CHAPTER 14 – Chemical Kinetics

Define the term reaction rate.

the speed at which a chemical reaction occurs

Define the term reaction mechanism.

a step by step, molecular-level view of the pathway from reactants to products

Section 14.1 – Factors That Affect Reaction Rates

(a) List the four factors that will cause the reaction rate to change.
Reactant concentration physical state of the reactants
reaction Temperature catalyst

(b) Explain why 10 g of powdered zinc will react with hydrochloric acid more quickly than a solid
zinc strip that weighs 10 g.
because powdered zinc has greater surface area than a strip of zinc. the
greater the surface area the more collisions between reactant particles
and a greater reaction rate.

(c) Explain why a sample of magnesium metal will react more quickly in 10 M HCl than it will react
in 1 M HCl.
a higher concentration of acid means that there are
more collisions between reactant particles and a
greater reaction rate

(d) Explain why an Alka-Seltzer tablet will dissolve more quickly in water @ 80oC than in water
@ 20oC.
The higher the temperature, the greater Kinetic energy, which means
particles move at a faster speed. This means there is more collision
between the reactants and products which means faster reaction rate

(e) Describe the role of a catalyst in a chemical reaction.

a catalyst speeds up a chemical reaction without itself being used up

 (f) As the frequency of collisions between reactant molecules increases, how will the rate of a
chemical reaction be affected?
The rate will speed up since the more the collisions, the
more kinetic energy to speed up a reactant

Section 14.2 – Reaction Rates

M/s or M/min
(a) What unit is used to measure the rate of a chemical reaction?

(b) In order to determine the reaction rate, the concentration of a reactant or a

product is measured over time to see how fast it changes.

(c) The table below is based on the chemical reaction A  B as described in Figure 14.3 on page
559. Fill in the missing values for the amount of B produced.

Time (s) 0 10 20 30 40 50 60
Moles of A in the 1.0 L flask 1.00 0.73 0.54 0.40 0.30 0.21 0.16
Moles of B in the 1.0 L flask 0.00 0.27 0.46 0.60 0.70 0.79 0.84

(d) Create a graph of the data from the table in part (c). Use a smooth line to connect the data
points for each substance. Use a solid line for A and a dashed line for B.
1.0

0.9

0.8
Concentration (M)

0.7

0.6
Concentration of A
0.5

0.4 Concentration of B

0.3

0.2

0.1

0.0
0 10 20 30 40 50 60
Time (s)
(e) How is the average rate of a reaction calculated for a particular time interval? See Equation
14.1 on page 560.

by dividing the difference of concentration within a time interval by the difference of time
average rate = (A)T2 - (B)T1 / T2 - T1
 (f) Based on the data table from part (c), calculate the average rate of disappearance of A for
each of the following time intervals. Units of rate should be M s-1
-0.027 -0.014 -0.009
0 s to 10 s 20 s to 30 s 40 s to 50 s
-0.019 -0.01 -0.005
10 s to 20 s 30 s to 40 s 50 s to 60 s

(g) Examine the values for average rate that you calculated in part (f). How are these values
changing over time? (e.g., increasing, decreasing, or staying constant)
You can see more examples of this trend in Table 14.1 and in Figure 14.4 on p. 561.

They are decreasing

(h) Why is it typical for reaction rates to decrease over time as a reaction proceeds?

it is typical because the concentration is being used up overtime meaning it decreases

which also means there will be less collisions, decreasing the reaction rates
The rate of reaction is the number of
successful collisions per second
(i) Define the term instantaneous rate of reaction.

The rate at a particular time. It is determined by finding the slope of the tangent to the
concentration vs time curve at that time.

(j) The instantaneous rate at t = 0 is called the initial rate of the reaction.

(k) Suppose that, in a certain reaction, Δ[A] = 2 x Δ[B]

Δt Δt

Which of the following reactions is consistent with this rate information? Explain.

