Name: ______________________________

Section: _____________________________

Student ID#:__________________________

Work in groups on these problems. You should try to answer the questions without referring to
your textbook. If you get stuck, try asking another group for help.

The half-life idea is most useful in conjunction with first-order kinetics, which include many
chemical reactions and all nuclear decay processes. The half life of a first-order process is a
constant that indicates the amount of time it takes for an initial concentration to diminish to half
as much material. From a consideration of the form of the integrated rate law, we can derive an
expression that relates the half-life period to the first-order rate constant, k.

All chemical reactions have a faster rate at higher temperature. From this we can conclude that
the magnitude of the rate constant, k, increases with rising temperature. This behavior is related
to the energy barriers associated with the mechanism of the reaction, the set of molecular-level
steps by which the reaction proceeds. Ultimately, the experimentally observed rate law is a
consequence of the particular mechanism of the reaction and the energy barriers of the individual
steps. Thus, if we propose a sequence of steps as a possible mechanism for a reaction, it should
predict the rate law relationships of the experimentally determined rate law equation. Knowing
the rate law, we can determine if a proposed mechanism is or is not reasonable for the reaction.

Learning Objectives
 Understand the concept of half life
 Understand the Arrhenius concept of the relationship between rate and temperature
 Know the various types of elementary steps that can compose a reaction mechanism
 Know how the molecularity of an elementary step relates to the rate expression for that
step
 Understand the connection between the observed differential rate law of a reaction and its
mechanism

Success Criteria
 Be able to carry out simple half-life calculations for first-order reactions
 Be able to sketch an Arrhenius reaction profile and calculate activation energies and
reaction enthalpies
 Be able to carry out calculations with the Arrhenius equation
 Be able to determine whether or not a proposed simple mechanism is consistent with
kinetic data
 Half Life
For any reaction we can define the half-life (symbolized t1/2t1/2) as that time required for the
concentration of a reactant to diminish to half of what its value was at some initial time. Thus,
at t=t1/2t=t1/2 we have [A]=½[A]o[A]=½[A]o. The half-life period is a constant for a first-
order reaction. (For second-order reactions, it depends on the initial concentration.) For first-
order reactions, we can obtain an expression for the relationship between the t1/2t1/2 value and
the value of the rate constant, kk, by substituting into the first-order integrated rate law
expression. Recall that the integrated rate law expression for a first-order reaction is given by

−ln([A][A]o)=kt(6.7.1)(6.7.1)−ln⁡([A][A]o)=kt

ln([A][A]o)=−kt(6.7.2)(6.7.2)ln⁡([A][A]o)=−kt

ln([A]o[A])=kt(6.7.3)(6.7.3)ln⁡([A]o[A])=kt

Using Equation 6.7.36.7.3, let us look at that point in the reaction when the initial concentration
of AA, [A]o[A]o, has diminished to half as much material, a value of ½[A]o½[A]o. This point
will occur at a period of time that defines the half life for the reaction, t1/2t1/2. Substituting the
values of initial concentration of AA and concentration at the end of the half-life period into the
integrated rate law expression, we can write

ln([A]o[A])=ln([A]o½[A]o)=kt1/2(6.7.4)(6.7.4)ln⁡([A]o[A])=ln⁡([A]o½[A]o)=kt1/2

ln2=kt1/2≈0.693(6.7.5)(6.7.5)ln⁡2=kt1/2≈0.693
t1/2≈0.693k(6.7.6)(6.7.6)t1/2≈0.693k

This shows that the half life, t1/2t1/2, is a characteristic constant of any first-order reaction, and
that it is inversely proportional to the rate constant, kk, of the reaction. The half-life concept
means that after each t1/2t1/2 period only half as much AA will remain, compared to what was
present at the beginning of the period. Let us define the number of half-life periods that have
elapsed as h=t/t1/2h=t/t1/2, the total time divided by the length of one half-life period. What
happens if we allow the reaction to continue to run through one, two, three, or more half-life time
periods? For an initial concentration [A]o[A]o , the table below shows the amount of AA, [A]
[A], that will remain after each successive half-life period.

