Energy Changes and

Rates of Reaction

UNIT 3 CONTENTS
CHAPTER 5
I n the nineteenth century, railway
tunnels were blasted through the
Energy and Change
Rocky Mountains to connect British
CHAPTER 6 Columbia with the rest of Canada.
Rates of Chemical Reactions Workers used nitroglycerin to blast
through the rock. This compound is
UNIT 3 PROJECT
so unstable, however, that accidents
Developing a Bulletin About
were frequent and many workers
Catalysts and Enzymes
died. Alfred B. Nobel found a way
to stabilize nitroglycerin, and make
UNIT 3 OVERALL EXPECTATIONS it safer to use, when he invented
What energy transformations dynamite.
and mechanisms are involved What makes nitroglycerin such
in chemical change? a dangerous substance? First, nitro-
What skills are involved in glycerin, C3H5(NO3)3() , gives off a
determining energy changes large amount of energy when it
for physical and chemical decomposes. In fact, about 1500 kJ
processes and rates of of energy is released for every mole
reaction? of nitroglycerin that reacts. Second,
How do chemical technologies the decomposition of nitroglycerin
and processes depend on occurs very quickly—in a fraction
the energetics of chemical of a second. This fast, exothermic
reactions? reaction is accompanied by a
tremendous shock wave, which is
Unit Project Prep caused by the expansion of the
gaseous products. Finally,
Look ahead to the project at the
end of Unit 3. Start preparing for nitroglycerin is highly shock-
the project now by listing what you sensitive. Simply shaking or jarring
already know about catalysts and it can cause it to react.
enzymes. Think about how catalysts Thus, nitroglycerin’s explosive
and enzymes affect chemical properties are caused by three fac-
reactions. As you work through the tors: the energy that is given off by
unit, plan how you will investigate
its decomposition, the rate at which
and present a bulletin about the
the reaction occurs, and the small
uses of catalysts and enzymes in
Canadian industries. amount of energy that is needed to
initiate the reaction. In this unit,
you will learn about the energy and
rates of various chemical reactions.

218
 Energy and Change

Chapter Preview T hink about a prehistoric family group building a fire. It may seem as
though this fire does not have much in common with a nuclear power
5.1 The Energy of Physical,
plant. Both the fire and the nuclear power plant, however, are technolo-
Chemical, and Nuclear
gies that harness energy-producing processes.
Changes
As you learned in Unit 2, humans continually devise new techno-
5.2 Determining Enthalpy
logies that use chemical reactions to produce materials with useful
of Reaction by
Experiment
properties. Since the invention of fire, humans have also worked to devise
technologies that harness energy. These technologies depend on the fact
5.3 Hess’s Law of Heat
that every chemical, physical, and nuclear process is accompanied by a
Summation
characteristic energy change. Consider the melting of an ice cube to cool a
5.4 Energy Sources
drink, the combustion of natural gas to cook a meal, and the large-scale
production of electricity via a nuclear power plant. All societies depend
on the energy changes that are associated with these physical, chemical,
and nuclear processes.
In this chapter, you will study the causes and magnitude of the
energy changes that accompany physical changes, chemical reactions,
and nuclear reactions. You will see that different processes involve vastly
Prerequisite
different amounts of energy. You will learn how to calculate the amount
Concepts and Skills of energy that is absorbed or released by many simple physical changes
and chemical reactions. This will allow you to predict energy changes
Before you begin this chapter,
without having to carry out the reaction—an important skill to have when
review the following concepts
and skills: dealing with dangerous reactions. Finally, you will examine the efficiency
and environmental impact of traditional and alternative energy sources.
■ writing balanced chemical
equations (Concepts and
Skills Review)
■ performing stoichiometric
calculations (Concepts
and Skills Review)

Enough radiant energy reaches Earth every day to meet

the world’s energy needs many times over. Since this is
the case, why do fossil fuels provide most of Canada’s
energy, while solar power supplies only a tiny fraction?

