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Thermochemistry: Energy Flow

and Chemical Change
Key Principles

to focus on while studying this chapter

Chemical or physical change is always accompanied by a change in the energy
content of the matter (Introduction).

To study a change in energy (E ), scientists conceptually divide the universe into
system (the part being studied) and surroundings (everything else). All energy
changes occur as heat (q) and/or work (w), transferred either from the surroundings to the system or from the system to the surroundings (E  q  w). Thus,
the total energy of the universe is constant (law of conservation of energy or first
law of thermodynamics) (Section 6.1).
The magnitude of E is the same no matter how a given change in energy occurs.
Because E is a state functiona property that depends only on the current state
of the systemE depends only on the difference between the initial and final
values of E (Section 6.1).
Enthalpy (H) is another state function and is related to E. The change in enthalpy
(H) equals the heat transferred at constant pressure, qP. Most laboratory, environmental, and biological changes occur at constant P, so H is more relevant
than E and easier to measure (Section 6.2).
The change in the enthalpy of a reaction, called the heat of reaction (Hrxn), is negative (0) if the reaction releases heat (exothermic) and positive (0) if it absorbs
heat (endothermic); for example, the combustion of methane is exothermic
(Hrxn  0) and the melting of ice is endothermic (Hrxn  0) (Section 6.2).
The more heat a substance absorbs, the higher its temperature becomes, but each
substance has its own capacity for absorbing heat. Knowing this capacity and
measuring the change in temperature in a calorimeter, we can find Hrxn
(Section 6.3).
The quantity of heat lost or gained in a reaction is related stoichiometrically to the
amounts of reactants and products (Section 6.4).
Because H is a state function, we can find H of any reaction by imagining the reaction occurring as the sum of other reactions whose heats of reaction we know
or can measure (Hesss law of heat summation) (Section 6.5).
Chemists have specified a set of conditions, called standard states, to determine
heats of different reactions. Each substance has a standard heat of formation
(Hf ), the heat of reaction when the substance is formed from its elements
under these conditions, and the Hf values for each substance in a reaction are
used to calculate the standard heat of reaction (Hrxn) (Section 6.6).

Heat Out and Heat In Combustion releases heat and

melting absorbs it.

Outline
6.1 Forms of Energy and Their
Interconversion
System and Surroundings
Energy Flow to and from a System
Heat and Work
Energy Conservation
Units of Energy
State Functions

6.2 Enthalpy: Heats of Reaction

and Chemical Change
Meaning of Enthalpy
Exothermic and Endothermic Processes

6.3 Calorimetry: Laboratory

Measurement of Heats of Reaction
Specific Heat Capacity
Practice of Calorimetry

6.4 Stoichiometry of Thermochemical

Equations
6.5 Hesss Law of Heat Summation
6.6 Standard Heats of Reaction (Hrxn)
Formation Equations
Determining Hrxn from Hf
Fossil Fuels and Climate Change

185

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186

Concepts & Skills to Review

before studying this chapter
energy and its interconversion
(Section 1.1)
distinction between heat and
temperature (Section 1.4)
nature of chemical bonding
(Section 2.7)
calculations of reaction stoichiometry
(Section 3.4)
properties of the gaseous state
(Section 5.1)
relation between kinetic energy and
temperature (Section 5.6)

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

henever matter changes, the energy content of the matter changes also. For
example, during the chemical change that occurs when a candle burns, the
wax and oxygen reactants contain more energy than the gaseous CO2 and H2O
products, and this difference in energy is released as heat and light. In contrast,
some of the energy in a flash of lightning is absorbed when lower energy N2 and
O2 in the air react to form higher energy NO. Energy content changes during a
physical change, too. For example, energy is absorbed when snow melts and is
released when water vapor condenses.
As you probably already know, the production and utilization of energy have
an enormous impact on society. Some of the largest industries manufacture products that release, absorb, or change the flow of energy. Common fuelsoil, wood,
coal, and natural gasrelease energy for heating and for powering combustion
engines and steam turbines. Fertilizers enhance the ability of crops to absorb solar
energy and convert it to the chemical energy of food, which our bodies then convert into other forms of energy. Metals are often used to increase the flow of
energy, while plastic, fiberglass, and ceramic materials serve as insulators that
limit the flow of energy.
Thermodynamics is the branch of physical science concerned with heat and
its transformations to and from other forms of energy. It will be our focus here
and again in Chapter 20. In this chapter, we highlight thermochemistry, which
deals with the heat involved in chemical and physical changes.

6.1 FORMS OF ENERGY AND THEIR INTERCONVERSION

In Chapter 1, we discussed the facts that all energy is either potential or kinetic
and that these forms are convertible from one to the other. An object has potential energy by virtue of its position and kinetic energy by virtue of its motion.
The potential energy of a weight raised above the ground is converted to kinetic
energy as it falls (see Figure 1.3, p. 7). When the weight hits the ground, it
transfers some of that kinetic energy to the soil and pebbles, causing them to
move, and thereby doing work. In addition, some of the transferred kinetic energy
appears as heat, as it slightly warms the soil and pebbles. Thus, the potential
energy of the weight is converted to kinetic energy, which is transferred to the
ground as work and as heat.
Modern atomic theory allows us to consider other forms of energysolar,
electrical, nuclear, and chemicalas examples of potential and kinetic energy on
the atomic and molecular scales. No matter what the details of the situation, when
energy is transferred from one object to another, it appears as work and/or as
heat. In this section, we examine this idea in terms of the loss or gain of energy
that takes place during a chemical or physical change.

The System and Its Surroundings

In order to observe and measure a change in energy, we must first define the
system, the part of the universe that we are going to focus on. The moment
we define the system, everything else relevant to the change is defined as the
surroundings. For example, in a flask containing a solution, if we define the
system as the contents of the flask, then the flask itself, other nearby equipment,
and perhaps the rest of the laboratory are the surroundings. In principle, the rest
of the universe is the surroundings, but in practice, we need to consider only
the portions of the universe relevant to the system. That is, its not likely that
a thunderstorm in central Asia or a methane blizzard on Neptune will affect the
contents of the flask, but the temperature, pressure, and humidity of the lab
might.

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6.1 Forms of Energy and Their Interconversion

If we define a weight falling to the ground as the system, then the soil and pebbles that are moved and warmed when it lands are the surroundings. An
astronomer may define a galaxy as the system and nearby galaxies as the surroundings. An ecologist in Africa can define a zebra herd as the system and the
animals, plants, and water supplies that the herd has contact with as the surroundings. A microbiologist may define a bacterial cell as the system and the
extracellular solution as the surroundings. Thus, in general, the nature of the
experiment and the focus of the experimenter define system and surroundings.

Energy Flow to and from a System

Each particle in a system has potential energy and kinetic energy, and the sum of
these energies for all the particles in the system is the internal energy, E, of the
system (some texts use the symbol U). When a chemical system changes from
reactants to products and the products return to the starting temperature, the internal energy has changed. To determine this change, E, we measure the difference
between the systems internal energy after the change (Efinal) and before the
change (Einitial):
E  Efinal  Einitial  Eproducts  Ereactants

(6.1)

where  (Greek delta) means change (or difference) in. Note especially that 
refers to the final state of the system minus the initial state.
Because the total energy must be conserved, a change in the energy of the
system is always accompanied by an opposite change in the energy of the surroundings. We often represent this change with an energy diagram in which the
final and initial states are horizontal lines on a vertical energy axis. The change
in internal energy, E, is the difference between the heights of the two lines. A
system can change its internal energy in one of two ways:
1. By losing some energy to the surroundings, as shown in Figure 6.1A:
Efinal  Einitial

E  0

(E is negative)

2. By gaining some energy from the surroundings, as shown in Figure 6.1B:

Efinal  Einitial

E  0

(E is positive)

Note that the change in energy is always an energy transfer from system to surroundings, or vice versa.

Final
state
Einitial

Final
state

Efinal < Einitial

E < 0
Energy lost to
surroundings

Energy, E

Energy, E

Initial
state

Efinal

Initial
state

Efinal > Einitial

E > 0
Energy gained
from surroundings

Efinal

A E of system decreases

Einitial

B E of system increases

FIGURE 6.1 Energy diagrams for the transfer of internal energy (E) between a system and its
surroundings. A, When the internal energy of a system decreases, the change in energy (E) is
lost to the surroundings; therefore, E of the system (Efinal  Einitial) is negative. B, When the systems internal energy increases, E is gained from the surroundings and is positive. Note that the
vertical yellow arrow, which signifies the direction of the change in energy, always has its tail at the
initial state and its head at the final state.

187

THINK OF IT THIS WAY

Wherever You Look,
There Is a System

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

188

Heat and Work: Two Forms of Energy Transfer

Just as we saw when a weight hits the ground, energy transfer outward from the
system or inward from the surroundings can appear in two forms, heat and work.
Heat (or thermal energy, symbol q) is the energy transferred between a system
and its surroundings as a result of a difference in their temperatures only. Energy
in the form of heat is transferred from hot soup (system) to the bowl, air, and
table (surroundings) because the surroundings have a lower temperature. All other
forms of energy transfer (mechanical, electrical, and so on) involve some type of
work (w), the energy transferred when an object is moved by a force. When you
(system) kick a football (surroundings), energy is transferred as work to move the
ball. When you inflate the ball, the inside air (system) exerts a force on the inner
wall of the ball (surroundings) and does work to move it outward.
The total change in a systems internal energy is the sum of the energy transferred as heat and/or work:
E  q  w

(6.2)

The numerical values of q and w (and thus E) can be either positive or negative, depending on the change the system undergoes. In other words, we define
the sign of the energy transfer from the systems perspective. Energy coming into
the system is positive. Energy going out from the system is negative. Of the innumerable changes possible in the systems internal energy, well examine the four
simplesttwo that involve only heat and two that involve only work.
Energy Transfer as Heat Only For a system that does no work but transfers energy
only as heat (q), we know that w  0. Therefore, from Equation 6.2, we have
E  q  0  q. There are two possibilities:
1. Heat flowing out from a system. Suppose a sample of hot water is the system; then, the beaker containing it and the rest of the lab are the surroundings.
The water transfers energy as heat to the surroundings until the temperature of
the water equals that of the surroundings. The systems energy decreases as heat
flows out from the system, so the final energy of the system is less than its initial energy. Heat was lost by the system, so q is negative, and therefore E is
negative (Figure 6.2A).
2. Heat flowing into a system. If the system consists of ice water, it gains
energy as heat from the surroundings until the temperature of the water equals
that of the surroundings. In this case, energy is transferred into the system, so the
final energy of the system is higher than its initial energy. Heat was gained by
the system, so q is positive, and therefore E is positive (Figure 6.2B).

Tsys > Tsurr

Tsys = Tsurr

Einitial
Tsys = Tsurr
E < 0

Room temp
H2O
Tsys
Tsurr

Heat (q) lost

to surroundings
(q < 0)

Energy, E

Energy, E

Hot H2O
Tsys
Tsurr

Room temp
H2O
Tsys
Tsurr
Efinal
Tsys < Tsurr

Ice H2O
Tsys
Tsurr

Einitial

Efinal

A E lost as heat

FIGURE 6.2 A system transferring energy as heat only. A, Hot water

(the system, sys) transfers energy as heat (q) to the surroundings (surr)
until Tsys  Tsurr. Here Einitial  Efinal and w  0, so E  0 and the sign

Heat (q) gained

from surroundings
(q > 0)

E > 0

B E gained as heat
of q is negative. B, Ice water gains energy as heat (q) from the surroundings until Tsys  Tsurr. Here Einitial  Efinal and w  0, so E  0
and the sign of q is positive.

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6.1 Forms of Energy and Their Interconversion

The functioning of two familiar appliances can clarify the loss or gain of heat and
the sign of q. The air in a refrigerator (surroundings) has a lower temperature than
a newly added piece of food (system), so the food loses energy as heat to the
refrigerator air, or q  0. The air in a hot oven (surroundings) has a higher temperature than a newly added piece of food (system), so the food gains energy as
heat from the oven air, or q  0.
Energy Transfer as Work Only For a system that transfers energy only as work
(w), q  0; therefore, E  0  w  w. Once again, there are two possibilities:
1. Work done by a system. Consider the reaction between zinc and hydrochloric acid as it takes place in an insulated container attached to a piston-cylinder
assembly. We define the system as the atoms that make up the substances. In the
initial state, the systems internal energy is that of the atoms in the form of the
reactants, metallic Zn and aqueous H and Cl ions. In the final state, the systems
internal energy is that of the same atoms in the form of the products, H2 gas and
aqueous Zn2 and Cl ions:

189

THINK OF IT THIS WAY

Thermodynamics in the Kitchen

Animation: Energy Flow

Zn(s)  2H(aq)  2Cl(aq) H2(g)  Zn2(aq)  2Cl(aq)

As the H2 gas forms, some of the internal energy is used by the system to do
work on the surroundings and push the piston outward. Energy is lost by the system as work, so w is negative and E is negative, as you see in Figure 6.3. The
H2 gas is doing pressure-volume work (PV work), the type of work in which a
volume changes against an external pressure. The work done here is not very useful because it simply pushes back the piston and outside air. But, if the system is
a ton of burning coal and O2, and the surroundings are a locomotive engine, much
of the internal energy lost from the system does the work of moving a train.
2. Work done on a system. If we increase the external pressure on the piston
in Figure 6.3, the system gains energy because work is done on the system by the
surroundings: w is positive, so E is positive.
Table 6.1 summarizes the sign conventions for q and w and their effect on
the sign of E.
FIGURE 6.3 A system losing energy as
work only. The internal energy of the system decreases as the reactants form
products because the H2(g) does work (w)
on the surroundings by pushing back the
piston. The reaction vessel is insulated, so
q  0. Here Einitial  Efinal, so E  0 and
the sign of w is negative.

Patm

Energy, E

System
HCl(aq)
Zn(s)
Einitial
Patm

P H2

E < 0

System
H2(g)

Work (w) done on

surroundings (w < 0)

ZnCl2(aq)
Efinal

Table 6.1 The Sign Conventions* for q, w, and E

q

 (heat gained)
 (heat gained)
 (heat lost)
 (heat lost)

 (work done on)

 (work done by)
 (work done on)
 (work done by)

*From the perspective of the system.

 (energy increased)
Depends on sizes of q and w
Depends on sizes of q and w
 (energy decreased)

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

The Law of Energy Conservation

As youve seen, when a system gains energy, the surroundings lose it, and when
a system loses energy, the surroundings gain it. Energy can be converted from
one form to another as these transfers take place, but it cannot simply appear or
disappearit cannot be created or destroyed. The law of conservation of energy
restates this basic observation as follows: the total energy of the universe is constant.
This law is also known as the first law of thermodynamics.
Conservation of energy applies everywhere. As gasoline burns in a car engine,
the released energy appears as an equivalent amount of heat and work. The heat
warms the car parts, passenger compartment, and surrounding air. The work appears
as mechanical energy to turn the cars wheels and belts. That energy is converted
further into the electrical energy of the clock and radio, the radiant energy of the
headlights, the chemical energy of the battery, the heat due to friction, and so forth.
If you took the sum of all these energy forms, you would find that it equals the
change in energy between the reactants and products as the gasoline is burned.
Complex biological processes also obey conservation of energy. Through photosynthesis, green plants convert radiant energy from the Sun into chemical
energy, transforming low-energy CO2 and H2O into high-energy carbohydrates
(such as wood) and O2. When the wood is burned in air, those low-energy compounds form again, and the energy difference is released to the surroundings.
Thus, energy transfers between system and surroundings can be in the forms
of heat and/or various types of workmechanical, electrical, radiant, chemical
but the energy of the system plus the energy of the surroundings remains constant:
energy is conserved. A mathematical expression of the law of conservation of
energy (first law of thermodynamics) is
Euniverse  Esystem  Esurroundings  0

(6.3)

This profound idea pertains to all systems, from a burning match to the movement of continents, from the inner workings of your heart to the formation of the
Solar System.

Units of Energy
The SI unit of energy is the joule (J), a derived unit composed of three base units:
1 J  1 kgm2/s2

Both heat and work are expressed in joules. Lets see how these units arise in
the case of work. The work (w) done on a mass is the force (F) times the distance (d ) that the mass moves: w  F d. A force changes the velocity of
(accelerates) a mass. Velocity has units of meters per second (m/s), so acceleration (a) has units of m/s2. Force, therefore, has units of mass (m, in kilograms)
times acceleration:
Therefore,

Fm a
wF d

in units of
has units of

kgm/s2
(kgm/s2) m  kgm2/s2  J

Potential energy, kinetic energy, and PV work are combinations of the same physical quantities and are also expressed in joules.
The calorie (cal) is an older unit that was defined originally as the quantity
of energy needed to raise the temperature of 1 g of water by 1C (from 14.5C
to 15.5C). The calorie is now defined in terms of the joule:
1 cal  4.184 J

or

1J

1
cal  0.2390 cal
4.184

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6.1 Forms of Energy and Their Interconversion

Because the quantities of energy involved in chemical reactions are usually quite
large, chemists use the unit the kilojoule (kJ), or sometimes the kilocalorie
(kcal):
1 kJ  1000 J  0.2390 kcal  239.0 cal

The nutritional Calorie (note the capital C), the unit used to measure the
energy available from food, is actually a kilocalorie. The British thermal unit
(Btu), a unit in engineering that you may have seen used to indicate energy output of appliances, is the quantity of energy required to raise the temperature of
1 lb of water by 1F and is equivalent to 1055 J. In general, the SI unit (J or kJ)
is used throughout this text.

SAMPLE PROBLEM 6.1

Determining the Change in Internal Energy of a System

Problem When gasoline burns in an automobile engine, the heat released causes the products

CO2 and H2O to expand, which pushes the pistons outward. Excess heat is removed by
the cars cooling system. If the expanding gases do 451 J of work on the pistons and the
system loses 325 J to the surroundings as heat, calculate the change in energy (E) in J,
kJ, and kcal.
Plan We must define system and surroundings, assign signs to q and w, and then calculate E with Equation 6.2. The system is the reactants and products, and the surroundings
are the pistons, the cooling system, and the rest of the car. Heat is released by the system, so q is negative. Work is done by the system to push the pistons outward, so w is
also negative. We obtain the answer in J and then convert it to kJ and kcal.
Solution Calculating E (from Equation 6.2) in J:
q  325 J
w  451 J
E  q  w  325 J  (451 J)
 776 J
Converting from J to kJ:
1 kJ
1000 J
 0.776 kJ

E  776 J
Converting from kJ to kcal:

E  0.776 kJ

1 kcal
4.184 kJ

 0.185 kcal
Check The answer is reasonable: combustion releases energy from the system, so Efinal

 Einitial and E should be negative. Given that 4 kJ  1 kcal, with rounding, nearly 0.8 kJ
should be nearly 0.2 kcal.

