Chapter 14-
Chemical
Reaction
Kinetics
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14.1 Reaction rates
14.2 Factors that affect reaction rate
14.3 Rate laws
14.4 Theory of chemical kinetics
14.5 Reaction mechanisms
14.1 Reaction rates
• Chemical kinetics is the study of the
rate of a reaction
• The reaction rate is the speed with
which reactants disappear and
products form
• Reaction rates are always reported as
positive values
• The unit is mol L–1 s–1
Figure 14.1 Reaction rates
The progress of the reaction A → 2B, showing the concentration
changes of A and B over time
14.1 Reaction rates
Consider the reaction A B
14.1 Reaction rates
• The concentration of the reactant, A,
decreases with time
conc of A at time t2 – conc of A at time t1 -Δ[A]
rate (A) = =
t2 – t1 Δt
• The concentration of the reactant, B,
increases with time
conc of B at time t2 – conc of B at time t1 Δ[B]
rate (B) = =
t2 – t1 Δt
14.1 Reaction rates
• Calculate the average rate at which
[A] changes in the first 50 seconds
-Δ[A]
rate (A) =
Δt
-([A]t=50 – [A]t=0)
=
50 s – 0 s
-(0.0629 mol L-1 – 0.0750 mol L-1)
=
50 s
= -(-2.4 × 10-4 mol L-1 s-1)
= 2.4 × 10-4 mol L-1 s-1
14.1 Reaction rates
• The rate at a particular time is called
the instantaneous rate
• This can be determined from the
slope of a tangent to the curve
• For example, figure 14.1 at t = 50 s
d[A]
rate = -(slope of tangent line) =
dt
= 2.3 × 10-4 mol L-1 s-1
For the general reaction:
where a to d are the stoichiometric coefficients of the reactants A and B and the
products C and D respectively, we define the rate of reaction as
Therefore, for our reaction A → 2B we would write
Estimating the Initial Rate of a Reaction
The following data have been measured at 508 °C for the reaction 2HI(g) → C H 2(g) + I2(g)
Time
Time (s) [HI] (mol L )
–1
(s) [HI] (mol L–1)
0 0.100 200 0.0387
50 0.0716 250 0.0336
100 0.0558 300 0.0296
150 0.0457 350 0.0265
What is the initial rate of decay of HI, and what is the initial rate of reaction
at this temperature
The initial rate of decay of HI is the instantaneous rate of decay of HI at time zero
The slope of the line can be calculated from the coordinates of any
two points (x1, y1) and (x2, y2) using the equation:
The initial rate of reaction can be calculated using the stoichiometry of the reaction.
Solution
To determine the slope of the tangent precisely, we should choose two points that
are as far apart as possible. The point on the curve (0 s, 0.10 mol L–1) and the
intersection of the tangent with the time axis (150 s, 0 mol L–1) are widely separated.
calculated the initial as being –6.7 × 6 10–4 mol L–1 s–1
the initial rate :
14.2 Factors that affect reaction
rate
• Five principal factors influence reaction
rates:
1. Chemical nature of the reactants
2. Ability of the reactants to come in contact
with each others
3. Concentrations of the reactants
4. Temperature
5. Availability of rate-accelerating agents
called catalysts
14.2 Factors that affect reaction
rate
• Chemical nature of the reactants
– During reactions, bonds break and new
bonds form
– Some reactions are fast by nature and
others are slow
14.2 Factors that affect reaction
rate
• Ability of the reactants to meet
– Most reactions involve two or more
reactants whose particles (atoms, ions or
molecules) must collide for the reaction to
occur
– In a homogeneous reaction, all of the
reactants are in the same phase
– In a heterogeneous reaction, the reactants
are present in different phases
14.2 Factors that affect reaction
rate
– The area of contact between the phases
determines the reaction rate
14.2 Factors that affect reaction
rate
• Concentrations of the reactants
– The rates of both homogeneous and
heterogeneous reactions are affected by
the concentrations of the reactants
• For example, red-hot steel wool bursts into
flame when thrust into pure oxygen
• Temperature of the system
– Almost all chemical reactions occur faster
at higher temperatures
14.2 Factors that affect reaction
rate
• Presence of catalysts
– Catalysts are substances that increase
the rate of chemical reactions without
being used up
– For example, enzymes that direct our
body chemistry are all catalysts
14.3 Rate laws
• A rate law is an equation in which the rate
is given as a function of reactant
concentrations
– for example, rate = k[HI]n
• k is the rate constant of the reaction
• n is the order of the reactant
• Both rate constant and order must be
experimentally determined
14.3 Rate laws
• The value of the rate constant depends
on the particular reaction being studied
and the temperature at which the
reaction occurs
• The order can be positive or negative,
an integer or a fraction
• The order cannot be deduced from the
balanced equation
14.3 Rate laws
• Worked example 14.2
2C4H10(g) + 13O2(g) 8CO2(g) + 10H2O(g)
– If the butane concentration is decreasing
at a rate of 0.20 mol L–1 s–1, at what rate
is the oxygen concentration decreasing?