220 MHR • Unit 3 Energy Changes and Rates of Reaction

The Energy of Physical, Chemical,
and Nuclear Processes
5.1
Most physical changes, chemical reactions, and nuclear reactions are Section Preview/
accompanied by changes in energy. These energy changes are crucial to Specific Expectations
life on Earth. For example, chemical reactions in your body generate the In this section, you will
heat that helps to regulate your body temperature. Physical changes, such ■ write thermochemical equa-
as evaporation, help to keep your body cool. On a much larger scale, there tions, expressing the energy
would be no life on Earth without the energy from the nuclear reactions change as a heat term in the
that take place in the Sun. equation or as ∆H
The study of energy and energy transfer is known as thermodynamics. ■ represent energy changes
Chemists are interested in the branch of thermodynamics known as using diagrams
thermochemistry: the study of energy involved in chemical reactions. ■ compare energy changes
In order to discuss energy and its interconversions, thermochemists have that result from physical
agreed on a number of terms and definitions. You will learn about these changes, chemical reac-
terms and definitions over the next few pages. Then you will examine the tions, and nuclear reactions
energy changes that accompany chemical reactions, physical changes, and ■ communicate your under-
nuclear reactions. standing of the following
terms: thermodynamics,
thermochemistry, law of
Studying Energy Changes conservation of energy,
The law of conservation of energy states that the total energy of the system, surroundings,
universe is constant. In other words, energy can be neither destroyed heat (Q), temperature (T),
nor created. This idea can be expressed by the following equation: enthalpy (H), enthalpy
change (∆H), endothermic
∆Euniverse = 0 reaction, exothermic reac-
Energy can, however, be transferred from one substance to another. It can tion, enthalpy of reaction
also be converted into various forms. In order to interpret energy changes, (∆Hrxn ), standard enthalpy
scientists must clearly define what part of the universe they are dealing of reaction (∆H˚rxn ), thermo-
with. The system is defined as the part of the universe that is being studied chemical equation, mass
defect, nuclear binding
and observed. In a chemical reaction, the system is usually made up of the
energy, nuclear fission,
reactants and products. By contrast, the surroundings are everything else nuclear fusion
in the universe. The two equations below show the relationship between
the universe, a system, and the system’s surroundings.
Universe = System + Surroundings
∆Euniverse = ∆Esystem + ∆Esurroundings = 0
From the relationship, we know that any change in the system is
accompanied by an equal and opposite change in the surroundings.
∆Esystem = −∆Esurroundings
Look at the chemical reaction that is taking place in the flask in
Figure 5.1. A chemist would probably define the system as the contents
of the flask—the reactants and products. Technically, the rest of the
universe is the surroundings. In reality, however, the entire universe
changes very little when the system changes. Therefore, the surroundings
are considered to be only the part of the universe that is likely to be
affected by the energy changes of the system. In Figure 5.1, the flask, the
lab bench, the air in the room, and the student who is carrying out the
reaction all make up the surroundings. The system is more likely to Figure 5.1 The solution in the
significantly influence its immediate surroundings than, say, a flask is the system. The flask, the
mountaintop in Japan (also, technically, part of the surroundings). laboratory, and the student are the
surroundings.

Chapter 5 Energy and Change • MHR 221

 Heat and Temperature
Heat, Q, refers to the transfer of kinetic energy. Heat is expressed in the
same units as energy— joules (J). Heat is transferred spontaneously from a
warmer object to a cooler object. When you close the door of your home on
a cold day to “prevent the cold from getting in,” you are actually preventing
the heat from escaping. You are preventing the kinetic energy in your warm
home from transferring to colder objects, including the cold air, outside.
Temperature, T, is a measure of the average kinetic energy of the particles
that make up a substance or system. You can think of temperature as a way
of quantifying how hot or cold a substance is, relative to another substance.
K ˚C 110
380
373.15 100.00
100
370
90
360
80
350
70
340
60
330
50
320
40
310
30
300
20
290
10
280 273.15 0.00
0
270
–10
260

20 –250
10 –260
0.00 –270 −273.15
0

Figure 5.2 Celsius degrees and Kelvin degrees are the same size. The Kelvin scale begins
at absolute zero. This is the temperature at which the particles in a substance have no kinetic
energy. Therefore, Kelvin temperatures are never negative. By contrast, 0˚C is set at the
melting point of water. Celsius temperatures can be positive or negative.

Temperature is measured in either Celsius degrees (˚C) or kelvins (K).

The Celsius scale is a relative scale. It was designed so that water’s
boiling point is at 100˚C and water’s melting point is at 0˚C. The Kelvin
scale, on the other hand, is an absolute scale. It was designed so that 0 K
is the temperature at which a substance possesses no kinetic energy. The
relationship between the Kelvin and Celsius scales is shown in Figure 5.2,
and by the following equation.
Temperature in Kelvin degrees = Temperature in Celsius degrees + 273.15

Enthalpy and Enthalpy Change

Chemists define the total internal energy of a substance at a constant
pressure as its enthalpy, H. Chemists do not work with the absolute
enthalpy of the reactants and products in a physical or chemical process.
Instead, they study the enthalpy change, ∆H, that accompanies a process.
That is, they study the relative enthalpy of the reactants and products in a
system. This is like saying that the distance between your home and your
school is 2 km. You do not usually talk about the absolute position of
your home and school in terms of their latitude, longitude, and elevation.
You talk about their relative position, in relation to each other.
The enthalpy change of a process is equivalent to its heat change at
constant pressure.