FOLLOW-UP PROBLEM 6.1 In a reaction, gaseous reactants form a liquid product.

The heat absorbed by the surroundings is 26.0 kcal, and the work done on the system is
15.0 Btu. Calculate E (in kJ).

State Functions and the Path Independence

of the Energy Change
An important point to understand is that there is no particular sequence by which
the internal energy (E) of a system must change. This is because E is a state function, a property dependent only on the current state of the system (its composition,

191

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

volume, pressure, and temperature), not on the path the system took to reach that
state; the current state depends only on the difference between the final and initial states.

The balance in your checkbook is a state function of your personal financial

system. For example, you can open a new account with a birthday gift of $50, or
you can open a new account with a deposit of a $100 paycheck and then write
two $25 checks. The two paths to the balance are different, but the balance
(current state) is the same.

Thus, the energy change of a system can occur by any one of countless combinations of heat (q) and work (w). No matter what the combination, however, the
same overall energy change occurs, because E does not depend on how the
change takes place. As an example, lets define a system in its initial state as 1 mol
of octane (a component of gasoline) together with enough O2 to burn it. In its
final state, the system is the CO2 and H2O that form (a fractional coefficient is
needed for O2 because we specified 1 mol of octane):

8CO2(g)  9H2O(g)
C8H18(l)  25
2 O2(g)
initial state (Einitial)

final state (Efinal)

Energy is released to warm the surroundings and/or do work on them, so E is

negative. Two of the ways the change can occur are shown in Figure 6.4. If we
burn the octane in an open container, E appears almost completely as heat (with
a small amount of work done to push back the atmosphere). If we burn it in a
car engine, a much larger portion (30%) of E appears as work that moves the
car, with the rest used to heat the car, exhaust gases, and surrounding air. If we
burn the octane in a lawn mower or a plane, E appears as other combinations
of work and heat.
Thus, for a given change, E (sum of q and w) is constant, even though q
and w can vary. Heat and work are not state functions because their values do
depend on the path the system takes in undergoing the energy change. The pressure (P) of an ideal gas or the volume (V ) of water in a beaker are other examples of state functions. This path independence means that changes in state
functionsE, P, and Vdepend only on their initial and final states. (Note
that symbols for state functions, such as E, P, and V, are capitalized.)

C8H18 (octane)
+ 25 O2
2

Energy, E

THINK OF IT THIS WAY

Your Financial State Function

Einitial

E lost as work
and heat

E lost as heat
8CO2 + 9H2O

Efinal

FIGURE 6.4 Two different paths for the energy change of a system. The change in internal energy when a given amount of octane burns in air is the same no matter how the energy is transferred. On the left, the fuel is burned in an open can, and the energy is lost almost entirely as heat.
On the right, it is burned in a car engine; thus, a portion of the energy is lost as work to move the
car, and less is lost as heat.

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6.2 Enthalpy: Heats of Reaction and Chemical Change

193

SECTION 6.1 SUMMARY

Energy is transferred as heat (q) when the system and surroundings are at different
temperatures; energy is transferred as work (w) when an object is moved by a force.
Heat or work gained by a system (q  0; w  0) increases its internal energy (E);
heat or work lost by the system (q  0; w  0) decreases E. The total change in the
systems internal energy is the sum of the heat and work: E  q  w. Heat and
work are measured in joules (J). Energy is always conserved: it changes from one
form into another, moving into or out of the system, but the total quantity of energy
in the universe (system plus surroundings) is constant. Energy is a state function,
which means that the same E can occur through any combination of q and w.

6.2 ENTHALPY: HEATS OF REACTION

AND CHEMICAL CHANGE
Most physical and chemical changes occur at virtually constant atmospheric
pressurea reaction in an open flask, the freezing of a lake, a drug response in
an organism. In this section, we define a thermodynamic variable that makes it
much easier to measure energy changes at constant pressure.

The Meaning of Enthalpy

To determine E, we must measure both heat and work. The two most important
types of chemical work are electrical work, the work done by moving charged
particles (Chapter 21), and PV work, the work done by an expanding gas. We find
the quantity of PV work done by multiplying the external pressure (P) by the
change in volume of the gas (V, or Vfinal  Vinitial). In an open flask (or a cylinder with a weightless, frictionless piston), a gas does work by pushing back the
atmosphere (Figure 6.5). Work done on the surroundings is a negative quantity
because V is positive; work done on the system is a positive quantity because
V is negative:
w  PV

H  E  PV

The change in enthalpy (H) is the change in internal energy plus the product
of the constant pressure and the change in volume:
(6.5)

Combining Equations 6.2 (E  q  w) and 6.4 leads to a key point about H:
E  q  w  q  (PV)  q  PV

At constant pressure, we denote q as qP and solve for it:

qP  E  PV

Notice the right side of this equation is identical to the right side of Equation 6.5:
qP  E  PV  H

P
P
V

System

System

Initial
state

Final
state

(6.4)

For reactions at constant pressure, a thermodynamic variable called

enthalpy (H) eliminates the need to consider PV work separately. The enthalpy
of a system is defined as the internal energy plus the product of the pressure
and volume:

H  E  PV

Surroundings

(6.6)

Thus, the change in enthalpy equals the heat gained or lost at constant pressure. Since most changes occur at constant pressure, H is more relevant than
E and easier to find: to find H, measure qP. We discuss the laboratory
method for measuring the heat involved in a chemical or physical change in
Section 6.3.

w = PV

FIGURE 6.5 Pressure-volume work.

When the volume (V ) of a system increases by an amount V against an
external pressure (P), the system pushes
back, and thus does PV work on the
surroundings (w  PV ).

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

H2O(l )

CH4 + 2O2

H final

H initial
H < 0

Heat out

CO2 + 2H2O

Enthalpy, H

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Enthalpy, H

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H > 0

Heat in

H2O(s)
H initial

H final

B Endothermic process

A Exothermic process

FIGURE 6.6 Enthalpy diagrams for exothermic and endothermic processes. A, Methane burns
with a decrease in enthalpy because heat leaves the system. Therefore, Hfinal  Hinitial, and the
process is exothermic: H  0. B, Ice melts with an increase in enthalpy because heat enters the
system. Therefore, Hfinal  Hinitial, and the process is endothermic: H  0.

Exothermic and Endothermic Processes

Because E, P, and V are state functions, H is also a state function, which means
that H depends only on the difference between Hfinal and Hinitial. The enthalpy
change of a reaction, also called the heat of reaction, Hrxn, always refers to
Hfinal minus Hinitial:
H  Hfinal  Hinitial  Hproducts  Hreactants

Therefore, because Hproducts can be either more or less than Hreactants, the sign of
H indicates whether heat is absorbed or released in the change. We determine
the sign of H by imagining the heat as a reactant or product. When
methane burns in air, for example, we know that heat is produced, so we show
it as a product (on the right):
CH4(g)  2O2(g) CO2(g)  2H2O(g)  heat

Because heat is released to the surroundings, the products (1 mol of CO2 and
2 mol of H2O) must have less enthalpy than the reactants (1 mol of CH4 and
2 mol of O2). Therefore, H (Hfinal  Hinitial) is negative, as the enthalpy diagram
in Figure 6.6A shows. An exothermic (heat out) process releases heat and
results in a decrease in the enthalpy of the system:
Exothermic:

Hfinal  Hinitial

H  0

(H is negative)

An endothermic (heat in) process absorbs heat and results in an increase

in the enthalpy of the system. When ice melts, for instance, heat flows into the
ice from the surroundings, so we show the heat as a reactant (on the left):
heat  H2O(s) H2O(l)

Because heat is absorbed, the enthalpy of the liquid water is higher than that of
the solid water, as Figure 6.6B shows. Therefore, H (Hwater  Hice) is positive:
Endothermic:

Hfinal  Hinitial

H  0

(H is positive)

In general, the value of an enthalpy change refers to reactants and products at the
same temperature.

SAMPLE PROBLEM 6.2

Drawing Enthalpy Diagrams and Determining

the Sign of H

Problem In each of the following cases, determine the sign of H, state whether the reaction is exothermic or endothermic, and draw an enthalpy diagram:
(a) H2(g)  12 O2(g) H2O(l)  285.8 kJ
(b) 40.7 kJ  H2O(l) H2O(g)

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195

(b) Heat is a reactant (on the left), so H  0 and the reaction is endothermic. The
enthalpy diagram appears in the margin (bottom).
Check Substances that are on the same side of the equation as the heat have less
enthalpy than substances on the other side, so make sure they are placed on the lower line
of the diagram.
Comment H values depend on conditions. In (b), for instance, H  40.7 kJ at 1 atm
and 100C; at 1 atm and 25C, H  44.0 kJ.
FOLLOW-UP PROBLEM 6.2 When 1 mol of nitroglycerine decomposes, it causes a vio-

lent explosion and releases 5.72 103 kJ of heat:

C3H5(NO3)3(l) 3CO2(g)  52 H2O(g)  14 O2(g)  32N2(g)
Is the reaction exothermic or endothermic? Draw an enthalpy diagram for it.

SECTION 6.2 SUMMARY

The change in enthalpy, H, is equal to the heat lost or gained during a chemical or
physical change that occurs at constant pressure, qP. A change that releases heat
is exothermic (H  0); a change that absorbs heat is endothermic (H  0).

6.3 CALORIMETRY: LABORATORY MEASUREMENT

OF HEATS OF REACTION
Data about energy content and use are everywherethe calories per serving of a
slice of bread, the energy efficiency rating of a washing machine, the gas mileage
of a new car, and so forth. How do we measure the heat released (or absorbed)
by a change? To determine the energy content of a teaspoon of sugar, for example, you might think we can simply measure the enthalpies of the reactants
(sucrose and O2) and subtract them from the enthalpies of the products (CO2 and
H2O). The problem is that the enthalpy (H ) of a system in a given state cannot
be measured because we have no starting point with which to compare it, no zero
enthalpy. However, we can measure the change in enthalpy (H) of a system. In
this section, well see how H values are determined.
To measure qP, which is equal to H, we construct surroundings that retain
the heat, and we observe the temperature change. Then, we relate the quantity of
heat released (or absorbed) to that temperature change through a physical property
called the specific heat capacity.

Specific Heat Capacity

You know from everyday experience that the more you heat an object, the higher
its temperature; that is, the quantity of heat (q) absorbed by an object is proportional to its temperature change:
q
T

or

q  constant T

or

q
 constant
T

Every object has its own heat capacity, the quantity of heat required to
change its temperature by 1 K. Heat capacity is the proportionality constant in
the preceding equation:
Heat capacity 

q
T

[in units of J/K]

H2(g) + 12 O2(g)

(reactants)
H = 285.8 kJ
Exothermic

H2O(l )
(a)

(product)

H2O(g)
(product)

Enthalpy, H

reactant (endothermic; H  0). For exothermic reactions, reactants are above products
on the enthalpy diagram; for endothermic reactions, reactants are below products. The H
arrow always points from reactants to products.
Solution (a) Heat is a product (on the right), so H  0 and the reaction is
exothermic. The enthalpy diagram appears in the margin (top).

Enthalpy, H

Plan From each equation, we see whether heat is a product (exothermic; H  0) or a

H = +40.7 kJ
Endothermic
H2O(l )

(b)

(reactant)

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196

Table 6.2 Specific Heat

Capacities of Some Elements,

Compounds, and Mixtures
Substance

Specific Heat
Capacity (J/gK)*

Elements

Aluminum, Al
Graphite, C
Iron, Fe
Copper, Cu
Gold, Au

0.900
0.711
0.450
0.387
0.129

Compounds

Water, H2O(l)
Ethyl alcohol,
C2H5OH(l)
Ethylene glycol,
(CH2OH)2(l)
Carbon
tetrachloride,
CCl4(l)

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4.184

A related property is specific heat capacity (c), the quantity of heat required to
change the temperature of 1 gram of a substance by 1 K:*
Specific heat capacity (c) 

[in units of J/gK]

If we know c of the substance being heated (or cooled), we can measure its mass
and temperature change and calculate the heat absorbed or released:
q  c mass T

(6.7)

Notice that when an object gets hotter, T (that is, Tfinal  Tinitial) is positive. The
object gains heat, so q  0, as we expect. Similarly, when an object gets cooler,
T is negative; so q  0 because heat is lost. Table 6.2 lists the specific heat
capacities of some common substances and mixtures.
Closely related to the specific heat capacity is the molar heat capacity (C;
note capital letter), the quantity of heat required to change the temperature of
1 mole of a substance by 1 K:

2.46
2.42

q
mass T

Molar heat capacity (C ) 

q
moles T

[in units of J/molK]

The specific heat capacity of liquid water is 4.184 J/gK, so

0.862

C of H2O(l)  4.184

18.02 g
J
J

 75.40
gK
1 mol
molK

Solid mixtures

Wood
Cement
Glass
Granite
Steel

1.76
0.88
0.84
0.79
0.45

*At 298 K (25C).

SAMPLE PROBLEM 6.3

Finding Quantity of Heat from Specific Heat Capacity

Problem A layer of copper welded to the bottom of a skillet weighs 125 g. How much

heat is needed to raise the temperature of the copper layer from 25C to 300.C? The specific heat capacity (c) of Cu is 0.387 J/gK.
Plan We know the mass and c of Cu and can find T in C, which equals T in K. We
use this T and Equation 6.7 to solve for the heat.
Solution Calculating T and q:
T  Tfinal  Tinitial  300.C  25C  275C  275 K
q  c mass (g) T  0.387 J/gK 125 g 275 K  1.33 104 J
Check Heat is absorbed by the copper bottom (system), so q is positive. Rounding shows
that the arithmetic seems reasonable: q  0.4 J/gK 100 g 300 K  1.2 104 J.
FOLLOW-UP PROBLEM 6.3 Find the heat transferred (in kJ) when 5.50 L of ethylene glycol (d  1.11 g/mL; see Table 6.2 for c) in a car radiator cools from 37.0C to 25.0C.

Stirrer

Thermometer

Styrofoam
cups
(insulation)
Water
(surroundings)
Sample
(system)

FIGURE 6.7 Coffee-cup calorimeter.

This apparatus is used to measure the
heat at constant pressure (qP).

The Practice of Calorimetry

The calorimeter is used to measure the heat released (or absorbed) by a physical or chemical process. This apparatus is the surroundings that change temperature when heat is transferred to or from the system. Two common types are
the constant-pressure and constant-volume calorimeters.
Constant-Pressure Calorimetry A constant-pressure calorimeter, simulated in the
lab by a coffee-cup calorimeter (Figure 6.7), is often used to measure the heat
transferred (qP) in processes open to the atmosphere. One common use is to find
the specific heat capacity of a solid that does not react with or dissolve in water.
The solid (system) is weighed, heated to some known temperature, and added to
a sample of water (surroundings) of known temperature and mass in the

*Some texts use the term specific heat in place of specific heat capacity. This usage is very
common but somewhat incorrect. Specific heat is the ratio of the heat capacity of 1 g of a substance to the heat capacity of 1 g of H2O and therefore has no units.

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calorimeter. With stirring, the final water temperature, which is also the final temperature of the solid, is measured.
The heat lost by the system (qsys, or qsolid) is equal in magnitude but
opposite in sign to the heat gained by the surroundings (qsurr, or qH2O):
qsolid  qH2O

Substituting Equation 6.7 for each side of this equality gives

(csolid masssolid Tsolid)  cH2O massH2O TH2O

All the quantities are known or measured except csolid:

csolid  

cH2O massH2O TH2O

masssolid Tsolid

For example, suppose you heat a 25.64-g solid in a test tube to 100.00C and
carefully add it to 50.00 g of water in a coffee-cup calorimeter. The water temperature changes from 25.10C to 28.49C, and you want to find the specific heat
capacity of the solid. Converting T directly from C to K, we know TH2O 
3.39 K (28.49C  25.10C) and Tsolid  71.51 K (28.49C  100.00C). Then,
assuming all the heat lost by the solid is gained by the water, we have
csolid  

cH2O massH2O TH2O

4.184 J/gK 50.00 g 3.39 K
 0.387 J/gK

masssolid Tsolid
25.64 g (71.51 K)

Follow-up Problem 6.4 applies this calculation, but Sample Problem 6.4 first shows
how to find the heat of a reaction that takes place in a coffee-cup calorimeter.
SAMPLE PROBLEM 6.4

Determining the Heat of a Reaction

Problem You place 50.0 mL of 0.500 M NaOH in a coffee-cup calorimeter at 25.00C and
carefully add 25.0 mL of 0.500 M HCl, also at 25.00C. After stirring, the final temperature is 27.21C. Calculate qsoln (in J) and Hrxn (in kJ/mol). (Assume the total volume is
the sum of the individual volumes and that the final solution has the same density and
specific heat capacity as water: d  1.00 g/mL and c  4.184 J/gK.)
Plan We first find the heat given off to the solution (qsoln) for the amounts given and
then use the equation to find the heat per mole of reaction. We know the solution
volumes (25.0 mL and 50.0 mL), so we can find their masses from the given density
(1.00 g/mL). Multiplying their total mass by the change in T and the given c, we can
find qsoln. Then, writing the balanced net ionic equation for the acid-base reaction, we
use the volumes and the concentrations (0.500 M) to find moles of reactants (H and
OH) and, thus, product (H2O). Dividing qsoln by the moles of water formed gives
Hrxn in kJ/mol.
Solution Finding masssoln and Tsoln:

Total mass (g) of solution  (25.0 mL  50.0 mL) 1.00 g/mL  75.0 g
T  27.21C  25.00C  2.21C  2.21 K
Finding qsoln:
qsoln  csoln masssoln Tsoln  (4.184 J/gK)(75.0 g)(2.21 K)  693 J
Writing the net ionic equation:

HCl(aq)  NaOH(aq)
H(aq)  OH(aq)

H2O(l)  NaCl(aq)
H2O(l)

Finding moles of reactants and products:

Moles of H  0.500 mol/L 0.0250 L  0.0125 mol H
Moles of OH  0.500 mol/L 0.0500 L  0.0250 mol OH
Therefore, H is limiting, so 0.0125 mol of H2O is formed.
Finding Hrxn: Heat gained by the water was lost by the reaction; that is,
Hrxn

so
qrxn  693 J
qsoln  qrxn  693 J
qrxn
1 kJ
693 J
1 kJ
(kJ/mol) 



 55.4 kJ/mol
mol H2O
1000 J
0.0125 mol
1000 J

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Check Rounding to check qsoln gives 4 J/gK 75 g 2 K  600 J. The volume of H

is half the volume of OH, so moles of H determines moles of product. Taking the negative of qsoln to find Hrxn gives 600 J/0.012 mol  5 104 J/mol, or 50 kJ/mol.
FOLLOW-UP PROBLEM 6.4 In a purity check for industrial diamonds, a 10.25-carat
(1 carat  0.2000 g) diamond is heated to 74.21C and immersed in 26.05 g of water in
a constant-pressure calorimeter. The initial temperature of the water is 27.20C. Calculate
T of the water and of the diamond (cdiamond  0.519 J/gK).

