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55 Thermochemistry Thermochemistry

chapter 5 5 Thermochemistry Thermochemistry In this chapter, you will be able to • compare the

In this chapter, you will be able to

compare the energy changes resulting from physical, chemical, and nuclear changes;

represent such energy changes using thermochemical equations and potential energy diagrams;

determine enthalpies of reaction both experimentally and by calculation from Hess’s law and standard enthalpies of formation;

compare conventional and alternative sources of energy;

recognize examples of technologies that depend on exothermic and endothermic changes.

Energy transformations are the basis for all of the activities that make up our lives. When we breathe or walk or ride a bicycle, we use the chemical process of respiration and a whole series of complex metabolic reactions to convert the chemical energy in food into mechanical energy. Our home furnaces burn fossil fuels such as wood, coal, oil, or nat-

ural gas to produce heat that keeps us comfortable in this northern climate. Plants in forests and our fields take in sunlight and change the solar energy into chemical potential energy

— stored carbohydrates — that may be further processed by animals and by ourselves

— consider the many transformation necessary to cook corn, for example.

You are already familiar with many energy changes, both chemical and physical. As a tennis player sprints for the ball, glucose molecules in muscle cells react to form carbon dioxide, water, and energy. At the same time a physical change — the evaporation of perspiration — consumes energy and helps the player maintain a constant body tem- perature. Many energy changes have significant effects on our way of life and our future. Transportation, whether in cars or by mass transit, depends to a large extent on the combustion of fossil fuels. This combustion produces energy of motion but also releases carbon dioxide, with its possible links to the greenhouse effect, and other pollutants. Even electrically powered vehicles use energy that is generated in part in nuclear or fossil fuel-burning power plants. Energy is a major factor in decision making on our planet. Most sources of energy are finite, and using each has its advantages and disadvantages. The control and use of our present energy resources and the decisions that we make for the future will continue to have far-reaching environmental, economic, social, and political effects for many years.

REFLECT on your learning 1. Consider the following changes: ice melting, water evaporating, water vapour
REFLECT on your learning
1. Consider the following changes: ice melting, water evaporating, water vapour con-
densing, photosynthesis, respiration, and combustion of gasoline. Classify these
changes as absorbing or releasing thermal energy.
2. Based on your current understanding of energy, how is electrical power produced in
Ontario? What are the sources of energy that produce this power?
3. How is nuclear power different from hydroelectric power? How is it similar?
TRYTHIS activity Burning Food

TRYTHIS activity

Burning Food

 

Have you heard of fat-burning exercises? Now you are going to not only burn fat, but also measure how much energy is released in the process. Engineers who design furnaces to heat homes and nutrition- ists who calculate the energy value of different foods need to analyze the energy-producing ability of different fuels. In experi- ments in which heat is absorbed by water, they use the formula:

• Place 50 mL of tap water in the tin can. Measure the temper- ature of the water.

• Suspend the can of water above the nut by putting the pencil through the holes under the rim of the can.

• Light the nut and allow the reaction to continue until the nut stops burning. Measure the final temperature of the water.

heat (mass of water) (temperature change of water) 4.18 J/(g°C)

(a)

Calculate how much energy was absorbed by the water.

(b)

Where did this energy come from?

Materials: eye protection; centigram balance; pecan or other nut; paper clip; small tin can, open at one end and punctured under the rim on opposite sides; pencil; ther- mometer; measuring cup; matches

Figure 1

Figure 1

(c)

Calculate the amount of heat produced per gram of fuel (nut) burned.

(d)

Compare this combustion reaction to the reaction that would happen if you were to eat the pecan instead of burning it. Possible areas of comparison could include:

reactants and products, total energy production, energy storage, efficiency of energy production, and so on.

(e)

What were some sources of experimental error? How would you improve this experiment?

• Measure the mass of the nut or assume that an average pecan weighs about 0.5 g.

nut or assume that an average pecan weighs about 0.5 g. Students with extreme sensitivity to

Students with extreme sensitivity to nuts or nut products should not perform this activity.

• Bend a paper clip so that it forms a stand that will sup- port a nut above the lab bench (Figure 1).

 

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5.15.1

Changes in Matter and Energy

5 . 1 5 . 1 Changes in Matter and Energy

thermochemistry the study of the energy changes that accompany physical or chemical changes in matter

What happens when matter undergoes change? Clearly, new substances or states are produced, but energy changes also occur. If chemistry is the study of matter and its transformations, then thermochemistry is the study of the energy changes that accom- pany these transformations. Changes that occur in matter may be classified as physical, chemical, or nuclear, depending on whether a change has occurred in the arrangements of the molecules, their electronic structure, or the nuclei of the atoms involved (Figure 1). Whether ice melts, iron rusts, or an isotope used in medical therapy undergoes radioac- tive decay, changes occur in the energy of chemical substances.

decay, changes occur in the energy of chemical substances. (a) Figure 1 Hydrogen may undergo a

(a)

changes occur in the energy of chemical substances. (a) Figure 1 Hydrogen may undergo a physical,
changes occur in the energy of chemical substances. (a) Figure 1 Hydrogen may undergo a physical,

Figure 1 Hydrogen may undergo a physical, chemical, or nuclear change.

(a)

Physical: Hydrogen boils at 252°C (or only about 20°C above absolute zero):

H 2(l) H 2(g)

(b)

Chemical: Hydrogen is burned

as

fuel in the space shuttle’s

main engines:

2 H 2(g) O 2(g) 2 H 2 O (l)

(c)

Nuclear: Hydrogen undergoes

nuclear fusion in the Sun, pro- ducing helium:

H H He

(b)

(c)

Heat and Energy Changes

Both physical and chemical changes are involved in the operation of an oxyacetylene torch to weld metals together. A chemical reaction, which involves ethyne (or acetylene) and oxygen as reactants, produces carbon dioxide gas, water vapour, and considerable

energy. This energy is released to the surroundings as thermal energy, a form of kinetic

energy that results from the motion of molecules. The result is a physical change — the melting of the metal — when the increased vibration of metal particles causes them to break out of their ordered solid pattern. When you are studying such transfers of energy,

it is important to distinguish between the substances undergoing a change, called the chemical system, and the system’s environment, called the surroundings. A system is

often represented by a chemical equation. For the burning of ethyne, the equation is:

thermal energy energy available from a substance as a result of the motion of its molecules

chemical system a set of reactants and products under study, usually represented by a chemical equation

surroundings all matter around the system that is capable of absorbing or releasing thermal energy

2 C 2 H 2(g) 5 O 2(g) 4 CO 2(g) 2 H 2 O (g)

energy

The surroundings in this reaction would include anything that could absorb the thermal energy that has been released, such as metal parts, the air, and the welder’s pro- tective clothing. When the reaction occurs, heat, q, is transferred between substances. (An object pos- sesses thermal energy but cannot possess heat.) When heat transfers between a system and its surroundings, measurements of the temperature of the surroundings are used to classify the change as exothermic or endothermic (Figure 2). The acetylene torch reaction is clearly an exothermic reaction because heat flows into the surroundings. Chemical potential energy in the system is converted to heat energy,

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Chapter 5

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Section 5.1

which is transferred to the surroundings and used to increase the thermal energy of the molecules of metal and air. Since the molecules in the surroundings have greater kinetic energy, the temperature of the surroundings increases measurably. Chemical systems may be further classified. A chemical reaction that produces a gas in a solution in a beaker is described as an open system, since both energy and matter can flow into or out of the system. The surroundings include the beaker itself, the sur- face on which the beaker sits, and the air around the beaker. In the same way, most explosive reactions are considered to be open systems because it is so difficult to contain the energy and matter produced. Figure 3 shows an open system. Most calculations of energy changes involve systems in which careful measurements of mass and temperature changes are made (Figure 4). These are considered to be isolated systems for the pur- pose of calculation. However, it is impossible to completely prevent energy from entering or leaving any system. In reality, the contents of a calorimeter, or of any container that prevents movement of matter, form a closed system.

that prevents movement of matter, form a closed system . Figure 3 A burning marshmallow is

Figure 3 A burning marshmallow is an example of an open system. Gases and energy are free to flow out of the system.