222 MHR • Unit 3 Energy Changes and Rates of Reaction

Enthalpy Changes in Chemical Reactions
In chemical reactions, enthalpy changes result from chemical bonds being
broken and formed. Chemical bonds are sources of stored energy. Breaking
a bond is a process that requires energy. Creating a bond is a process that
releases energy. For example, consider the combustion reaction that takes
place when nitrogen reacts with oxygen.
N2(g) + O2(g) → 2NO(g)
In this reaction, one mole of nitrogen-nitrogen triple bonds and one mole
of oxygen-oxygen double bonds are broken. Two moles of nitrogen-oxygen
bonds are formed. This reaction absorbs energy. In other words, more
energy is released to form two nitrogen-oxygen bonds than is used to break
one nitrogen-nitrogen bond and one oxygen-oxygen bond. When a reaction
results in a net absorption of energy, it is called an endothermic reaction.
On the other hand, when a reaction results in a net release of energy,
it is called an exothermic reaction. In an exothermic reaction, more energy
is released to form bonds than is used to break bonds. Therefore, energy is
released. Figure 5.3 shows the relationship between bond breaking, bond
formation, and endothermic and exothermic reactions.

Reactants Products
Figure 5.3 The energy changes
bonds broken bonds made that result from bonds breaking and
endothermic reaction:
forming determine whether a reac-
energy absorbed energy released system absorbs E
tion is exothermic or endothermic.

bonds broken bonds made

exothermic reaction:
energy absorbed energy released system releases E

Representing Enthalpy Changes

The enthalpy change of a chemical reaction is known as the enthalpy CHEM
of reaction, ∆Hrxn . The enthalpy of reaction is dependent on conditions FA C T
such as temperature and pressure. Therefore, chemists often talk about the Chemists use different sub-
standard enthalpy of reaction, ∆H˚rxn : the enthalpy change of a chemical scripts to represent enthalpy
reaction that occurs at SATP (25˚C and 100 kPa). Often, ∆H˚rxn is written changes for specific kinds
simply as ∆H˚ . The ˚ symbol is called “nought.” It refers to a property of of reactions. For example,
a substance at a standard state or under standard conditions. You may ∆Hcomb represents the enthalpy
see the enthalpy of reaction referred to as the heat of reaction in other change of a combustion
reaction.
chemistry books.

Representing Exothermic Reactions

There are three different ways to represent the enthalpy change of an
exothermic reaction. The simplest way is to use a thermochemical
equation: a balanced chemical equation that indicates the amount of heat
that is absorbed or released by the reaction it represents. For example,
consider the exothermic reaction of one mole of hydrogen gas with half
a mole of oxygen gas to produce liquid water. For each mole of hydrogen
gas that reacts, 285.8 kJ of heat is produced. Notice that the heat term is
included with the products because heat is produced.
1
H2(g) + O
2 2(g)
→ H2O() + 285.8 kJ

Chapter 5 Energy and Change • MHR 223

 H2(g) + 1–2 O2(g) You can also indicate the enthalpy of reaction as a separate expression
beside the chemical equation. For exothermic reactions, ∆H˚ is always
(reactants)
negative.
1
H2(g) + O → H2O() ∆H˚rxn = −285.8 kJ
enthalpy, H

2 2(g)
A third way to represent the enthalpy of reaction is to use an enthalpy
∆H ˚ = −285.8 kJ
diagram. Examine Figure 5.4 to see how this is done.

Representing Endothermic Reactions

H2O() The endothermic decomposition of solid magnesium carbonate produces
solid magnesium oxide and carbon dioxide gas. For each mole of magne-
(products) sium carbonate that decomposes, 117.3 kJ of energy is absorbed. As for an
Figure 5.4 In an exothermic exothermic reaction, there are three different ways to represent the
reaction, the enthalpy of the system enthalpy change of an endothermic reaction.
decreases as energy is released to You can include the enthalpy of reaction as a heat term in the
the surroundings. chemical equation. Because heat is absorbed in an endothermic reaction,
the heat term is included on the reactant side of the equation.
117.3 kJ + MgCO3(s) → MgO(s) + CO2(g)
You can also indicate the enthalpy of reaction as a separate expression
beside the chemical reaction. For endothermic reactions, the enthalpy of
reaction is always positive.
MgO(s) + CO2(g) MgCO3(s) → MgO(s) + CO2(g) ∆H˚rxn = 117.3 kJ
(products) Finally, you can use a diagram to show the enthalpy of reaction.
Figure 5.5 shows how the decomposition of solid magnesium carbonate
can be represented graphically.
enthalpy, H

