during the formation of the activated
Number of Molecules

lower
complex threshold higher
energy threshold
energy

Figure 2
At a given temperature, the molecules with enough
energy to create a successful collision are represented by Ea
1
the area enclosed under the graph line and to the right of
the (dashed) minimum energy level. Note the very large Ea
increase in the number of these molecules when the 2

threshold energy is decreased. Kinetic Energy

392 Chapter 6 NEL

 Section 6.5

The chemical nature of reactants affects the threshold energy (and the fraction of col-
lisions that are effective) in two possible ways.
(1) Some molecules have bonds that are relatively weak and small activation energy
barriers, so the threshold energy is relatively low and a large fraction of molecules is
capable of colliding effectively. In the student field trip analogy, this is equivalent to the
students choosing a different ride with a lower “threshold height” so that a larger frac-
tion of students can go on the ride. Other molecules have strong bonds and high acti-
vation energy barriers, so most collisions are ineffective.
(2) A second factor is what is sometimes called collision geometry — some reactions
involve complicated molecular substances or complex ions that are often less reactive
because more bonds have to be broken and the molecules have to collide in the correct
orientation relative to each other for a reaction to occur.
In conclusion, reactions that occur quickly, such as the reaction between magnesium
and acid, have lower activation energies than those that are slow to occur, such as nickel
reacting in acid.

Theoretical Effect of Concentration and Surface Area DID YOU KNOW ?

When zinc is added to concentrated sulfuric acid, the reaction occurs much more quickly Targeted Attack on Cancer
than in dilute acid. Similarly, a flammable liquid burns much more quickly when the Catalysts have been applied in
cancer research. Many cancer
surface area of the fuel that is exposed to air is increased. Concentration and surface
drugs act indiscriminately: They
area both affect the collision frequency. eliminate cancer cells, but kill
many healthy cells too. It is pos-
Concentration sible, however, to render the drugs
If the initial concentration of a reactant is increased, the reaction rate generally increases. biologically inactive upon inges-
A higher concentration of a reactant means a greater number of particles per unit tion and then activate them in the
presence of a catalyst. Such cata-
volume, which are more likely to collide as they move randomly within a fixed space. If lysts, called catalytic antibodies,
twice as many particles are present, there should be twice the probability of an effective bind to cancer cells. When the
collision. Therefore, for elementary reactions, the rate of reaction is generally directly pro- drug is ingested, it remains harm-
portional to the concentration of a reactant. less until it encounters a cancer
cell with a catalytic antibody. At
this point, the drug becomes
Surface Area active and the “blast” from the
This factor applies only to heterogeneous reactions, such as those where a gas reacts drug is localized to the region
with a solid or a solid with a liquid. Surface area affects collision frequency because reac- around the cancer cell, thus mini-
tants can collide only at the surface where the substances are in contact. The number mizing damage to other cells.

threshold
height 1
Number of Students

threshold
height 2

Figure 3
In a student height distribution graph, there is a range of
heights with most heights concentrated in the mid-range. The
“threshold height” is the minimum allowable height, deter-
mined by the amusement park, for a student to be allowed on
a ride. If the “threshold height” is lowered, a larger fraction of
Height students will be able to go on the ride.