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Gases and energy are free to flow out of the system. N E L Exothermic Endothermic
Exothermic Endothermic system
Exothermic
Endothermic
system

Figure 2

In exothermic changes, energy is

released from the system, usually causing an increase in the tempera- ture of the surroundings. In endothermic changes, energy is absorbed by the system, usually causing a decrease in the tempera- ture of the surroundings.

heat amount of energy transferred between substances

exothermic releasing thermal energy as heat flows out of the system

endothermic absorbing thermal energy as heat flows into the system

temperature average kinetic energy of the particles in a sample

of matter

open system one in which both matter and energy can move in or out

isolated system an ideal system in which neither matter nor energy can move in or out

closed system one in which energy can move in or out, but not matter

Figure 4

A bomb calorimeter is a device in

which a fuel is burned inside an insulated container to obtain accu- rate measurements of heat transfer during chemical reactions. Because neither mass nor energy can escape, the chemical system is described as

isolated.

Thermochemistry

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299

299

Figure 5 The fuel in the burner releases heat energy that is absorbed by the

Figure 5 The fuel in the burner releases heat energy that is absorbed by the sur- roundings, which include the beaker, water, and air.

calorimetry the technological process of measuring energy changes in a chemical system

Practice
Practice

Understanding Concepts

1. Identify each of the following as a physical, chemical, or nuclear change, with reasons for your choice:

(a)

a

gas barbecue operating

(b)

an ice cube melting in someone’s hand

(c)

white gas burning in a camping lantern

(d)

wax melting on a hot stove

(e)

zinc metal added to an acid solution in a beaker

(f)

ice applied to an athletic injury

2. Identify the system and surroundings in each of the examples in the previous question.

3. Identify the following as examples of open or isolated systems and explain your iden- tification:

(a)

gasoline burning in an automobile engine

(b)

snow melting on a lawn in the spring

(c)

a

candle burning on a restaurant table

(d)

the addition of baking soda to vinegar in a beaker

(e)

a

gas barbecue operating

4. A thimbleful of water at 100°C has a higher temperature than a swimming pool full of water at 20°C, but the pool has more thermal energy than the thimble. Explain.

5. Identify each of the following as an exothermic or endothermic reaction:

(a)

hydrogen undergoes nuclear fusion in the Sun to produce helium atoms;

(b)

the butane in a lighter burns;

(c)

the metal on a safety sprinkler on the ceiling of an office melts when a flame is brought near it.

Making Connections

6. List five changes that you might encounter outside your school laboratory. Create

(a)

 

table to classify each change as physical, chemical, or nuclear; endothermic or exothermic; and occurring in an open or an isolated system.

a

(b)

What are the most commonly encountered types of chemical reactions in terms of energy flow?

7. The energy content of foods is sometimes stated in “calories” rather than the SI unit of joules. Physical activity is described as “burning calories”. Research the answers to the following questions:

(a)

What are the relationships among a calorie, a Calorie, and a joule?

(b)

Are calories actually burned? Why is this terminology used?

(c)

What laboratory methods are used to determine the energy content of foods?

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Measuring Energy Changes: Calorimetry

When methane reacts with oxygen in a lab burner, enough heat is transferred to the surroundings to increase the temperature and even to cause a change of state (Figure 5). How is this amount of heat measured? The experimental technique is called calorimetry and it depends on careful measurements of masses and temperature changes. When a fuel like methane burns, heat is transferred from the chemical system into the surroundings (which include the water in the beaker). If more heat is transferred, the observed tem- perature rise in the water is greater. Similarly, given the same amount of heat, a small amount of water will undergo a greater increase in temperature than a large amount of water. Finally, different substances vary in their ability to absorb amounts of heat.

Section 5.1

These three factors — mass (m), temperature change (T), and type of substance — are combined in an equation to represent the quantity of heat (q) transferred:

q

mc T

where c is the specific heat capacity, the quantity of heat required to raise the tem- perature of a unit mass (e.g., one gram) of a substance by one degree Celsius or one kelvin. For example, the specific heat capacity of water is 4.18 J/(g•°C). (Recall that the SI unit for energy is the joule, J.) Specific heat capacities vary from substance to sub- stance, and even for different states of the same substance (Table 1). As the equation indicates, the quantity of heat, q, that flows varies directly with the quan- tity of substance (mass m), the specific heat capacity, c, and the temperature change, T. Cancelling units in your calculations will help ensure that you have applied the for- mula correctly. In this book, quantities of heat transferred are calculated as absolute values by subtracting the lower temperature from the higher temperature.

specific heat capacity quantity of heat required to raise the tempera- ture of a unit mass of a substance 1°C or 1K

Table 1

Specific Heat Capacities of Substances

Substance

Specific heat

capacity, c

ice

2.01J/(g•°C)

water

4.18 J/(g•°C)

steam

2.01J/(g•°C)

aluminum

0.900

J/(g•°C)

iron

0.444

J/(g•°C)

methanol

2.918

J/(g•°C)

Calculating Quantity of Heat SAMPLE problem When 600 mL of water in an electric kettle
Calculating Quantity of Heat
SAMPLE problem
When 600 mL of water in an electric kettle is heated from 20°C to 85°C to make a
cup of tea, how much heat flows into the water?
First, use the density formula to calculate the mass of water.
m
dV
1.00 g/mL
600
mL
600 g
Use the heat formula, q mc T, to calculate the quantity of heat transferred.
q
?
m
600 g
c
4.18 J/(g•°C) (from Table 1)
T 85°C
20°C
65°C
q mc T
4
.
1 8 J
600 g
65°C
( g ° C )
1.63
10 5 J or 163 kJ.
163 kJ of heat flows into the water.
Example
What would the final temperature be if 250.0 J of heat were transferred into 10.0 g of
methanol initially at 20.0°C?
Solution
m
10.0 g
c
2.918 J/(g•°C)
T 1 20.0 °C
T T 2 – T 1 T 2 – 20.0°C
q
250 J

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Answers

9.

506 kJ

10.

38 g

11.

20ºC

12.

(a)

15 M

(b)

$77

13.

(a)

1.0 10 4 kJ

(b)

$55

q mc T

q

T

m c

250 J 10.0 g 2.918 J /(g •°C)

8.57°C

T 2 20°C 8.57°C

T 2 20.0 8.57

T 2 28.6°C

The final temperature of the methanol is 28.6°C.

Practice
Practice

Understanding Concepts

8.

If the same amount of heat were added to individual 1-g samples of water, methanol, and aluminum, which substance would undergo the greatest tempera- ture change? Explain.

9.

There is 1.50 kg of water in a kettle. Calculate the quantity of heat that flows into

the water when it is heated from 18.0°C to 98.7°C.

10.

On a mountaineering expedition, a climber heats water from 0°C to 50°C. Calculate the mass of water that could be warmed by the addition of 8.00 kJ of heat.

11.

Aqueous ethylene glycol is commonly used in car radiators as an antifreeze and coolant. A 50% ethylene glycol solution in a radiator has a specific heat capacity of 3.5 J/(g•°C). What temperature change would be observed in a solution of 4 kg of ethylene glycol if it absorbs 250 kJ of heat?

12.

Solar energy can preheat cold water for domestic hot-water tanks.

(a)

What quantity of heat is obtained from solar energy if 100 kg of water is pre-

 

heated from 10°C to 45°C?

 

(b)

If natural gas costs 0.351¢/MJ, calculate the money saved if the volume of water in part (a) is heated 1500 times per year.

13.

The solar-heated water in the previous question might be heated to the final temperature in a natural gas water heater.

(a)

What quantity of heat flows into 100 L (100 kg) of water heated from 45°C to

70°C?

(b)

At 0.351¢/MJ, what is the cost of heating 100 kg of water by this amount, 1500 times per year?

Heat Transfer and Enthalpy Change

Chemical systems have many different forms of energy, both kinetic and potential. These include the kinetic energies of

• moving electrons within atoms;

• the vibration of atoms connected by chemical bonds; and

• the rotation and translation of molecules that are made up of these atoms.

More importantly, they also include

• the nuclear potential energy of protons and neutrons in atomic nuclei; and

• the electronic potential energy of atoms connected by chemical bonds.