2A + B  C A + 2B  C

Change in A overtime is twice as much as the change in B so the molecules of

A are disappearing at a faster rate, which is twice as fast compared to B. This
means there has to be twice as much moles in A than in B
 2 HI(g)  H2(g) + I2(g)

(l) At a certain moment in time, the rate of formation of H2 is equal to 1.8 x 10-6 M/s. Calculate the
rate of disappearance of HI at this moment in time.
Since HI is a reactant and consumes 2 moles for every 1 mole of H2, then the rate of
disappearance of HI at this moment in time is: -2(1.8 x 10-6) = -3.6 x 10-6 M/s
(m) The graph below displays the change in concentration for each species in the following
reaction: 2A  2B + C Label each curve on the graph below as A, B, or C.

A is a reactant so its decreasing

B is twice as much as C
Concentration (M)

Time (s)

Section 14.3 – Concentration and Rate Laws

Table 14.2 is shown below.

(a) In experiments 1-3, the independent variable is the concentration of NH4+; the dependent
variable is the observed initial rate of reaction. The concentration of NO2– is held constant.
Discuss the relationship between the independent variable and the dependent variable in
experiments 1 and 2.
the concentration of NH4 and its initial
rate is doubles when comparing
experiment 1 and 2

(b) Discuss the relationship between the independent variable and the dependent
variable in experiments 1 and 3.
The concentration of NH4 and its initial rate are quadrupled from
experiment 1 to experiment 3
(c) In experiments 4-6, the independent variable is the concentration of NO2–; the dependent
variable is the observed initial rate of reaction. The concentration of NH4+ is held constant.
Discuss the relationship between the independent variable and the dependent variable in
experiments 4 and 5.
Concentration of NO2 is doubled and so is the initial rate

(d) Discuss the relationship between the independent variable and the dependent
variable in experiments 4 and 6.
The concentration of NO2 and its initial rate are quadrupled from
experiment 4 to experiment 6

(e) Define the term rate law. Give an example of a rate law by using Equation 14.6 on p. 565.

A rate law is an equation that shows how the rate depends on the concentration of the
reactants in a chemical reaction
rate = K(NH4)(NO2)
rate is directly proportional to both the concentration of NH4 and NO2

(f) Discuss the meaning of the terms k, m, and n in Equation 14.7.

k = rate constant
m and n are called reaction orders

rate = (A)m(B)n

(g) Use Equation 14.6 and the data from Table 14.2 to calculate the value of the rate constant k.
Include units in your answer.

rate = K(NH4)(NO2)
experiment 1: 5.4 x 10-7 M/s = K(0.0100M)(0.200M)
K = 2.7 x 10-4 M-1S-1
(h) Does it matter which experimental data (1 – 6) we use in Table 14.2 in order to calculate the
value of the rate constant k? Use data from several different experiments in order to justify
your answer.
No it does not matter because whatever data you use from any experiment, you still
would've gotten the same value of K which is 2.7 x 10-4 M-1S-1

(i) Once we have both the rate law and the value of k for a reaction, we can calculate the rate of
the reaction for any set of concentrations. Calculate the rate law at 25oC when the initial
concentrations of NH4+ and NO2– are both 0.100 M.

Rate = K(NH4)(NO2)
Rate = (2.7 x 10-4M-1S-1)(0.100M(0.100M)
Rate = 2.7 x 10-6 M/s-1
The exponents m and n are called reaction orders. If the exponent is 1, we say that the
reaction is 1st order with respect to that reactant. If the exponent is 2, we say that the
reaction is 2nd order with respect to that reactant. The overall reaction order is the sum of the
orders with respect to each reactant. In most of the rate laws that you will encounter in chemistry,
the order with respect to a reactant will either be 0, 1, or 2.

(j) Is the statement below true or false? Explain.

“The exponent for each substance in a rate law should be the same as the coefficient for
that substance in the overall balanced chemical equation.”

FALSE
rate law must be determined experimentally

(k) Is the statement below true or false? Explain.

“The exponents in the rate law should always be determined from experimental data.”

TRUE

(l) The best way to determine if a reaction is fast or slow is to look at the magnitude of the

rate constant, k

(m) The units of the rate constant will depend on the overall reaction order of the rate law.
For each rate law, assume that the units of the rate are M/s.
Fill in the missing information in the table below.