Constant-Volume Calorimetry In the coffee-cup calorimeter, we assume all the

heat is gained by the water, but some must be gained by the stirrer, thermometer, and so forth. For more precise work, as in constant-volume calorimetry, the
heat capacity of the entire calorimeter must be known. One type of constantvolume apparatus is the bomb calorimeter, designed to measure very precisely the
heat released in a combustion reaction. As Sample Problem 6.5 will show, this
need for greater precision requires that we know (or determine) the heat capacity of the calorimeter.
Figure 6.8 depicts the preweighed combustible sample in a metal-walled chamber (the bomb), which is filled with oxygen gas and immersed in an insulated water
bath fitted with motorized stirrer and thermometer. A heating coil connected to an
electrical source ignites the sample, and the heat evolved raises the temperature of
the bomb, water, and other calorimeter parts. Because we know the mass of the
sample and the heat capacity of the entire calorimeter, we can use the measured
T to calculate the heat released.

FIGURE 6.8 A bomb calorimeter. This

device (not drawn to scale) is used to
measure heat of combustion at constant
volume (qV).

Electrical
source

Motorized
stirrer
Thermometer

System
(combustible
substance and
compressed
oxygen)
O2
Cutaway of
steel bomb
Ignition
coil

SAMPLE PROBLEM 6.5

Cutaway of
insulated
jacket
Water bath

Heat being
transferred

Calculating the Heat of a Combustion Reaction

Problem A manufacturer claims that its new dietetic dessert has fewer than 10 Calories

per serving. To test the claim, a chemist at the Department of Consumer Affairs places
one serving in a bomb calorimeter and burns it in O2 (heat capacity of the calorimeter 
8.151 kJ/K). The temperature increases 4.937C. Is the manufacturers claim correct?

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Plan When the dessert burns, the heat released is gained by the calorimeter:

qsample  qcalorimeter
To find the heat, we multiply the given heat capacity of the calorimeter (8.151 kJ/K) by
T (4.937C).
Solution Calculating the heat gained by the calorimeter:
qcalorimeter  heat capacity  T  8.151 kJ/K  4.937 K  40.24 kJ
Recall that 1 Calorie  1 kcal  4.184 kJ. Therefore, 10 Calories  41.84 kJ, so
the claim is correct.
Check A quick math check shows that the answer is reasonable: 8 kJ/K  5 K  40 kJ.
Comment With the volume of the steel bomb fixed, V  0, and thus PV  0. Thus,
the energy change measured is the heat at constant volume (qV), which equals E, not H:
E  q  w  qV  0  qV
However, in most cases, H is usually very close to E. For example, H is only 0.5% larger
than E for the combustion of H2 and only 0.2% smaller for the combustion of octane.
FOLLOW-UP PROBLEM 6.5 A chemist burns 0.8650 g of graphite (a form of carbon) in a

new bomb calorimeter, and CO2 forms. If 393.5 kJ of heat is released per mole of graphite
and T increases 2.613 K, what is the heat capacity of the bomb calorimeter?

SECTION 6.3 SUMMARY

We calculate H of a process by measuring the heat at constant pressure (qP). To do
this, we determine T of the surroundings and relate it to qP through the mass of the
substance and its specific heat capacity (c), the quantity of energy needed to raise the
temperature of 1 g of the substance by 1 K. Calorimeters measure the heat released
from a system either at constant pressure (qP  H) or at constant volume (qV  E).

6.4

STOICHIOMETRY OF THERMOCHEMICAL EQUATIONS

A thermochemical equation is a balanced equation that includes the heat of reaction (Hrxn). Keep in mind that the Hrxn value shown refers to the amounts
(moles) of substances and their states of matter in that specific equation. The
enthalpy change of any process has two aspects:
1. Sign. The sign of H depends on whether the reaction is exothermic ()
or endothermic (). A forward reaction has the opposite sign of the reverse reaction.
Decomposition of 2 mol of water to its elements (endothermic):
2H2O(l) 2H2(g)  O2(g)

Hrxn  572 kJ

Formation of 2 mol of water from its elements (exothermic):

2H2(g)  O2(g) 2H2O(l)

Hrxn  572 kJ

2. Magnitude. The magnitude of H is proportional to the amount of substance

reacting.
Formation of 1 mol of water from its elements (half the amount in the preceding equation):
H2(g)  12O2(g) H2O(l)

Hrxn  286 kJ

Note that, in thermochemical equations, we often use fractional coefficients to

specify the magnitude of Hrxn for a particular amount of substance. Moreover,
in a particular reaction, a certain amount of substance is thermochemically equivalent to a certain quantity of energy. In the reaction just shown,
286 kJ is thermochemically equivalent to 1 mol of H2(g)
286 kJ is thermochemically equivalent to 12 mol of O2(g)
286 kJ is thermochemically equivalent to 1 mol of H2O(l)

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200

Just as we use stoichiometrically equivalent molar ratios to find amounts of

substances, we use thermochemically equivalent quantities to find the heat of reaction for a given amount of substance. Also, just as we use molar mass (in g/mol
of substance) to convert moles of a substance to grams, we use the heat of reaction (in kJ/mol of substance) to convert moles of a substance to an equivalent
quantity of heat (in kJ). Figure 6.9 shows this new relationship, and Sample Problem 6.6 applies it.
FIGURE 6.9 Summary of the relationship
between amount (mol) of substance
and the heat (kJ) transferred during
a reaction.

AMOUNT (mol)
of compound A

molar ratio
from balanced
equation

SAMPLE PROBLEM 6.6

AMOUNT (mol)

Hrxn (kJ/mol)

of compound B

HEAT (kJ)
gained or lost

Using the Heat of Reaction (Hrxn) to Find Amounts

Problem The major source of aluminum in the world is bauxite (mostly aluminum oxide).

Its thermal decomposition can be represented by



Al2O3(s) 2Al(s)  32O2(g) Hrxn  1676 kJ

Heat (kJ)
1676 kJ 2 mol Al

If aluminum is produced this way (see Comment), how many grams of aluminum can
form when 1.000103 kJ of heat is transferred?
Plan From the balanced equation and the enthalpy change, we see that 2 mol of Al forms
when 1676 kJ of heat is absorbed. With this equivalent quantity, we convert the given kJ
transferred to moles formed and then convert moles to grams.
Solution Combining steps to convert from heat transferred to mass of Al:
Mass (g) of Al  (1.000103 kJ) 

Amount (mol) of Al
multiply by (g/mol)

Mass (g) of Al

2 mol Al 26.98 g Al
 32.20 g Al

1676 kJ
1 mol Al

Check The mass of aluminum seems correct: 1700 kJ forms about 2 mol of Al (54 g),
so 1000 kJ should form a bit more than half that amount (27 g).
Comment In practice, aluminum is not obtained by heating but by supplying electrical
energy (Chapter 21). Because H is a state function, however, the total energy required
for this chemical change is the same no matter how it occurs.
FOLLOW-UP PROBLEM 6.6 Organic hydrogenation reactions, in which H2 and an unsaturated organic compound combine, are used in the food, fuel, and polymer industries. In
the simplest case, ethene (C2H4) and H2 form ethane (C2H6). If 137 kJ is given off per
mole of C2H4 reacting, how much heat is released when 15.0 kg of C2H6 forms?

SECTION 6.4 SUMMARY

A thermochemical equation shows the balanced equation and its Hrxn. The sign of
H for a forward reaction is opposite that for the reverse reaction. The magnitude of
H depends on the amount and physical state of the substance reacting and the H
per mole of substance. We use the thermochemically equivalent amounts of substance and heat from the balanced equation as conversion factors to find the quantity
of heat when a given amount of substance reacts.

6.5 HESSS LAW OF HEAT SUMMATION

Many reactions are difficult, even impossible, to carry out separately. A reaction
may be part of a complex biochemical process; or it may take place only under
extreme environmental conditions; or it may require a change in conditions while

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it is occurring. Even if we cant run a reaction in the lab, it is still possible to find
its enthalpy change. One of the most powerful applications of the state-function
property of enthalpy (H) allows us to find the H of any reaction for which we
can write an equation.
This application is based on Hesss law of heat summation: the enthalpy
change of an overall process is the sum of the enthalpy changes of its individual
steps. To use Hesss law, we imagine an overall reaction as the sum of a series
of reaction steps, whether or not it really occurs that way. Each step is chosen
because its H is known. Because the overall H depends only on the initial and
final states, Hesss law says that we add together the known H values for the
steps to get the unknown H of the overall reaction. Similarly, if we know the H
values for the overall reaction and all but one of the steps, we can find the unknown
H of that step.
Lets see how we apply Hesss law in the case of the oxidation of sulfur to
sulfur trioxide, the central process in the industrial production of sulfuric acid
and in the formation of acid rain. (To introduce the approach, well simplify the
equations by using S as the formula for sulfur, rather than the more correct S8.)
When we burn S in an excess of O2, sulfur dioxide (SO2) forms, not sulfur trioxide (SO3). Equation 1 shows this step and its H. If we change conditions
and then add more O2, we can oxidize SO2 to SO3 (Equation 2). In other words,
we cannot put S and O2 in a calorimeter and find H for the overall reaction
of S to SO3 (Equation 3). But, we can find it with Hesss law. The three equations are
Equation 1:
Equation 2:
Equation 3:

S(s)  O2(g) SO2(g)

2SO2(g)  O2(g) 2SO3(g)
S(s)  32O2(g) SO3(g)

H1  296.8 kJ
H2  198.4 kJ
H3  ?

Hesss law tells us that if we manipulate Equations 1 and/or 2 so that they add
up to Equation 3, then H3 is the sum of the manipulated H values of Equations 1 and 2.
First, we identify Equation 3 as our target equation, the one whose H we
want to find, and we carefully note the number of moles of each reactant and
product in it. We also note that H1 and H2 are the values for Equations 1 and
2 as written. Now we manipulate Equations 1 and/or 2 as follows to make them
add up to Equation 3:
Equations 1 and 3 contain the same amount of S, so we leave Equation 1
unchanged.
Equation 2 has twice as much SO3 as Equation 3, so we multiply it by 12, being
sure to halve H2 as well.
With the targeted amounts of reactants and products now present, we add
Equation 1 to the halved Equation 2 and cancel terms that appear on both sides:
S(s)  O2(g)

Equation 1:
1
2 (Equation

2):

SO2(g) 

Equation 3: S(s)  O2(g)  SO2(g) 

or
S(s) 

1
2 O2(g)
1
2 O2(g)
3
2 O2(g)

SO2(g)
H1  296.8 kJ
1
SO3(g)
2 (H2)  99.2 kJ
SO2(g)  SO3(g) H3  ?
SO3(g)

Adding the H values gives

H3  H1  12 (H2)  296.8 kJ  (99.2 kJ)  396.0 kJ

Once again, the key point is that H is a state function, so the overall H
depends on the difference between the initial and final enthalpies only. Hesss law
tells us that the difference between the enthalpies of the reactants (1 mol of S and
3
2 mol of O2) and that of the product (1 mol of SO3) is the same, whether S is
oxidized directly to SO3 (impossible) or through the formation of SO2 (actual).

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

To summarize, calculating an unknown H involves three steps:

1. Identify the target equation, the step whose H is unknown, and note the number of moles of each reactant and product.
2. Manipulate the equations with known H values so that the target numbers of
moles of reactants and products are on the correct sides. Remember to:
Change the sign of H when you reverse an equation.
Multiply numbers of moles and H by the same factor.
3. Add the manipulated equations to obtain the target equation. All substances
except those in the target equation must cancel. Add their H values to obtain
the unknown H.

SAMPLE PROBLEM 6.7

Using Hesss Law to Calculate an Unknown H

Problem Two gaseous pollutants that form in auto exhaust are CO and NO. An environmental chemist is studying ways to convert them to less harmful gases through the following equation:
CO(g)  NO(g) CO2(g)  12N2(g) H  ?

Given the following information, calculate the unknown H:

Equation A:
Equation B:

CO(g)  12 O2(g) CO2(g) HA  283.0 kJ

N2(g)  O2(g) 2NO(g) HB  180.6 kJ

Plan We note the numbers of moles of each substance in the target equation, manipulate

Equations A and/or B and their H values, and then add them together to obtain the target equation and the unknown H.
Solution Noting moles of substances in the target equation: There are 1 mol each of reactants CO and NO, 1 mol of product CO2, and 12 mol of product N2.
Manipulating the given equations: Equation A has the same number of moles of CO and
CO2 as the target, so we leave it as written. Equation B has twice the needed amounts of
N2 and NO, and they are on the opposite sides from the target; therefore, we reverse Equation B, change the sign of HB, and multiply both by 12 :

N2(g)  O2(g)] H  12(HB)  12(180.6 kJ)

NO(g) 12N2(g)  12 O2(g) H  90.3 kJ

1
2 [2NO(g)

or

Adding the manipulated equations to obtain the target equation:

Equation A:
1
2 (Equation B reversed):
Target:

CO(g)  12O2(g)
NO(g)

CO2(g)
12 N2(g)  12O2(g)
CO(g)  NO(g) CO2(g)  12 N2(g)

H  283.0 kJ
H  90.3 kJ
H  373.3 kJ

Check Obtaining the desired target equation is its own check. Be sure to remember to
change the sign of H for any equation you reverse.
FOLLOW-UP PROBLEM 6.7 Nitrogen oxides undergo many interesting reactions in the
environment and in industry. Given the following information, calculate H for the overall equation 2NO2(g)  12 O2(g) N2O5(s):

N2O5(s) 2NO(g)  32 O2(g) H  223.7 kJ

NO(g)  12 O2(g) NO2(g)
H  57.1 kJ

SECTION 6.5 SUMMARY

Because H is a state function, H  Hfinal  Hinitial and does not depend on how the
reaction takes place. Using Hesss law (Htotal  H1  H2  . . .  Hn), we
can determine H of any equation by manipulating the coefficients of other appropriate equations and their known H values.

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6.6 Standard Heats of Reaction (Hr xn)

6.6 STANDARD HEATS OF REACTION (H rxn)

In this section, we see how Hesss law is used to determine the H values of an
enormous number of reactions. To begin we must take into account that thermodynamic variables, such as H, vary somewhat with conditions. Therefore, to use
heats of reaction, as well as other thermodynamic data that we will encounter in later
chapters, chemists have established standard states, a set of specified conditions
and concentrations:
For a gas, the standard state is 1 atm* with the gas behaving ideally.
For a substance in aqueous solution, the standard state is 1 M concentration.
For a pure substance (element or compound), the standard state is usually the
most stable form of the substance at 1 atm and the temperature of interest. In
this text, that temperature is usually 25C (298 K).
We use the standard-state symbol (shown here as a degree sign) to indicate these
standard states. In other words, when the heat of reaction, Hrxn, has been measured with all the reactants and products in their standard states, it is referred
to as the standard heat of reaction, Hrxn.

Formation Equations and Their Standard Enthalpy Changes

In a formation equation, 1 mole of a compound forms from its elements. The
standard heat of formation ( Hf ) is the enthalpy change for the formation
equation when all the substances are in their standard states. For instance, the
formation equation for methane (CH4) is
C(graphite)  2H2(g) CH4(g) Hf  74.9 kJ

Thus, the standard heat of formation of methane is 74.9 kJ/mol. Some other
examples are
Na(s)  12 Cl2(g) NaCl(s)
2C(graphite)  3H2(g)  12 O2(g) C2H5OH(l)

Hf  411.1 kJ
Hf  277.6 kJ

Standard heats of formation have been tabulated for many substances. Table 6.3
shows Hf values for several, and a much more extensive table appears in
Appendix B.
The values in Table 6.3 were selected to make two points:
1. An element in its standard state is assigned a Hf of zero. For example, note
that Hf  0 for Na(s), but Hf  107.8 kJ/mol for Na(g). These values mean
that the gaseous state is not the most stable state of sodium at 1 atm and 298.15 K,
and that heat is required to form Na(g). Note also that the standard state of
chlorine is Cl2 molecules, not Cl atoms. Several elements exist in different
forms, only one of which is the standard state. Thus, the standard state of carbon
is graphite, not diamond, so Hf of C(graphite)  0. Similarly, the standard
state of oxygen is dioxygen (O2), not ozone (O3), and the standard state of
sulfur is S8 in its rhombic crystal form, rather than its monoclinic form.
2. Most compounds have a negative Hf. That is, most compounds have exothermic formation reactions under standard conditions: heat is given off when the
compound forms.
*The definition of the standard state for gases has been changed to 1 bar, a slightly lower
pressure than the 1 atm standard on which the data in this book are based (1 atm 
101.3 kPa  1.013 bar). For most purposes, this makes very little difference in the standard
enthalpy values.

In the case of phosphorus, the most common form, white phosphorus (P4), is chosen as the
standard state, even though red phosphorus is more stable at 1 atm and 298 K.