NEL Chemical Kinetics 393


Figure 4
Heating green copper(II) carbonate
produces black copper(II) oxide.
Heating causes the decomposition
of many carbonates into solid oxides
and carbon dioxide gas.
Figure 5
Experiment shows that when the
temperature increases from T1 to T2,
the shape of the Maxwell-
Boltzmann distribution curve flat-
tens and shifts to the right. Note the
very large increase in the fraction of
molecules able to react at the
higher system temperature.
394 Chapter 6
of particles per square millimetre of surface of a solid is fixed. However, the area of sur-
face exposed for a given quantity depends on how finely divided the sample of solid is.
We make use of this in cooking by finely grinding pepper to add flavour and by using icing
sugar (finely powdered) and ground coffee to increase the rate at which they dissolve.
Dividing a solid into finer and finer pieces has a limit — when you reach the elementary
particles of which the solid is composed. Sugar cannot be divided more finely than into
its individual molecules. Dissolving divides a solid or liquid solute into the theoretical
maximum number of separate particles, creating the maximum possible surface area. This
is why so many reactions occur more quickly in solution, including nearly all of the
reactions of human physiology.
Theoretical Effect of Temperature
At room temperature, copper(II) carbonate is stable but, when heated (Figure 4), it rapidly
decomposes to copper(II) oxide. The reactants have not changed; only the temperature has
changed. An increase in temperature has a dramatic effect on rate of reaction, because tem-
perature affects both the collision frequency and the fraction of collisions that are effective.
Theoretically, temperature is believed to be a measure of the average kinetic energy of
the particles in a sample. Experimental evidence shows that a relatively small increase in
temperature seems to have a very large effect on reaction rate. An increase of about 10°C
will often double or triple the rate of a reaction. When you consider that a rise from
27°C to 37°C represents an absolute increase from 300 K to 310 K, you can see that a 3%
increase in temperature seems to cause a 100% increase in reaction rate.
The explanation for the temperature effect is that increasing temperature causes mol-
ecules to collide both more often and with more force on average, making any individual
collision more likely to be effective. The concept of activation energy is a significant part
of the explanation: For a given activation energy, Ea, a much larger fraction of molecules
has the required kinetic energy at a higher temperature than at a lower temperature. A tem-
perature rise that is a small increase in overall energy might cause a very large increase in
the number of particles that have energy exceeding the activation energy (Figure 5). In
the student field trip analogy used previously, an increase in temperature corresponds
to a new group of students. This new group has the same number of students, but they
are two years older and have a greater height on average. The height distribution is shifted
to taller heights, so a larger fraction of the students are able to go on the ride.
Maxwell-Boltzmann Distribution at Two Temperatures
minimum (threshold)
Number of Molecules
activation energy
T1
T2
molecules with enough
energy to create a
successful collision
Kinetic Energy
NEL
 Section 6.5

Theoretical Effect of Catalysis ACTIVITY 6.5.1

When margarine is manufactured in the food industry, vegetable oils that are too runny to Catalysts in Industry and
spread on bread must be made solid. The process of hydrogenation adds hydrogen to some Biochemical Systems (p. 405)
of the double bonds in unsaturated fats. The product molecules pack more closely and have Identify similarities and differences
stronger intermolecular interactions and a higher melting point. The reaction is slow under among industrial catalysts and
enzymes.
normal conditions but is catalyzed by use of nickel metal.
Theoretically, catalysts
Effects of a Catalyst Figure 6
accelerate a reaction by pro- The reaction shown here proceeds
viding an alternative lower activation uncatalyzed by a three-step mechanism when a
energy pathway from reac- energies catalyst is present, but nonetheless
tants to products. That is, a for forward proceeds much faster than by the
reactions one-step uncatalyzed mechanism.
catalyst allows the reaction catalyzed
Ep The catalyzed mechanism has a
to occur by a different lower activation energy, so more
mechanism, inserting dif- collisions are successful.
ferent intermediate steps,
but resulting in the same
products overall. If the new Reaction Progress
pathway (mechanism) has a
lower activation energy, a greater fraction of molecules possesses the minimum required
energy and the reaction rate increases (Figure 6).
The actual mechanism by which catalysis occurs is not well understood for most reac-
tions, and discovering acceptable catalysts has traditionally been a hit-and-miss process.
A few catalyzed reactions, studied in detail, suggest some general mechanism changes are
involved. For example, the action of platinum as a catalyst in the reaction of hydrogen Figure 7
and oxygen gases to produce water has a practical application in fuel cell technology, as The Ballard fuel cell consists of two
electrodes, each coated on one side
shown in Figure 7. The reaction of these gases is slow under normal conditions, but the with a thin layer of platinum catalyst.
platinum catalyzes the process so that the hydrogen and oxygen can combine at a sig- Hydrogen fuel dissociates into free
nificant rate. Because the platinum is a solid and the reactants are gases, platinum is electrons and positive hydrogen
called a heterogeneous catalyst for this reaction. The nickel catalyst described above is ions in the presence of the platinum
also a heterogeneous catalyst. catalyst, and the protons migrate
through a membrane electrolyte to a
The reaction between aqueous tartrate ions and hydrogen peroxide is an example of the
second electrode where they com-
action of a homogeneous catalyst: cobalt(II) ions. At room temperature this reaction is bine with oxygen from air.
very slow, with no noticeable activity. When a solution containing cobalt ions is added,
the pink solution reacts to form a green intermediate (aqueous cobalt(III) ion), which then heterogeneous catalyst a catalyst
in a reaction in which the reactants
further reacts to regenerate the cobalt(II) catalyst (Figure 8). Even though the cobalt(II) and the catalyst are in different
ions react in the first step of the mechanism, they are a catalyst because they are regen- physical states
erated in the final step. A catalyst speeds up a reaction without being consumed.
homogeneous catalyst a catalyst
in a reaction in which the reactants
and the catalyst are in the same
physical state