elapsed time 0 t1/2t1/2 2t1/22t1/2 3t1/23t1/2

number of half-life periods, hh 0 1 2 3
amount of A remaining, [A][A] [A]o[A]o 12[A]o12[A]o 14[A]o14[A]o 18[A]o18[A

Looking at the pattern of the decline in [A][A] with number of elapse half-life periods, hh, we
can see that it follows the relationship

[A]=(12)h[A]o(6.7.7)(6.7.7)[A]=(12)h[A]o

This equation is valid even when hh is not an integer. For example, suppose we allowed the
reaction to run for one and a quarter half-life periods; i. e., h=1.25h=1.25. Then, the amount
of AA remaining would be

A]=(12)1.25[A]o=0.421[A]o(6.7.8)(6.7.8)A]=(12)1.25[A]o=0.421[A]o

Notice that the amount of AA remaining in this case is less than 0.50[A]o0.50[A]o and more
than 0.25[A]00.25[A]0, the amounts that remain after one and two half-life periods,
respectively.

Q1

Consider the first-order decomposition reaction AB(s)→A(s)+B(g)AB(s)→A(s)+B(g), for

which t1/2=10st1/2=10s at 1000 K. If a 16.0-mol sample of AB(s) is allowed to decompose at
1000 K, how much material will remain after (a) 10 s, (b) 20 s, (c) 30 s, (d) 40 s?

Q2

A first-order reaction X2→2XX2→2X initially has a reactant concentration of 4.80 mol/L.

After running for 96 s, X2X2 concentration is 0.600 mol/L. What is the half-life period of the
reaction? What is the value of the rate constant, k?

Q3

A first-order reaction A→BA→B initially has a reactant concentration of 12.0 mol/L. If the

reaction has a half life of 36.0 seconds, how much reactant will remain after 54.0 seconds?
Information

Rate and Temperature

All chemical reactions speed up as temperature increases. For example, in a typical chemical
reaction it is not unusual for the rate to double for every 10 °C increase in temperature. In terms
of the differential rate law, this means that the rate constant, k, increases with temperature. The
first successful interpretation of the relationship between kk and TT was made by Arrhenius in
1887 who reasoned that any reaction process must proceed through a transition state, involving
formation of a high-energy species, called the activated complex, which then breaks apart to
form products. Suppose we have the hypothetical reaction

A+B→C+D(6.7.9)(6.7.9)A+B→C+D

which proceeds by a single-step mechanism in which AA and BB molecules come together to

form products. We might imagine the reaction proceeding through the following process

A+B→[AB‡]→C+D(6.7.10)(6.7.10)A+B→[AB‡]→C+D

in which [AB‡][AB‡] is the transition state species, the activated complex, which decomposes

to give the products CC and DD.

This can be illustrated with an Arrhenius plot, which is a semi-quantitative representation of the
energy of the system in the process of converting from reactants to products. For this exothermic,
one-step reaction, the Arrhenius plot might look like Figure 6.7.16.7.1 (left) and for an
endothermic one-step reaction, the Arrhenius plot might look like Figure 6.7.16.7.1 (right).
 Figure  6.7.16.7.1:  The Arrhenius plots for one-step reaction. (left) An exothermic reaction.
(right) An endothermic.

In both cases, EfaEaf is the activation energy of the forward reaction, and EraEar is

the activation energy for the reverse reaction. In either direction, the activation energy
represents an energy barrier that must be overcome for reaction to occur. Note:

 If Efa<EraEaf<Ear, then ΔHrxn<0ΔHrxn<0 (exothermic)
 If Efa>EraEaf>Ear, then ΔHrxn>0ΔHrxn>0 (endothermic)

Q4
The reaction, 2NOCl(g)→2NO(g)+Cl2(g)2NOCl(g)→2NO(g)+Cl2(g) is believed to
proceed by a one-step mechanism. Its standard enthalpy is ΔH o = +75.5 kJ/mol. The activation
energy of the forward reaction is 98.2 kJ/mol. Sketch the Arrhenius plot for the reaction. What is
the value of Ea r, the activation energy of the reverse reaction?