203

Table 6.3 Selected Standard Heats

of Formation at 25C (298 K)
Formula

H f (kJ/mol)

Calcium

Ca(s)
CaO(s)
CaCO3(s)

0
635.1
1206.9

Carbon

C(graphite)
C(diamond)
CO(g)
CO2(g)
CH4(g)
CH3OH(l)
HCN(g)
CS2(l)

0
1.9
110.5
393.5
74.9
238.6
135
87.9

Chlorine

Cl(g)
Cl2(g)
HCl(g)

121.0
0
92.3

Hydrogen

H(g)
H2(g)

218.0
0

Nitrogen

N2(g)
NH3(g)
NO(g)

0
45.9
90.3

Oxygen

O2(g)
O3(g)
H2O(g)
H2O(l)

0
143
241.8
285.8

Silver

Ag(s)
AgCl(s)

0
127.0

Sodium

Na(s)
Na(g)
NaCl(s)

0
107.8
411.1

Sulfur

S8(rhombic)
S8(monoclinic)
SO2(g)
SO3(g)

0
0.3
296.8
396.0

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

SAMPLE PROBLEM 6.8

Writing Formation Equations

Problem Write balanced equations for the formation of 1 mole of each of the following
compounds from their elements in their standard states, and include Hf.
(a) Silver chloride, AgCl, a solid at standard conditions
(b) Calcium carbonate, CaCO3, a solid at standard conditions
(c) Hydrogen cyanide, HCN, a gas at standard conditions
Plan We write the elements as the reactants and 1 mol of the compound as the product,
being sure all substances are in their standard states. Then, we balance the atoms and
obtain the Hf values from Table 6.3 or Appendix B.
Solution (a) Ag(s)  12Cl2(g) AgCl(s) Hf  127.0 kJ

(b) Ca(s)  C(graphite)  32O2(g)

(c)

1
2 H2(g)

 C(graphite) 

CaCO3(s)
HCN(g)

1
2 N2(g)

Hf  1206.9 kJ
Hf  135 kJ

FOLLOW-UP PROBLEM 6.8 Write balanced equations for the formation of 1 mol of
(a) CH3OH(l), (b) CaO(s), and (c) CS2(l) from their elements in their standard states.
Include Hf for each reaction.

 from H f Values of Reactants and Products

Determining H rxn
By applying Hesss law, we can use Hf values to determine Hrxn for any reaction. All we have to do is view the reaction as an imaginary two-step process.
Step 1. Each reactant decomposes to its elements. This is the reverse of the formation reaction for each reactant, so each standard enthalpy change is Hf.
Step 2. Each product forms from its elements. This step is the formation reaction
for each product, so each standard enthalpy change is Hf.
According to Hesss law, we add the enthalpy changes for these steps to obtain
the overall enthalpy change for the reaction (Hrxn). Figure 6.10 depicts the conceptual process. Suppose we want Hrxn for
TiCl4(l)  2H2O(g) TiO2(s)  4HCl(g)

We write this equation as though it were the sum of four individual equations,
one for each compound. The first two of these equations show the decomposition
of the reactants to their elements (reverse of their formation), and the second two
show the formation of the products from their elements:
H [TiCl
TiCl4(l) Ti(s)  2Cl2(g)
f
4(l)]
O(g)]
2H2O(g) 2H2(g)  O2(g) 2H [H
f
2
H [TiO
Ti(s)  O2(g) TiO2(s)
f
2(s)]
2H2(g)  2Cl2(g) 4HCl(g)
4H [HCl(g)]
f
TiCl4(l)  2H2O(g)  Ti(s)  O2(g)  2H2(g)  2Cl2(g)
Ti(s)  2Cl2(g)  2H2(g)  O2(g)  TiO2(s)  4HCl(g)
TiCl4(l)  2H2O(g) TiO2(s)  4HCl(g)

or

Its important to realize that when titanium(IV) chloride and water react, the reactants dont actually decompose to their elements, which then recombine to form

Reactants

Decomposition

Enthalpy, H

Elements

H f

H f

Formation

FIGURE 6.10 The general process for

determining Hrxn from Hf values. For
any reaction, Hrxn can be considered as
the sum of the enthalpy changes for the
decomposition of reactants to their elements [nHf(reactants)] and the formation of products from their elements
[mHf(products)]. [The factors m and n
are the amounts (mol) of the products and
reactants and equal the coefficients in the
balanced equation, and  is the symbol
for sum of.]

H initial
H rxn
Products
H final


H rxn = mH f(products) nH f(reactants)

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6.6 Standard Heats of Reaction (Hr xn)

the products. But that is the great usefulness of Hesss law and the state-function
concept. Because Hrxn is the difference between two state functions, Hproducts
minus Hreactants, it doesnt matter how the change actually occurs. We simply
add the individual enthalpy changes to find Hrxn:
Hrxn  Hf [TiO2(s)]  4Hf [HCl(g)]  {Hf [TiCl4(l)]}  {2Hf [H2O(g)]}
 {Hf [TiO2(s)]  4Hf [HCl(g)]}  {Hf [TiCl4(l)]
 2Hf [H2O(g)]}

aeefffffffffbffffffffffec

aeefffffffffffbffffffffffec

Products

Reactants

By generalizing the result shown here, we see that the standard heat of reaction is the sum of the standard heats of formation of the products minus the sum
of the standard heats of formation of the reactants (see Figure 6.10):
Hrxn  mHf (products)  nHf(reactants)

(6.8)

where the symbol  means sum of, and m and n are the amounts (mol) of the
products and reactants indicated by the coefficients from the balanced equation.
SAMPLE PROBLEM 6.9

Calculating the Heat of Reaction from Heats of Formation

Problem Nitric acid, whose worldwide annual production is nearly 10 billion kilograms,

is used to make many products, including fertilizers, dyes, and explosives. The first step
in the production process is the oxidation of ammonia:
4NH3(g)  5O2(g)

4NO(g)  6H2O(g)

Calculate Hrxn from Hf values.

Plan We use values from Table 6.3 (or Appendix B) and apply Equation 6.8 to find Hrxn.
Solution Calculating Hrxn:
Hrxn  mHf (products)  nHf (reactants)
 {4Hf [NO(g)]  6Hf [H2O(g)]}  {4Hf [NH3(g)]  5Hf[O2(g)]}
 (4 mol)(90.3 kJ/mol)  (6 mol)(241.8 kJ/mol)
[(4 mol)(45.9 kJ/mol)  (5 mol)(0 kJ/mol)]
 361 kJ  1451 kJ  184 kJ  0 kJ  906 kJ
Check One way to check is to write formation equations for the amounts of individual
compounds in the correct direction and take their sum:
4NH3(g) 2N2(g)  6H2(g) 4(45.9 kJ)   184 kJ
4(90.3 kJ)   361 kJ
2N2(g)  2O2(g) 4NO(g)
6H2(g)  3O2(g) 6H2O( g)
6(241.8 kJ)  1451 kJ
4NH3(g)  5O2(g) 4NO(g)  6H2O( g)

 906 kJ

Comment In this problem, we know the individual Hf values and find the sum, Hrxn.
In the follow-up problem, we know the sum and want to find an individual value.
FOLLOW-UP PROBLEM 6.9 Use the following information to find Hf of methanol

[CH3OH(l)]:
CH3OH(l)  32 O2(g) CO2(g)  2H2O( g)
Hf of CO2(g)  393.5 kJ/mol

Hrxn  638.5 kJ

Hf of H2O(g)  241.8 kJ/mol

Fossil Fuels and Climate Change

Out of the necessity to avoid catastrophe, the nations of the world are finally beginning to radically rethink the issue of energy use. No scientific challenge today is
greater than reversing the climatic effects of our increasing dependence on the
combustion of fossil fuelscoal, petroleum, and natural gas. Because these fuels
form so much more slowly than we consume them, they are nonrenewable. In contrast, wood and other fuels derived from plant and animal matter are renewable.
All carbon-based fuels release CO2 when burned, and in the past few decades
it has become increasingly clear that our use of these fuels is changing Earths

205

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206

NATURAL GREENHOUSE EFFECT

ENHANCED GREENHOUSE EFFECT

CFCS
8%
Ozone
12%

Sunlight reflected
by surface

Nitrous oxide
5%

Sunlight reflected
by atmosphere

Methane
15%

CO2
IR radiation trapped
by atmosphere

IR radiation (heat)
emitted by Earth

CO2

CO2
CO2

CO2

Carbon
dioxide
60%

More CO2 in
atmosphere
traps more heat

CO2

CO2
CO2

FIGURE 6.11 The trapping of heat by the atmosphere. Of the total

sunlight reaching Earth, some is reflected by the atmosphere and
some by the surface (especially snow, ice, and water). The remainder
is absorbed by the surface and converted to IR radiation (heat). When
this IR radiation is emitted by the surface, some is trapped by atmospheric components, especially CO2. Without this natural greenhouse

effect (left), Earths surface would have an average temperature of

18C, far below waters freezing point, rather than its current average
of 13C. Since the early 19th century, and particularly in the past several decades, human activity has increased the amount of CO2, along
with several other greenhouse gases (pie chart), and created an
enhanced greenhouse effect (right).

climate. The ability of CO2 to absorb heat plays a key temperature-regulating role
in the atmosphere. Much of the sunlight that shines on Earth is absorbed by the
land and oceans and converted to heat. Like the glass of a greenhouse, atmospheric CO2 does not absorb visible light from the Sun, but it traps some of the
heat radiating back from Earths surface and, thus, helps warm the atmosphere.
This process is called the natural greenhouse effect (Figure 6.11, left).
Over several billion years, due largely to the spread of plant life, which uses
CO2 in photosynthesis, the amount of CO2 originally present in Earths atmosphere decreased to 0.028% by volume. However, today, as a result of the human
use of fossil fuels for the past 200 years, this amount has increased to slighty over
0.036%. Thus, although the same amount of solar energy passes through the
atmosphere, more is trapped as heat, which has created an enhanced greenhouse
effect that is changing the climate through global warming (Figure 6.11, right).
Based on current trends in fossil fuel use, the CO2 concentration will increase to
between 0.049% and 0.126% by 2100.
Computer-based models that simulate the climates behavior are the best tools
available for answering questions about how much the temperature will rise and how
it will affect life on Earth. Even with ever-improving models, answers are difficult
to obtain. Natural fluctuations in temperature and cyclic changes in solar activity
must be taken into account. Moreover, as the amount of CO2 increases from fossilfuel burning, so does the amount of particulate matter, which may block sunlight and

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Chapter Review Guide

207

have a cooling effect. Water vapor also traps heat, and as temperatures rise, more
water evaporates, which may thicken the cloud cover and also lead to cooling.
Despite these complicating factors, the best models predict a net warming of
the atmosphere, and for the past several years, scientists have been documenting the
predicted effects. The average temperature has increased by 0.6  0.2C since the
late 19th century, of which 0.20.3C has occurred over just the past 25 years.
Globally, the 10 warmest years on record occurred in the last 15 years. Snow
cover and glacier extent in the Northern Hemisphere and floating ice in the Arctic
Ocean have decreased dramatically. Globally, sea level has risen 48 inches
(1020 cm) over the past century, and flooding and other extreme weather events
have increased through much of the United States and Europe.
Today, the models predict a future temperature rise more than 50% higher
than the 1.03.5C rise predicted only 10 years ago. Such increases would significantly alter rainfall patterns and crop yields throughout the world and could
increase sea level as much as 1 meter, thereby flooding low-lying regions, such
as the Netherlands, half of Florida, much of southern Asia, and many Pacific
island nations. To make matters worse, as we burn fossil fuels that release CO2,
we cut down the forests that absorb it.
In addition to developing alternative energy sources to reduce fossil-fuel consumption, researchers are studying CO2 sequestration through large-scale tree
planting and by liquefying CO2 released from coal-fired power plants and burying it underground or injecting it deep into the oceans.
In 1997, the United Nations Conference on Climate Change in Kyoto, Japan,
created an international treaty that set legally binding limits on release of greenhouse gases. It was ratified by 189 countries, but the largest emitter of CO2, the
United States, refused to do so. The 2005 conference in Montreal, Canada, presented overwhelming scientific evidence that confirmed the human impact on climate change, and the 2007 conference in Bali, Indonesia, issued a roadmap
leading to a 2012 binding agreement on ways to address the effects of climate
change and eventually reverse it.
SECTION 6.6 SUMMARY
Standard states are chosen conditions for substances. When 1 mol of a compound forms from its elements with all substances in their standard states, the enthalpy
change is Hf. Hesss law allows us to picture a reaction as the decomposition of
reactants to their elements, followed by the formation of products from their elements.
We use tabulated Hf values to find Hrxn or use known Hrxn and Hf values to
find an unknown Hf. As a result of increased fossil-fuel combustion, the amount of
atmospheric CO2 is climbing, which is seriously affecting Earths climate.

CHAPTER REVIEW GUIDE

The following sections provide many aids to help you study this chapter. (Numbers in parentheses refer to pages, unless noted otherwise.)

LEARNING OBJECTIVES

These are concepts and skills to review after studying this chapter.

Related section (), sample problem (SP), and end-of-chapter

problem (EP) numbers are listed in parentheses.

1. Interconvert energy units; understand that E of a system

appears as the total heat and/or work transferred to or from its
surroundings; understand the meaning of a state function ( 6.1)
(SP 6.1) (EPs 6.16.9)
2. Understand the meaning of H, why we measure H, and the
distinction between exothermic and endothermic reactions; draw
enthalpy diagrams for chemical and physical changes ( 6.2)
(SP 6.2) (EPs 6.106.18)

3. Understand the relation between specific heat capacity and heat

transferred in both constant-pressure (coffee-cup) and constantvolume (bomb) calorimeters ( 6.3) (SPs 6.36.5) (EPs 6.196.32)
4. Understand the relation between heat of reaction and amount
of substance ( 6.4) (SP 6.6) (EPs 6.336.42)
5. Explain the importance of Hesss law and use it to find an unknown H ( 6.5) (SP 6.7) (EPs 6.436.48)
6. View a reaction as the decomposition of reactants followed
by the formation of products; understand formation equations
and how to use Hf values to find Hrxn ( 6.6) (SPs 6.8, 6.9)
(EPs 6.496.58)

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208

KEY TERMS

These important terms appear in boldface in the chapter and are defined again in the Glossary.

law of conservation of energy

(first law of
thermodynamics) (190)
joule (J) (190)
calorie (cal) (191)
state function (191)

thermodynamics (186)
thermochemistry (186)
Section 6.1

system (186)
surroundings (186)
internal energy (E) (187)
heat (q) (188)
work (w) (188)
pressure-volume work
(PV work) (189)

Section 6.2

enthalpy (H) (193)

change in enthalpy (H ) (193)
heat of reaction (Hrxn) (194)

KEY EQUATIONS AND RELATIONSHIPS

enthalpy diagram (194)

exothermic process (194)
endothermic process (194)

Section 6.5

Section 6.3

Section 6.6

heat capacity (195)

specific heat capacity (c) (196)
molar heat capacity (C ) (196)
calorimeter (196)

standard states (203)

standard heat of reaction
(Hrxn ) (203)
formation equation (203)
standard heat of formation
(Hf ) (203)
fossil fuel (205)

Hesss law of heat

summation (201)

Section 6.4

thermochemical equation (199)

Numbered and screened equations are listed for you to refer to or memorize.

6.1 Defining the change in internal energy (187):

6.5 Relating the enthalpy change to the internal energy change at

E  Efinal  Einitial  Eproducts  Ereactants

6.2 Expressing the change in internal energy in terms of heat and
work (188):
E  q  w
6.3 Stating the first law of thermodynamics (law of conservation
of energy) (190):
Euniverse  Esystem  Esurroundings  0
6.4 Determining the work due to a change in volume at constant
pressure (PV work) (193):
w  PV

constant pressure (193):

H  E  PV
6.6 Identifying the enthalpy change with the heat gained or lost
at constant pressure (193):
qP  E  PV  H
6.7 Calculating the heat absorbed or released when a substance
undergoes a temperature change (196):
q  c mass T
6.8 Calculating the standard heat of reaction (205):
Hrxn  mHf (products)  nHf (reactants)

BRIEF SOLUTIONS TO FOLLOW-UP PROBLEMS

6.1 E  q  w

Compare your own solutions to these calculation steps and answers.

 

C3H5(NO3)3(l )
Enthalpy, H

qsample  qcalorimeter
1 mol C
(0.8650 g C)
(393.5 kJ/mol C)  (2.613 K)x
12.01 g C
x  10.85 kJ/K
6.6 C2H4(g)  H2(g) C2H6(g)  137 kJ
137 kJ
1000 g
1 mol C2H6
Heat (kJ)  15.0 kg


1 kg
30.07 g C2H6
1 mol
 6.83 104 kJ
6.5

4.184 kJ
1.055 kJ
 26.0 kcal
 15.0 Btu
1 kcal
1 Btu
 93 kJ
6.2 The reaction is exothermic.

6.7
H = 5.72 103 kJ
3CO2(g) + 5 H2O(g) + 1 O2(g) + 3 N2(g)
2
4
2

6.3 T  25.0C  37.0C  12.0C  12.0 K

Mass (g)  1.11 g/mL

1000 mL
5.50 L  6.10 103 g
1L

q  c mass T
1 kJ
 (2.42 J/gK)
(6.10 103 g)(12.0 K)
1000 J
 177 kJ
6.4
qsolid  qwater
[(0.519 J/gK)(2.050 g)(x  74.21)]
 [(4.184 J/gK)(26.05 g)(x  27.20)]
x  27.65 K
Tdiamond  46.56 K and Twater  0.45 K

2NO(g)  32 O2(g) N2O5(s)

2NO2(g) 2NO(g)  O2(g)

H  223.7 kJ
H  114.2 kJ

2NO(g)  12 32 O2(g)  2NO2(g)

N2O5(s)  2NO(g)  O2(g)
H  109.5 kJ
2NO2(g)  12 O2(g) N2O5(s)
1
6.8 (a) C(graphite)  2H2(g)  2O2(g) CH3OH(l)
Hf  238.6 kJ
(b) Ca(s)  12 O2(g) CaO(s) Hf  635.1 kJ
(c) C(graphite)  14S8(rhombic) CS2(l)
Hf  87.9 kJ
6.9 Hf of CH3OH(l)
 Hrxn  2Hf [H2O(g)]  Hf [CO2(g)]
 638.5 kJ  (2 mol)(241.8 kJ/mol)
 (1 mol)(393.5 kJ/mol)
 238.6 kJ

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Problems

209

PROBLEMS
Problems with colored numbers are answered in Appendix E.
Sections match the text and provide the numbers of relevant
sample problems. Bracketed problems are grouped in pairs
(indicated by a short rule) that cover the same concept. Comprehensive Problems are based on material from any section or previous chapter.

Forms of Energy and Their Interconversion

(Sample Problem 6.1)
6.1 If you feel warm after exercising, have you increased the in-

ternal energy of your body? Explain.

6.2 An adiabatic process is one that involves no heat transfer.

What is the relationship between work and the change in internal

energy in an adiabatic process?
6.3 Name a common device that is used to accomplish each energy change:
(a) Electrical energy to thermal energy
(b) Electrical energy to sound energy
(c) Electrical energy to light energy
(d) Mechanical energy to electrical energy
(e) Chemical energy to electrical energy
6.4 Imagine lifting your textbook into the air and dropping it onto
a desktop. Describe all the energy transformations (from one
form to another) that occur, moving backward in time from a
moment after impact.
6.5 A system receives 425 J of heat and delivers 425 J of work to

its surroundings. What is the change in internal energy of the

system (in J)?
6.6 A system conducts 255 cal of heat to the surroundings while
delivering 428 cal of work. What is the change in internal energy
of the system (in cal)?