∆H ˚ = 117.3 kJ Stoichiometry and Thermochemical Equations

The thermochemical equation for the decomposition of magnesium
carbonate, shown above, indicates that 117.3 kJ of energy is absorbed
MgCO3(s) when one mole, or 84.32 g, of magnesium carbonate decomposes. The
decomposition of two moles of magnesium carbonate absorbs twice as
(reactants) much energy, or 234.6 kJ.
Figure 5.5 In an endothermic MgCO3(s) → MgO(s) + CO2(g) ∆H˚rxn = 117.3 kJ
reaction, the enthalpy of the system 2MgCO3(s) → 2MgO(s) + 2CO2(g) ∆H˚rxn = 234.6 kJ
increases as heat energy is
absorbed from the surroundings. Enthalpy of reaction is linearly dependent on the quantity of products.
That is, if the amount of products formed doubles, the enthalpy change
also doubles. Figure 5.6 shows the relationship between the stoichiometry
of a reaction and its enthalpy change. Because of this relationship, an
exothermic reaction that is relatively safe on a small scale may be
extremely dangerous on a large scale. One of the jobs of a chemical
engineer is to design systems that allow exothermic reactions to be carried
out safely on a large scale. For example, the blast furnaces used in steel
making must withstand temperatures of up to 2000˚C, produced by the
exothermic combustion reaction of coal with oxygen.

amount of varies directly with amount of varies directly with heat absorbed
compound A compound B or released
(mol) (factor: molar ratio) (mol) (factor: ∆H rxn ) (kJ)

Figure 5.6 This diagram summarizes the relationship between the stoichiometry
of a reaction and ∆H.

224 MHR • Unit 3 Energy Changes and Rates of Reaction

Sample Problem
Stoichiometry and Thermochemical Reactions

Problem
Aluminum reacts readily with chlorine gas to produce aluminum
chloride. The reaction is highly exothermic.
2Al(s) + 3Cl2(g) → 2AlCl3(s) ∆H˚rxn = −1408 kJ
What is the enthalpy change when 1.0 kg of Al reacts completely with
excess Cl2?

What Is Required?
You need to calculate the enthalpy change, ∆H, when the given amount
of Al reacts.

What Is Given?
You know the enthalpy change for the reaction of two moles of Al
with one mole of Cl2. From the periodic table, you know the molar
mass of Al.
2Al(s) + 3Cl2(g) → 2AlCl3(s) ∆H˚rxn = −1408 kJ
MAl = 26.98 g/mol

Plan Your Strategy

Convert the given mass of Al to moles. The enthalpy change is linearly
dependent on the quantity of reactants. Therefore, you can use a ratio to
determine the enthalpy change for 1.0 kg of Al reacting with Cl2.

Act on Your Strategy

Determine the number of moles of Al in 1 kg. Remember to convert to
grams.
m
n mol Al = Al
MAl
1.0 × 103 g
=
26.98 g/mol
= 37 mol
Use ratios to compare the reference reaction with the known enthalpy
change ( ∆H1) to the reaction with the unknown enthalpy change (∆H2).
∆H2 n mol Al
= 2
∆H1 n1 mol Al
∆H2 37 mol Al
=
−1408 kJ 2 mol Al
∆H2 = −2.6 × 104 kJ

Check Your Solution

The sign of the answer is negative, which corresponds to an exothermic
reaction. The 1 kg sample contained about 20 times more moles of Al.
Therefore, the enthalpy change for the reaction should be about 20 times
greater, and it is.