Section 5.1

Researchers have not yet found a way to measure the sum of all these kinetic and potential energies of a system. For this reason chemists usually study the enthalpy change, or the energy absorbed from or released to the surroundings when a system

changes from reactants to products.

An enthalpy change is given the symbol H, pronounced “delta H,” and can be deter- mined from the energy changes of the surroundings. A useful assumption that will be applied in more detail later in this chapter is that the enthalpy change of the system equals the quantity of heat that flows from the system to its surroundings, or from the surroundings to the system (Figure 6). This assumption applies as long as there is no sig- nificant production of gas, which is the case in most reactions you will encounter. This idea is consistent with the law of conservation of energy — energy may be con- verted from one form to another, or transferred from one set of molecules to another, but the total energy of the system and its surroundings remains the same.

energy of the system and its surroundings remains the same. H system  q surroundings 

H system q surroundings

For example, consider the reaction that occurs when zinc metal is added to hydrochloric acid in a flask:

Zn (s) 2 HCl (aq) H 2(g) ZnCl 2(aq)

Some of the chemical potential energy in the system is converted initially to increased kinetic energy of the products. Eventually, through collisions, this kinetic energy is trans- ferred to particles in the surroundings. The enthalpy change in the system is equal to the heat released to the surroundings. We can observe this transfer of energy, and can measure it by recording the increase in temperature of the surroundings (which include the solvent water molecules, the flask, and the air around the flask). Our calculations of the heat released will involve the masses of the various substances as well as their tem- perature change and specific heat capacities. In order to control variables and allow comparisons, energy changes in chemical sys- tems are measured at standard conditions of temperature and pressure, such as SATP, before and after the reaction. Under these conditions, the enthalpy change of a chemical

Energy

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Changes in Kinetic and Potential Energy high potential energy high kinetic energy low kinetic energy
Changes in Kinetic and Potential Energy
high potential energy
high kinetic energy
low kinetic energy
low potential energy

Reaction Progress

enthalpy change ( H) the differ- ence in enthalpies of reactants and products during a change

LEARNING TIP

LEARNING TIP In searching through references you may find the terms enthalpy of reaction, heat of

In searching through references you may find the terms enthalpy of reaction, heat of reaction, change in heat content, enthalpy change, and H. They all mean the same thing.

INVESTIGATION 5.1.1

INVESTIGATION 5.1.1

Medical Cold Packs (p. 347) Can you identify the active chemical in a medical cold pack?

DID YOU KNOW ??

Setting Hard The setting of concrete is quite exothermic, and the rate at which it sets or cures determines the hardness of the concrete. If the concrete sets too quickly (for example, if the heat of reaction is not dissipated quickly enough into the air), the concrete may expand and crack.

Figure 6 In this example of an exothermic change, the change in potential energy of the system ( H ) equals the change in kinetic energy of the surroundings (q). This is consistent with the law of conservation of energy.

Thermochemistry

303

physical change a change in the form of a substance, in which no chemical bonds are broken

chemical change a change in the chemical bonds between atoms, resulting in the rearrangement of atoms into new substances

nuclear change a change in the protons or neutrons in an atom, resulting in the formation of new atoms

10 24 J

10 21 J

10 18 J

10 15 J

10 12 J

10 9 J

10 6 J

10 3 J

10 0 J

10 3 J

10 6 J

10 9 J

10 –12 J

10 –15 J

10 –18 J

10 21 J

daily solar energy falling on Earth energy of a strong earthquake daily electrical output of
daily solar energy
falling on Earth
energy of a strong
earthquake
daily electrical
output of hydroelectric
plant
1000 tonnes of
coal burned
1
tonne of TNT exploded
1 kilowatt-hour of
electrical energy
heat released from
combustion of 1 mol
glucose
1
calorie (4.184 J)
heat absorbed during
division of one bacterial cell
energy from fission of
one 235 U atom
average kinetic energy of
a molecule in air at 300 K

Figure 7 Log scale of the enthalpy changes resulting from a variety of physical, chemical, and nuclear changes

system is the change in the chemical potential energy of the system because the kinetic energies of the system’s molecules stay constant (for our purposes at this stage). We can observe enthalpy changes during phase changes, chemical reactions, or nuclear reactions. Although the magnitudes of the enthalpy changes that accompany these events vary considerably (Table 2 and Figure 7), the basic concepts of enthalpy change and heat transfer apply. Notice how much more energy is produced in a nuclear change than in a chemical change, and in a chemical change than in a physical change.

Table 2

Types of Enthalpy Changes

Physical changes

• Energy is used to overcome or allow intermolecular forces to act.

• Fundamental particles remain unchanged at the molecular level.

• Temperature remains constant during changes of state (e.g., water vapour sublimes to form frost: H 2 O (g) H 2 O (s) + heat).

• Temperature changes during dissolving of pure solutes (e.g., potassium chloride dissolves: KCl (s) + heat KCl (aq) ).

• Typical enthalpy changes are in the range H 10 0 10 2 kJ/mol.

Chemical changes

• Energy changes overcome the electronic structure and chemical bonds within the particles (atoms or ions).

• New substances with new chemical bonding are formed

(e.g., combustion of propane in a barbecue: C 3 H 8(g) 5 O 2(g) 3 CO 2(g) + 4 H 2 O (g) heat);

(e.g., calcium reacts with water: Ca (s) 2 H 2 O (l) H 2(g) Ca(OH) 2(aq) heat).

• Typical enthalpy changes are in the range H 10 2 – 10 4 kJ/mol.

Nuclear changes

• Energy changes overcome the forces between protons and neutrons in nuclei.

• New atoms, with different numbers of protons or neutrons, are formed

(e.g., nuclear decay of uranium-238: 238

92

U

4 2 He

234

90

Th

heat).

• Typical enthalpy changes are in the range H 10 10 10 12 kJ/mol. The magnitude of the energy change is a consequence of Einstein’s equation (Figure 8).

Practice
Practice

Understanding Concepts

14. Explain how H system and q surroundings are different and how they are similar.

15. How do enthalpy changes of physical, chemical, and nuclear changes compare?

Applying Inquiry Skills

16. Design an experiment to determine the identity of an unknown metal, clearly

describing the set of observations that you would make and the calculations that you would perform (including units), given the following information:

• The metal is zinc, magnesium, or aluminum, all of which are shiny, silvery metals.

• These metals react when placed in dilute acid solution.

• Dilute acid has the same density and specific heat capacity as water.

• A Chemical Handbook provides values for the heat (in J) released per unit mass (g) of metal reacting in acid.

Section 5.1

Section 5.1 Figure 8 In Einstein’s famous equation, large amounts of energy, E , are produced

Figure 8 In Einstein’s famous equation, large amounts of energy, E, are produced when a small amount of mass, m, is destroyed because c, the speed of light, is such a large value (3.0 10 8 m/s).

Section 5.1 Questions
Section 5.1 Questions

Understanding Concepts

1. For the three states of matter (solid, liquid, and gas), there are six possible changes of state. Which changes of state are exothermic? Which are endothermic?

2. What three factors are involved in calculations of the amount of heat absorbed or released in a chemical reac- tion?

3. Identify each of the following as a physical, chemical, or nuclear change, giving reasons for your choice:

(a)

gasoline burning in a car engine

(b)

water evaporating from a lake

(c)

uranium fuel encased in concrete in a reactor

4. Identify the chemical system and the surroundings in each of the examples in question 3.

5. Identify each of the examples in question 3 as an open or an isolated system. Explain your classifications.

6. Describe the chemical system in each of the examples in question 3. Compare the relative amounts of energy per

mole that would be transferred in each of the changes of state (to the nearest power of ten).

Making Connections

7. The bomb calorimeter is a commonly used laboratory apparatus. Research and write a brief report describing the applications of this technology.

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8. Hot packs and cold packs use chemical reactions to produce or absorb energy. Write a brief report describing the chemical systems used in these products and their usefulness.