6.14 Write a balanced equation and draw an approximate enthalpy

diagram for each of the following: (a) the formation of 1 mol of

sodium chloride from its elements (heat is released); (b) the conversion of liquid benzene to gaseous benzene.
6.15 Write a balanced equation and draw an approximate enthalpy

diagram for each of the following changes: (a) the combustion of

1 mol of liquid methanol (CH3OH); (b) the formation of 1 mol
of nitrogen dioxide from its elements (heat is absorbed).
6.16 Write a balanced equation and draw an approximate enthalpy
diagram for each of the following changes: (a) the sublimation
of dry ice [conversion of CO2(s) directly to CO2(g)]; (b) the reaction of 1 mol of sulfur dioxide with oxygen.
6.17 The circles below represent a phase change occurring at con-

stant temperature:

Is the value of each of the following positive (), negative (),

or zero: (a) qsys; (b) Esys; (c) Euniv?
6.18 The piston-cylinder assemblies below represent a physical
change occurring at constant pressure:
1.05 atm

6.7 Complete combustion of 2.0 metric ton of coal (assuming

pure carbon) to gaseous carbon dioxide releases 6.61010 J of

heat. Convert this energy to (a) kilojoules; (b) kilocalories;
(c) British thermal units.
6.8 Thermal decomposition of 5.0 metric tons of limestone to lime
and carbon dioxide requires 9.0106 kJ of heat. Convert this
energy to (a) joules; (b) calories; (c) British thermal units.
6.9 The nutritional calorie (Calorie) is equivalent to 1 kcal. One

pound of body fat is equivalent to about 4.1103 Calories.

Express this quantity of energy in joules and kilojoules.

1.05 atm

(a) Is wsys , , or 0? (b) Is Hsys , , or 0? (c) Can you determine whether Esurr is , , or 0? Explain.

Calorimetry: Laboratory Measurement of Heats of Reaction

(Sample Problems 6.3 to 6.5)

Enthalpy: Heats of Reaction and Chemical Change

(Sample Problem 6.2)

6.19 Why can we measure only changes in enthalpy, not absolute

enthalpy values?

6.10 Classify the following processes as exothermic or endother-

6.20 What data do you need to determine the specific heat capac-

mic: (a) freezing of water; (b) boiling of water; (c) digestion of

food; (d) a person running; (e) a person growing; (f) wood being
chopped; (g) heating with a furnace.

6.21 Is the specific heat capacity of a substance an intensive or ex-

6.11 Draw an enthalpy diagram for a general exothermic reaction;

6.22 Calculate q when 22.0 g of water is heated from 25.C to

ity of a substance?
tensive property? Explain.

label axis, reactants, products, and H with its sign.

6.12 Draw an enthalpy diagram for a general endothermic reaction; label axis, reactants, products, and H with its sign.

6.23 Calculate q when 0.10 g of ice is cooled from 10.C to

6.13 Write a balanced equation and draw an approximate enthalpy

6.24 A 295-g aluminum engine part at an initial temperature of

diagram for each of the following: (a) the combustion of 1 mol

of ethane in oxygen; (b) the freezing of liquid water.

13.00C absorbs 75.0 kJ of heat. What is the final temperature of

the part (c of Al  0.900 J/gK)?

100.C.
75C (cice  2.087 J/gK).

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210

6.25 A 27.7-g sample of ethylene glycol, a car radiator coolant,

loses 688 J of heat. What was the initial temperature of the

ethylene glycol if the final temperature is 32.5C (c of ethylene
glycol  2.42 J/gK)?
6.26 Two iron bolts of equal massone at 100.C, the other at

55Care placed in an insulated container. Assuming the heat

capacity of the container is negligible, what is the final temperature inside the container (c of iron  0.450 J/gK)?
6.27 One piece of copper jewelry at 105C has exactly twice the
mass of another piece, which is at 45C. Both pieces are placed
inside a calorimeter whose heat capacity is negligible. What is
the final temperature inside the calorimeter (c of copper 
0.387 J/gK)?
6.28 When 155 mL of water at 26C is mixed with 75 mL of water

at 85C, what is the final temperature? (Assume that no heat is

lost to the surroundings; d of water  1.00 g/mL.)
6.29 An unknown volume of water at 18.2C is added to 24.4 mL
of water at 35.0C. If the final temperature is 23.5C, what was
the unknown volume? (Assume that no heat is lost to the surroundings; d of water  1.00 g/mL.)
6.30 High-purity benzoic acid (C6H5COOH; Hrxn for combus-

tion  3227 kJ/mol) is used as a standard for calibrating bomb

calorimeters. A 1.221-g sample burns in a calorimeter (heat
capacity  1365 J/C) that contains exactly 1.200 kg of water.
What temperature change is observed?
6.31 Two aircraft rivets, one of iron and the other of copper, are
placed in a calorimeter that has an initial temperature of 20.C.
The data for the metals are as follows:
Mass (g)
Initial T (C)
c (J/gK)

Iron

Copper

30.0
0.0
0.450

20.0
100.0
0.387

(a) Will heat flow from Fe to Cu or from Cu to Fe?

(b) What other information is needed to correct any measurements that would be made in an actual experiment?
(c) What is the maximum final temperature of the system (assuming the heat capacity of the calorimeter is negligible)?
6.32 When 25.0 mL of 0.500 M H2SO4 is added to 25.0 mL of
1.00 M KOH in a coffee-cup calorimeter at 23.50C, the temperature rises to 30.17C. Calculate H of this reaction. (Assume
that the total volume is the sum of the individual volumes and
that the density and specific heat capacity of the solution are the
same as for pure water.)

Stoichiometry of Thermochemical Equations

(Sample Problem 6.6)
6.33 Would you expect O2(g)

negative Hrxn? Explain.

2O(g) to have a positive or a

6.34 Is H positive or negative when 1 mol of water vapor con-

denses to liquid water? Why? How does this value compare with
that for the conversion of 2 mol of liquid water to water vapor?
6.35 Consider the following balanced thermochemical equation

for a reaction sometimes used for H2S production:

1
H2S(g) Hrxn  20.2 kJ
8 S8(s)  H2(g)
(a) Is this an exothermic or endothermic reaction?
(b) What is Hrxn for the reverse reaction?

(c) What is H when 2.6 mol of S8 reacts?

(d) What is H when 25.0 g of S8 reacts?
6.36 Consider the following balanced thermochemical equation
for the decomposition of the mineral magnesite:
MgCO3(s) MgO(s)  CO2(g) Hrxn  117.3 kJ
(a) Is heat absorbed or released in the reaction?
(b) What is Hrxn for the reverse reaction?
(c) What is H when 5.35 mol of CO2 reacts with excess MgO?
(d) What is H when 35.5 g of CO2 reacts with excess MgO?
6.37 When 1 mol of NO(g) forms from its elements, 90.29 kJ of

heat is absorbed. (a) Write a balanced thermochemical equation

for this reaction. (b) How much heat is involved when 3.50 g of
NO decomposes to its elements?
6.38 When 1 mol of KBr(s) decomposes to its elements, 394 kJ of
heat is absorbed. (a) Write a balanced thermochemical equation
for this reaction. (b) How much heat is released when 10.0 kg of
KBr forms from its elements?
6.39 Liquid hydrogen peroxide, an oxidizing agent in many rocket

fuel mixtures, releases oxygen gas on decomposition:

2H2O2(l) 2H2O(l)  O2(g) Hrxn  196.1 kJ
How much heat is released when 652 kg of H2O2 decomposes?
6.40 Compounds of boron and hydrogen are remarkable for their
unusual bonding (described in Section 14.5) and also for their
reactivity. With the more reactive halogens, for example, diborane
(B2H6) forms trihalides even at low temperatures:
B2H6(g)  6Cl2(g) 2BCl3(g)  6HCl(g)
Hrxn  755.4 kJ
How much heat is released per kilogram of diborane that reacts?
6.41 Ethylene (C2H4) is the starting material for the preparation of
polyethylene. Although typically made during the processing of
petroleum, ethylene occurs naturally as a fruit-ripening hormone
and as a component of natural gas.
(a) The heat of reaction for the combustion of C2H4 is
1411 kJ/mol. Write a balanced thermochemical equation for
the combustion of C2H4.
(b) How many grams of C2H4 must burn to give 70.0 kJ of heat?
6.42 Sucrose (C12H22O11, table sugar) is oxidized in the body
by O2 via a complex set of reactions that ultimately produces
CO2(g) and H2O(g) and releases 5.64 103 kJ/mol sucrose.
(a) Write a balanced thermochemical equation for this reaction.
(b) How much heat is released per gram of sucrose oxidized?

Hesss Law of Heat Summation

(Sample Problem 6.7)
6.43 Express Hesss law in your own words.
6.44 Calculate Hrxn for

Ca(s)  12O2(g)  CO2(g) CaCO3(s)

given the following set of reactions:
Ca(s)  12 O2(g) CaO(s)
H  635.1 kJ
CaCO3(s) CaO(s)  CO2(g) H  178.3 kJ
6.45 Calculate Hrxn for
2NOCl(g) N2(g)  O2(g)  Cl2(g)
given the following set of reactions:
1
1
NO(g)
H  90.3 kJ
2 N2(g)  2 O2(g)
NO(g)  12 Cl2(g) NOCl(g) H  38.6 kJ

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Problems

6.46 Write the balanced overall equation for the following

B
A

Enthalpy, H

Enthalpy, H

process (equation 3), calculate Hoverall, and match the number of each equation with the letter of the appropriate arrow in
Figure P6.46:
H  180.6 kJ
(1) N2(g)  O2(g) 2NO(g)
(2) 2NO(g)  O2(g) 2NO2(g)
H  114.2 kJ
(3)
Hoverall  ?
6.47 Write the balanced overall equation for the following process
(equation 3), calculate Hoverall, and match the number of each
equation with the letter of the appropriate arrow in Figure P6.47:
H  1148 kJ
(1) P4(s)  6Cl2(g) 4PCl3(g)
(2) 4PCl3(g)  4Cl2(g) 4PCl5(g)
H  460 kJ
(3)
Hoverall  ?

B
A
C

C
Figure P6.46

Figure P6.47

6.48 Diamond and graphite are two crystalline forms of carbon. At

1 atm and 25C, diamond changes to graphite so slowly that the

enthalpy change of the process must be obtained indirectly. Determine Hrxn for
C(diamond) C(graphite)
with equations from the following list:
H  395.4 kJ
(1) C(diamond)  O2(g) CO2(g)
H  566.0 kJ
(2) 2CO2(g) 2CO(g)  O2(g)
H  393.5 kJ
(3) C(graphite)  O2(g) CO2(g)
H  172.5 kJ
(4) 2CO(g) C(graphite)  CO2(g)

Standard Heats of Reaction (Hrxn)

(Sample Problems 6.8 and 6.9)
6.49 What is the difference between the standard heat of formation

and the standard heat of reaction?

6.50 Make any changes needed in each of the following equations

to make Hrxn equal to Hf for the compound present:

(a) Cl(g)  Na(s) NaCl(s)
(b) H2O(g) 2H(g)  12 O2(g)
(c) 12 N2(g)  32 H2(g) NH3(g)

6.51 Write balanced formation equations at standard conditions

for each of the following compounds: (a) CaCl2; (b) NaHCO3;

(c) CCl4; (d) HNO3.
6.52 Write balanced formation equations at standard conditions
for each of the following compounds: (a) HI; (b) SiF4; (c) O3;
(d) Ca3(PO4)2.
6.53 Calculate Hrxn for each of the following:

(a) 2H2S(g)  3O2(g) 2SO2(g)  2H2O(g)

(b) CH4(g)  Cl2(g) CCl4(l)  HCl(g) [unbalanced]
6.54 Calculate Hrxn for each of the following:
(a) SiO2(s)  4HF(g) SiF4(g)  2H2O(l)
(b) C2H6(g)  O2(g) CO2(g)  H2O(g) [unbalanced]

211

6.55 Copper(I) oxide can be oxidized to copper(II) oxide:

Cu2O(s)  12 O2(g) 2CuO(s) Hrxn  146.0 kJ

Given that Hf of Cu2O(s)  168.6 kJ/mol, what is Hf
of CuO(s)?
6.56 Acetylene burns in air according to the following equation:
C2H2(g)  52 O2(g) 2CO2(g)  H2O(g)
Hrxn  1255.8 kJ
Given that Hf of CO2(g)  393.5 kJ/mol and that
Hf of H2O(g)  241.8 kJ/mol, what is Hf of C2H2(g)?
6.57 Nitroglycerine, C3H5(NO3)3(l), a powerful explosive used in

mining, detonates to produce a hot gaseous mixture of nitrogen,

water, carbon dioxide, and oxygen.
(a) Write a balanced equation for this reaction using the smallest
whole-number coefficients.
(b) If Hrxn  2.29 104 kJ for the equation as written in
part (a), calculate Hf of nitroglycerine.
6.58 The common lead-acid car battery produces a large burst of
current, even at low temperatures, and is rechargeable. The reaction that occurs while recharging a dead battery is
2PbSO4(s)  2H2O(l) Pb(s)  PbO2(s)  2H2SO4(l)
(a) Use Hf values from Appendix B to calculate Hrxn.
(b) Use the following equations to check your answer in part (a):
(1) Pb(s)  PbO2(s)  2SO3(g) 2PbSO4(s)
H  768 kJ
H  132 kJ
(2) SO3(g)  H2O(l) H2SO4(l)

Comprehensive Problems
Problems with an asterisk (*) are more challenging.
6.59 Stearic acid (C18H36O2) is a typical fatty acid, a molecule

with a long hydrocarbon chain and an organic acid group

(COOH) at the end. It is used to make cosmetics, ointments,
soaps, and candles and is found in animal tissue as part of many
saturated fats. In fact, when you eat meat, chances are that you
are ingesting some fats that contain stearic acid.
(a) Write a balanced equation for the complete combustion of
stearic acid to gaseous products.
(b) Calculate Hrxn for this combustion (Hf  948 kJ/mol).
(c) Calculate the heat (q) in kJ and kcal when 1.00 g of stearic
acid is burned completely.
(d) The nutritional information for a candy bar states that one
serving contains 11.0 g of fat and 100. Cal from fat (1 Cal 
1 kcal). Is this information consistent with your answer for part (c)?
6.60 A balloonist is preparing to make a trip in a helium-filled balloon. The trip begins in early morning at a temperature of 15C.
By midafternoon, the temperature has increased to 30.C. Assuming the pressure remains constant at 1.00 atm, for each mole
of helium, calculate:
(a) The initial and final volumes
(b) The change in internal energy, E [Hint: Helium behaves
like an ideal gas, so E  32 nRT. Be sure the units of R are consistent with those of E.]
(c) The work (w) done by the helium (in J)
(d) The heat (q) transferred (in J)
(e) H for the process (in J)
(f) Explain the relationship between the answers to (d) and (e).
6.61 In winemaking, the sugars in grapes undergo fermentation by
yeast to yield CH3CH2OH and CO2. During cellular respiration,
sugar and ethanol are burned to water vapor and CO2.

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CHAPTER 6 Thermochemistry: Energy Flow and Chemical Change

(a) Write a balanced equation and use Appendix B to calculate

Hrxn. (b) If each molecule of product represents 1.50 102
mol, what quantity of heat (in J) is released or absorbed?
6.63 Iron metal is produced in a blast furnace through a complex
series of reactions that involve reduction of iron(III) oxide with
carbon monoxide.
(a) Write a balanced overall equation for the process, including
the other product.
(b) Use the equations below to calculate Hrxn for the
overall equation:
(1) 3Fe2O3(s)  CO(g) 2Fe3O4(s)  CO2(g)
H  48.5 kJ
H  11.0 kJ
(2) Fe(s)  CO2(g) FeO(s)  CO(g)
(3) Fe3O4(s)  CO(g) 3FeO(s)  CO2(g) H  22 kJ
6.64 Pure liquid octane (C8H18; d  0.702 g/mL) is used as the
fuel in a test of a new automobile drive train.
(a) How much energy (in kJ) is released by complete combustion of the octane in a 20.4-gal fuel tank to gases (Hrxn 
5.45 103 kJ/mol)?
(b) The energy delivered to the wheels at 65 mph is 5.5 104 kJ/h.
Assuming all the energy is transferred to the wheels, what is the
cruising range (in km) of the car on a full tank?
(c) If the actual cruising range is 455 miles, explain your answer
to part (b).
6.65 Four 50.-g samples of different liquids are placed in beakers
at Tinitial of 25.00C. Each liquid is heated until 450. J is absorbed; Tfinal is shown on each beaker below. Rank the liquids in
order of increasing specific heat capacity.
27.15C

35.59C

28.96C

30.29C

6.66 When simple sugars, called monosaccharides, link to-

gether, they form a variety of complex sugars and, ultimately,

polysaccharides, such as starch, glycogen, and cellulose. Glucose and fructose have the same formula, C6H12O6, but different
arrangements of atoms. They link together to form a molecule of
sucrose (table sugar) and a molecule of liquid water. The Hf
values of glucose, fructose, and sucrose are 1273 kJ/mol,
1266 kJ/mol, and 2226 kJ/mol, respectively. Write a balanced equation for this reaction and calculate Hrxn.

