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Study Guide in SCIENCE 101: General and Inorganic Chemistry Module No. 8

STUDY GUIDE FOR MODULE NO. 8

CHEMICAL KINETICS
MODULE OVERVIEW

Chemical reactions vary not only with the products that they produce, but also how fast or slow they
occur. Some chemical reactions occur slowly, such as the formation of rust while others, like the explosion of
fireworks, occur quickly and instantaneously. For this Module, we would be concerned with chemical kinetics,
the area of chemistry which concerns reaction rates.

MODULE LEARNING OBJECTIVES

At the end of this Module, you should be able to:

1. explain how certain factors affect rates of reactions
2. determine the rate law of reactions
3. use the Arrhenius equation to relate rate constant to temperature and activation energy
4. identify the factors affecting effective collisions
5. Differentiate homogeneous and heterogeneous catalysis
6. sketch a potential energy profile showing activation energies for the forward and reverse reactions, and
how they are affected by the addition of a catalyst

FACTORS AFFECTING REACTION RATES

Four factors affect the rate at which any particular reaction occurs:

1. Physical state of reactants. For a reaction to occur, the reactants should come in contact. The more
opportunities for contact, the faster the reactions may occur. For heterogeneous reactions (those
reactions where the reactants are of different phases), the rate is increased when the reactants have
more areas of contact.

2. Concentration of reactants. Generally, the higher the concentration of reactants, the faster that a
reaction occurs. This is because the more concentrated the reactants are, the more opportunities that
they have to collide, resulting to a faster rate.

3. Temperature. You have learned from previous Modules that the higher the temperature, the higher
the kinetic energy of the particles, resulting to more rapid movements and increased collision. Because
of this, reactions occur more rapidly.

4. Presence of a catalyst. A catalyst is a substance which increases the rate of a certain chemical
reaction but is not used up. When a catalyst is used to speed up a reaction, the collisions that occur
between the reactants are affected, which leads to a faster rate.

Why these factors affect reaction rate will be discussed in more detail as we move on with this module.

LEARNING ACTIVITY 1

Cite at least three (3) examples or instances where the each of the given factors can be observed affecting
reaction rates. Justify your answers.

REACTION RATES

Before delving into the next parts of the module, you may want to watch the video clip Introduction to
kinetics | Energy and enzymes | Biology | Khan Academy using the link
https://www.youtube.com/watch?v=__zy-oOLPug&list=PL166048DD75B05C0D&index=40. This will help you
to have an background on the concept of kinetics and the connections of each topic for this module. You may
also want to refer to this video as you move on with the module to have a more visual and deep understanding
of reaction rates.

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The rate of a certain reaction refers to the change of the concentration of reactants or products per unit
time. Usually, reaction rates are expressed as M/s or change in concentration in molarity per second. For
example, consider the reaction A(g) → B(g). Suppose we start with 1 mol of A in a 1 L closed container. As
time passes, A becomes B.

t=0s t = 10 s t = 20 s t = 30 s t = 40 s
Amount of A 1.0 mol 0.90 mol 0.84 mol 0.79 mol 0.75 mol
Amount of B 0 mol 0.10 mol 0.16 mol 0.21 mol 0.25 mol

Notice that as time passes, the amount (and concentration) of A increases and the amount (and
concentration) of B increases. However, the total concentration remains the same. This means that the average
rate of reaction (how fast a reaction proceeds) can be measured from the disappearance of A or the appearance
of B. In the case of the above hypothetical reaction:

−∆[𝐴] ∆[𝐵]
𝑅𝑎𝑡𝑒 = =
∆𝑡 ∆𝑡

For example, the rate of reaction from t=0 s to t=10 s is

𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
−[0.90 − 1.0 ] [0.10 −0 ] 𝑀
𝐿 𝐿 𝐿 𝐿
𝑅𝑎𝑡𝑒 = = = 0.010
[10 𝑠 − 0 𝑠] [10 𝑠 − 0 𝑠] 𝑠

The average rate of the reaction from t=0 s to t=40 s is

𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
−[0.75 − 1.0 ] [0.25 −0 ] 𝑀
𝐿 𝐿 𝐿 𝐿
𝑅𝑎𝑡𝑒 = = = 0.0063
[40 𝑠 − 0 𝑠] [40 𝑠 − 0 𝑠] 𝑠

Take note that the negative sign in A indicates disappearance. Rates generally are expressed as
positive quantities.