Arrhenius Equation
Arrhenius was able to take this model and develop an equation for the relationship between a
reaction’s rate constant, k, and the absolute temperature, T. The Arrhenius equation is

k=Ae−Ea/RT(6.7.11)(6.7.11)k=Ae−Ea/RT

where AA is a constant (called the Arrhenius constant) and EaEa is the activation energy. The
value of AA for a reaction is determined by the characteristics of the reactants, including
possible orientation requirements for effective reaction.

If we take logarithms of both sides of the Arrhenius equation we obtain

lnk=lnA−Ea/RT(6.7.12)(6.7.12)ln⁡k=ln⁡A−Ea/RT

Rearranging Equation 6.7.126.7.12,

lnk=−EaR(1T)+lnA(6.7.13)(6.7.13)ln⁡k=−EaR(1T)+ln⁡A

This is a straight line equation, in which lnkln⁡k is the yy variable, 1/T1/T is the xx variable,

and lnAln⁡A is yy-intercept.

Because only two points are needed to define a straight line, only two pairs
of lnkln⁡k and 1/T1/T data are needed to define the slope. This being the case, we can obtain a
single equation that relates the two pairs of lnkln⁡k and 1/T1/T data to the value of EaEa. At
any two temperatures, T1T1 and T2T2 , we can write

lnk1=−EaR(1T1)+lnA(6.7.14)(6.7.14)ln⁡k1=−EaR(1T1)+ln⁡A

lnk2=−EaR(1T2)+lnA(6.7.15)(6.7.15)ln⁡k2=−EaR(1T2)+ln⁡A

Subtracting the Equation 6.7.156.7.15 from Equation 6.7.146.7.14, we obtain

 lnk1−lnk2=−EaR(1T1)+lnA−−EaR(1T2)−lnA(6.7.16)
(6.7.16)ln⁡k1−ln⁡k2=−EaR(1T1)+ln⁡A−−EaR(1T2)−ln⁡A

lnk1k2=EaR(1T2−1T1)(6.7.17)(6.7.17)ln⁡k1k2=EaR(1T2−1T1)

Equation 6.7.176.7.17 allows us to calculate EaEa from kinetic data that give the rate constant

for the reaction at two temperatures. Moreover, proceeding in this manner we do not need to
know AA, the Arrhenius constant (although we can calculate that by then using knowledge
of EaEa and Equation 6.7.126.7.12.

Q5

Sketch a plot of ln k vs. 1/T. What is the value of the slope? What information can be obtained
from the y intercept?

Q6

For the reaction

2NOCl(g)→2NO(g)+Cl2(g)(6.7.18)(6.7.18)2NOCl(g)→2NO(g)+Cl2(g)

the experimentally determined rate law is

Rate=d[Cl2]dt=k[NOCl]2(6.7.19)(6.7.19)Rate=d[Cl2]dt=k[NOCl]2

The rate constant, k, is 2.6×10–8L/mol⋅s2.6×10–8L/mol⋅s at 300 K

and 4.9×10−4L/mol⋅s4.9×10−4L/mol⋅s at 400 K. What is the activation energy, EaEa, of
the reaction?

Mechanisms, Elementary Reactions, and Rate Law

The mechanism of a reaction is composed of a series of molecular-level steps, called elementary
reactions or elementary steps. In representing the mechanism, these elementary reactions are
written in the same way that we write overall reaction equations. However, in this context, they
are given a special meaning: they are representations of what is presumed to occur on the
molecular level. Unlike reaction equations in general, we can make a direct connection between
the stoichiometry of the elementary reaction and the order with respect to each species in
differential rate law expression for that step.

On the molecular level, we can conceive of three plausible kinds of elementary reactions,
depending on whether one, two, or three molecules are involved. Hence, every elementary
reaction in a mechanism can be categorized as either unimolecular, bimolecular,
or termolecular. These terms refer to the molecularity of the elementary reaction.

We can relate the molecularity of an elementary reaction to the rate law expression for that step
by applying the Law of Mass Action:

For any elementary reaction, the rate law expression for that step is proportional to the
concentration of each reactant such that the molecularity determines the overall order.