– Solution:
0.20 mol C4H10 13 mol O2 1.3 mol O2
rate (O2) = x =
Ls 2 mol C4H10 Ls
– Oxygen reacts at a rate of 1.3 mol L–1 s–1
Solution
From our definition of rate of reaction, we can write:
We are told that:
we can therefore use this, together with our expression for the rate of reaction to
determine
– Oxygen reacts at a rate of 1.3 mol L–1 s–1
14.3 Rate laws
• Types of rate laws:
– A differential rate law expresses the rate as a
function of concentration
– An integrated rate law expresses the
concentration as a function of time
– Rate laws help to identify the steps by which
a chemical reaction occurs
– The sum of the individual reaction steps is
called the reaction mechanism
14.3 Rate laws
• The differential rate law
– Consider the hypothetical reaction:
A + B products
– The rate law for the reaction is:
rate = k[A]n[B]m
– The values of n and m can be
discovered by looking for patterns in the
rate data
14.3 Rate laws
– Suppose that the data in the table below
has been obtained in a series of five
experiments:
A+BC
14.3 Rate laws
– For experiments 1, 2 and 3 [B] is held
constant. Any changes in the rate must
be due to the change in [A]
– The rate law says that at constant [B] the
rate must be proportional to [A]n
rateexp 2 [A]exp 2 n
rateexp 2 0.40 mol L-1 s-1
= = =2
rateexp 1 [A]exp 1 rateexp 1 0.20 mol L s -1 -1
and
[A]exp 2 0.20 mol L-1
= =2
[A]exp 1 0.10 mol L -1
14.3 Rate laws
– So doubling [A] from experiment 1 to
experiment 2 doubles the rate
– The relationship reduces to:
2.0 = 2.0n
– The only value of n that makes this
equation true is n = 1
– The reaction must be first order with
respect to A
14.3 Rate laws
– In the final three experiments, the
concentration of B changes while the
concentration of A is held constant
– This time it is [B] that affects the rate
rateexp 4 [B]exp 4 m
=
rateexp 3 [B]exp 3
– For experiments 3 and 4, we have:
4.0 = 2.0m
– Therefore, m must equal 2
14.3 Rate laws
– We now know that the rate law for the
reaction must be:
rate = k[A]1[B]2
– The overall order is the sum of the orders
for each reactant in the rate law
– Thus, our hypothetical reaction has an
overall order of three
To calculate the value of kfor the A + B products reaction, we need only
substitute rate and concentration data into the rate law.
rate = k[A]1[B]2
from experiment 1 in table 14-3:
After cancelling units, the value of k with the net units is:
Note that the unit of a third-order rate constant is concentration–2 time–1.
14.3 Rate laws
• The integrated rate law
– Integrated rate laws express
concentration as a function of time
– Consider the hypothetical reaction:
A products
– The (differential) rate law has the form:
d[A]
rate = – = k[A]
dt
14.3 Rate laws
• First-order rate laws
– Assume A products
is first order in A
– The differential rate law is then:
d[A]
rate = – = k[A]
dt
– The integrated rate law is:
[A]0
ln = kt or [A]t = [A]0e-kt
[A]t
ln[A]t = – kt + ln[A]0
First-order rate laws
Let's assume that our hypothetical reaction A → products is first order in A.
The differential rate law is then:
Rearrangement gives
the
the concentration from beginning of the reaction (at t = 0) until a certain
reaction time t
The equation ln[A]t = – kt + ln[A]0 is of the form y = m x + b,
where a plot of y versus x gives a straight line with the slope ‘m’ and
the intercept ‘b’ (the intercept may also be denoted by a ‘c’).
For the reaction A → products,
the plot of ln[A]t versus t is a straight line, if the reaction is first order.
Conversely, if the plot doesn't give a straight line,
then the reaction is not first order.
14.3 Rate laws
– For first order reactions a plot of the
natural logarithm of concentration versus
reaction time always gives a straight line
EXAMPLE 14.6
The following data are for the reaction N2O5(g) → (N2O4(g) + 12O2(g).
Time [N2OO5] (mol Time [N2O5] (mol
(s) L–1) (s) L–1)
0 0.2000 200 0.0500
50 0.1414 300 0.0250
100 0.1000 400 0.0125
(a) Show that the rate law is first order in [N2O5].
(b) Calculate the value of the rate constant.
Analysis
(a) If a plot of ln[N2O5] versus time, according to ln[N2O5] = –kt + ln[N2O5]0,
gives a straight line, the reaction must be first order in [N2O5].