If we look at the average rates for every 10-second interval, we have

t=0s t = 10 s t = 20 s t = 30 s t = 40 s
Amount of A 1.0 mol 0.90 mol 0.84 mol 0.79 mol 0.75 mol
Amount of B 0 mol 0.10 mol 0.16 mol 0.21 mol 0.25 mol
Rate 0.010 M/s 0.0060 M/s 0.0050 M/s 0.0040 M/s

Notice that the rate as time proceeds slows down. This is typical for many reactions since the amount
of the reactant decreases as time passes.

For the reaction above, the proportion of A and B is 1:1. Consider the following reaction where the
proportions of the reactants and products are not 1:1:

aA + bB → cC + dD

For this reaction, we can say that for every a moles of A that disappears, c moles of C appears.
Consequently, for every d moles of D that appears, b moles of B disappears. Therefore, we can monitor the
rate of the reaction by inspecting the changes of concentration of A, B, C, or D through the following relationship:

−∆[𝐴] −∆[𝐵] ∆[𝐶] ∆[𝐷]

𝑅𝑎𝑡𝑒 = = = =
𝑎∆𝑡 𝑏∆𝑡 𝑐∆𝑡 𝑑∆𝑡

For example if the reaction is

A + 2B → 3C + 4D

For every 1 mole of A that disappears, 4 moles of D appears. This means that the rate of appearance
of one mole of D is four times faster than the rate of disappearance of one mole of A. Thus, to get the rate, we
need to divide the rate of appearance of D by 4.

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LEARNING ACTIVITY 2

1. Consider the following hypothetical aqueous reaction:

A(aq) → B(aq)

A flask is charged with 0.200 mol of A in a total volume of 100.0 mL. The following data are collected:

Time (min) 0 20 40 60 80
Moles of A 0.200 0.140 0.100 0.070 0.050

a. Calculate the number of moles of B at each time in the table, assuming that there are no molecules
of B at time zero and that A cleanly converts to B with no intermediates.
b. Calculate the average rate of disappearance of A for each 20-min interval in units of M/s.
c. Calculate the average rate of disappearance of A from the start of reaction to t = 80 min in units of
M/s.
d. Between t = 0 min and t = 60 min, what is the average rate of appearance of B in units of M/s?
Assume that the volume of the solution is constant.

2. For each of the following gas-phase reactions, write the rate expression in terms of the appearance of
each product and disappearance of each reactant:
a. O3(g) + H2O(g) → 2 O2(g) + H2(g)
b. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)
c. 2 C2H2(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(g)
d. C3H7NH2(g) → C3H6(g) + NH3(g)

3. Consider the reaction O3(g) + H2O(g) → 2 O2(g) + H2(g). If the concentration of O3 is decreasing at the
rate of 0.025 M/s, what are the rates of change in the concentrations of O2 and H2?

INSTANTANEOUS RATES

Suppose we have the reaction W(g) → X(g). The rate of the reaction was measured by measuring the
concentration of W every 15-s intervals for t=90 s. The data for the said hypothetical reaction is as follows:

Time [W] Average Rate (M/s)

0 0.100
15 0.072 0.0019
30 0.049 0.0015
45 0.030 0.0013
60 0.016 0.00093
75 0.0063 0.00065
90 0.0010 0.00035

Graphing the data, we get the following:

0.1000
0.0800
0.0600
[W]

0.0400
0.0200
0.0000
-10 10 30 50 70 90
t (s)

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With this graph, we can determine the rate of the reaction at a certain time. The rate at a certain time
is called the instantaneous rate. This can be obtained by getting the slope of the line tangent to the graph.
Suppose we want to get the rate of reaction at t = 20 s. By drawing a line tangent to t = 20 s, we get the
instantaneous rate. We also call the instantaneous rate at t = 0 the initial rate of reaction. For the rest of the
Module, reaction rate will refer to instantaneous rate.

RATE LAWS

We have learned previously that the rates of reaction depend on the concentrations of the species
involved. Suppose an experiment was conducted for the following hypothetical reaction at a certain
temperature:

A+B→C+D

Suppose the concentrations of A and B were varied and the initial rates of the reactions were measured
and the following data were collected.