Suppose we consider the elementary process of chlorine molecules, Cl2Cl2 , dissociating to

form chlorine atoms (free radicals), Cl∙Cl•:

Cl2→2Cl∙(6.7.20)(6.7.20)Cl2→2Cl•

The more Cl2Cl2 we have, the more Cl∙Cl• will form, or in other words the rate is directly
proportional to the concentration of Cl2Cl2 and nothing else. Thus, for this elementary reaction,
occurring at the molecular level, we can write its rate as

rate=k[Cl2](6.7.21)(6.7.21)rate=k[Cl2]

Note that this unimolecular process has a first-order rate law. [We will use rate (not capitalized)
to refer to the rate of an elementary reaction, and Rate (capitalized) to refer to the rate of an
overall reaction; the two are not generally the same.]

By a similar reasoning, we can conclude that a bimolecular elementary process should have a
rate law that is second-order overall, first order in each of the two participating species. For
example, if the elementary process is A+B→productsA+B→products, then the rate law for
this step would be rate=k[A][B]rate=k[A][B]. Likewise, a termolecular elementary step
should have a rate law that is third-order overall, first order in each of the participating species.
For example, if the elementary process is A+B+C→productsA+B+C→products, then the
rate law for this step would be

rate=k[A][B][C].(6.7.22)(6.7.22)rate=k[A][B][C].

Q7

Answer the following questions about elementary step molecularity and the rate expression for
the step:

a. Consider the elementary reaction 2NO2→N2O42NO2→N2O4. What is the

molecularity of this step? What is the rate law expression for this step?
b. Consider the elementary reaction Cl∙+H2→HCl+H∙Cl•+H2→HCl+H•. What is the
molecularity of this step? What is the rate law expression for this step?
 c. Consider the elementary reaction H++Br–+H2O2→HOBr+H2OH++Br–
+H2O2→HOBr+H2O. What is the molecularity of this step? What is the rate law
expression for this step?
d. The highest conceivable molecularity is termolecular. Why?

Proposing Mechanisms and the Rate Determining Step

Concept
The mechanism of a reaction, consisting of one or more elementary steps, must add up to give
the overall stoichiometry of the reaction. Moreover, the sequence of steps and the individual
rates of each elementary process must result in a predicted overall rate law expression that has
the same form as the overall rate law for the reaction determined by experiment. Thus, the initial
piece of information the chemist uses is the observed rate law, with its various orders with
respect to reacting species. Then, using knowledge about the reactivity of the various species, the
chemist proposes a series of steps that will add to give the overall stoichiometry and that can be
shown to yield a rate law with the same orders as the observed rate law. Except in very carefully
chosen cases, this process is beyond reasonable expectations for a beginning chemistry student
(i.e., you’re not going to be asked to propose mechanisms on a test!) However, it is important to
be able to understand how a proposed mechanism is consistent (or not) with the observed rate
law.

In many cases, one step in the proposed mechanism may be significantly slower than others.
Such a step is called a rate determining step, because the overall reaction rate can be no faster
than the rate at that step. If a rate determining step occurs, the overall rate expression must be
equivalent to the rate expression at that step. In terms of the Arrhenius concept, the rate
determining step has the highest activation energy, EaEa, of all the steps in the mechanism, and
therefore it has the smallest rate constant, k. For example, consider the hypothetical
reaction A→DA→D, proceeding by a three-step mechanism in which the second step is
significantly slower than the others and therefore rate determining.

Elementary Step Speed of Step rate law

A→BA→B fast rate1=k1[A]rate1=k1[A]
B→CB→C slow rate2=k2[B]rate2=k2[B]
C→DC→D fast rate3=k3[C]rate3=k3[C]

The overall reaction is

A→D(6.7.23)(6.7.23)A→D

with the following observed rate

Rate=rate2(6.7.24)(6.7.24)Rate=rate2
The reaction profile for this hypothetical mechanism is shown below.

Because the second step is the slowest, the overall rate of the reaction is equivalent to the rate at
step 2.