(b) The slope of the plot in (a) gives the rate constant.
Solution
First we calculate the natural logarithm of [N2O5], which gives the
following data
Time (s) ln[N2O5] Time (s) ln[N2O5]
0 –1.609 200 –2.996
50 –1.956 300 –3.689
100 –2.303 400 –4.382
The plot is a straight line, which confirms that the reaction is first order in [N 2O5]
(we could also use a calculator to do this analysis). In this case, the slope of the
line equals –k. This gives us:
Half-life of first-order reactions
The half-life ( ) of a reactant is a convenient way to describe how fast
it reacts, particularly for an overall first-order process. A reactant's half-life,
, is the time required for half of the reactant to disappear
For a first-order reaction, the half-life of the reactant can be obtained from:
by setting [A]t equal to half of the initial concentration [A]0.
=
14.3 Rate laws
• Second-order rate laws
– Assume B products is second order
– The differential rate law is:
d[B]
rate = – = k[B]2
dt
– The integrated rate law would be:
1 1
= kt +
[B]t [B]0
When a reaction is second order, a plot of 1/[B]t versus t should
yield a straight line with a slope k
for the decomposition of HI, according to 2HI(g) → H2(g) + I2(g),
using data from worked example 14.1.
14.3 Rate laws
– When a reaction is second order, a plot
of 1/[B]t versus t should yield a straight
line with a slope k
14.3 Rate laws
• Zero-order rate laws
– The differential rate law is:
rate = k[C]0 = k(1) = k
– The integrated rate law is:
[C]t = – kt + [C]0
– A plot of [C] versus time gives a straight
line of slope –k
14.3 Rate laws
14.4 Theory of chemical kinetics
• Collision theory
– One of the simplest models to explain
reaction rates is collision theory
– Collision theory says that the rate of a
reaction is proportional to the number of
effective collisions per second among the
reactant molecules
– An effective collision is one that actually
gives product molecules
14.4 Theory of chemical kinetics
– Concentration can influence the number of
effective collisions per second
– As reactant concentrations increase, the
number of effective collisions increases
– Not every collision between reactant
molecules actually results in a chemical
change
– Only a very small fraction of all the collisions
can really lead to a net change
– Why is this so?
14.4 Theory of chemical kinetics
• Molecular orientation
– When two reactant molecules collide they
must be oriented correctly for a reaction to
occur (see next slide)
14.4 Theory of chemical kinetics
14.4 Theory of chemical kinetics
• Activation energy
– The activation energy (Ea) is the minimum
energy required for a reaction to occur
– The activation energy determines the rate
of a reaction
– At a given temperature, only a certain
fraction of the collisions possess enough
energy to be effective and form products
14.4 Theory of chemical kinetics
14.4 Theory of chemical kinetics
– The arrangement found on the top of the
potential energy ‘hill’ is called the
activated complex or transition state
– Once the transition state is reached, the
reaction proceeds to give products, with
the release of energy
– A reaction intermediate corresponds to
an energy minimum between two
transition states
14.4 Theory of chemical kinetics
• Temperature effects
– The rate of a reaction increases with
increasing temperature
14.4 Theory of chemical kinetics
– The activation energy is related to the
rate constant by the Arrhenius equation
k = Ae-Ea/RT
k = rate constant
Ea = activation energy
R = universal gas constant
T = temperature (in Kelvin)
A = pre-exponential or frequency factor
14.4 Theory of chemical kinetics
– The activation energy can also be
obtained from two rate components
measured at different temperatures
– Most reactions obey the Arrhenius
equation to a good approximation
k2 –Ea 1 1
ln = –
k1 R T2 T1
14.5 Reaction mechanisms
• Most reactions do not occur in a single
step
• The net overall reaction is the result of
a series of simple reactions
• Each of these is called an elementary
process
• The entire set of elementary processes
is the reaction mechanism
14.5 Reaction mechanisms
• The rate law of an elementary process
can be written from its chemical equation
• This rule only applies to elementary
processes
• The overall rate law derived from the
mechanism must agree with the
observed rate law for the overall reaction
14.5 Reaction mechanisms
• The rate-determining step
– Consider the gaseous reaction:
2NO2Cl 2NO2 + Cl2
– The actual mechanism of the reaction is the
following two-step sequence of elementary
processes:
NO2Cl NO2 + Cl• (slow)
NO2Cl + Cl• NO2 + Cl2 (fast)
– The Cl atom formed is an intermediate
14.5 Reaction mechanisms
• In any multistep mechanism, one step
is usually much slower than the others