Experiment [A] [B] Initial Rate (M/s)

1 1.00 2.00 3.00 x 10-8
2 2.00 2.00 6.00 x 10-8
3 1.00 4.00 6.00 x 10-8

Notice that the initial rate doubled when the concentration of A is doubled while the concentration of B
is held constant. It can also be observed than when the concentration of B is doubled, the initial rate also
doubled when the concentration of A is held constant. This means that increasing the concentration of either
A or B will increase the rate of reaction. In this case, the rate of the reaction depends on the concentrations of
the reactants. This can be expressed as a rate law, an equation that relates the concentration of reactants to
the rate of the chemical reaction. For the given reaction, the rate law for a given temperature can be expressed
as

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑚 [𝐵]𝑛

where k is the rate constant at a given temperature and m and n are reaction orders.

For the given rate law, the reaction order with respect to A is m and the reaction order with respect to
be is n. The overall reaction order is m + n. For example, if the rate law is

𝑅𝑎𝑡𝑒 = 𝑘 [𝐴][𝐵]

the reaction order is 1 with respect to A and 1 with respect B. The over-all reaction order is 2.

However, if the rate law is

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 [𝐵]

the reaction order is 2 with respect to A and 1 with respect B. The over-all reaction order is 3.

The reaction order determines how much the reactant affects the rate. The higher the value of the
reaction order for a certain reactant, the greater its influence in the reaction rate. It should be noted, however,
that m and n are not necessarily the coefficients of the reactants in the chemical equation. This is because rate
laws are determined experimentally.

The rate constant k is an indication of how fast or slow a certain reaction is. The higher the value of k
the faster the reaction rate. Usually, reactions with a k value of around 109 are deemed fast, while those with
value of 10 or lower are slow.

The unit for k depends on the reaction order. For example, if the rate law is

𝑅𝑎𝑡𝑒 = 𝑘 [𝐴][𝐵]

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The unit for k is

𝑅𝑎𝑡𝑒 𝑢𝑛𝑖𝑡 = (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡)(𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑢𝑛𝑖𝑡)

𝑀
= (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡)(𝑀)(𝑀)
𝑠
𝑀
1
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡 = 𝑠 2 = 𝑜𝑟 𝑀 −1 𝑠 −1
𝑀 𝑀∙𝑠

However, if the rate law is

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 [𝐵]

The the unit for k is

𝑅𝑎𝑡𝑒 𝑢𝑛𝑖𝑡 = (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡)(𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑢𝑛𝑖𝑡)

𝑀
= (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡)(𝑀)2 (𝑀)
𝑠
𝑀
1
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑢𝑛𝑖𝑡 = 𝑠 3 = 2 𝑜𝑟 𝑀 −2 𝑠 −1
𝑀 𝑀 ∙𝑠

For more examples on how to calculate the unit for k, you may want to visit
https://www.youtube.com/watch?v=fLL8xxjhDPI&list=PL166048DD75B05C0D&index=117 for the video entitle
Finding units of rate constant k | Knetics | Chemistry | Khan Academy.

LEARNING ACTIVITY 3

1. A reaction is zero order in A, second order in B and first order in C.

a. Write the rate law for the reaction.
b. What happens to the rate is the concentration of A is doubled and B and C are held constant?
c. What happens to the rate is the concentration of B is tripled and A and C are held constant?
d. What happens to the rate is the concentration of C is halved and B is doubled while A is held
constant?

2. The following reaction is first order in H2 and second order in NO

2 NO(g) + 2 H2(g) → N2(g) + 2 H2O(g)

a. Write the rate law of the reaction.

b. What is the unit for k in the reaction?
c. If the magnitude of k is 6.0 x 104 at 1000 K, what is the reaction rate when [NO] = 0.035 M and
[H2] = 0.015 M?
d. What is the reaction rate at 1000 K when the concentration of NO is increased to 0.10 M, while
the concentration of H2 is 0.010 M?

DETERMINING RATE LAWS

Now that you have learned what rate laws are, how can one derive the rate law for a certain reaction?
Let us remember that rate laws are determined experimentally, and thus, we need experimental data to
determine the rate law of a certain reaction. We also need to remember that the rate constant does not change
for any concentration for the same reaction for a certain temperature. Thus, changing the concentration of the
reactants will not change the rate constant.