Rate Law Overall reaction order Units of the rate constant k

rate = k 0 order M/s
rate = k [A] First Order 1/s or s-1
rate = k [A]2 Second Order M-1s-1
rate = k [A][B] second order M-1s-1
rate = k [A]2[B] Third Order M-2s-1

(n) Suppose that the rate law for a reaction is as follows: rate = k
If you double the concentration of A, NO AFFECT
what effect would this have on the rate?

(o) Suppose that the rate law for a reaction is as follows: rate = k [A]
If you double the concentration of A,
what effect would this have on the rate? DOUBLE THE RATE

(p) Suppose that the rate law for a reaction is as follows: rate = k [A]2
If you double the concentration of A, QUADRUPLE THE RATE
what effect would this have on the rate?
(q) The following problem requires you to determine the rate law from experimental data.

2 HgCl2(aq) + C2O42–(aq)  2 Cl–(aq) + 2 CO2(g) + Hg2Cl2(aq)

The equation for the reaction between mercury(II) chloride and the oxalate ion in aqueous solution
is shown above. The initial rate of formation of chloride ion was calculated for various initial
concentrations of the reactants as shown in the following table.

Initial [HgCl2] Initial [C2O42–] Initial Rate of Formation of Cl–

Experiment
(M) (M) (M/min)
1 0.0836 0.202 5.20 x 10-5
2 0.0836 0.404 2.08 x 10-4
3 0.0418 0.404 1.04 x 10-4
4 0.0316 0.514 ?

(i) What is the order of the reaction with respect to HgCl2? Justify your answer.
Rate for exp. 2/Rate for exp. 3 = K(0.836M)m(0.404M)n/K(0.0418M)m(0.404M)n = 2.08 x 10-4/1.04 x 10-4
= 2m=2
m=1
order of reaction is first order with respect to HgCl2

(ii) What is the order of the reaction with respect to C2O42–? Justify your answer.
Rate for exp. 2/Rate for exp. 1 = K(0.836M)m(0.404M)n/K(0.836M)m(0.202M)n = 2.08 x 10-4/5.20 x 10-5
= 2n = 4
n=2
Order of reaction is second order with respect to C2O4

(iii) Write the rate law for this reaction. Rate = K(HgCl2)(C2O4)2

(iv) What is the overall order of this reaction? 1+2 = 3

(v) Calculate the value of the rate constant k. Specify the units in your answer.
Exp. 1: 5.20 x 10-5 M/min= K(0.0836)(0.202)2
K = 0.0152M-2min-1

(vi) What is the value for the initial rate of disappearance of C2O42– for Experiment 1?
since C2O4 is a reactant and for every 2 moles of Cl produced, 1 mole of C2O4 is consumed,
then the initial rate of disappearance for C2O4 will be a negative and half of Initial rate of
formation for Cl. = -1/2(5.20 x 10-5) = -2.60 x 10-5 M/min
(vii) Calculate the initial rate of formation of Cl– for Experiment 4.

rate = K(HgCl2)(C2O4)2
rate = 0.0152(0.0316)(0.514)2
rate = 1.27 x 10-4 M/min
Section 14.4 – The Change of Concentration with Time

For a first-order reaction, the rate law can be written as follows: rate = k [A]

From calculus, the following integrated rate law can be obtained: ln[A]t – ln[A]o = –kt

(a) Define the meaning of each the following terms in the integrated rate law:

[A]o = initial concentration of A at time 0

[A]t = the concentration of A at some later time, t
k = rate constant

t = time

(b) Re-write the first-order integrated rate law so that it is the form “y = mx + b”
ln(A)t = -kt + ln(A)0

(c) The following represents data from a first-order reaction. Fill in the missing data in the table.
Then plot the data on the two graphs below.

Time (s) [A] (M) ln[A]

0 10.0 2.30
10 7.94 2.07
20 6.30 1.84
30 5.00 1.61
40 3.97 1.38
50 3.15 1.15
60 2.50 0.916

2.4

10.0 2.3
2.2
9.0
2.1

8.0 2.0
1.9
7.0
1.8

6.0 1.7
[A] (M)

ln [A]

1.6
5.0
1.5
4.0 1.4
1.3
3.0
1.2
2.0 1.1
1.0
1.0
0.9
0.0 0.8
0 10 20 30 40 50 60 0 10 20 30 40 50 60

Time (s) Time (s)

(d) For a first-order reaction, which of the following will generate a straight-line plot?