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5.25.2

Molar Enthalpies

5.2 5.2 Molar Enthalpies

When we write an equation to represent changes in matter, the chemical symbols may represent individual particles but usually they represent numbers of moles of particles. Thus, the thermochemical equation

molar enthalpy, H x the enthalpy change associated with a physical, chemical, or nuclear change involving one mole of a substance

1 H 2(g)

1

2 O 2(g)

1 H 2 O (g)

241.8 kJ

represents the combustion reaction of 1 mol of hydrogen with 0.5 mol of oxygen to form 1 mol of water vapour. The enthalpy change per mole of a substance undergoing

a change is called the molar enthalpy and is represented by the symbol H x , where x is

a letter or a combination of letters to indicate the type of change that is occurring. Thus, the molar enthalpy of combustion of hydrogen is

H comb 241.8 kJ/mol

Note the negative sign in the value of H. Changes in matter may be either endothermic or exothermic. The following sign convention has been adopted.

• Enthalpy changes for exothermic reactions are given a negative sign.

• Enthalpy changes for endothermic reactions are given a positive sign.

Stating the molar enthalpy is a convenient way of describing the energy changes involved in a variety of physical and chemical changes involving 1 mol of a particular reac- tant or product. Table 1 shows some examples.

Table 1

Some Molar Enthalpies of Reaction ( H x )

Type of molar enthalpy

Example of change

solution ( H sol )

NaBr (s) Na + (aq) Br (aq)

combustion ( H comb )

CH 4(g) 2 O 2(g) CO 2(g) H 2 O (l)

vaporization ( H vap )

CH 3 OH (l) CH 3 OH (g)

freezing ( H fr )

H 2 O (l) H 2 O (s)

neutralization ( H neut )*

2 NaOH (aq) H 2 SO 4(aq) 2 Na 2 SO 4(aq) 2 H 2 O (l)

neutralization ( H neut )*

NaOH (aq) 1/2 H 2 SO 4(aq) 1/2 Na 2 SO 4(aq) H 2 O (l)

formation ( H f )**

C (s) 2 H 2(g) 1/2 O 2(g) CH 3 OH (l)

* Enthalpy of neutralization can be expressed per mole of either base or acid consumed.

** Molar enthalpy of formation will be discussed in more detail in Section 5.5.

We can express the molar enthalpy of a physical change, such as the vaporization of water, as follows:

H 2 O (l)

40.8 kJ

H 2 O (g)

What we may think of as the change in potential energy in the system, the molar enthalpy of vaporization for water, is

H vap 40.8 kJ/mol

Section 5.2

Molar enthalpy values are obtained empirically and are listed in reference books in tables such as Table 2.

Table 2

Molar Enthalpies for Changes in State of Selected Substances

   

Molar enthalpy of

Molar enthalpy of

Chemical Name

Formula

fusion (kJ/mol)

vaporization (kJ/mol)

sodium

Na

 

2.6

101

chlorine

Cl

2

 

6.40

20.4

sodium chloride

NaCl

28

171

water

H

2 O

6.03

40.8

ammonia

NH

3

1.37

freon-12

CCl

2 F 2

34.99

methanol

CH

3 OH

39.23

ethylene glycol

C

2 H 4 (OH) 2

58.8

The amount of energy involved in a change (the enthalpy change H, expressed in kJ) depends on the quantity of matter undergoing that change. This is logical: twice the mass of ice will require twice the amount of energy to melt. To calculate an enthalpy change H for some amount of substance other than a mole, you need to obtain the molar enthalpy value H x from a reference source, and then use the formula H nH x . Note the cancellation of units in the following problem.

Using Molar Enthalpies in Heat Calculations

A common refrigerant (Freon-12, molar mass 120.91 g/mol) is alternately vaporized in tubes inside a refrigerator, absorbing heat, and condensed in tubes outside the refrigerator, releasing heat. This results in energy being transferred from the inside to the outside of the refrigerator. The molar enthalpy of vaporiza- tion for the refrigerant is 34.99 kJ/mol. If 500.0 g of the refrigerant is vaporized, what is the expected enthalpy change H?

H vap 34.99 kJ/mol

H

?

First, find the amount of refrigerant, n, in moles. From the problem statement,

M refrigerant 120.91 g/mol, and m refrigerant 500.0 g, so

n refrigerant 500.0 g

12

1

m o l

0 .9 1 g

4.35 mol

Then calculate the enthalpy change, H.

H n H vap

4.35

144.7 kJ

34 .9 9 k J

mol

1 l

m

o

H

Because the refrigerant vaporizes by absorbing heat, the enthalpy change is positive.

SAMPLE problem
SAMPLE problem

LEARNING TIP

In calculations involving molar enthalpies, we assume that the number of moles indicated in the chemical equation is exact (has infinite certainty) and so does not affect the number of significant digits in the answer.

equation is exact (has infinite certainty) and so does not affect the number of significant digits
infinite certainty) and so does not affect the number of significant digits in the answer. N

NEL

Thermochemistry

307

 

Example

 

What amount of ethylene glycol would vaporize while absorbing 200.0 kJ of heat?

Solution

 

H 200.0 kJ

H vap 58.8 kJ/mol (from Table 2)

n

?

 

H n H vap

 

n

H H

vap

2

kJ

0 0 .0

.

58 8 Jm ol

k

n

3.40 mol

 

The amount of ethylene glycol that would vaporize is 3.40 mol.

Practice
Practice

Understanding Concepts

Answers

1. Calculate the enthalpy change H for the vaporization of 100.0 g of water at

1. 227 kJ

100.0°C (Table 2).

2. 474 kJ

2. Ethylene glycol is used in automobile coolant systems because its aqueous solutions lower the freezing point of the coolant liquid and prevent freezing of the system during Canadian winters. What is the enthalpy change needed to completely vaporize 500.0 g of ethylene glycol? (See Table 2)

3. Under certain atmospheric conditions, the temperature of the surrounding air rises as a snowfall begins, because energy is released to the atmosphere as water changes to snow. What is the enthalpy change H for the freezing of 1.00 t of water at 0.0°C to 1.00 t of snow at 0.0°C? (Recall that 1 t 1000 kg.)

3. 3.4 10 5 kJ

Calorimetry of Physical Changes

So far, you have been provided with values for molar enthalpies. How are these values obtained? Studying energy changes requires an isolated system, that is, one in which neither matter nor energy can move in or out. Carefully designed experiments and pre- cise measurements are also needed. Two nested disposable polystyrene cups are a fairly effective calorimeter for making such measurements (Figure 1). When we investigate energy changes we base our analysis on the law of conservation of energy: the total energy change of the chemical system is equal to the total energy change of the surroundings.

H system q surroundings

Section 5.2

Section 5.2 There are three simplifying assumptions often used in calorimetry: • no heat is transferred

There are three simplifying assumptions often used in calorimetry:

• no heat is transferred between the calorimeter and the outside environment;

• any heat absorbed or released by the calorimeter materials, such as the container, is negligible; and

• a dilute aqueous solution is assumed to have a density and specific heat capacity equal to that of pure water (1.00 g/mL and 4.18 J/g°C or 4.18 kJ/kg °C).

Figure 1 A simple laboratory calorimeter consists of an insulated container made of two nested polystyrene cups, a measured quantity of water, and a ther- mometer. The chemical system is placed in or dissolved in the water of the calorimeter. A third cup, with a hole punched in the bottom, can be inverted and used as a lid. Energy transfers between the chemical system and the surrounding water are monitored by measuring changes in the temperature of the water.

Chemical system

dissolved in

surrounding

water

Using Calorimetry to Find Molar Enthalpies

In a calorimetry experiment, 7.46 g of potassium chloride is dissolved in 100.0 mL (100.0 g) of water at an initial temperature of 24.1°C. The final temperature of the solution is 20.0°C. What is the molar enthalpy of solution of potassium chloride?

First, calculate the amount of potassium chloride.

m KCl

7.46 g

M KCl 74.6 g/mol

n KCl 7.46 g

7 4 .6 g

1

m

o l

n KCl 0.100 mol KCl

The next step is to recognize the law of conservation of energy.