Consider the reaction A + B → C + D and the experiment given above. Since the values of k, m, and
n for all experiments are the same, we can say that

𝑅𝑎𝑡𝑒1 = 𝑘[𝐴]1𝑚 [𝐵]1𝑛

𝑅𝑎𝑡𝑒2 = 𝑘[𝐴]𝑚 𝑛
2 [𝐵]2

𝑅𝑎𝑡𝑒3 = 𝑘[𝐴]𝑚 𝑛
3 [𝐵]3

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To determine m, we could divide the rate for Experiment 1 and 2. We can have

𝑅𝑎𝑡𝑒1 𝑘[𝐴]1𝑚 [𝐵]1𝑛

=
𝑅𝑎𝑡𝑒2 𝑘[𝐴]𝑚2 [𝐵]2
𝑛

3.00 × 10−8 𝑀/𝑠 𝑘[1.00 𝑀]1𝑚 [2.00]1𝑛

=
6.00 × 10−8 𝑀/𝑠 𝑘[2.00 𝑀]𝑚2 [2.00]2
𝑛

Since k, m and n are the same for the reaction, we would be left with

1 1 𝑚
=( )
2 2
Therefore,
𝑚 = 1.

To determine n, we could divide the rate for Experiment 1 and 3. We can have

𝑅𝑎𝑡𝑒1 𝑘[𝐴]1𝑚 [𝐵]1𝑛

=
𝑅𝑎𝑡𝑒3 𝑘[𝐴]𝑚3 [𝐵]3
𝑛

3.00 × 10−8 𝑀/𝑠 𝑘[1.00 𝑀]1𝑚 [2.00]1𝑛

=
6.00 × 10−8 𝑀/𝑠 𝑘[1.00 𝑀]𝑚2 [4.00]2
𝑛

Since k, m and n are the same for the reaction, we would be left with

1 1 𝑛
=( )
2 2
Therefore,
𝑛 = 1.

To obtain k, we could substitute the values of m and n to any of the equations given. If Experiment 1
is chosen, this would give us:
𝑅𝑎𝑡𝑒1 = 𝑘[𝐴]1𝑚 [𝐵]1𝑛

3.00 × 10−8 𝑀/𝑠 = 𝑘[1.00 𝑀]1 [2.00]1

1.50 × 10−8
𝑘=
𝑀2 ∙ 𝑠

The rate law for the given reaction is

1.50 × 10−8
𝑅𝑎𝑡𝑒 = [𝐴][𝐵]
𝑀2 ∙ 𝑠

For additional examples on how to determine rate laws, you may want to visit https://youtu.be/6Ng8ayarWHw
for the video Rate law and reaction order | Knetics | Chemistry | Khan Academy.

LEARNING ACTIVITY 4

The reaction 2 ClO2(aq) + 2 OH-(aq) → ClO3- (aq) +ClO2- (aq) + H2O(l) was studied with the following results:

Experiment [ClO2] (M) [OH-] (M) Initial Rate (M/s)

1 0.060 0.030 0.0248
2 0.020 0.030 0.00276
3 0.020 0.090 0.00828

Calculate the rate when [ClO2] = 0.100 M and [OH-] = 0.050 M.

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RATE LAWS AND TIME

The previous lesson showed how we can use rate laws to calculate the rate of reactions using the rate
constant and concentration of reactants. We can also use these rate laws to relate the concentrations of
products or reactants and time. A good calculus background will help you understand how we can relate these
quantities. However, if you do not have a calculus background, you may still be able to use the resulting
equations.

First-Order Reactions

If a reaction is in the first order, the rate of the reaction only depends on the concentration of just one
reactant. This means that increasing or decreasing the concentration of other reactants does not affect the
rate. Such reactions will have a rate law of

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]
Integrating the rate law, we get

ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0

where [A]t is the concentration of reactant at time t and [A] 0 is the initial concentration of the reactant. You may
use the equation to solve a variety of quantities, such as the concentration of the remaining reactants at any
given time during a reaction or the time required for a reactant’s concentration below a certain level.

Second-Order Reactions

If a reaction is in the second order, the rate of the reaction depends on the concentration of either one
reactant but with a reaction order of 2 or two reactants. For the first case, the rate law is

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2

Integrating the reaction, we get

1 1
= 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0

where [A]t is the concentration of reactant at time t and [A] 0 is the initial concentration of the reactant. For the
second case, the rate law is

𝑅𝑎𝑡𝑒 = 𝑘 [𝐴][𝐵]

Integrating the reaction, we get

[𝐴]𝑡 [𝐴]0
ln = 𝑘 ([𝐴]0 − [𝐵]0 )𝑡 + ln
[𝐵]𝑡 [𝐵]0

where [A]t is the concentration of reactant A at time t, [A] 0 is the initial concentration of the reactant A at time t,
[B]t is the concentration of reactant B at time t, and [B] 0 is the initial concentration of the reactant B at time t.