[A] vs. time ln[A] vs. time 1/[A] vs. time

(e) Calculate the slope of the straight line that was generated from the data in part (c). Include
units in your answer.
2.07 -2.30/10 s = -0.023 s-1

(f) What does the value of this slope represent in the first-order rate law equation? the rate constant

For a second-order reaction, the rate law can be written as follows: rate = k [A]2

From calculus, the following integrated rate law can be obtained: 1 – 1 = kt

[A]t [A]o

(g) Re-write the second-order integrated rate law so that it is the form “y = mx + b”
1/(A)t = kt + 1/(A)0

(h) The following represents data from a second-order reaction. Fill in the missing data in the
table. Then plot the data on the three graphs below.

Time (s) [A] (M) ln[A] 1/[A] (M-1)

0 10.0 2.30 0.10
10 6.67 1.90 0.15
20 5.00 1.61 0.20
30 4.00 1.39 0.25
40 3.33 1.20 0.30
50 2.86 1.05 0.35
60 2.50 0.92 0.40

2.4
2.3
10.0
2.2
9.0 2.1
2.0 0.50
8.0
1.9 0.45
7.0
1.8
0.40
6.0 1.7
[A] (M)

ln [A]

1.6 0.35
5.0
1 / [A] (M-1)

1.5 0.30
4.0 1.4
0.25
1.3
3.0
1.2 0.20

2.0 1.1 0.15

1.0
1.0 0.10
0.9
0.0 0.8 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60

Time (s) Time (s) Time (s)

(i) For a second-order reaction, which of the following will generate a straight-line plot?

[A] vs. time ln[A] vs. time 1/[A] vs. time

(j) Calculate the slope of the straight line that was generated from the data in part (h). Include
units in your answer.
0.15 - 0.10 / 10s = 0.005 M-1s-1

(k) What does the value of this slope represent in the second-order rate law equation? rate constant, k

For a zero-order reaction, the rate of the reaction (i.e., the disappearance of A) does NOT depend
on the concentration of the reactant A. The rate law for a zero-order reaction can be written as
follows: rate = k
The following integrated rate law can be obtained: [A]t – [A]o = –kt

(l) For a zero-order reaction, which of the following will generate a straight-line plot?

[A] vs. time ln[A] vs. time 1/[A] vs. time

(m) Define the term half-life (t½).

the time required for the concentration of a reactant to reach half its initial value
(A)t1/2 = 1/2(A)0

(n) The following exercise will help you to understand the concept of half-life for a first-order
reaction.
ln(A)t = -kt + ln(A)0
(i) Write the integrated rate law for a first-order reaction:

(ii) Substitute the following values for [A]o and [A]t into the equation: [A]o = 100 [A]t = 50
ln(50) = -kt + ln(100) ln(1/2) = -kt t1/2 = 0.693/k
(iii) Simplify the equation and solve for t: ln(50) - ln(100) = -kt -0.693 = -kt

(o) Notice that the half-life for a first-order rate law does NOT depend on the initial concentration
of the reactant. The half-life remains constant over time throughout the reaction.
Go back to the first-order data table in part (c).

How much time was required for the reactant

concentration to change from 10.0 M to 5.0 M? 30s

How much time was required for the reactant

concentration to change from 5.0 M to 2.5 M? 30s

(p) You may recall that the rate constant for that first-order reaction in part (c) was equal to

0.023 s-1. Verify that 0.693 = t½ 0.693/0.023s-1 = 30s

k

If a decomposition reaction yields data that shows that the half-life is constant over time,
then the reaction must be a first-order reaction.
(q) The half-life for a second-order reaction is NOT constant over time. To verify this, go back to
the second-order data table in part (h).

How much time was required for the reactant

20s
concentration to change from 10.0 M to 5.0 M?

How much time was required for the reactant

concentration to change from 5.0 M to 2.5 M? 40s

Section 14.5 – Temperature and Rate

(a) Most chemical reactions will occur at a faster rate when the temperature of the
reaction is increased.

(b) If the temperature of a chemical reaction is increased, the value of the rate constant
increase
should .