6.67 Oxidation of gaseous ClF by F2 yields liquid ClF3, an impor-

tant fluorinating agent. Use the following thermochemical equations to calculate Hrxn for the production of ClF3:
H 167.5 kJ
(1) 2ClF(g)  O2(g) Cl2O(g)  OF2(g)
H 43.5 kJ
(2) 2F2(g)  O2(g) 2OF2(g)
(3) 2ClF3(l)  2O2(g) Cl2O(g)  3OF2(g)
H 394.1 kJ
6.68 Silver bromide is used to coat ordinary black-and-white photographic film, while high-speed film uses silver iodide.
(a) When 50.0 mL of 5.0 g/L AgNO3 is added to a coffee-cup
calorimeter containing 50.0 mL of 5.0 g/L NaI, with both solutions at 25C, what mass of AgI forms?
(b) Use Appendix B to find Hrxn.
(c) What is Tsoln (assume the volumes are additive and the solution has the density and specific heat capacity of water)?
* 6.69 Whenever organic matter is decomposed under oxygen-free
(anaerobic) conditions, methane is one of the products. Thus,
enormous deposits of natural gas, which is almost entirely
methane, exist as a major source of fuel for home and industry.
(a) It is estimated that known sources of natural gas can produce
5600 EJ of energy (1 EJ  1018 J). Current total global energy
usage is 4.0 102 EJ per year. Find the mass (in kg) of known
sources of natural gas (Hrxn for the combustion of CH4 
802 kJ/mol).
(b) For how many years could these sources supply the worlds
total energy needs?
(c) What volume (in ft3) of natural gas, measured at STP, is
required to heat 1.00 qt of water from 25.0C to 100.0C (d of
H2O  1.00 g/mL; d of CH4 at STP  0.72 g/L)?
(d) The fission of 1 mol of uranium (about 4 104 ft3) in a nuclear reactor produces 2 1013 J. What volume (in ft3) of natural
gas would produce the same amount of energy?
6.70 The heat of atomization (Hatom) is the heat needed to form
separated gaseous atoms from a substance in its standard state.
The equation for the atomization of graphite is
C(graphite) C(g)
Use Hesss law to calculate Hatom of graphite from these data:
(1) Hf of CH4  74.9 kJ/mol
(2) Hatom of CH4  1660 kJ/mol
(3) Hatom of H2  432 kJ/mol
6.71 A reaction is carried out in a steel vessel within a chamber
filled with argon gas. Below are molecular views of the argon
adjacent to the surface of the reaction vessel before and after the
reaction. Was the reaction exothermic or endothermic? Explain.
Container Wall

(a) Using C6H12O6 for sugar, calculate Hrxn of fermentation

and of respiration (combustion).
(b) Write a combustion reaction for ethanol. Which has a higher
Hrxn for the combustion per mol of C, sugar or ethanol?
6.62 The following scenes represent a gaseous reaction between
compounds of nitrogen (blue) and oxygen (red) at 298 K:

Container Wall

212

Before reaction

After reaction

6.72 Benzene (C6H6) and acetylene (C2H2) have the same empiri-

cal formula, CH. Which releases more energy per mole of CH

(Hf of gaseous C6H6  82.9 kJ/mol)?
6.73 An aqueous waste stream that has a maximum concentration
of 0.50 M H2SO4 (d  1.030 g/mL at 25C) will be neutralized
by controlled addition of 40% caustic soda (NaOH; d  1.430 g/L)
before it goes to the process sewer and then to the chemical plant

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Problems

waste treatment facility. However, a safety review finds that the

waste stream could meet a small stream of an immiscible organic compound, which could form a flammable vapor in air at
40.C. The maximum temperature of the caustic soda and the
waste stream is 31C. Could the temperature increase due to
the heat of neutralization cause the vapor to explode? Assume
the specific heat capacity of each solution is 4.184 J/gK.
6.74 Kerosene, a common space-heater fuel, is a mixture of
hydrocarbons whose average formula is C12H26.
(a) Write a balanced equation, using the simplest whole-number
coefficients, for the complete combustion of kerosene to gases.
(b) If Hrxn  1.50 104 kJ for the combustion equation as
written in part (a), determine Hf of kerosene.
(c) Calculate the heat produced by combustion of 0.50 gal of
kerosene (d of kerosene  0.749 g/mL).
(d) How many gallons of kerosene must be burned for a
kerosene furnace to produce 1250. Btu (1 Btu  1.055 kJ)?
* 6.75 Coal gasification is a multistep process to convert coal into
cleaner-burning gaseous fuels. In one step, a certain coal sample
reacts with superheated steam:
Hrxn  129.7 kJ
C(coal)  H2O(g) CO(g)  H2(g)
(a) Combine this reaction with the following two to write an
overall reaction for the production of methane:
Hrxn  41 kJ
CO(g)  H2O(g) CO2(g)  H2(g)
Hrxn  206 kJ
CO(g)  3H2(g) CH4(g)  H2O(g)
(b) Calculate Hrxn for this overall change.
(c) Using the value in (b) and calculating the Hrxn for combustion of methane, find the total heat for gasifying 1.00 kg of coal
and burning the methane formed (assume water forms as a gas
and  of coal  12.00 g/mol).
6.76 Phosphorus pentachloride is used in the industrial preparation of organic phosphorus compounds. Equation 1 shows its
preparation from PCl3 and Cl2:
(1) PCl3(l)  Cl2(g) PCl5(s)
Use equations 2 and 3 to calculate Hrxn for equation 1:
H  1280 kJ
(2) P4(s)  6Cl2(g) 4PCl3(l)
H  1774 kJ
(3) P4(s)  10Cl2(g) 4PCl5(s)
6.77 A typical candy bar weighs about 2 oz (1.00 oz  28.4 g).
(a) Assuming that a candy bar is 100% sugar and that 1.0 g of
sugar is equivalent to about 4.0 Calories of energy, calculate the
energy (in kJ) contained in a typical candy bar.
(b) Assuming that your mass is 58 kg and you convert chemical
potential energy to work with 100% efficiency, how high would
you have to climb to work off the energy in a candy bar? (Potential energy  mass g height, where g  9.8 m/s2.)
(c) Why is your actual conversion of potential energy to work
less than 100% efficient?
6.78 Silicon tetrachloride is produced annually on the multikiloton
scale for making transistor-grade silicon. It can be made directly
from the elements (reaction 1) or, more cheaply, by heating sand
and graphite with chlorine gas (reaction 2). If water is present in
reaction 2, some tetrachloride may be lost in an unwanted side
reaction (reaction 3):
(1) Si(s)  2Cl2(g) SiCl4(g)
(2) SiO2(s)  2C(graphite)  2Cl2(g) SiCl4(g)  2CO(g)
(3) SiCl4(g)  2H2O(g) SiO2(s)  4HCl(g)
Hrxn  139.5 kJ
(a) Use reaction 3 to calculate the heats of reaction of reactions
1 and 2. (b) What is the heat of reaction for the new reaction that
is the sum of reactions 2 and 3?

213

6.79 Use the following information to find Hf of gaseous HCl:

Hrxn  91.8 kJ
N2(g)  3H2(g) 2NH3(g)
N2(g)  4H2(g)  Cl2(g) 2NH4Cl(s) Hrxn  628.8 kJ
NH3(g)  HCl(g) NH4Cl(s) Hrxn  176.2 kJ
* 6.80 You want to determine H for the reaction
Zn(s)  2HCl(aq) ZnCl2(aq)  H2(g)
(a) To do so, you first determine the heat capacity of a calorimeter using the following reaction, whose H is known:
NaOH(aq)  HCl(aq) NaCl(aq)  H2O(l)
H  57.32 kJ
Calculate the heat capacity of the calorimeter from these data:
Amounts used: 50.0 mL of 2.00 M HCl and 50.0 mL of
2.00 M NaOH
Initial T of both solutions: 16.9C
Maximum T recorded during reaction: 30.4C
Density of resulting NaCl solution: 1.04 g/mL
c of 1.00 M NaCl(aq)  3.93 J/gK
(b) Use the result from part (a) and the following data to determine Hrxn for the reaction between zinc and HCl(aq):
Amounts used: 100.0 mL of 1.00 M HCl and 1.3078 g of Zn
Initial T of HCl solution and Zn: 16.8C
Maximum T recorded during reaction: 24.1C
Density of 1.0 M HCl solution  1.015 g/mL
c of resulting ZnCl2(aq)  3.95 J/gK
(c) Given the values below, what is the error in your experiment?
Hf of HCl(aq)  1.652 102 kJ/mol
Hf of ZnCl2(aq)  4.822 102 kJ/mol

* 6.81 One mole of nitrogen gas confined within a cylinder by a piston is heated from 0C to 819C at 1.00 atm.
(a) Calculate the work of expansion of the gas in joules (1 J 
9.87 103 atmL). Assume all the energy is used to do work.
(b) What would be the temperature change if the gas were heated
with the same amount of energy in a container of fixed volume?
(Assume the specific heat capacity of N2 is 1.00 J/gK.)
6.82 The chemistry of nitrogen oxides is very versatile. Given the
following reactions and their standard enthalpy changes,
Hrxn  39.8 kJ
(1) NO(g)  NO2(g) N2O3(g)
(2) NO(g)  NO2(g)  O2(g) N2O5(g) Hrxn  112.5 kJ
Hrxn  57.2 kJ
(3) 2NO2(g) N2O4(g)
Hrxn  114.2 kJ
(4) 2NO(g)  O2(g) 2NO2(g)
Hrxn  54.1 kJ
(5) N2O5(s) N2O5(g)
calculate the heat of reaction for
N2O3(g)  N2O5(s) 2N2O4(g)

* 6.83 Liquid methanol (CH3OH) is used as an alternative fuel in

truck engines. An industrial method for preparing it uses the catalytic hydrogenation of carbon monoxide:
catalyst

CO(g)  2H2(g) CH3OH(l)

How much heat (in kJ) is released when 15.0 L of CO at 85C
and 112 kPa reacts with 18.5 L of H2 at 75C and 744 torr?
* 6.84 (a) How much heat is released when 25.0 g of methane burns
in excess O2 to form gaseous products?
(b) Calculate the temperature of the product mixture if the
methane and air are both at an initial temperature of 0.0C.
Assume a stoichiometric ratio of methane to oxygen from the
air, with air being 21% O2 by volume (c of CO2  57.2 J/molK;
c of H2O(g)  36.0 J/molK; c of N2  30.5 J/molK).

198

Stolchlometry III. Calculations Based on Concentrations of Solutions

NaOH, we will know the number of moles of H2SO4 used by the Na 2 CO 3 This will
tell us how much Na 2 CO 3 must have been present originally
Total moles H2SO4 at outset = (o 06322

mol s

e H2SOA

(Q Q5QQQ

= 0003161 moles H2SO4

moles of H 2 SO 4 used by NaOH
= 0 ,079
, "" (0 00936 liters) .,,
,
V
liter
/
\2 moles
= 0 000505 moles H 2 SO 4
Moles of H 2 SO 4 not used by NaOH = 0 003,61 - 0 000505
= 0 002656 moles H 2 SO 4 used by Na 2 CO 3
The chemical equation shows that 1 mole of Na 2 CO 3 is used per mole of H2SO4, so
weight of Na-jCQs present
= (0 002656 moles HzSOJ (' mole ^ff^3) (,06 0 ^ff^' )
V 1 mole H 2 SO 4 / \
mole Na 2 COj/
= 0 2815 g Na 2 CO 3 in sample

02815eNa,CO
0 33,2 g sample

* > = ^ 00%

PROBLEM:

An iron ore is a mixture of Fe2O3 and inert impurities One method of iron analysis
is to dissolve the ore sample in HCl, convert all of the iron to the Fe-+ state with
metallic zinc, then titrate the solution with a standard KMnO 4 solution The reac
tion is
KMnO 4 + 5FeCl 2 + 8HC1 -> KCl + MnCl 2 + 5FeClj + 4H2O
MnO 4 + 5Fe J+ + 8H + ^ Mn 2+ + 5Fe3+ + 4H2O
At the endpomt, there is no more FeCl2 for reaction, so the further addition of
purple KMnO 4 will make the whole solution purple because it can no longer be
converted to colorless MnCl 2 If aO 3778 g ore sample requires 38 60 ml of 0 02 1 01^
M KMnO 4 for titration, calculate the percentage of iron in the original sample
SOLUTION:

1 From the given amount of KMnO 4 , calculate the moles of KMnO 4 used
moles KMn0 4 used = (o 02105

mole
mole

MnO
^MnOj

(Q

= 8 125 x 10 4 moles KMnO 4

Problems A

199

2 From the given moles of KMnO 4 , calculate the moles of Fe used up The
chemical equation shows that 5 moles of Fe (as FeCl2) are used per mole of
KMnO 4 , so
moles of Fe used up = (8 125 x 10

moles KMnOJ ( 5 "?es e )

V mole KMnO 4 /

= 4 063 x I0~ ! moles Fe present

3 From the number of moles of Fe present, calculate the weight of Fe, and
from that the percentage of Fe in the original sample
Weight of Fe present = (4 063 x 10~3 moles Fe)(5<i 8

= 0 2267 g Fe
% Fe present =

0 2267 g Fe

x 100 = 60 00% Fe
0 3778 g sample

PROBLEMS A
1 Tell how you would prepare each of the following solutions
(a) 3 00 liters of 0 750 M NaCl from solid NaCl
(b) 55 0 ml of 2 00 M ZnSO4 from solid ZnSO4 7H2O
(c) 180 ml of 0 100 M Ba(NO3)2 from solid Ba(NO3)2
(d) 12 liters of 6 0 M KOH from solid KOH
(e) 730 ml of 0 0700 M Fe(NO3)j from solid Fe(NO 3 )j 9H2O
2 Tell how you would prepare each of the following solutions
(a) 15 0 ml of 0 200 M H2SO4 from 6 00 M H2SO4
(b) 280 ml of 0 600 M CoCI2 from 3 00 M CoCl2
(c) 5 70 liters of 0 0300 M ZnSO4 from 2 50 M ZnSO4
(d) 60 0 ml of 0 00350 M K 3 Fe(CN) 6 from 0 800 M K 3 Fe(CN) 6
(e) 25 0 ml of 2 70 M UO 2 (NO 3 ) 2 from 8 30 M UO 2 (NO 3 ) 2
3 Find molanties and molahties of each of the following solutions

Solution

(a) KOH
(b) HN03
(c) H2S04
(d) Mg02
(e) Na 2 Cr 2 O 7
(f) Na2S203
(g) Na3As04
(h) A12(S04)3

Density
(g/ml)

1
1
1
1
1
1
1
1

344
334
834
119
140
100
113
253

Weight
pen entage

350
540
950
290
200
120
100
220

200

Stolchlometry III Calculations Based on Concentrations of Solutions

4 Give the weight of metal ion in each of the following solutions

(a) 250 ml of 0 10 M CuSO4
(e) 75 ml of 0 10 M A1C13
(b) 125 ml of 0 050 M CdCl2
(f) 1 5 liters of 3 0 M AgNOj
(c) 50 ml of 0 15 M MgSO4
(g) 2 0 liters of 0 333 M Fe2(SO4)3
(d) 50 ml of 0 075 M Na2SO4
5 The density of a 7 00 M HC1 solution is 1 113 g/ml Find the percentage of HC1
by weight
6 (a) What is the percentage of HNO 3 by weight in a 21 2 M solution of HNO3
whose density is 1.483 g/ml 9
(b) What is the molahty of this solution9
7 If 3 0 liters of 6 0 M HC1 are added to 2 0 liters of 1 5 M HC1, what is the
resulting concentration 9 Assume the final volume to be exactly 5 0 liters
8 What volume of 15 0 M HNO3 should be added to 1250 ml of 2 00 M HNO 3 to
prepare 14 0 liters of 1 00 M HNO 3 9 Water is added to make the final volume
exactly 14 0 liters
9 The density of a 2 04 M Cd(NO 3 ) 2 solution is 1 382 g/ml If 500 ml of water is
added to 750 ml of this solution, (a) what will be the percentage by weight of
Cd(NO3)2 in the new solution 9 (b) What will be its molahty'
10 If 40 00 ml of an HC1 solution is titrated by 45 00 ml of 0 1500 M NaOH, what
is the molanty of the HC19
11 We need 35 45 ml of an NaOH solution to titrate a 2 0813 g sample of pure
benzoic acid, HC7H5O2 What is the molanty of the NaOH solution'
12 What is the molanty of a K 2 C 2 O 4 solution if 35 00 ml of it is needed for the
titration of 47 65 ml of 0 06320 M KMnO 4 solution 9 The reaction is
2MnO4- + 5C2Or + 16H+ - 2Mn 2+ + 10CO2 + 8H2O
13. How many millihters of a solution containing 31 52 g KMnO 4 per liter will
react with 3 814 g FeSO4 7H2O9 The reaction is
MnO4- + 5Fe2+ + 8H+ -H Mn 2+ + 5Fe3+ + 4H2O
14 It takes 35 00 ml of 0 1500 M KOH to react with 40 00 ml of H3PO4 solution
The titration reaction is
H3P04 + 20H -> HPOr + 2H 2 O
What is the molanty of the H3PO4 solution9
15 A 19 75 ml sample of vinegar of density 1 061 g/ml requires 43 24 ml of 0 3982
M NaOH for titration What is the percentage by weight of acetic acid,
HC2H3O2, in the vinegar 9
16 If we add 39 20 ml of 0 1333 M H2SO4 to 0 4550 g of a sample of soda ash that
is 59 95% Na 2 CO 3 , what volume of 0 1053 M NaOH is required for backtitration 9

Problems B

201

17 A 0 500 g sample of impure CaCO3 is dissolved in 50 0 ml of 0 100 M HC1 and

the residual acid titrated by 5 00 ml of 0 120 M NaOH Find the percentage of
CaCO3 in the sample The reaction is
CaC03 + 2HC1 -^ CaCl2 + H2O + CO2
18 It takes 45 00 ml of a given HC1 solution to react with 0 2435 g calcite CaCO3
This acid is used to determine the percent purity of a Ba(OH) 2 sample as
follows
Wt of impure Ba(OH) 2 sample = 0 4367 g
Vol of HC1 used - 35 27 ml
Vol of NaOH used for back-titration = 1 78 ml
1 200 ml of HC1 titrates 1 312 ml of NaOH
What is the percentage of Ba(OH) 2 in the sample'
19 (a) What weight of AgCl can be obtained by precipitating all the Ag+ from 50
ml of 0 12 M AgNO 3 '
(b) What weight of NaCl is required to precipitate the AgCl'
(c) What volume of 0 24 M HC1 would be needed to precipitate the AgCl 9
20 What volume of 10 0 M HC1 is needed to prepare 6 40 liters H2S at 750 torr and
27C9 The reaction is
FeS + 2HC1 -> FeCl2 + H 2 S
21 What volume of 12 5 M NaOH is needed to prepare 25 0 liters of H2 at 735 torr
and 18C by the reaction
2A1 + 2NaOH + 2H2O -> 2NaAlO 2 + 3H2
22 (a) What weight of silver and what volume of 6 00 M HNO 3 are needed for the
preparation of 500 ml of 3 00 M AgNO 3 '
(b) What volume of NO, collected over water at 725 torr and 27C, will be
formed"7 The reaction is
3Ag + 4HNO 3 -^ 3AgNO, + NO + 2H2O
23 Fuming sulfunc acid is a mixture of H2SO4 and SO3 A 2 500 g sample of
fuming sulfunc acid requires 47 53 ml of 1 1513 M NaOH for titration What is
the percentage of SO3 in the sample 9

PROBLEMS B
24 Tell how you would prepare each of the following solutions
(a) 125 ml of 0 62 M NH 4 C1 from solid NH 4 C1
(b) 2 75 liters of 1 72 M Ni(NO3)2 from solid Ni(NO,)2 6H2O
(c) 65 0 ml of 0 25 M Al(NOi)3 from solid Al(NO 3 )j 9H2O