H

(KCl dissolving)

q

(calorimeter water)

By combining this with the mathematical formulas used earlier in this chapter,

H

n H sol and q

mc T,

we can derive a formula to determine the enthalpy change of potassium chloride dis- solving to form a solution:

n H sol mc T

Assuming that the dilute solution has the same physical properties as pure water, we can now find the molar enthalpy of solution by rearranging this new equation to isolate the quantity we wish to solve for and substituting the given information and the appro- priate constants. Note that the mass quantity we are considering is the mass of water in the solution.

m water 100.0 g

c water 4.18 J/(g•°C)

T 24.1°C

20.0°C

4.1°C

SAMPLE problem
SAMPLE problem

KEY EQUATION

n H sol mc T

where n and H sol refer to the solute, and m, c, and T refer to the solvent (assuming the solution has the same physical proper- ties as the solvent — as it will if it is dilute).

to the solvent (assuming the solution has the same physical proper- ties as the solvent —
solution has the same physical proper- ties as the solvent — as it will if it

NEL

Thermochemistry

309

n H sol mc T mc T H sol(KCl) n 100.0 g 4.18 J/g •°C
n H sol mc T
mc
T
H sol(KCl)
n
100.0 g 4.18 J/g •°C 4.1°C
0.100 mol
H sol(KCl) 1.7 10 4 J/mol or 17 kJ/mol
The enthalpy change for each mole of potassium chloride that dissolves is 17 kJ/mol.
Because the reaction is endothermic, the molar enthalpy of solution for potassium
chloride is reported as 17 kJ/mol. Note that the certainty of the final answer (two
significant digits) is determined by the certainty of the temperature change, 4.1°C.
Example
What mass of lithium chloride must have dissolved if the temperature of 200.0 g of
water increased by 6.0°C? The molar enthalpy of solution of lithium chloride is
37 kJ/mol.
Solution
m water 200.0 g
T 6.0°C
H sol 37 kJ/mol
c water 4.18 kJ/kg•°C
M LiCl 42.4 g/mol
?
m LiCl
n H sol
q water
mc T
n H sol
m c T
n LiCl
H
so l
4 .1 8 J
k
0.2000 kg 6.0°C
k g C
•°
n LiCl
37
kJ/mol
0.14 mol
4 2 .4 g
0.14 mol
m LiCl
1 l
m
o
5.7 g
m LiCl
The mass of lithium chloride required to raise the temperature of the water 6.0°C is 5.7 g.
Practice
Understanding Concepts
Answers
4. 13.9 kJ/mol
5. 5.54 kJ/mol
4. In a chemistry experiment to investigate the properties of a fertilizer, 10.0 g of urea,
NH 2 CONH 2(s) , is dissolved in 150 mL of water in a simple calorimeter. A tempera-
ture change from 20.4°C to 16.7°C is measured. Calculate the molar enthalpy of
solution for the fertilizer urea.
5. A 10.0-g sample of liquid gallium metal, at its melting point, is added to 50.0 g of water
in a polystyrene calorimeter. The temperature of the water changes from 24.0°C to
27.8°C as the gallium solidifies. Calculate the molar enthalpy of solidification for gallium.

Section 5.2

Calorimetry of Chemical Changes

Chemical reactions that occur in aqueous solutions can also be studied using a poly- styrene calorimeter. The chemical system usually involves aqueous reactant solutions that are considered to be equivalent to water. The assumptions and formulas applied are iden- tical to those used in the analysis of energy changes during state changes and dissolving. When aqueous solutions of acids and bases react, they undergo a neutralization reac- tion. For example, potassium hydroxide and hydrobromic acid solutions react to form water and aqueous potassium bromide:

KOH (aq) HBr (aq) H 2 O (l) KBr (aq)

INVESTIGATION 5.2.1

INVESTIGATION 5.2.1

Molar Enthalpy of a Chemical Change (p. 348) How are molar enthalpies deter- mined? Use the equations and gen- eralizations you’ve learned to determine a value for the molar enthalpy of neutralization of sodium hydroxide by sulfuric acid.

The molar enthalpy of reaction for systems such as this is sometimes called the heat

of neutralization, or enthalpy of neutralization.

the heat of neutralization, or enthalpy of neutralization. Practice Understanding Concepts 6. List three
Practice
Practice

Understanding Concepts

6. List three assumptions made in student investigations involving simple calorimeters.

7. The energy involved in the process H 2 O (g) H 2 O (l) could be described as a molar enthalpy of condensation. Describe the type of molar enthalpy that would be associ- ated with each of the following reactions:

(a)

(b)

(c)

(d)

(e)

Br 2(l) Br 2(g)

CO 2(g) CO 2(s)

LiBr (s) Li + (aq) + Br

(aq)

C 3 H 8(g)

5 O 2(g)

3 CO 2(g) +

4 H 2 O (l)

NaOH (aq) + HCl (aq) 2 NaCl (aq) +

H 2 O (l)

Applying Inquiry Skills

8.

In a calorimetry experiment in which you are measuring mass and temperature using equipment available to you in your school lab, which measurements limit the certainty

of

the experimental result? Explain.

9.

(a)

A laboratory technician adds 43.1 mL of concentrated, 11.6 mol/L hydrochloric acid to water to form 500.0 mL of dilute solution. The temperature of the solution changes from 19.2°C to 21.8°C. Calculate the molar enthalpy of dilution of hydrochloric acid.

(b)

What effect would there be on the calculated value for the molar enthalpy of dilu- tion if the technician accidentally used too much water so that the total volume was actually more than 500.0 mL? Explain.

(c)

The dissolving of an acid in water is a very exothermic process. Dilute acid solu- tions should always be made by adding acid to water. Explain why adding water to acid is very dangerous.

10.

In a laboratory investigation into the reaction

Ba(NO 3 ) 2(s) K 2 SO 4(aq) BaSO 4(s) 2 KNO 3(aq)

a researcher adds a 261-g sample of barium nitrate to 2.0 L of potassium sulfate solu- tion in a polystyrene calorimeter.

Evidence

As the barium nitrate dissolves, a precipitate is immediately formed.

T 1 26.0°C

T 2 29.1°C

Analysis

(a) Calculate the molar enthalpy of reaction of barium nitrate.

NEL

Answers

9.

(a)

10.9 kJ/mol

10.

(a)

26 kJ/mol

Thermochemistry

311

Section 5.2 Questions
Section 5.2 Questions

Understanding Concepts

1. If the molar enthalpy of combustion of ethane is 1.56 MJ/mol, how much heat is produced in the burning of

(a)

5.0 mol of ethane?

(b)

40.0 g of ethane?

2. The molar enthalpy of solution of ammonium chloride is +14.8 kJ/mol. What would be the final temperature of a solution in which 40.0 g of ammonium chloride is added to 200.0 mL of water, initially at 25°C?

3. The molar enthalpy of combustion of decane (C 10 H 22 ) is –6.78 MJ/mol. What mass of decane would have to be burned in order to raise the temperature of 500.0 mL of water from 20.0°C to 55.0°C?

4. During sunny days, chemicals can store solar energy in homes for later release. Certain hydrated salts dissolve in their water of hydration when heated and release heat when they solidify. For example, Glauber’s salt, Na 2 SO 4 •10 H 2 O (s) , solidifies at 32°C, releasing 78.0 kJ/mol of salt. What is the enthalpy change for the solidification of 1.00 kg of Glauber’s salt used to supply energy to a home (Figure 2)?

salt used to supply energy to a home ( Figure 2 )? Figure 2 Glauber’s salt

Figure 2 Glauber’s salt is an ideal medium for storing solar energy during the day and releasing it at night. Its melting point is convenient, at 32°C, and it has a high enthalpy of fusion, so a lot of energy can be stored by a small mass of salt. Tubes filled with this salt are part of the heat system in a solar-heated home.

Applying Inquiry Skills

5.

In a laboratory investigation into the neutralization reaction

HNO 3(aq)

KOH (s) KNO 3(aq) +

H 2 O (l)

a researcher adds solid potassium hydroxide to nitric acid solution in a polystyrene calorimeter.

Evaluation mass KOH 5.2 g volume of nitric acid solution 200 mL T 1 21.0°C T 2 28.1°C

Analysis

(a) Calculate the molar enthapy of neutralization of

6.

potassium hydroxide.

A student noticed that chewing fast-energy dextrose

tablets made her mouth feel cold. Design an investigation, including a Question, Hypothesis, Experimental Design, Materials list, and Procedure, to find out whether there really is a temperature change.