Zero-Order Reactions

If a reaction is in the zero order, the rate of the reaction does not depend on the concentration of the
reactant. For the first case, the rate law is

𝑅𝑎𝑡𝑒 = 𝑘

Integrating the reaction, we get

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0

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LEARNING ACTIVITY 5

Consider the following reaction:

2 C4H6(g) → C8H12(g)

The rate constant at 500 K is 1.4 x 10-2 M-1·s-1 and the initial concentration of C4H6 is 0.020 M.
a. What is the order of the reaction?
b. How much C4H6(g) will remain after 1 hour at the same temperature?

TEMPERATURE AND REACTION RATE

The previous lesson showed that the reaction rate if affected by concentration. Aside from this factor,
temperature also affects the rates of reactions. For this lesson, we will see how temperature affects rate and
how it relates to the rate law.

Generally, an increase in temperature increases the rate. An increase in temperature increases the
value of k in the rate law, effectively increasing the rate of the reaction. How this affects the rate can be
explained by the collision model.

The Collision Model

According to the collision model, for a reaction to occur, the particles involved in the reaction should
collide. Therefore, the more collisions that occur for a particular time, the faster the reaction rate. This could
happen if the concentration of the reactants is high or if the movement of the particles is fast. High
concentrations of reactants and high temperatures allow for more frequent and energetic collisions.

However, it is not enough that the molecules collide; they should collide properly. This means that the
orientation of the molecules colliding should be correct in order for a reaction to occur. Consider the reaction
below:

Cl + NOCl → Cl2 + NO

If the green spheres are Cl atoms, the blue spheres are N atoms, and the red spheres are O atoms, we could
see that collisions between Cl and NOCl atoms does not always result in a reaction. In the case of (a), the
NOCl and Cl atoms are oriented properly, allowing for the formation of Cl2. However, for (b), the NOCl atoms
are not properly oriented, and thus, no Cl2 is formed.

Another factor that determines whether a collision produces a reaction is energy. According to Svante
Arrhenius, colliding molecules must have a certain minimum energy for a reaction to occur. This energy comes
from the kinetic energies of the molecules that is used to transform the potential energy for bond formation and
breaking. This minimum energy is called the activation energy (Ea). This energy varies, depending on the
reaction that occurs.

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The concept of activation energy can be pictured in the energy profile diagram below.

The energy profile shows an exothermic reaction where the energy of the initial state is greater than
the energy of the final state; thus, energy is released. We can see that for the reaction to progress from its
initial state to its final state, we need to overcome a certain energy barrier. This is the activation energy.

If we reverse the reaction, the energy profile would look like the diagram below:

Notice that reversing the reaction will make it endothermic. Just like in exothermic reactions, it still
needs to overcome the activation energy for it to progress. However, notice that the activation energy increased.
Since the reaction constant is related to the activation energy, the two reactions differ in rate. The lower the
activation energy, the higher the value of the reaction constant, and therefore the faster the rate. Thus, the
reverse reaction is slower than the forward reaction.

Even though the activation energy changed when we reverse the reaction, notice that the energy
difference (ΔE) between the reactants and products did not change. This means that activation energy does
not affect the energy difference between the reactants and products.

ARRHENIUS EQUATION

The Arrhenius equation relates the number of collisions per second, the collisions that have proper
orientation, activation energy. This equation is expressed as
−𝐸𝑎
−𝐸𝑎
𝑘 = 𝐴𝑒 𝑅𝑇 or ln 𝑘 = + ln 𝐴
𝑅𝑇

where k is the rate constant, Ea is the activation energy, T is absolute temperature, R is the ideal gas constant
𝐽
(8.314 𝑚𝑜𝑙∙𝐾) and A is the frequency factor, which relates to the number of collisions and the probability that the
collisions are properly oriented. We can also use this equation to calculate the activation energy of a reaction
occurring at two different temperatures, provided that A does not change much as temperature changes and
that the rate constants are known for each temperature. For this we have
−𝐸𝑎 −𝐸𝑎
ln 𝑘1 = + ln 𝐴 and ln 𝑘2 = + ln 𝐴
𝑅𝑇1 𝑅𝑇2