(c) Use the collision model to explain why increasing the concentration of a reactant should
normally cause the reaction rate to increase.

according to the collision model, molecules must collide with each other in order to react.
The greater the number of collisions per second, the greater the reaction rate. When
reactant concentration increases, the number of collisions increases, leading to a faster rate

(d) Use the collision model to explain why increasing the temperature of a reaction causes the
reaction rate to increase.
At a higher temperature, molecules move faster, which leads to an increase in both the force of the
collisions and the frequency of collisions, leading to a faster rate

(e) Consider the reaction between hydrogen and iodine to form hydrogen iodide.

Is it true that every time a hydrogen molecule collides with an iodine molecule,

a molecule of HI is formed? no

(f) In most reactions, reactant molecules must be oriented in a certain way

during a collision in order for a reaction to occur.

(g) In 1888, the Swedish chemist Arrhenius suggested that molecules must
possess a certain amount of energy
in order to react.

This is known as the activation energy, Ea.

The top of the “hill” in an energy diagram represents the activated complex or transition
state. This represents a situation where bonds are partially broken and partially formed.
(h) In the diagram below, label the following

potential energy of CH3N≡C activation energy

potential energy of CH3C≡N overall ΔE for the reaction

activated complex

CH3N≡C  CH3C≡N

activate complex

potential energy of
reactants
potential energy of products

(i) The rate of a reaction depends on the magnitude of Ea. Explain.

The lower the value of the activation energy, the faster the rxn. A relatively low value of Ea means that it is
relatively easy for the reactants to be converted into products. Conversely, a relatively high value of Ea means
that it is more difficult for the reactants to be converted into the products; the rxn would proceed at a slower
rate
(j) In terms of the activation energy, explain why the reaction rate tends to increase at higher
temperatures.
The kinetic energies of the reactant molecules are distributed over a wide range. At a
higher temperature, the average kinetic energy of the reactant increases. This means that a
greater fraction of the molecules have enough kinetic energy to overcome the activation
energy. This leads to a faster reaction rate
 3
(k) Which reaction above (1, 2, or 3) is endothermic?
2
(l) Which reaction should occur at the slowest rate?

Which reaction should occur at the fastest rate? 1

(m) Calculate the activation energy for the reverse reactions.

25 15
1: kJ/mol 2: 40 kJ/mol 3: kJ/mol

Section 14.6 – Reaction Mechanisms

(a) At the beginning of this chapter, the term reaction mechanism was defined as
a step by step, molecular-level view of the pathway form reactants to products

Each event in a reaction mechanism is called an elementary reaction or an elementary step.

If there is only one molecule as the reactant in an elementary step, the reaction is said to be
unimolecular. If an elementary step involves two reactant molecules, the reaction is said to be
bimolecular. Termolecular reactions that involve the simultaneous collision of three particles are
rare.

Consider the following two-step mechanism:

Step 1: NO2 + NO2  NO3 + NO

Step 2: NO3 + CO  NO2 + CO2

(b) What is the overall reaction that is described by this two-step mechanism?

NO2 + CO ---> NO + CO2

(c) The species NO3 is neither a reactant nor a product in this reaction. It is formed in Step 1 and

consumed in Step 2. This is an example of an intermediate .

(d) An intermediate is not the same as a transition state,
because intermediates can be stable and can
sometimes be isolated. Transition states are always
unstable and can never be isolated. If an intermediate
can be detected in an experiment, it can help to
support why a particular reaction mechanism is likely
to occur. Label the intermediate on the diagram at right.

Step 1: Mo(CO)6  Mo(CO)5 + CO

Step 2: Mo(CO)5 + P(CH3)3  Mo(CO)5P(CH3)3

(e) In the proposed two-step reaction mechanism shown above, Mo(CO)5 is classified as

a(n) intermediate and CO is classified as a(n) product .

In Section 14.3, it was mentioned that a rate law must be determined from experimental data. One
cannot determine the order with respect to a reactant by simply looking at its coefficient in the
overall balanced chemical equation. However, the rate law can be determined by examining the
elementary steps of a reaction mechanism. If the experimentally-determined rate law is consistent
with the rate law from a reaction mechanism, it supports the fact that the mechanism is valid.