Figure 8
The reaction between colourless
tartrate ions and colourless
Ep hydrogen peroxide is catalyzed by
Co2 ions:
C4H4O62(aq)  5 H2O2(aq) →
6 H2O(l)  4 CO2(g)  2 OH (aq)
The reactants and pink Co2 react
to form an intermediate and green
Co3, which further reacts to form
colourless products and pink Co2.
Reaction Progress The catalyst reacts but is regener-
ated at the end.
NEL Chemical Kinetics 395
DID YOU KNOW ? SUMMARY
DIY Reactions
Some reactions are autocatalytic in
that they produce their own catalyst
as the reaction proceeds. For
example, the reaction between
oxalate ions and acidified perman-
ganate ions produces manganese(II)
ions as one of the products:
 
(aq)  2 MnO4 (aq)  16 H(aq) →
5 C2O42
(aq)  10 CO2(g)  8 H2O(l)
2 Mn2
The manganese(II) ion is a catalyst
so, once started, the reaction rapidly
accelerates.
396 Chapter 6
Explaining Reaction Rates
• Particles require a minimum activation energy and correct alignment for a colli-
sion to be effective. The collision must provide sufficient energy to cause the
breaking and forming of bonds, producing new particles.
• Many reactions occur as a sequence of elementary steps that make up the overall
reaction mechanism.
• The rate of any reaction depends on the nature of the chemical substances
reacting, because both the strength of bond(s) to be broken and the location of
the bond(s) in the particle structure affect the likelihood that any given collision
is effective.
• An increase in initial reactant concentration or in reactant surface area increases
the rate of a reaction because the total number of collisions possible per unit
time is increased proportionately.
• A rise in temperature increases the rate of a reaction for two reasons: the total
number of collisions possible per unit time is increased slightly; and, more
importantly, the fraction of collisions that are sufficiently energetic to be effective
is increased dramatically.
• A catalyst increases the rate of a reaction by providing an alternative pathway,
with lower activation energy, to the same product formation. A much larger frac-
tion of collisions is effective following the changed reaction mechanism. Catalysts
are involved in the reaction mechanism at some point, but are regenerated before
the reaction is complete.
Practice
Understanding Concepts
1. Which of the five factors that affect rate of reaction do so by
(a) increasing the collision frequency?
(b) increasing the fraction of collisions that are effective?
2. The reaction of hydrogen and oxygen is exothermic and self-sustaining.
(a) Write the equation for this reaction, and provide a reason why it is not likely that
the reaction occurs as a single step.
(b) This reaction is catalyzed by platinum metal, which provides a surface on which
hydrogen gas splits to form Pt–H units that react readily with oxygen molecules.
Suggest a possible mechanism for this process, given that a catalyst must be
regenerated in any change.
3. Identify each of the following as examples of the action of homogeneous or
heterogeneous catalysts:
(a) Rhodium and platinum metals are used in an automobile catalytic converter to
convert exhaust gases into safer gases.
(b) Gaseous chlorofluorocarbons (CFCs) have been shown to catalyze the
breakdown of ozone in the upper atmosphere.
(c) Aqueous sulfuric acid catalyzes the decomposition of aqueous formic acid to
carbon monoxide and water.
(d) Powdered TiCl4 is used in the formation of polyethylene polymer from gaseous
ethylene.
NEL
 Section 6.5

4. Use collision theory to explain each of the following observations.

(a) Permanganate ion (MnO4) reacts much more quickly with iron(II) ions (Fe2)
than with oxalate ions (C2O42).
(b) When heated in a flame, steel wool burns but a steel nail just glows.
(c) Liquid nitroglycerin is a dangerous explosive, but people with heart conditions
take nitroglycerin tablets.