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Manipulating the equations we can have

𝑘1 −𝐸𝑎 1 1
ln = ( − )
𝑘2 𝑅 𝑇2 𝑇1

LEARNING ACTIVITY 7

1. In which of the following reactions would you expect the orientation factor to be more important in
leading to reaction: O3 + O → 2O2 or NO + NO3 → 2NO2? Justify your answer.
2. Indicate whether each statement is TRUE or FALSE. Justify your answer.
a. A reaction that has a small rate constant must have a small frequency factor.
b. A smaller ratio of effectively oriented collisions to all possible collisions, would lead to a smaller
orientation factor.
c. Exothermic reactions are faster than endothermic reactions.
d. If you compare two reactions with similar collision factors, the one with the larger activation
energy will be faster.
e. If you double the temperature for a reaction, you cut the activation energy in half.
f. If you measure the rate constant for a reaction at different temperatures, you can calculate the
overall enthalpy change for the reaction.
g. Increasing the reaction temperature increases the fraction of successful collisions between
reactants
3. For the elementary process N2O5(g) → NO2(g) + NO3(g) the activation energy and overall ∆E are 154
kJ/mol and 136 kJ/mol, respectively.
a. Sketch the energy profile for this reaction, and label Ea and ∆E.
b. Is the reaction exothermic or endothermic?
c. What is the activation energy for the reverse reaction?
4. Based on their activation energies and energy changes and assuming that all collision factors are the
same, rank the REVERSE of following reactions from slowest to fastest.
a. Ea = 75 kJ/mol; ∆E = -20 kJ/mol
b. Ea = 100 kJ/mol; ∆E = +30 kJ/mol
c. Ea = 85 kJ/mol; ∆E = -50 kJ/mol
5. 2NO(g) → N2(g) and O2(g) is second order with a rate constant of 0.0796 M-1s-1 at 737 °C and 0.0815
M-1s-1 at 947 °C. Calculate the activation energy for the reaction.

REACTION MECHANISMS

Consider the following reaction:

2ICl(l) + H2(g) →2HCl(g) + I2(s)

From this reaction, we know that the reactants become the products. However, it does not tell us what
happens in the molecular level when this reaction occurs. It does not tell us which bonds are broken and which
are formed and when and how the reactants change orientations to produce the product. This information can
be seen from the reaction mechanism.

This means that the reaction 2ICl(l) + H2(g) →2HCl(g) + I2(s) is an oversimplification in what actually
happens in the molecular level. This reaction may occur in just one step, or several steps. Each step or event
that happens in in a reaction is called an elementary reaction. The molecularity of a reaction is determined
by the number of molecules that participate in an elementary reaction. If an elementary reaction only involves
one molecule, the reaction is unimolecular. If two molecules are involved, the reaction is bimolecular. If three
needs to collide in an elementary step, the reaction is termolecular. However, most elementary reactions are
unimolecular and bimolecular, and we rarely see termolecular reactions (or reactions with even higher
molecularity).

If a reaction mechanism is composed of several elementary reactions, the reaction has a multistep
mechanism. The example given above example has actually a two-step mechanism, with each elementary
reaction being bimolecular

Step 1: ICl + H2 →HCl + HI

Step 2: ICl + HI →HCl + I2

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2ICl + H2 →2HCl + I2

Notice that HI is not found in the over-all reaction. This means that HI is an intermediate, which is formed in
one elementary reaction but is also consumed. Multi-step mechanisms will have one or more intermediates.

Each elementary reaction in a multi-step mechanism will have a certain reaction rate. The rate law of
a certain elementary reaction is directly based on its molecularity. This means that for a unimolecular reaction,
the reaction is in the first order. For a bimolecular reaction, the reaction is in the second order. This is the
reason why we do not use the coefficients of a balanced chemical equation in determining the reaction order of
a certain reaction: we have to look at the elementary reactions since each have their own reaction rate.

Rate-Determining Step

As was mentioned, for a multi-step mechanism, each elementary reaction has their own reaction rates.
Their reaction rates may not be the same; some may be slow, some may be fast. In a series of elementary
reaction, the slowest reaction is the one which limits the reaction rate of the over-all reaction. Thus, this is called
the rate-determining step.