202

Stolchlometry III: Calculations Based on Concentrations of Solutions

(d) 230 ml of 0.460 M LiOH from solid LiOH

(e) 7.57 liters of 1.10 M KCr(SO4)2 from solid KCr(SO 4 ) 2 - 12H2O
25. Tell how you would prepare each of the following solutions.
(a) 750 ml of 0.55 M H3PO4 from 3.60 M H3PO4
(b) 12 liters of 3.0 M NH 3 from 15 M NH 3
(c) 25 ml of 0.020 M Pr2(SO4)3 from 0.50 M Pr2(SO4)3
(d) 365 ml of 0.0750 M K4Fe(CN)6 from 0.950 M K 4 Fe(CN) 6
26. Tell how you would prepare each of the following solutions (weight percentage
given).
(a) 650 ml of 0.350 M A1C13 from a 16.0% solution whose density is 1.149g/ml
(b) 1.35 liters of 4.35 M NH 4 NO 3 from a 62.0% solution whose density is 1.294
g/ml
(c) 465 ml of 3.70 M H3PO4 from an 85.0% solution whose density is 1.689
g/ml
(d) 75.0 ml of 1.25 M CuCl2 from a 36.0% solution whose density is 1.462 g/ml
(e) 8.32 liters of 1.50 M ZnCl2 from a 60.3% solution whose density is 1.747
g/ml
27. Find the molalities of the original solutions used in Problem 26.
28. The density of a 3.68 M sodium thiosulfate solution is 1.269 g/ml.
(a) Find the percentage of Na2S2O3 by weight.
(b) What is the molality of this solution?
29. The solubility of Hg2Cl2 is 7.00 x 1Q-" g per 100 g of water at 30C.
(a) Assuming that the density of water (1 g/ml) is not appreciably affected by
the presence of this amount of Hg2Cl2, determine the molarity of the
saturated solution of Hg2Cl2.
(b) What is the molality of this solution?
30. A pharmaceutical house wishes to prepare a nonirritating nose-drop preparation. To do this, it will put the active agent in a "normal saline" solution, which
is merely 0.90% NaCl by weight. What quantities of material will be needed if
it is desired to make 3000 gal of nose-drop solution that is normal saline and
contains 0.10% active agent? (The density of 0.90% NaCl solution is 1.005
g/ml.)
31. If 500ml of 3.00 M H2SO4 is added to 1.50 liters of 0.500 M H 2 SO 4 , what is the
resulting concentration?
32. What volume of 15.0 M NH 3 should be added to 3.50 liters of 3.00 M NH3 in
order to give 6.00 liters of 5.00 M NH 3 on dilution with water?
33. The density of a 1.660 M Na2Cr 2 O 7 solution is 1.244 g/ml.
(a) Find the percentage of Na2Cr2O7 by weight.
(b) If 1.50 liters of water are added to 1.00 liter of this solution, what is the
percentage by weight of Na2Cr 2 O 7 in the new solution?
34. If 35.0 ml of 0.750 M A1(NO3)3 are added to 100 ml of 0.150 M A1(NO3)3, what
will be the resulting concentration 9

Problems B

203

35 What volume of 4 00 M NaOH should be added to 5 00 liters of 0 500 M NaOH

m order to get 15 0 liters of 1 00 M NaOH on dilution with water 0
36 How would you make a standard solution that contains 10 0-y of Hg2+ per liter
of solution 0 (Start with HgCl2, and use volumetric flasks, pipets, and a balance
sensitive to 0 2 mg A y is a millionth of a gram )
37 It takes 31 00 ml of 0 2500 M H2SO4 to react with 48 00 ml NH 3 solution What
is the molanty of the NIV
38 How many milligrams of Na2CO3 will react with 45 00 ml of 0 2500 M HC1
39 What is the molanty of a KMnO 4 solution if 30 00 ml of it is needed for the
titration of 45 00 ml of 0 1550 M Na2C2O4 solution0 (See Problem 12 for the
equation )
40 What is the molanty of a cenc sulfate solution if 46 35 ml is required for the
titration of a 0 2351 g sample of Na 2 C 2 O 4 that is 99 609?: pure' The reaction is
2Ce4+ + C2042- -> 2Ce'i+ + 2CO2
41 A 0 2120 g sample of pure iron wire is dissolved, reduced to Fe2+, and titrated
by 40 00 ml KMnO 4 solution The reaction is
MnOj + 5Fe2+ + 8H+ -> Mn-+ + 5Fe3+ + 4H2O
Find the molanty of the KMnO 4 solution
42 A 0 220 g sample of H2SO4 is diluted with water and titrated by 40 0 ml of
0 100 M NaOH Find the percentage by weight of H2SO4 in the sample
43 A sample of vinegar weighs 14 36 g and requires 42 45 ml of 0 2080 M NaOH
for titration Find the percentage of acetic acid, HC 2 HsO 2 , in the vinegar
44 From the following data, compute the molanty of (a) the H2SO4 solution and
(b) the KOH solution
Wt of sulfamic acid, H(NH 2 )SO, - 0 2966 g
Vol of KOH to neutralize the H(NH2)SO, = 34 85 ml
31 08 ml of H2SO4 titrates 33 64 ml of KOH
45 A crystal of calcite, CaCO3, is dissolved in excess HC1 and the solution boiled
to remove the CO2 The unneutralized acid is then titrated by a base solution
that has previously been compared with the acid solution Calculate the molar
ity of (a) the acid, and (b) the base solutions
Wt of calcite - 1 9802 g
Vol of HC1 added to calcite = 45 00 ml
Vol of NaOH used in back titration = 14 43 ml
30 26 ml of acid titrates 21 56 ml of base
46 A 2 500 g sample of an ammonium salt of technical grade is treated with
concentrated NaOH and the NH 3 that is liberated is distilled and collected in

204

Stolchlometry III: Calculations Based on Concentrations of Solutions

50.00 ml of 1.2000 M HC1; 3.65 ml of 0.5316 M NaOH is required for backtitration. Calculate the percentage of NH3 in the sample.
47. A 0.5000 g sample of impure CaO is added to 50.00 ml of 0.1000 M HC1. The
excess HC1 is titrated by 5.00 ml of 0.1250 M NaOH. Find the percentage of
CaO in the sample. The reaction is
CaO + 2HC1 -+ CaCl2 + H2O
48. Silver nitrate solution is prepared by dissolving 85.20 g of pure AgNO3 and
diluting to 500.0 ml.
(a) What is its molarity?
(b) A CaCl2 sample is titrated by 40.00 ml of this AgNO 3 solution. What is the
weight of CaCl2 in the sample?
49. (a) What weight of MnO2 and (b) what volume of 12.0 M HC1 are needed for
the preparation of 750 ml of 2.00 M MnCl2? (c) What volume of C12 at 745 torr
and 23C will be formed? The reaction is
MnO2 + 4HC1 -* MnCl2 + C12 + 2H 2 O
50. What volume of 12.0 M HC1 is needed to prepare 3.00 liters of C12 at 730 torr
and 25C by the reaction
2KMn0 4 + 16HC1 -* 2MnCl2 + 5C12 + 8H2O + 2KC1
51. (a) What volume of 6.00 M HNO3 and what weight of copper are needed for
the production of 1.50 liters of a 0.500 M Cu(NO3)2 solution?
(b) What volume of NO, collected over water at 745 torr and 18C, will be
produced at the same time? The reaction is
3Cu + 8HNO3 -* 3Cu(NO3)2 + 2NO + 4H2O
52. What volume of 10.0 M HC1 is needed to prepare 12.7 liters of CO2 at 735 torr
and 35C? The reaction is
CaCO3 + 2HC1 - CaCl2 + CO2 + H2O
53. A 20.00 ml sample of a solution containing NaNO 2 and NaNO 3 is acidified
with H 2 SO 4 and then treated with an excess of NaN 3 (sodium azide). The
hydrazoic acid so formed reacts with and completely removes the HNO 2 . It
does not react with the nitrate. The reaction is
HN 3 + HNO 2 -> H2O + N2 + N2O
The volume of N2 and N 2 O is measured over water and found to be 36.50 ml at
740.0 torr and 27C. What is the molar concentration of NaNO 2 in this solution?
54. You have a 0.5000 g mixture of oxalic acid, H 2 C 2 O 4 -2H 2 O, and benzoic acid,
HC7H5O2. This sample requires 47.53 ml of 0.1151 M KOH for titration. What
is the percentage composition of this mixture?

14
Thermochemistry

Thermochemistry is the study of the thermal (heat) changes that are associated
with physical and chemical changes. Thermodynamics is much broader in
scope because it includes the study of all forms of energy, including work.
Some of these aspects are considered in later chapters.
CHANGES IN TEMPERATURE

If heat is applied to a substance, the temperature is raised; if heat is withdrawn,

the temperature is lowered. The unit of heat is the calorie (cal), which is defined
as the quantity of heat required to raise the temperature of 1 g of water 1 degree
Celsius. We shall not deal with problems so accurately as to be concerned about
the very small difference between a "15 calorie" (the heat needed to raise 1 g
of water from 14.5C to 15.5C), or the "mean calorie" (1 one-hundredth of the
heat needed to raise 1 g of water from 0C to 100C).
The number of calories required to raise the temperature of an object 1C is
called the heat capacity of the object. The molar heat capacity of a substance is
the number of calories needed to raise the temperature of a mole of the substance rc.
The specific heat of any substance is the number of calories required to raise
one gram of it 1C. From our definition of the calorie, it follows that the specific
heat of water is 1 cal/g C.

206

Thermochemistry

PROBLEM:

The specific heat of Fe2O3 is 0 151 cal/g C How much heat is needed to raise the
temperature of 200 g of Fe2O3 from 20 0C to 30 0C 7 What is the molar heat
capacity of Fe2O39
SOLUTION.

Because 0 151 cal raises 1 g of Fe2O3 1C,

cal \
(100C)
( 0 151 g-
C/
= 302 cal needed
The molar heat capacity is the product of specific heat and mole weight
Molar heat capacityy = f 0 151 -^) f l 5 9 6 }
\
g ' C / \
mole/
cal
= 24 1
mole C

CALORIMETRY

The amount of heat that is absorbed or liberated in a physical or chemical

change can be measured in a well-insulated vessel called a calonmeter (Figure
14-1) Calonmetry is based on the principle that the observed temperature
change resulting from a chemical reaction can be simulated with an electrical
heater The electrical measurements of current (/), heater resistance (/?), and
duration (?) of heating make it possible to calculate how much heat is equivalent
to the amount of heat produced by the chemical change, using the formula
I2Rt/4 184 By using weighed quantities of reactants, one can calculate the heat
change per gram or per mole
The formula is derived as follows Electrical current, measured in amperes, is
the rate of flow of electrical charge (coulombs), by definition, it is
amperes

coulombs
-3
seconds

The common relationship between volts (), amperes (/), and resistance (R) is
known as Ohm's law

E = IR

207

FIGURE 14-1
One type of calorimeter.

Electrical energy is given by

- /coulombs\
energy = (volts)(amperes)(seconds) = (volts)
: (seconds)
\ seconds /
= Elt = I'2Rt volt coulombs (or joules)
By definition,
I joule = I volt coulomb (the Si-approved unit of energy)
I calorie = 4.184 joules (the so-called mechanical equivalent of heat)
By combining these laws and definitions, we get
electrical energy =

I2Rt

calories

208

Thermochemistry

The insulation surrounding the calorimeter minimizes heat loss or gain

through the walls. The cover (C) supports the electrical heater (H); it has two
holes, one to permit the insertion of a sensitive differential thermometer (T), and
one through which reactants can be added. The solution is stirred by a Tefloncovered magnet (M) that is rotated by the motor-driven magnet (M'). The
electrical heating is controlled and measured as follows. The double-pole
switch (S) controls two things simultaneously: the timer (W), and the battery
(B), which supplies a constant current to the immersion heater (H). The current
(/) that flows through the heater is read from the ammeter (A), and the duration
( t ) of time that the current flows is read from the timer. The resistance (R) of
the heater is known from a separate measurement. The following problems are
based on the calorimeter shown in Figure 14-1.

PROBLEM:

A calorimeter contains 200 ml of 0.100 M NaCl solution at room temperature

(25.038C according to the thermometer). With the magnetic stirrer going, exactly
10.00 ml of 1.000 M AgNO 3 solution (also at room temperature) is added dropwise
through the porthole of the calorimeter. The temperature, as indicated by the
thermometer, rises to 25.662C. A current of 0.700 ampere is then passed through
the electrical heater (whose resistance is 6.50 ohms) for a period of 4 min 5 sec,
and the temperature rises by 0.742C. Calculate the number of calories produced
when one mole of AgCl precipitates from aqueous solution.
SOLUTION:

The electrical heater and thermometer tell you how many calories it takes to raise
the reaction mixture by 1C:
(0.700 amp)2(6.50 ohm)(245 sec)
energy

4.184^
cal
0.742C

186.5 cal
" 0.742C

The chemical reaction caused the temperature of the same mixture to rise by
0.624C, corresponding to an energy release of
energy from reaction = (0.624C) ( 251 j = 157 cal

(' f) -

You will note that there was added (0.200 liter) (0.100 mole/liter) = 0.0200 mole
NaCl and (0.0100 liter) (1.00 mole/liter) = 0.0100 mole AgNO3. Only half of the
NaCl is used, and just 0.0100 mole of AgCl is formed. It is the formation of this
0.0100 mole of AgCl that produces the 157 cal, so

Calorimetry

209

157 cal
, f
cal
energy per mole = ..-,-:r- = 15,700
0.0100 mole AgCl
'
mole AgCl

If you want to measure the specific heat of a liquid, you need know only the
electrical energy needed to heat a known weight of the liquid and the measured
temperature change, but you must use ^calibrated calorimeter, so that a correction can be made for the amount of electrical energy that was absorbed by the
calorimeter walls rather than by the liquid.

PROBLEM:

A calorimeter requires a current of 0.800 amp for 4 min 15 sec to raise the temperature of 200.0 ml of H2O by 1.100C. The same calorimeter requires 0.800 amp for 3
min 5 sec to raise the temperature of 200.0 ml of another liquid (whose density is
0.900 g/ml) by 0.950C. The heater resistance is 6.50 ohms. Calculate the specific
heat of the liquid.
SOLUTION:

The total heat energy produced by the electrical heater in water was used to raise
the temperature of the water and the calorimeter walls by 1.100C; it is
total energy =

(0.800 amp) 2 (6.50 ohms)(255 sec)

TTT;
= 254 cal

The energy required to raise just the water by 1.100C (assuming the density and
specific heat of water are both 1.000) is
cal \
(1.100C) = 220 cal
( 1.00 J

The energy required to raise the temperature of the calorimeter walls is the difference between the total energy and that required for the waterthat is, 254 220 =
34 cal. The heat capacity of the calorimeter (calories required to raise that part of
its walls in contact with the liquid by 1.0C) is
, .
34 cal , cal
heat capacity of calorimeter =
= 31

The total electrical energy produced when the heater was in the liquid is
(0.800 amp)2(6.50 ohms)(185 sec) _
4.184
~

Ca

Of this total amount, the part required to raise the calorimeter walls by 0.950C is
energy for calorimeter = (31 cal/C)(0.950C) = 29 cal
The difference between 184 cal and 29 cal is 155 cal; this is the amount required to
raise the temperature of the liquid by 0.950C. The amount of heat required to

210

Thermochemistry

raise 1 g of the liquid by 1C (its specific heat) is

.. ,
... .,
specific heatt of liquid =

155 cal
(200.0 ml)(0.900 g/ml)(0.950C)

= 0.910^

An alternative method of calorimetry that gives less accurate results, but is

simpler in concept, uses only a single insulated container and a thermometer.
Temperature changes in the calorimeter are brought about by adding hot (or
cold) objects of known weight and temperature. Calculations are based on the
principle that the heat lost by the added hot object is equal to that gained by the
water in the calorimeter and the calorimeter walls. This simple approach is
illustrated in the next two problems.

PROBLEM:

The temperature in a calorimeter containing 100 g of water is 22.7C. Fifty grams

of water are heated to boiling (99.1C at this location) and quickly poured into the
calorimeter. The final temperature is 44.8C. From these data, calculate the heat
capacity of the calorimeter.
SOLUTION:

The heat loss from the hot water is equal to the heat gain by the calorimeter and
the water initially in it.
Heat lost by hot water = (wt of H 2 O)(sp ht of H 2 O)(temp change)
= (50 g) (l.OO ^} (99.1C - 44.8C)
= 2715 cal

Heat gained by calorimeter water = (wt of H 2 O)(sp ht of H 2 O)(temp change)

= (ioogm:oo -^M (44.8c - 22.ro

= 2210 cal
Heat gained by calorimeter = (ht capacity of calorimeter)(temp change)
= (x ^rj (44.8C - 22.TC)

= 22. IA cal
We equate the heat lost to the heat gained and solve for x, the heat capacity of the
calorimeter:

The Rule of Dulong and Petit

211

2715 cal = 2210 cal + 22.lv cal

2715 - 2210

0 cal

PROBLEM:

The calorimeter of the preceding problem is used to measure the specific heat of a
metal sample, A 100 g sample of water is put into the calorimeter at a temperature
of 24.1C. A 45.32 g sample of metal filings is put into a dry test tube that is
immersed in a bath of boiling water until the metal is at the temperature of the
latter, 99.1C. The hot metal is then quickly poured into the calorimeter and the
water stirred by a thermometer that is read at frequent intervals until the temperature reaches a maximum of 27.6C. Compute the specific heat of the metal.
SOLUTION:

The heat lost by the metal sample is equal to the heat gained by the calorimeter.
Heat gained by water = (wt of H 2 O)(sp ht of H 2 O)(temp change)
= (100 g) ( 1.00 -^) (27.6C - 24.TC)

= 350 cal
Heat gained by calorimeter = (ht capacity of calorimeter)(temp change)
= (22.8 ^^\ (27.6C - 24.TC)

= 80 cal
Total heat gained = 350 cal + 80 cal

= 430 cal
Heat lost by metal = (wt of metal)(sp ht of metal)(temp change)
430 cal = (45.32 g) L ~\ (99.1C - 27.6C)

_
430 cal
'V ~ (45.32g)(7!.5C)
cal
Specific heat = 0.133 g C

THE RULE OF DULONG AND PETIT

Many years ago, Pierre Dulong and Alexis Petit observed that the molar heat
capacity for most solid elements is approximately 6.2 cal/mole C. That is, the

212

Thermochemistry

number of calories required to raise one mole of a solid element by l.OC is

given by
cal
}( s6 V m o l e/ /\ \ggC /
'"moleC
'

This rule of Dulong and Petit provides a simple way to find the approximate
values of the atomic weights of solid elements. For example, if you had an
unknown solid element in a finely divided state, you could put a weighed
sample of it into your calibrated calorimeter and quickly find its specific heat;
then, using the rule of Dulong and Petit, you could find its approximate atomic
weight.