• The slow step in a mechanism is
called the rate-determining step
• The rate law for the rate-determining
step is directly related to the rate law
for the overall reaction
14.5 Reaction mechanisms
• The steady-state approximation
– In complex reaction mechanisms, the rate-
determining step may vary when reaction
conditions are changed
– In such cases, the steady-state
approximation is used
– This method is the assumption that the
concentration of an intermediate remains
constant as the reaction proceeds
14.5 Reaction mechanisms
– Consider the hypothetical reaction:
2AB + C2 → A2B + C2B
– This reaction may proceed via the
following mechanism:
2AB ↔ A2B2
A2B2 + C2 → A2B + C2B
– The intermediate in this mechanism is
A2B2. Thus:
d[A2B2]
=0
dt
14.5 Reaction mechanisms
– The steady-state approximation is applied
by setting:
rate of A2B2 production = rate of A2B2 consumption
– All steps that are producing and
consuming intermediate A2B2 need to be
identified
– The rate law for each also has to be
written
14.5 Reaction mechanisms
(a) Rate of production of A2B2
– In this mechanism, A2B2 is only produced
in the forward reaction
– The rate law for this step is:
d[A2B2]
= k1[AB]2
dt
14.5 Reaction mechanisms
(b) Rate of consumption of A2B2
– A2B2 is consumed in the reverse reaction
of the first step and in the second step
– The rate laws for these steps are:
– d[A2B2]
= k-1[A2B2]
dt
– d[A2B2]
= k2[A2B2][C2]
dt
14.5 Reaction mechanisms
(c) Application of steady-state condition
– Under steady-state conditions, we have for the
intermediate A2B2:
k1[AB]2 = k-1[A2B2] + k2[A2B2][C2]
– If we solve for the concentration of A2B2:
k1[AB]2
[A2B2] =
k-1 + k2[C2]
– Now the rate law for the overall reaction is
written
14.6 Catalysts
• A catalyst is a substance that changes
the rate of a chemical reaction without
being used up
• The action caused by a catalyst is called
catalysis
• Positive catalysts speed up reactions
• Negative catalysts (inhibitors) slow
reactions down
14.6 Catalysts
• The catalyst provides a path to the
products that has a rate-determining
step with a lower activation energy
(see next slide)
14.6 Catalysts
14.6 Catalysts
• Homogeneous catalysts
– Exist in the same phase as the reactants
• An example is found in the lead chamber
process for manufacturing sulfuric acid.
• The reaction is:
S + O2 SO2
SO2 + ½ O2 SO3
SO3 + H2O H2SO4
• Unassisted, the second reaction, oxidation of
SO2 to SO3, occurs slowly.
14.6 Catalysts
• The SO2 is combined with a mixture of NO,
NO2, air and steam
• The NO2 serves as a catalyst by being an
oxygen carrier and providing a low-energy
path for the oxidation of SO2 to SO3
• The NO is then reoxidised to NO2 by oxygen
• The reaction is:
NO2 + SO2 NO +SO3
NO + ½ O2 NO2
• The NO2 is regenerated
14.6 Catalysts
• Heterogeneous catalysts
– Are a separate phase from the reactants
– They are commonly solids
– Usually functions by promoting a reaction
on its surface
• An example is the Haber-Bosch process
3H2 + N2 2NH3
• The reaction takes place on the surface of an
iron catalyst that contains traces of aluminium
and potassium oxides.
14.6 Catalysts
14.6 Catalysts
• Enzyme kinetics
– Enzymes consist of proteins, and are some
of the most powerful homogenous catalysts
– Enzyme catalysis can be represented by a
series of reactions
– There are two different hypotheses for how
a substrate is bound into an enzyme
• The lock-and-key hypothesis assumes that the
substrate simple ‘fits’ into the active site
14.6 Catalysts
• The induced fit hypothesis assumes that the
enzyme molecule changes shape as the substrate
molecule comes close
– The action of an enzyme can be described
by the Michaelis-Menten mechanism
Summary
• Chemical kinetics is the study of the rate
of a reaction
• Reaction rates are controlled by five
factors
• The differential rate law shows how
reaction rate depend on concentration
• The integrated rate law shows how
concentration depends on time
Summary
• According to collision theory, the rate of a
reaction depends on the number of
effective collisions per second
• Colliding molecules must possess a
minimum kinetic energy, called the
activation energy, Ea
• The Arrhenius equation relates how
changes in activation energy and
temperature affect a rate constant
Summary
• The detailed sequence of elementary
processes that lead to the next
chemical change is the mechanism of
the reaction
• For the rate-determining step the
corresponding rate law has exponents
equal to the coefficients in the
balanced equation
Summary
• In more complicated reaction
mechanisms the steady-state
approximation can be used to derive
the rate law
• Catalysts are substances that change a
reaction rate but are not consumed by
the reaction
• Catalysts in living systems are called
enzymes