Making Connections

7. The propane refrigerator seems to be a contradiction in terms: the exothermic combustion of a hydrocarbon is used to cool food.

(a)

Find out how this device functions and what changes in matter occur in its operation.

(b)

Calculate enthalpy changes expected in a typical example.

GO
GO

www.science.nelson.com

Representing Enthalpy Changes 5.3 5.3

Representing Enthalpy Changes

5.35.3

How do scientists communicate to each other the size of enthalpy changes and determine whether they are endothermic or exothermic? Combustion reactions are often spectacular and are obviously exothermic. However, it is usually not obvious whether a chemical change will absorb or release energy, so, when we are discussing thermochemical reactions, we must indicate this information clearly. The equations we use to do this are called themochemical equations. You have already seen that the value of an enthalpy change, H, depends on the quantity of a substance that undergoes a change. For example, one mole of hydrogen as it burns has an enthalpy change of –285.8 kJ, and the enthalpy change for two moles of hydrogen is twice that: –571.6 kJ. You have also learned that a sign convention identifies reactions as endothermic or exothermic:

• endothermic enthalpy changes are reported as positive values; and

• exothermic enthalpy changes are reported as negative values.

When water decomposes, the system gains energy from the surroundings and so the molar enthalpy is reported as a positive quantity to indicate an endothermic change:

H 2 O (l)

H 2(g)

1 2 O 2(g)

H decomp 285.8 kJ/mol H 2 O

2 ( g ) H d e c o m p 285.8 kJ/mol H 2 O

The law of conservation of energy implies that the reverse process (combustion of hydrogen) has an equal and opposite energy change.

H 2(g)

1 2 O 2(g) H 2 O (l)

H comb –285.8 kJ/mol H 2

Figure 1 Hydrocarbons such as acetone burn with a readily visible flame. The flame produced by combusting methanol (right) is difficult to see, and so more dangerous.

The sign convention represents the change from the perspective of the chemical system itself, not from that of the surroundings. An increase in the temperature of the sur- roundings implies a decrease in the enthalpy of the chemical system, because the change was exothermic. Most information about energy changes, for example, the enthalpy change that accom- panies the burning of methanol (Figure 1), comes from the experimental technique of calorimetry. We can communicate the energy changes, obtained from these empirical studies, in four different ways. Three use thermochemical equations and one uses a diagram:

• by including an energy value as a term in the thermochemical equation

3

e.g., CH 3 OH (l) + 2 O 2(g) CO 2(g) + 2 H 2 O (g) + 726 kJ

• by writing a chemical equation and stating its enthalpy change

3

e.g., CH 3 OH (l) + 2 O 2(g) CO 2(g) + 2 H 2 O (g)

H –726 kJ

• by stating the molar enthalpy of a specific reaction

e.g., H combustion or H c –726 kJ/mol CH 3 OH

Potential Energy Diagram for an Exothermic Reaction

E p

CH 3 OH (l) + O 2(g) ∆H CO 2(g) + H 2 O (l)
CH 3 OH (l) + O 2(g)
∆H
CO 2(g) + H 2 O (l)

Reaction Progress

Figure 2

• by drawing a chemical potential energy diagram (Figure 2)

All four of these methods of expressing energy changes are equivalent and are described in more detail as follows.

NEL

Thermochemistry

313

LEARNING TIP

LEARNING T I P Fractions are convenient in many thermochemical equations. Note that these apply to

Fractions are convenient in many thermochemical equations. Note

that these apply to fractions of

3

moles of substances (e.g., mol

2

represents 1.5 mol) rather than

fractions of actual molecules.

LEARNING TIP

LEARNING TIP Oxygen is often the reactant given a fractional coefficient in combus- tion equations because

Oxygen is often the reactant given a fractional coefficient in combus- tion equations because it occurs as a diatomic molecule and the total numbers of oxygen atoms in the products are often odd numbers.

Figure 3 Combustion reactions are the most familiar exothermic reactions. The searing heat produced by a burning building is a formidable obstacle facing firefighters.

Method 1:

Thermochemical Equations with Energy Terms

You are already familiar, from your grade 11 Chemistry course, with the first way to

describe the enthalpy change in a chemical reaction: include it as a term in a thermo-

chemical equation. If a reaction is endothermic, it requires a certain quantity of energy to be supplied to the reactants. This energy (like the reactants) is “consumed” as the reaction progresses and is listed along with the reactants. For example, in the electrolysis of water, energy is absorbed. For our purposes, SATP conditions are usually assumed for all equations.

H 2 O (l)

+

285.8 kJ

H 2(g) +

1 O 2(g)

2

If a reaction is exothermic, energy is released as the reaction proceeds (Figure 3) and is listed along with the products. For example, magnesium burns in oxygen as follows:

Mg (s) +

2 1 O 2(g) MgO (s) + 601.6 kJ

+ 2 1 O 2 ( g ) → MgO ( s ) + 601.6 kJ
SAMPLE problem Writing Thermochemical Equations with Energy Terms Write a thermochemical equation to represent the
SAMPLE problem
Writing Thermochemical Equations with Energy Terms
Write a thermochemical equation to represent the exothermic reaction that
occurs when two moles of butane burn in excess oxygen gas. The molar enthalpy
of combustion of butane is –2871 kJ/mol.
First, write the equation for the combustion of butane:
2 C 4 H 10(g) 13 O 2(g) → 8 CO 2(g) 10 H 2 O (l)
Then obtain the amount of butane, n , from the balanced equation. In this case, n 2 mol.
From the problem, H c –2871 kJ/mol,
H n H c
28 71 kJ
2
mol
1 ol
m
H –5742 kJ
The reaction is exothermic, so the energy term must be a product. Report the enthalpy
change for the reaction by writing it as a product in the thermochemical equation, as follows:
5742 kJ
2 C 4 H 10(g)
13 O 2(g)
8 CO 2(g)
10 H 2 O (l)

Section 5.3

Example

Write a thermochemical equation to represent the dissolving of one mole of silver nitrate in water. The molar enthalpy of solution is + 22.6 kJ/mol.

Solution

AgNO 3(s)

22.6 kJ

Ag

(aq)

NO 3 (aq)

Method 2: Thermochemical Equations with H Values

A second way to describe the enthalpy change in a reaction is to write a balanced chem- ical equation and then the H value beside it, making sure that H is given the correct sign. Thus, the production of methanol from carbon monoxide and hydrogen could be written as:

CO (g)

+

2 H 2(g)

CH 3 OH (l)

H

–128.6 kJ

Note that the units for the enthalpy change are kilojoules (not kJ/mol), because the enthalpy change applies to the reactants and products as written, with the numbers of moles of reactants and products given in the equation. The same equation could be written as:

1

2 CO (g) +

H 2(g)

1

CH 3 OH (l)

2

H

–64.3 kJ

Writing Thermochemical Equations with H Values SAMPLE problem Sulfur dioxide and oxygen react to form
Writing Thermochemical Equations with H Values
SAMPLE problem
Sulfur dioxide and oxygen react to form sulfur trioxide (Figure 4). The molar
enthalpy for the combustion of sulfur dioxide, H comb , in this reaction is
98.9 kJ/mol SO 2 . What is the enthalpy change for this reaction?
First, write the balanced chemical equation:
2 SO 2(g)
O 2(g) → 2 SO 3(g)
Then obtain the amount of sulfur dioxide, n, from the balanced equation and use
H n H c
n
2 mol and H c 98.9 kJ/mol, so
98.9 kJ
H
2 mol
1
mol
–197.8 kJ
The enthalpy change and the reaction are
H
197.8 kJ
2 SO 2(g)
O 2(g) → 2 SO 3(g)
Figure 4
Most sulfuric acid is produced in
plants like this by the contact
process, which includes two
exothermic combustion reactions.
Sulfur reacts with oxygen, forming
sulfur dioxide; sulfur dioxide, in
contact with a catalyst, reacts with
oxygen, forming sulfur trioxide.
Example
Write a thermochemical equation, including a H value, to represent the exothermic reac-
tion between xenon gas and fluorine gas to produce solid xenon tetrafluoride, given that
the reaction produces 251 kJ per mol of Xe reacted.

