Chemistry
Chemistry
Chemistry
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
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.
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.
minimum (threshold)
Number of Molecules
activation energy
T1
Figure 5 T2
Experiment shows that when the molecules with enough
temperature increases from T1 to T2, energy to create a
the shape of the Maxwell- successful collision
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. Kinetic Energy
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 Explaining Reaction Rates
DIY Reactions
Some reactions are autocatalytic in
that they produce their own catalyst • Particles require a minimum activation energy and correct alignment for a colli-
as the reaction proceeds. For sion to be effective. The collision must provide sufficient energy to cause the
example, the reaction between breaking and forming of bonds, producing new particles.
oxalate ions and acidified perman-
ganate ions produces manganese(II) • Many reactions occur as a sequence of elementary steps that make up the overall
ions as one of the products: reaction mechanism.
• The rate of any reaction depends on the nature of the chemical substances
(aq) 2 MnO4 (aq) 16 H(aq) →
5 C2O42
reacting, because both the strength of bond(s) to be broken and the location of
(aq) 10 CO2(g) 8 H2O(l)
2 Mn2
the bond(s) in the particle structure affect the likelihood that any given collision
The manganese(II) ion is a catalyst
so, once started, the reaction rapidly
is effective.
accelerates. • 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.
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.
GO www.science.nelson.com
7. List at least four different general methods of food preservation. Write a few
sentences about each, explaining the chemical theory behind its effectiveness.
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.
Making Connections
6. (a) Suggest why some chemical reactions occur slowly
3. Both nitric oxide (NO) and chlorine (Cl) atoms generated while others occur quickly.
by the decomposition of CFCs catalyze the decomposition
(b) How does your answer differ from the one that you
of ozone in the stratosphere.
gave for Reflect on your Learning, question 3, at the
(a) Why is the decomposition of ozone in the stratosphere
beginning of this chapter? Explain how your new
a problem?
answer shows a change in your understanding.