Chapter 5 Energy and Change • MHR 225

 Practice Problems

1. Consider the following reaction.

N2(g) + O2(g) → 2NO(g) ∆H˚rxn = +180.6 kJ
(a) Rewrite the thermochemical equation, including the standard
enthalpy of reaction as either a reactant or a product.
(b) Draw an enthalpy diagram for the reaction.
(c) What is the enthalpy change for the formation of one mole of
nitrogen monoxide?
(d) What is the enthalpy change for the reaction of 1.000 × 102 g of
nitrogen with sufficient oxygen?
2. The reaction of iron with oxygen is very familiar. You can see the
resulting rust on buildings, vehicles, and bridges. You may be sur-
prised, however, at the large amount of heat that is produced by this
reaction.
4Fe(s) + 3O2(g) → 2Fe2O3(s) + 1.65 × 103 kJ
(a) What is the enthalpy change for this reaction?
(b) Draw an enthalpy diagram that corresponds to the thermochemical
equation.
(c) What is the enthalpy change for the formation of 23.6 g of iron(III)
oxide?
3. Consider the following thermochemical equation.
1 1
25.9 kJ + H
2 2(g)
+ I
2 2(g)
→ HI(g)
(a) What is the enthalpy change for this reaction?
(b) How much energy is needed for the reaction of 4.57 × 1024
molecules of iodine, I2 , with excess hydrogen, H2 ?
(c) Draw and label an enthalpy diagram that corresponds to the given
thermochemical equation.
4. Tetraphosphorus decoxide, P4O10 , is an acidic oxide. It reacts with
water to produce phosphoric acid, H3PO4 , in an exothermic reaction.
P4O10(s) + 6H2O() → 4H3PO4(aq) ∆H˚rxn = −257.2 kJ
(a) Rewrite the thermochemical equation, including the enthalpy
change as a heat term in the equation.
(b) How much energy is released when 5.00 mol of P4O10 reacts with
excess water?
(c) How much energy is released when 235 g of H3PO4(aq) is formed?

Heat Changes and Physical Changes

Enthalpy changes are associated with physical changes as well as with
chemical reactions. You have observed examples of these enthalpy
changes in your daily life. Suppose that you want to prepare some pasta.
You put an uncovered pot of water on a stove element. The heat from the
element causes the water to become steadily hotter, until it reaches 100˚C
(the boiling point of water at 100 kPa). At this temperature, heat is still
being added to the water. The average kinetic energy of the liquid water
molecules does not increase, however. Instead, the energy is used to break
the intermolecular bonds between the water molecules as they change
from liquid to vapour. The temperature of the liquid water remains at

226 MHR • Unit 3 Energy Changes and Rates of Reaction

100˚C until all the water has been vaporized. If you add heat to the
vapour, the temperature of the vapour will increase steadily.
When you heat ice that is colder than 0˚C, a similar process occurs.
The temperature of the ice increases until it is 0˚C (the melting point of
water). If you continue to add heat, the ice remains at 0˚C but begins to
melt, as the bonds between the water molecules in the solid state begin
to break.
Figure 5.7 shows the relationship between temperature and heat for
a solid substance that melts and then vaporizes as heat is added to it.

gas
boiling
point
Temperature

Figure 5.7 As heat is added to a

liquid
substance, the temperature of the
melting ∆H ˚vap substance steadily increases until it
point reaches its melting point or boiling
solid
point. The temperature then remains
∆H ˚melt steady as the substance undergoes
a phase change.
Heat added

You can represent the enthalpy change that accompanies a phase

change—from liquid to solid, for example— just like you represented the
enthalpy change of a chemical reaction. You can include a heat term in
the equation, or you can use a separate expression of enthalpy change.
For example, when one mole of water melts, it absorbs 6.02 kJ of energy. CHEM
FA C T
H2O(s) + 6.02 kJ → H2O()
The process of melting is also
H2O(s) → H2O() ∆H = 6.02 kJ known as fusion. Therefore,
Normally, however, chemists represent enthalpy changes associated with you will sometimes see the
phase changes using modified ∆H symbols. These symbols are described enthalpy of melting referred to
below. as the enthalpy of fusion.

• enthalpy of vaporization, ∆Hvap : the enthalpy change for the phase

change from liquid to gas
• enthalpy of condensation, ∆Hcond: the enthalpy change for the phase
change of a substance from gas to liquid
• enthalpy of melting, ∆Hmelt : the enthalpy change for the phase change of
a substance from solid to liquid
• enthalpy of freezing, ∆Hfre : the enthalpy change for the phase change of
a substance from liquid to solid
Vaporization and condensation are opposite processes. Thus, the
enthalpy changes for these processes have the same value but opposite
signs. For example, 6.02 kJ is needed to vaporize one mole of water.
Therefore, 6.02 kJ of energy is released when one mole of water freezes.
∆Hvap = −∆Hcond
Similarly, melting and freezing are opposite processes.
∆Hmelt = −∆Hfre
Several enthalpies of melting and vaporization are shown in Table 5.1.
Notice that the same units (kJ/mol) are used for the enthalpies of melting,
vaporization, condensation, and freezing. Also notice that energy changes
associated with phase changes can vary widely.

Chapter 5 Energy and Change • MHR 227