NEL

Thermochemistry

315

Solution

Xe (g) 2 F 2(g) XeF 4(s)

H 251 kJ

As previously described, the enthalpy change H depends on the chemical equation as written. Therefore, if the balanced equation for the reaction is written differently, the enthalpy change should be reported differently. For example,

1

SO 2(g) +

2 O 2(g) SO 3(g)

H –98.9 kJ

Both this thermochemical equation and the one in the sample problem above agree with the empirically determined molar enthalpy for sulfur dioxide in this reaction.

H c 1 9 7.8 kJ 2 m ol

– 98 .9 k J

1 m o l

–98.9 kJ/mol SO 2

The enthalpy changes for most reactions must be accompanied by a balanced chem- ical equation that includes the state of matter of each substance.

molar enthalpy of reaction, H x the energy change associated with the reaction of one mole of a sub- stance (also called molar enthalpy change)

standard molar enthalpy of reaction, H° x the energy change associated with the reaction of one mole of a substance at 100 kPa and a specified temperature (usually 25°C)

LEARNING TIP

LEARNING T I P For the purposes of this text- book, tabulated values will be standard

For the purposes of this text- book, tabulated values will be standard values at 25°C, so that molar enthalpies will be assumed to be standard molar enthalpies. For example, the values for H c and H ° c will be equivalent.

Method 3: Molar Enthalpies of Reaction

As you have seen in the previous section, molar enthalpies are convenient ways of describing the energy changes involved in a variety of physical and chemical changes. In each case, one mole of a particular reactant or product is specified. For example, the enthalpy change involved in the dissolving of one mole of solute is called the molar enthalpy of solution and can be symbolized by H sol . In Table 1, the substance under con- sideration in each reaction is highlighted in red. A molar enthalpy that is determined when the initial and final conditions of the chem- ical system are at SATP is called a standard molar enthalpy of reaction. The symbol H distinguishes standard molar enthalpies from molar enthalpies, H x , which are measured at other conditions of temperature and pressure. Standard molar enthalpies allow chemists to create tables to compare enthalpy values, as you will see in the next two sections.

x

°

Table 1

Some Molar Enthalpies of Reaction

Type of molar enthalpy

Example of change

solution ( H sol )

NaBr (s) Na + (aq)

Br (aq)

combustion ( H comb )

CH 4(g) + 2 O 2(g) CO 2(g) H 2 O (l)

vaporization ( H vap )

CH 3 OH (l) CH 3 OH (g)

freezing ( H fr )

H 2 O (l) H 2 O (s)

neutralization ( H neut )*

2 NaOH (aq) H 2 SO 4(aq) 2 Na 2 SO 4(aq) + 2 H 2 O (l)

neutralization ( H neut )*

NaOH (aq) 1/2 H 2 SO 4(aq) 1/2 Na 2 SO 4(aq) H 2 O (l)

formation ( H f )**

C (s) + 2 H 2(g) + 1/2 O 2(g) CH 3 OH (l)

*

Enthalpy of neutralization can be expressed per mole of either base or acid consumed.

**

Molar enthalpy of formation will be discussed in more detail in Section 5.5.

 

Section 5.3

For an exothermic reaction, the standard molar enthalpy is measured by taking into account all the energy required to change the reaction system from SATP, in order to ini- tiate the reaction, and all the energy released following the reaction, as the products are cooled to SATP. For example, the standard molar enthalpy of combustion of methanol (Figure 5) is

°

H c 726 kJ/mol CH 3 OH

This quantity takes into account the energy input to initiate the reaction, the burning of 1 mol of methanol in oxygen to produce 1 mol CO 2(g) and 2 mol H 2 O (g) , then the energy released as the products are cooled to SATP. Molar enthalpies can be used to describe reactions other than combustion, as long as the reaction is clearly described. For example, methanol is produced industrially by the high-pressure reaction of carbon monoxide and hydrogen gases.

CO (g)

2 H 2(g)

CH 3 OH (l)

Chemists have determined the standard molar enthalpy of reaction for methanol in this reaction, H r ° , to be –128.6 kJ/mol CH 3 OH. To describe the reaction fully, we would write the thermochemical equation

CO (g)

2 H 2(g)

CH 3 OH (l)

H ° r –128.6 kJ/mol CH 3 OH

The symbol for the molar enthalpy of reaction uses the subscript “r” to refer to the reac- tion under consideration, with the stated number of moles of reactants and products. Since two moles of hydrogen are consumed as 128.6 kJ of heat are produced, the stan- dard molar enthalpy of reaction in terms of hydrogen could be described as half the above value, or 64.3 kJ/mol H 2 .

as half the above value, or 64.3 kJ/mol H 2 . Figure 5 Methanol burns more

Figure 5 Methanol burns more completely than gasoline, producing lower levels of some pollutants. The tech- nology of methanol-burning vehicles was originally developed for racing cars because methanol burns faster than gasoline. However, its energy content is lower so it takes twice as much methanol as gasoline to drive a given distance.

LEARNING TIP

LEARNING TIP The combustion of fuels is always exothermic: heat is released to the surroundings. Enthalpies

The combustion of fuels is always exothermic: heat is released to the surroundings. Enthalpies of com- bustion are often called heats of combustion and given as absolute values. For example,

H comb(methanol) 726 kJ/mol.

Describing Molar Enthalpies of Reaction SAMPLE problem Write an equation whose energy change is the
Describing Molar Enthalpies of Reaction
SAMPLE problem
Write an equation whose energy change is the molar enthalpy of combustion of
propanol (C 3 H 7 OH).
Hydrocarbons such as propanol undergo combustion in air by reacting with oxygen gas to
produce carbon dioxide gas and water. Since SATP is assumed unless further information
is provided, water is produced in liquid form.
Since it is a molar enthalpy, we must write the equation for 1 mol of C 3 H 7 OH, which
requires a fractional coefficient in front of oxygen gas.
The equation is
9
+
C 3 H 7 OH (g)
2 O 2(g) → 3 CO 2(g)
4 H 2 O (l)
Example
Write an equation whose enthalpy change is the molar enthalpy of reaction of calcium
with hydrochloric acid to produce hydrogen gas and calcium chloride solution.
Solution
Ca (s)
2 HCl (aq) → H 2(g)
CaCl 2(aq)

NEL

Thermochemistry

317

potential energy diagram a graphical representation of the energy transferred during a physical or chemical change

INVESTIGATION 5.3.1

INVESTIGATION 5.3.1

Combustion of Alcohols (p. 349) Do different alcohols produce dif- ferent quantities of heat when they combust? How do their molar enthalpies compare?

Figure 6

(a)

During an exothermic reaction, the enthalpy of the system decreases and heat flows into the surroundings. We observe a temperature increase in the surroundings.

(b)

During an endothermic reac- tion, heat flows from the sur- roundings into the chemical system. We observe a tempera- ture decrease in the surround- ings. This corresponds to an increase in the enthalpy of the chemical system.

Figure 7

(a)

The reaction in which one mole of magnesium oxide is formed from its elements is exothermic, so the reactants must have a higher potential energy than

the product.

(b)

The reaction in which water decomposes to form hydrogen and oxygen gases is endothermic, so the reactant (water) must have a lower potential energy than the prod- ucts (hydrogen and oxygen).