From the Law of Mass Action, we can always write down the rate expression for each
mechanism step, including the rate-determining step, from its molecularity. However, unless the
rate determining step is the first in the mechanism, its rate expression may depend upon
concentrations of species that are not initially present in the reaction mixture. Instead, the rate
expression for the rate-determining step may involve species that are created temporarily in a
prior step and then destroyed in the course of the mechanism. Such transient species are called
reaction intermediates. In the example above, both BB and CC are reaction
intermediates, because they are produced in one step and consumed in a subsequent step. The
dependence of the rate determining step on the concentration of a reaction intermediate
(here, BB) means that the rate expression for the rate-determining step will not have the same
form as the experimentally observed rate expression, which is always cast in terms of reactants
present at the start of the reaction. In order to show that the proposed mechanism is consistent
with the experimental data, it is often necessary to derive from the rate-determining step's rate
expression an equivalent expression in terms of observable reactants (and sometimes products).
The final proof of a proposed reaction mechanism is that it predicts the rate law expression
observed by experiment, which is always cast in terms of observable reactants, not unobservable
intermediates.
Q8

Refer to the plot shown above for the three-step mechanism by which the hypothetical
reaction A→DA→D proceeds.

a. From the plot, is the overall reaction exothermic or endothermic?

b. If a reaction is exothermic or endothermic, must all its steps be the same (exothermic or
endothermic)?
c. Step 2 in the hypothetical mechanism is rate determining. Why must it have the highest
activation energy?
d. Look at the proposed mechanism. Why would a slow rate at step 2 slow down the whole
reaction? In other words, what does it do that makes its rate the rate-determining step?

Q9

Consider the following chemical reaction in aqueous solution,

2I–+2H++H2O2→I2+2H2O(6.7.25)(6.7.25)2I–+2H++H2O2→I2+2H2O

for which the experimentally determined rate law expression is

Rate=k[I–][H2O2](6.7.26)(6.7.26)Rate=k[I–][H2O2]

The following mechanism has been proposed:

Elementary Step Speed of Step

I–+H2O2→HOI+OH–I–+H2O2→HOI+OH– slow
HOI+I–→OH–+I2HOI+I–→OH–+I2 fast
H++OH–→H2OH++OH–→H2O fast
a. Show that his series of steps gives the overall stoichiometry of the reaction. [Note:
sometimes it is necessary to multiply one or more steps by appropriate factors to make
everything add up to the overall stoichiometry. These factors are usually omitted when
writing the series of mechanism steps, as this case illustrates.]
b. From the molecularity, write the rate law expression for each step.
c. Identify the reaction intermediates in this mechanism.
d. Explain how this mechanism is consistent with the experimentally observed rate law.

Q10

Consider the gas phase reaction

2N2O5→4NO2+O2(6.7.27)(6.7.27)2N2O5→4NO2+O2
for which the observed rate law expression is

Rate=k[N2O5](6.7.28)(6.7.28)Rate=k[N2O5]

The following mechanism has been proposed:

Elementary Step Speed of Step ra

N2O5⇌NO2+NO3N2O5⇌NO2+NO3 fast equilibrium k1(forward)k1(forwa
NO2+NO3→NO+NO2+O2NO2+NO3→NO+NO2+O2 slow
NO3+NO→2NO2NO3+NO→2NO2 fast

Carry out the following steps to show that this is a plausible mechanism.

a. Show that this series of steps adds to give the overall stoichiometry of the reaction. [Hint:
One step needs to be multiplied by an integer factor.]
b. Write the rate law for each step. The first step (fast equilibrium) is reversible, so you will
need to write two rate law expressions, one for each direction.
c. Which step is rate determining? Write its rate law expression.
d. What species are reaction intermediates?
e. Your rate expression, based on the rate expression for the rate-determining step, contains
a concentration term for an unobservable reaction intermediate. We need to express the
rate law for the rate determining step in terms of observable starting materials. Note that
the first step is a rapidly established equilibrium, which means its rate in the forward
direction is exactly the same as in the reverse direction. Write an equality between your
two expressions for the two directions, and rearrange it to solve for [NO3][NO3].
f. Substitute your expression for [NO3][NO3] into your expression for the rate law of the
rate determining step. Does this agree with the experimentally observed rate law
expression?