(f) The rate law of an elementary step is based directly on its molecularity. This means that the
first-order
rate of a unimolecular step is and the rate of a bimolecular step is
second-order .

(g) A reaction mechanism often involves two or more steps. Each elementary step has its own
rate, rate constant, and activation energy. It is often true that one step is much slower than the
others in the mechanism. The overall reaction rate cannot be any faster than the rate of the
slowest elementary step. Because the slow step limits the overall reaction rate, it is called the
rate-determining step , and this step governs the rate law for

the overall reaction.

Consider the following two-step mechanism again. It has been labeled with a slow initial step.

Step 1: NO2 + NO2  NO3 + NO (slow) rate determining step

Step 2: NO3 + CO  NO2 + CO2 (fast)

(h) Based on this mechanism, write the balanced equation for the overall reaction and write the
rate law for the overall reaction.
NO2 + CO ----> NO + CO2

rate = k(NO2)2
the rate of the overall rxn depends on the rate of step 1. The rate determining step is bimolecular
meaning it involves 2 molecules of NO2
(i) A reaction mechanism can never be “proved.” It can only be stated that the rate law predicted
consistent with the experimental data
by the proposed mechanism is

Consider the following two-step mechanism with a slow initial step.

Step 1: N2O  N2 + O (slow)

Step 2: N2O + O  N2 + O2 (fast)

(j) Based on this mechanism, write the balanced equation for the overall reaction and write the
rate law for the overall reaction.
rate of overall rxn depends on the rate of the
2N2O ----> 2N2 + O2 slow reaction, or the rate determining step. The
rate-determining step is unimolecular which
rate = k(N2O) means it involves only one molecule of N2O

Consider the following two-step mechanism with a slow second step.

k1
Step 1: NO + Br2 NOBr2 (fast)
k–1
k2
Step 2: NOBr2 + NO 2 NOBr (slow)

(k) Since Step 2 is the rate-determining step, the rate law for that step governs the rate of the
overall reaction. Write this rate law based on the bimolecular step 2 reaction.
rate = k(NOBr2)(NO)

(l) We cannot accept the rate law written in part (k) as our final answer, because intermediates

are usually unstable and have a low, unknown concentration. We need to rewrite

this rate law so that it is expressed in terms of the reactants.

Since the first step in the mechanism is a fast, reversible process, we can write the following.

k1 [NO][Br2] = k–1[NOBr2]

(m) The equation above is true because the rate of the forward reaction in step 1
is equal to
the rate of the reverse reaction.

(n) Solving for [NOBr2], we get

[NOBr2] = k1/k-1 x (NO)(BR2)

(o) Substituting this relationship into the equation written in part (k), we get

rate = k(NOBr2)(NO) = K(NO)2(Br2)

In general, when a fast step precedes a slow step in a mechanism, we can solve for the
concentration of the intermediate by assuming that an equilibrium is established in the first
step.

Section 14.7 – Catalysis

(a) Define the term catalyst.

a substance that changes the speed of a chemical rxn without
undergoing a permanent change itself

Step 1: 2 Br– + H2O2 + 2 H+  Br2 + 2 H2O

Step 2: Br2 + H2O2  2 Br– + 2 H+ + O2

(b) Based on the mechanism above, write the balanced equation for the overall reaction.
2H2O2 ----> 2H2O + O2

(c) In this mechanism, Br2 is classified as a(n) intermediate because it is formed

as a product in Step 1 and later consumed as a reactant in Step 2.
catalyst
(d) In this mechanism, Br– is classified as a(n) because it is present
as a reactant in Step 1 and it is formed as a product in Step 2.
lower
(e) Catalysts may function by stabilizing a transition state. This would the
activation energy of an elementary step, increasing the rate of that step but leave the
mechanism otherwise unchanged.

(f) Catalysts may also participate in the formation of a new intermediate ,

which provides a new mechanism that provides a faster pathway between reactants and
products.

(g) Label the catalyzed pathway

and the uncatalyzed pathway
in the diagram at right. uncatalyzed rxn

catalyzed rxn

(h) A biological catalyst is known as an enzyme . They can form a bond to the
substrate molecules at the active site. The lock-and-key model provides a simple explanation
for how a particular substrate molecule can bind very specifically to the active site.