Making Connections
5. The reaction of hydrogen with chlorine at room temperature is so slow as to be unde-
tectable if the container is completely dark, but is explosively fast if sunlight is allowed
to fall on the reactants. The following reaction mechanism has been suggested for
this reaction:
Cl2(g)  light energy → Cl(g)  Cl(g)
Cl(g)  H2(g) → HCl(g)  H(g)
H(g)  Cl2(g) → HCl(g)  Cl(g)
Cl(g)  Cl(g) → Cl2(g)
(a) Write the overall reaction equation.
(b) Identify the reaction intermediates.
(c) Compare the activation energy for the collision of molecular chlorine with molec-
ular hydrogen to the activation energy for the collision of atomic chlorine with
molecular hydrogen. Which reaction must have the greater activation energy, and
what evidence can be used to support your argument?
6. “Platinum should be described as a precious metal, not because of its use in jewellery
but because of its use as a catalyst.” Do you agree or disagree with the statement?
Back up your opinion with references to specific applications of platinum.
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7. List at least four different general methods of food preservation. Write a few
sentences about each, explaining the chemical theory behind its effectiveness.

EXPLORE an issue Decision-Making Skills

Debate: Food Preservation
For thousands of years people have tried to preserve food so
that it will still be available to them when the source of fresh
food has dwindled. Inuit hunters stashed butchered carcasses
close to the permafrost, under piles of rocks, to keep the meat
frozen until times of shortage. Newfoundland fishers dried their
cod on fish flakes to make it last through the winter, while the
indigenous Mi’qmaq gathered and dried wild berries. The Haida
Gwai, on Canada’s west coast, smoked their abundant seasonal
catch of salmon, and Aboriginal peoples on the prairies dried
buffalo meat into high-protein pemmican. All of these traditional
ways of preserving food used readily available materials and cir-
cumstances: brisk, dry winds; smoke from wood fires; or the
long, cold northern winters.
In the last hundred years, however, we have modified these
preserving methods and developed many new ones: We still
freeze food to keep it fresh, but now we have indoor freezers.
Some of our foods are dried, but generally with the help of com-
mercial dehydrators. And salting and smoking are more often
used for flavouring than for preserving these days — consider
bacon and smoked salmon. More commonly, our foods are
cooked at very high temperatures and vacuum-packed in cans
or plastic packages, or prepared with chemical preservatives, or
irradiated with gamma rays, or genetically modified to be more
resistant to rotting....
Define the Issue Analyze the Issue Research
Defend the Position Identify Alternatives Evaluate
Which of these many ways of preserving food is best for our
health? For our planet? For our wallets? For our community?
• In small groups, select at least five different ways of pre-
serving food. Choose some traditional and some more recent
techniques. Discuss what you know about each of these
methods, looking at them from several different perspectives.
• As a class, decide on a proposition to debate, on the subject
of food preservation. Take a preliminary vote: How many
people in the class support the proposition?
• Your class will then be divided into one team supporting the
proposition, and another opposing it.
(a) Carry out research and assemble your research into evi-
dence to back up your arguments.
• Debate your proposition, following the rules of debating, and
conclude with a vote.
(b) Did the voting results change from the preliminary vote
to the final one? What were the most convincing
arguments? Which arguments seemed least effective?
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NEL Chemical Kinetics 397

 Section 6.5

The Arrhenius Equation

The rate law equation
r  k[A]n[B]m

clearly describes quantitative rate dependence with respect to concentrations of reactants

— specifically, reactants that are involved in the rate-determining step of the reaction mech-
anism. But how do we explain the large quantitative effect of temperature and catalysis?
The rate constant, k, incorporates the quantitative effects of temperature, nature of reactant,
and catalysts as described by the Arrhenius equation for k.