Consider the multi-step reaction:

k1
Step 1: NO2 (g) + NO2 (g) → NO3 (g) + NO(g) (slow)
k2
Step 2: NO3 (g) + CO(g) → NO2 (g) + CO2 (g) (fast)
NO2 (g) + CO(g) → NO(g) + CO2 (g)

When the rate law for this reaction is measured, it was found out that the rate law is

𝑅𝑎𝑡𝑒 = 𝑘[𝑁𝑂2 ]2

This is consistent with the rates of the elementary reactions: the rate k 1 is much slower than the rate k2.
Thus, k1 is the rate-determining step.

Consider another example

k1
Step 1: NO(g) + Br2 (g) ⇌ NOBr2 (g) (fast)
k2
Step 2: NOBr2 (g) + NO(g) → 2NOBr(g) (slow)
2NO(g) + Br2 (g) → 2NOBr(g)

Experimentally, the rate law of the reaction is

𝑅𝑎𝑡𝑒 = 𝑘[𝑁𝑂]2 [𝐵𝑟2 ]

If the rate law is based on the slower reaction, the rate law would be expressed as

𝑅𝑎𝑡𝑒 = 𝑘2 [𝑁𝑂𝐵𝑟2 ][𝑁𝑂]

However, since NOBr2 is an intermediate, its concentration is usually very low and it could be unstable.
Therefore, the rate law is better expressed using the reactants. In this case, we can assume that the formation
of NOBr2 depends on NO and Br2. Since the first reaction is reversible, we could have the following:

k−1
NOBr2 (g) → NO(g) + Br2 (g)

If we write the rate law for both the forward and reverse reactions and solve for NOBr2, we will have

𝑅𝑎𝑡𝑒𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑅𝑎𝑡𝑒𝑟𝑒𝑣𝑒𝑟𝑠𝑒

𝑘1 [𝑁𝑂][𝐵𝑟2 ] = 𝑘−1 [𝑁𝑂𝐵𝑟2 ]

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𝑘1 [𝑁𝑂][𝐵𝑟2 ]
= [𝑁𝑂𝐵𝑟2 ]
𝑘−1
If we substitute this in the rate law of the slow elementary reaction, we will have

𝑘1 [𝑁𝑂][𝐵𝑟2 ]
𝑅𝑎𝑡𝑒 = 𝑘2 [𝑁𝑂]
𝑘−1

𝑅𝑎𝑡𝑒 = 𝑘[𝑁𝑂]2 [𝐵𝑟2 ]

which is consistent with the experimentally-derived rate law.

CATALYSIS

In the first sections we have looked at how temperature and concentration affect the rates of reactions.
There is another factor can affect the rate of a reaction that is extremely important, especially in biological
systems. This involves a substance called a catalyst, which makes the reaction rate faster but does not get
consumed. Catalysts can either be a homogeneous catalyst (the same phases as the reactants) or a
heterogeneous catalyst (a different phase as the reactants).

Consider the slow reaction

2 H2O2(aq) → 2 H2O(l) + O2(g)

When bromide ion is added, a series of reaction occurs

2 Br-(aq) + H2O2(aq) + 2 H+(aq) → Br2(aq) + 2 H2O(l)

Br2(aq) + H2O2(aq) → 2 Br-(aq) + 2 H+(aq) + O2(g)

Notice that the bromide ion initially reacts with the hydrogen peroxide in the first reaction, but is reformed in the
second. The net reaction will still be 2 H2O2(aq) → 2 H2O(l) + O2(g). This makes bromide ion a catalyst for the
reaction (bromine, on the other hand, is an intermediate because it will be formed reaction in the first but
consumed in the second reaction).

To visualize a catalyzed reaction of hydrogen peroxide, you may visit https://youtu.be/kV0BqG0On9E

and watch the video Chemistry - 3Sec - The effect of catalysts on the rate of chemical reactions. In the video,
take note of the catalysts used.

Considering the Arrhenius equation, catalysts can achieve this effect by either affecting the value of A
or Ea: either ensure better molecular orientation or provide better reaction mechanisms that has lower activation
energy. For the reaction above, the energy profile for the catalyzed and uncatalyzed reaction is

Notice that the catalyzed reaction has more steps, but both have lower activation energies, and
therefore, faster rates.