Method 4: Potential Energy Diagrams

Chemists sometimes explain observed energy changes in chemical reactions in terms of chemical potential energy. This stored energy is related to the relative positions of particles and the strengths of the bonds between them. Potential energy is stored or released as the positions of the particles change, just as it is when a spring is stretched and then released. As bonds break and re-form and the positions of atoms are altered, changes occur in potential energy. As you have seen before, the potential energy change in the system is equivalent to the heat transferred to or from the surroundings. We can visually communicate this energy transferred by using a potential energy diagram. In this theoretical description, the energy transferred during a change is rep- resented as changes in the chemical potential energy of the particles as bonds are broken or formed. The vertical axis on the diagram represents the potential energy of the system. Since the reactants are written on the left and the products on the right, the horizontal axis is sometimes called a reaction coordinate or reaction progress. In an exothermic change (Figure 6(a)), the products have less potential energy than the reactants: energy is released to the surroundings as the products form. In an endothermic change (Figure 6(b)), the products have more potential energy than the reactants: energy is absorbed from the surroundings. Neither of the axes is numbered; only the numerical change in potential energy (enthalpy change, H) of the system is shown in the diagrams. Potential energy diagrams can be used to describe a wide variety of chemical changes

as shown in Figure 7.

a wide variety of chemical changes as shown in Figure 7 . Exothermic Reaction Endothermic Reaction

Exothermic Reaction

Endothermic Reaction

reactants products E p E p ∆H products reactants (a) (b) Reaction Progress Reaction Progress
reactants
products
E p
E p
∆H
products
reactants
(a)
(b)
Reaction Progress
Reaction Progress
Exothermic Chemical Change
Endothermic Chemical Change
1
Mg (s) +
2
O 2(g)
H 2(g) +
1
2 O 2(g)
∆H f ˚ = –601.6 kJ
E p
E p
∆H ˚ decomp = +285.8 kJ
(kJ)
(kJ)
MgO (s)
H 2 O (l)
(a)
(b)
Reaction Progress
Reaction Progress

Section 5.3

SUMMARY

Communicating Enthalpy Changes

Figure 8 uses the chemical reactions for photosynthesis and respiration to summarize the four methods of communicating the molar enthalpy or change in enthalpy of a chemical reaction. Each method has advantages and disadvantages. To best communi- cate energy changes in chemical reactions, you should learn all four methods.

1

2

3

4

E p

(kJ)

C 6 H 12 O 6(s) + 6O 2(g)

C 6 H 12 O 6(s) + 6O 2(g)

6 CO 2(g) + 6H 2 O (l) + 2802.7 kJ

6 CO 2(g) + 6H 2 0 (l)

H = –2802.7 kJ

Molar enthalpy for cellular respiration:

H respiration = –2802.7 kJ/mol glucose

Potential energy diagram for cellular respiration:

Cellular Respiration of Glucose

C 6 H 12 O 6(s) + 6O 2(g)

H = –2802.7 kJ

6CO 2(g) + 6H 2 O (l)

Reaction Progress

1

2

6 CO 2(g) + 6H 2 O (l) + 2802.7 kJ

C 6 H 12 O 6(s) + 6O 2(g)

6 CO 2(g) + 6H 2 O (l)

C 6 H 12 O 6(s) + 6O 2(g)

H = +2802.7 kJ

3 Molar enthalpy for photosynthesis:

H photosynthesis = +2802.7 kJ/mol glucose

4 Potential energy diagram for photosynthesis:

E p

(kJ)

Photosynthesis

C 6 H 12 O 6(s) + 6O 2(g)

H = +2802.7 kJ

6CO 2(g) + 6H 2 O (l)

Reaction Progress

Practice
Practice

Understanding Concepts

1. Communicate the enthalpy change by using the four methods described in this sec- tion for each of the following chemical reactions. Assume standard conditions (SATP) for the measurements of initial and final states.

(a)

The formation of acetylene (ethyne, C 2 H 2 ) fuel from solid carbon and gaseous hydrogen ( +228 kJ/mol acetylene)

(b)

The simple decomposition of aluminum oxide powder ( +1676 kJ/mol aluminum oxide)

(c)

The complete combustion of pure carbon fuel ( 393.5 kJ/mol CO 2 )

2. For each of the following balanced chemical equations and enthalpy changes, write the symbol and calculate the molar enthalpy of combustion for the substance that reacts with oxygen.

(a)

(b)

(c)

(d)

2H 2(g) O 2(g) 2H 2 O (g) 483.6 kJ

4 NH 3(g) 7O 2(g) 4 NO 2(g) 6 H 2 O (g)

2N 2(g)

3 Fe (s)

O 2(g)

2O 2(g)

163.2 kJ

Fe 3 O 4(s)

2N 2 O (g)

1134.4 kJ

1118.4 kJ

3. The neutralization of a strong acid and a strong base is an exothermic process.

H 2 SO 4(aq)

2 NaOH (aq) Na 2 SO 4(aq)

2 H 2 O (l)

114 kJ

(a)

What is the enthalpy change for this reaction?

(b)

Write this thermochemical equation, using the x to produce H 2 O (g) notation.

(c)

Calculate the molar enthalpy of neutralization in kJ/mol sulfuric acid.

(d)

Calculate the molar enthalpy of neutralization in kJ/mol sodium hydroxide.

in kJ/mol sulfuric acid. (d) Calculate the molar enthalpy of neutralization in kJ/mol sodium hydroxide.

Figure 8 Energy is transformed in cellular respiration and in photosynthesis. Cellular respiration, a series of exothermic reactions, is the breakdown of foodstuffs, such as glucose, that takes place within cells. Photosynthesis, a series of endothermic reactions, is the process by which green plants use light energy to make glucose from carbon dioxide and water.

Answers

2. (a)

241.8 kJ/mol H 2

(b)

283.6 kJ/mol NH 3

(c)

81.6 kJ/mol N 2

(d)

372.8 kJ/mol Fe

3. (c)

114 kJ/mol H 2 SO 4

(d)

57 kJ/mol NaOH

NEL

Thermochemistry

319

4. The standard molar enthalpy of combustion for hydrogen to produce H 2 0 (g) is –241.8 kJ/mol. The standard molar enthalpy of decomposition for water vapour is 241.8 kJ/mol.

(a)

Write both chemical equations as thermochemical equations with a value.

(b)

How does the enthalpy change for the combustion of hydrogen compare with the enthalpy change for the simple decomposition of water vapour? Suggest a gen- eralization to include all pairs of chemical equations that are the reverse of one another.

5. Classify the reactions in Figure 9 as endothermic or exothermic. Explain your classifi- cation.

Figure 9

E p

(a)

exothermic. Explain your classifi- cation. Figure 9 E p (a) ∆ H Reaction Progress E p

H

Explain your classifi- cation. Figure 9 E p (a) ∆ H Reaction Progress E p (b)

Reaction Progress

E p

(b)

H

Reaction Progress

Section 5.3 Questions
Section 5.3 Questions

Understanding Concepts

1. Draw a potential energy diagram with appropriately labelled axes to represent

(a)

the exothermic combustion of octane ( –5.47 MJ)

(b)

the endothermic formation of diborane (B 2 H 6 ) from its elements ( +36 kJ)

2. Translate each of the molar enthalpies given below into a balanced thermochemical equation, including the enthalpy change, H.

(a)

The enthalpy change for the reaction in which solid magnesium hydroxide is formed from its elements at SATP is 925 kJ/mol.

(b)

The standard molar enthalpy of combustion for pen- tane, C 5 H 12 , is 2018 kJ/mol.

(c)

The standard molar enthalpy of simple decomposition, H ° decomp , for nickel(II) oxide to its elements is 240 kJ/mol.

3. For each of the following reactions, write a thermochemical equation including the energy as a term in the equation.

(a)

Butane obtained from natural gas is used as a fuel in lighters (Figure 10). The standard molar enthalpy of combustion for butane is 2.86 MJ/mol.

(b)

Carbon exists in two different forms, graphite and dia- mond, which have very different crystal forms. The molar enthalpy of transition of graphite to diamond is 2 kJ.

(c)

Ethanol, obtained from the fermentation of corn and other plant products, can be added to gasoline to act as a cheaper alternative. The standard molar enthalpy of combustion for ethanol is 1.28 MJ/mol.

molar enthalpy of combustion for ethanol is 1.28 MJ/mol. Figure 10 Butane is the fuel used

Figure 10 Butane is the fuel used in lighters.

Applying Inquiry Skills

4.

A calorimeter is used to determine the enthalpy change

involved in the combustion of eicosane (C 20 H 42 ), a solid

hydrocarbon found in candle wax. Complete the Analysis and Evaluation sections of the investigation report.

Experimental Design

A candle is placed under a copper can containing water,

and a sample of candle wax (eicosane) is burned such that the heat from the burning is transferred to the calorimeter.

Section 5.3

Evidence

Table 2

Observations When Burning Candle Wax

Quantity

Measurement

mass of water, m

200.0

g

specific heat capacity of copper, c copper

0.385