The Arrhenius Equation

k  AeEa /RT
where Ea is the activation energy (in J)
A is a constant related to the geometry of the molecules
R is the gas constant (8.31 J/(mol• K))
T is the temperature (in K)

Note that changes in both the activation energy and temperature have exponential
effects on the value of k and therefore, the rate of reaction. Mathematical calculations show
how a relatively small change in either the temperature or the activation energy has a very
large effect on the numerical value of k and, hence, the rate of reaction.
For example, consider a typical reaction in which the activation energy is 150.0 kJ/mol
and the temperature is 27.0°C, or 300.0 K. The effects on rate can be measured by cal-
E
culating the exponential factor (a ) for each set of conditions.
RT
For the given set of starting conditions,
Ea 150.0 kJ/mol

  
RT 8.31 J/mol
•K   300 
K
 60.2
e60.2  7.2  1027

If the temperature is increased from 27°C to 37°C, or 310 K, the exponential factor
becomes
Ea 150.0 kJ/mol

  
RT 8.31 J/mol
•K   310 
K
 58.2
e58.2  5.3  1026

An increase in temperature of 10°C has multiplied the exponential factor and there-
fore, the rate, more than seven times (5.3  1026/7.2  1027).
If a catalyst is used that reduces the activation energy from 150 kJ to 130 kJ at 300 K,
the exponential factor becomes
Ea 130.0 kJ/mol

  
RT 8.31 J/mol
•K   300 
K
 52.1
e52.1  2.4  1023

The use of a catalyst has multiplied the rate more than 3000 times (2.4  1023/7.2
 1027).
Thus, changes in temperature, changes in reactants, and the use of catalysts that affect
the activation energy all have dramatic effects on rate.

NEL Chemical Kinetics 399

 Practice
Understanding Concepts
Answers 9. Use the Arrhenius equation (with the realistic values A  1027 L/mol• s, and
9. (a) approx.  4 Ea  200 kJ/mol) to calculate
(b) approx.  3600 (a) the change in the rate constant if the temperature of a system is raised from
20°C to 25°C, and
(b) the change produced by the use of a catalyst that lowers the activation energy
by 10%.
Section 6.5 Questions
Understanding Concepts
` 1. Draw a potential energy diagram for an endothermic ele-
mentary reaction. On the same diagram draw a reasonable
curve to represent the same reaction catalyzed. Summarize
the effects of a catalyst by labelling
(a) the ∆H for the overall reaction, catalyzed or uncat-
alyzed;
(b) the Ea for the reaction uncatalyzed;
(c) the Ea for the reaction catalyzed.
2. Draw a kinetic energy distribution diagram with labelled
curves for lower (T1) and higher (T2) temperatures. On the
diagram draw lines to represent threshold energies for cat-
alyzed (Ecat) and uncatalyzed (Euncat) reactions. Summarize
the effects of temperature and a catalyst by shading and
labelling areas to represent the fraction of molecules able
to react
(a) at a lower temperature uncatalyzed;
(b) at a higher temperature uncatalyzed;
(c) at a lower temperature catalyzed;
(d) at a higher temperature catalyzed.
Making Connections
3. Both nitric oxide (NO) and chlorine (Cl) atoms generated
by the decomposition of CFCs catalyze the decomposition
of ozone in the stratosphere.
(a) Why is the decomposition of ozone in the stratosphere
a problem?
400 Chapter 6
(b) When NO reacts with ozone in the rate-determining
step, the activation energy Ea is about 12 kJ/mol but
the activation energy for the reaction of Cl with ozone
in a separate mechanism is about 2 kJ/mol. Which of
nitric oxide and atomic chlorine is the more effective
catalyst? Explain.
4. Create a table with two columns, one headed Fast
Reactions and the other Slow Reactions. In each column list
at least 10 everyday reactions that we want to control. Give
reasons for your categorization of each example (e.g., you
might write “iron rusting” in the Slow Reactions column,
because we generally want iron to maintain its strength as
a metal). In your table, include methods that can be used
to control the rate of each of these reactions.
5. Enzymes have application in both body chemistry and
industrial reactions. Write a brief report describing the
function of an enzyme (not yet mentioned in this chapter)
in the human body or in industry.
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6. (a) Suggest why some chemical reactions occur slowly
while others occur quickly.
(b) How does your answer differ from the one that you
gave for Reflect on your Learning, question 3, at the
beginning of this chapter? Explain how your new
answer shows a change in your understanding.
NEL