Now that we have looked at the different aspects of reaction rates, you may want to visit the link
https://youtu.be/JpoOfrPKgmM to have a synthesis of why and how each factor mentioned at the beginning of

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the module affect reaction rates.

LEARNING ACTIVITY 8

1. Consider the energy profile below:

a. How many elementary reactions are in the reaction mechanism?

b. How many intermediates are formed in the reaction?
c. Which step is rate limiting?
d. For the overall reaction, is ∆E positive, negative, or zero?

2. Consider the mechanism of the iodide-catalyzed decomposition of hydrogen peroxide

H2O2(aq) + I-(aq) → H2O(l) + IO-(aq) (slow)

IO-(aq) + H2O2(aq) → H2O(l) + O2(g) + I-(aq) (fast)

a. Write the chemical equation for the overall process.

b. Identify the intermediate, if any, in the mechanism.
c. Predict the rate law for the overall process.

After answering the Learning Activities in this Module, be ready for a quiz covering aspects of Chemical
Kinetics

SUMMARY

The following learning points summarize what you have learned in this section:

• Chemical kinetics is the study of reaction rates. Factors that affect reaction rate are the physical state
of the reactants; concentration; temperature; and the presence of catalysts.

• Reaction rates are usually expressed as changes in concentration per unit time. For most reactions, a
plot of molarity versus time shows that the rate slows down as the reaction proceeds. The instantaneous
rate is the slope of a line drawn tangent to the concentration-versus-time curve at a specific time.

• The quantitative relationship between rate and concentration is expressed by a rate law. Rate laws
must be determined experimentally. Rate laws can be used to determine the concentrations of reactants
or products at any time during a reaction.

• The collision model, which assumes that reactions occur as a result of collisions between molecules,
helps explain why the magnitudes of rate constants increase with increasing temperature. The greater
the kinetic energy of the colliding molecules, the greater is the energy of collision. The minimum energy
required for a reaction to occur is called the activation energy.

• The reactants must also be correctly oriented relative to one another in order for a collision to be
effective.

• Because the kinetic energy of molecules depends on temperature, the rate constant of a reaction is
very dependent on temperature. The relationship between k and temperature is given by the Arrhenius
equation.

• A reaction mechanism details the individual steps that occur in the course of a reaction. Each of these
steps, called elementary reactions, has a well-defined rate law that depends on the number of
molecules (the molecularity) of the step.

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• Many reactions occur by a multistep mechanism, involving two or more elementary reactions, or steps.
When a mechanism has several elementary steps, the overall rate is limited by the slowest elementary
step, called the rate-determining step.

• A catalyst is a substance that increases the rate of a reaction without undergoing a net chemical change
itself. It does so by providing a different mechanism for the reaction, one that has a lower activation
energy.

REFERENCES

1. Brown, T. et al. (2018). Chemistry: The Central Science (14th Edition). Pearson Education South Asia
PTE. LTD.
2. Elmoasser Books (2 November 2017). Chemistry - 3Sec - The effect of catalysts on the rate of chemical
reactions. Retrieved from https://youtu.be/kV0BqG0On9E.
3. Khan Academy (16 May 2016). Finding units of rate constant k | Knetics | Chemistry | Khan Academy.
Retrieved from:
https://www.youtube.com/watch?v=fLL8xxjhDPI&list=PL166048DD75B05C0D&index=117.
4. Khan Academy (3 September 2009). Introduction to kinetics | Energy and enzymes | Biology | Khan
Academy. Retrieved from: https://www.youtube.com/watch?v=__zy-
oOLPug&list=PL166048DD75B05C0D&index=40.
5. Khan Academy Organic Chemistry (12 October 2014). Rate law and reaction order | Knetics | Chemistry
| Khan Academy. Retrieved from: https://youtu.be/6Ng8ayarWHw.
6. Masterton, William L. and Cecile N. Hurley. (2009). Chemistry: Principles and Reactions. 6th edition.
C&E Publishing.
7. Silberberg, Martin S. (2013). Principles of General Chemistry. 3rd edition. McGraw-Hill.
8. The Organic Chemistry Tutor (21 November 2017). Factors Affecting the Rate of the Reaction -
Chemical Kinetics. Retrieved from:
https://www.youtube.com/watch?v=JpoOfrPKgmM&feature=youtu.be

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