PROBLEM:

A 50.0 g sample of a finely divided metal, insoluble and unreactive to water, is put
into 200.0 ml of water in the calorimeter that was calibrated in the preceding
problems. A current of 0.800 amp is passed through the heater for 15 min 50 sec in
order to raise the temperature by 4.00C. What is the specific heat of the metal?
SOLUTION:

The total electrical energy required to raise the water, the calorimeter, and the
metal by 4.00C is
(0.800 amp)2(6.50 ohms)(950 sec)
Together, the water and the calorimeter require 231 cal/C, so the total energy
required by them for 4.00C is
4.00C) = 924 cal
The difference, 945 - 924 = 21 cal, is required to raise the 50.0 g of metal by
4.00C. Therefore, the specific heat of the metal is
21.0 cal
(50.0 g)(4.00C)

., cal
'
g C

Approximate atomic weight of the metal =

0.105

= 59

mole

ENTHALPY OF TRANSITION

When substances melt or vaporize, they absorb energy but do not change
temperature. Instead, this energy is used to overcome the mutual attraction of

Enthalpy of Transition

213

the molecules or ions and permit them to move more independently than they
could in their former state; the new state with its added energy always has less
molecular order. For example, liquid water at 0C is a less-ordered state than
crystalline water at 0C, and water vapor at 100C is chaotic in its molecular
organization compared to liquid water at 100C.
These statements are made more precise and quantitative in the following
way. It is said that, at a given temperature and pressure, the molecules of each
substance in "state 1" (say, liquid) have a heat content of//,, whereas in "state
2" (say, vapor) they have a heat content of H2. The "heat of transition" (in this
case, vaporization) is simply "the change in heat content" (A//T):
A//T = // 2 - //,

To avoid the use of the ambiguous term "heat" in connection with "heat
content," it is customary to use the term enthalpy. At a given temperature and
pressure, every substance possesses a characteristic amount of enthalpy (//),
and the heat changes associated with chemical and physical changes at constant
pressure are called changes in enthalpy (A//); A//T is the enthalpy of transition.
Two common enthalpies of transition are A//f = 1435 cal/mole for the enthalpy
effusion (melting) of ice at 0C, and A//x = 9713 cal/mole for the enthalpy of
vaporization of water at 100C.
Energy also is involved in transitions from one allotropic form to another, or
from one crystal form to another. To change a mole of red phosphorus to yellow
phosphorus, we must supply 4.22 kilocalories (A//T = +4.22 kcal/mole), and
when 1 mole of yellow silicon disulfide changes to white silicon disulfide, 3.11
kcal is liberated (A//T = -3.11 kcal/mole).
In the following problem we apply the principles involved in both specific
heat and heats of transition.

PROBLEM:

What is the resulting temperature if 36.0 grams of ice at 0C are put into 200 g of
H2O at 25.0C, contained in the calibrated calorimeter used in the preceding
problems?
SOLUTION:

The energy required to melt the ice is supplied by the water and the calorimeter
walls which, as a result, are cooled. Let T be the final temperature.
Calories needed to melt ice at 0C =

'

(18.0 g/mole)

= 2870 cal

( 1 gcalC/-\ UrC) = 36.0T cal

Total calories needed = 2870 + 36.07

214

Thermochemistry

Cell \
1 -;) (25C - TC)
& ^'

\
) (25C - 7C)
( 31 cal

Total calories lost = (231)(25.0 - T)

Going on the principle that
total calories needed = total calories lost
we have
2870 + 36.07 = (231)(25.0 - T)
267 T = 2905
T = 10.9C, the resultant temperature

ENTROPY OF TRANSITION

The enthalpy of transition, divided by the absolute temperature at which it

occurs, is a common measure of the change in molecular order that occurs
during the transition. We refer to this change in molecular order as the "change
in entropy" (A5 T ), or the "entropy of transition." If A5T is positive, the change
results in an increase in molecular disorder. Changes in state offer some of the
simplest examples from which one can obtain a feeling for the relationship
between changes in entropy and changes in molecular order. Crystals have a
very high degree of order; in them, the movement of atoms, ions, or molecules
is restricted primarily to vibration about their locations in the crystalline lattice.
When crystals melt, the component atoms, ions, or molecules can move fairly
independently of each other in the liquid, slowly changing their neighbors by
diffusion; the molecular order represented by the lattice disappears. When
liquids vaporize, the component atoms or molecules, now in the gaseous phase,
move about independently in a chaotic, random manner. Each stage, melting
and vaporization, represents an increase in molecular chaos, and is described in
terms of an increase in entropy.
Just as A//T represents the difference in enthalpies between "state 2" and
"state 1," so does A5T represent the difference between the entropies in "state
2" and "state 1":
A5T = S2 ~ Si
A5x

cal
mole C

Enthalpy of Reaction

215

For water,

1435 _^L
Ao
mole
. ., cal
^
,,,. .
_._,
ASf = -_ = 5 . 2 6 : = entropy of fusion at 0 C
. I j V--

1I1O1C

\^s

9713 L
^
AS V = --.Op = 26.0 : = entropy of vaporization at 100C
For very many liquids, the entropy of vaporization at the normal boiling point is
approximately 21 cal/mole C; water is not typical. The units for changes in
entropy are the same as those for molar heat capacity, and care must be used to
avoid confusion. When referring to an entropy change, a cal/mole C is often
called an entropy unit, abbreviated e.u. In order to avoid later misunderstanding, note now that this method of calculating AS from A///T is valid only under
equilibrium conditions. For transitions, for example, this method can be used
only at temperatures where the two phases in question can coexist in equilibrium with each other.
ENTHALPY OF REACTION

Most reactions either liberate or absorb heat. To say that heat is liberated
means that the atoms, in the molecular arrangement they have as products,
must possess less energy than they did in their arrangement as reactants, and
that this difference in energy is evolved as heat; the reaction is exothermic.
When it is important to show this heat change, one way to do so is to include it
as part of the chemical equation, as illustrated by the burning of methane gas:
CH4(9) + 20 2<9) -+ C0 2(fl) + 2H20,n + 212,800 cal
Another, more useful, way is to say that the enthalpy of the reactants ("state
1") is HI, that the enthalpy of the products ("state 2") is// 2 , and that the "heat
of reaction" is simply the "change in enthalpy" (A//):
A7f = H2 - HI = heat of reaction = enthalpy of reaction
The actual amount of heat we measure experimentally for a given reaction
depends somewhat on (a) the temperature of the experiment and (b) whether
the experiment is run at constant volume or constant pressure. The basic reasons for this are that (a) each reactant and product has a characteristic specific
heat that varies individualistically with temperature, and (b) at constant
pressure, some of the heat of reaction may expand or compress gases if they are

216

Thermochemistry

not confined to a fixed volume. We shall avoid these complications here by

saying that A# refers only to changes occurring at 25C and at a constant
pressure of I atm; that is, the reactants and the products are in their standard
states .
Also, A// will always be negative for an exothermic reaction, because the
products collectively have a smaller enthalpy than the reactants. For the burning of CH 4 ,
CH4<9) + 2O2(9) - CO2(9) + 2H2O(0

A// = -212,800 cal

For an endothermic reaction, A// is positive. For example,

- H 2(9) + Cl 2(fl)

A// = +44,120 cal

If we had written the previous equation in the reverse order, the sign of A//
would have been negative. The positive sign means that it takes energy to
decompose HC1, and the negative sign means that energy is liberated when HC1
is formed from the elements, H2 and C12:
iH 2(ff) + iCl2(9) - HC1<9)

A# = -22,060 cal

The proper way to interpret the calorimeter experiment on p 208 is to say that
the enthalpy of reaction between Ag+ and Cl~ is - 15,700 cal/mole AgCl:
Ag-U, + Cl-^, - AgCU |

A// = - 15,700 cal

The energy changes associated with chemical reactions are determined solely
by the state of the reactants and the state of the products, and are totally
independent of the path or method of preparation. As a result, if a reaction can
be considered to be the sum of two or more other reactions, A// for that
reaction must be the sum of the A// values for the other reactions; this is known
as Hess's law. For example, CO2 may be made directly from the elements, or
indirectly by first making CO which is subsequently burned to CO2:
Q s > + i02(9) - C0(9)

A// = -26.42 kcal

CO (9) + K> B) - C0 2(ff)

A# = -67.63 kcal

Q s , + 0 2(9) - C0 2(9)

A// = -94.05 kcal

You can see that the sum of the first two reactions gives the third, just as the
sum of the A// values for the first two gives the A// for the third.
When a reaction produces a compound from elements in their common physical state at 25.0C and 1 atm, the value of A//f is called the standard enthalpy of

217
TABLE 14-1
Standard Enthalpies of Formation at 25 C and 1 atm (AH, in kcal/mole)
Substance

State

Any element

Normal

State

CO

CO2

Cu"

aq

F (atom)

F-

aq

351

FeO

9
s

171 70

Fe203
H (atom)
H+

HBr

HCI

HI

9
/

aq

AgCI

Br (atom)

Br-

aq

BrCI
C (atom)
C (diamond)

000

045

aq

-12977

aq
1

-1730
-5702
-4808
-6636
-5624
-2981
11 72
1982
2901
-4002
-31 41

9
1

C2H5OH
C2H5OH

C4H10
C6H6

9
1

C,H6

Cl (atom)

9
aq

cicio4-

Substance

2531
-3036
2671
-2890

Ag*

Ca2+
Cd"
CH3OH
CH3OH

AH?

aq

H2O

aq

I (atom)

g
g
g

I-

aq

ICI

9
aq
aq

H2O
H2S

K+
Li+

AH?

Substance

-2642
-94 05

N (atom)

Na (atom)

9
aq

2598
-5730

9
aq

-11 04

NH3

NH4+

aq

-31 74

NO

NO2

9
aq

1549
1830
-7866
-6370
-19650
5209

State

Na+
NH3

000

N03-

-866
-2206

N20

O (atom)

g
g

620

OH-

aq

P (atom)

g
g
g
g

-68 32
-5780
-482
2548
-1337

PCI,

PCI5
S (atom)

s2-

aq

420

SO2

-6004
-6654

S0|-

aq

Zn 2+

aq

AH?

8556

-1932

21 60
809

-4937
1949
5916

-5496
75 18
-7322
-9535
5325
1000

-7096
-21690
-3643

NOTE The state aq represents a very dilute aqueous solution

formation. The standard enthalpy of formation of 1 mole of HCI is

-22.06 kcal/mole. The standard enthalpies of formation of hundreds of compounds have been determined and are listed in tables in chemistry handbooks.
A few are listed here in Table 14-1. The standard enthalpy of formation of all
elements, in their common form at 25.0C and 1 atm pressure, is assumed to be
zero.
One real value of tables of standard enthalpies of formation is that they
permit the calculation of the standard enthalpy of any reaction for which all the
reactants and products are listed; it is not necessary to do an experimental
measurement. Based on Hess's law, the basic premise of the use of tables is
that the enthalpy of reaction is the difference between the sum of the enthalpies
of the formation of the products and the sum of the enthalpies of formation of
the reactants. That is,
= 2 (standard enthalpies of formation of products)
2 (standard enthalpies of formation of reactants)

218

Thermochemistry

In the following problems, we first write the chemical equation. Then, below
each substance, we write its standard enthalpy of formation, multiplied by the
number of moles of the substance used in the balanced equation. The standard
enthalpy of reaction is the difference between the sum of the enthalpies of
formation of the products and the sum of the enthalpies of formation of the
reactants.

PROBLEM:

Compute the standard enthalpy of reaction for the gaseous dissociation of PC15
into PC13 and C12.
SOLUTION:

Write the balanced chemical equation and take the needed values of A//? from
Table 14-1.
Pd5( 9 )

?*

(1 mole) (-95.35-^-)
\
mole/

PCl3 <0)

(1 mole) (-73.22
\
mole/
(

CI 2 ( 9 )

y...iv^yiv.v<u

mole/

Volets = dX-73.22) + (1X0.00) = -73.22 kcal

auanis = (l)(-95.35) = -95.35 kcal
^H)r,Mtmn = (-73.22 kcal) - (-95.35 kcal) = +22.13 kcal
The positive sign of the answer indicates that the reaction is endothermic and that
the dissociation at 25.0C requires 22,130 cal/mole.

PROBLEM:

What is the standard enthalpy of combustion of ethyl alcohol, C2H5OH?

SOLUTION:

Write the balanced chemical equation and take the needed values of A// from
Table 14-1.
C2H5OH,,,

(I mole) (-66 36-^L)

\
mole/

302IO,
(3 moles) (o 00 }
\
mole/

->

2C02(a)
(2 moles) (~94 0^ )
\
mole/

1H20,,,
(3 moles) (-68 12 }
\
mole/

S(A//a,raiucts = (2X-94.05) + (3X-68.32) = -393.06 kcal

2(A//9re,c.ants = (1)(-66.36) + (3)(0.00) = -66.36 kcal
(A//) r e.Ki,m = (-393.06 kcal) - (-66.36 kcal) = -326.70 kcal
The reaction is exothermic.

Enthalpies of combustion are relatively simple to determine, and they often

are used to find other energy values that are very difficult or impossible to

Bond Energies (Enthalpies)

219

determine directly. For example, the enthalpy of formation of methyl alcohol

corresponds to the reaction
2H 2(9) + C (s) + |O2(S) > CH 3 OH U)
yet it is impossible to make CH3OH directly from the elements. However, we
can burn CH3OH in an excess of O2 in a bomb calorimeter and measure the heat
produced (A// = -173.67 kcal/mole) in the reaction
CH 3 OH ( ,,

(I mo\e)(bH? ^-}
\
mole/

?0 2(B)

-*

(1 5 moles) (o 00 ^-}
\
mole/

C0 2(B)
( 1 mole) f -94 05 ^L)
V
mole/

2H 2 0 ( I )
(2 moles) (-68 32 ^IA
V
mole/

2(A# f ) products = (1X-94.05) + (2X-68.32) = -230.69 kcal

2(A// f ) re aaams = U)(A#f) + (1.5)(0.00) = A/f f

eacuon = (-230.69 kcal) - A#f = - 173.67 kcal

A//f = (-230.69 kcal) + (173.67 kcal) = -57.02 kcal
= standard enthalpy of formation of CH3OH,, ()
You will note that Table 14-1 also contains standard enthalpies of formation
for ions in aqueous solution. It is worth noting here that calorimetry was a
strong argument favoring the view that all strong acids and bases exist in dilute
water solution only as ions and not as molecules. No matter which combination
of strong acid and base is used in a neutralization reaction, the heat value
obtained is always very close to the value of A// = 13.36 kcal per mole of
water formed. The implication of course is that, although the chemicals are
different in each case, the reaction is the same; it must be
H<+9) + OHfa,, - H20(n

A// = - 13.36 kcal

If weak acids or bases are used, the observed heat values are always less and
quite variable. In essence, the reaction is also the same for the weak ones,
except that some of the enthalpy of the reaction (some of the 13.36 kcal) must
be used to remove the H + or OH~ from the weak acids or bases. The subscript
aq refers to the fact that the substance in question is in dilute aqueous solution;
A//? for H^,,,, in Table 14-1 has also been set arbitrarily equal to zero, just as
were the elements in their standard states.

BOND ENERGIES (ENTHALPIES)

The term bond energy is defined as the A// required to break a bond between
two atoms in an isolated gaseous molecule, producing the dissociated fragments

220

Thermochemistry

in the isolated gaseous state. At first, you might think that the value of A// =
+ 22.06 kcal/mole would be the H-C1 bond energy, but it is not. The value of
+ 22.06 represents the difference between the energy required to dissociate the
HC1 molecule and the energy liberated when the H atoms and Cl atoms combine to form H2 and C12 molecules. The bond energy, however, corresponds to
the reaction
HCl< fl) > H (s) + Cl( ff)
We could calculate A// for this if we knew (for the elements) the enthalpy of
formation of molecules from their atoms. Some crystalline elements (especially
metals) vaporize as monatomic gases, and it is not too difficult to determine
their heats of sublimation. Some elementssuch as H2, O 2 , and Br2are
diatomic gases that dissociate into atoms at high temperature; these dissociation energies may also be determined. Table 14-1 also includes the standard
enthalpies of formation of a number of atoms; these are based on the normal
physical form of the element at 25.0C. For HC1 we find
2(A//,)produc,s = (+52.09 kcal) + ( + 29.01 kcal) = 81.10 kcal
2(A//a e actan, s = -22.06 kcal
(A//)reaction = (81.10 kcal) - (-22.06 kcal) = +103.16 kcal
The bond energy is 103.16 kcal. There is additional discussion of bond energies
onpp 113-115.
CHANGES IN INTERNAL ENERGY

In the definition of enthalpy change (p 215) and in all of the examples of heat
changes and transfers we have discussed, there has been the limitation of
constant pressure.
Most experiments are performed at constant atmospheric pressure in vessels
and flasks open to the air. In the illustrative examples involving the combustion
of C2H5OH and CH3OH, however, the measurements had to be carried out in a
heavy-walled "bomb" calorimeter at constant volume.
In comparing the heat effects associated with these two different limitations,
we must look at three different constant-pressure situations.
1. If there are more moles of gaseous products than gaseous reactants in
the balanced chemical equation, then the extra gaseous moles will expand against the atmospheric pressure and the work energy required
for this will come at the expense of some of the heat that is liberated. A
smaller amount of heat will be liberated than if the reaction had occurred at constant volume.

Changes in Internal Energy

221

2. If there are fewer moles of gaseous products than gaseous reactants in

the balanced chemical equation, then the atmospheric pressure will do
work on the reaction mixture as it contracts due to the diminished
number of gaseous moles, and this work energy will be added to the
heat that is liberated. A larger amount of heat will be liberated than if
the reaction had occurred at constant volume.
3. If there are the same number of gaseous moles of products as reactants, there will be no contraction or expansion of the reaction mixture.
The heat liberated at constant pressure will be the same as at constant
volume.
We next offer a simple way to calculate the heat effect at constant pressure
from that observed at constant volume, or vice versa. First, note that the product of P and V always has the units of energy. A simple bit of evidence for this
observation comes from the ideal gas law, using the value of 1.987 cal/mole K
forfl:
PV = (n moles) ( 1.987 C.al .. W K ) = l-987(n7) calories
\
mole Ky
It is said that every substance has an internal energy (designated as E ) , and
that the heat effect associated with a change at a constant volume and temperature is AE. As the molecules go from "state 1" to "state 2," AE = E2 - El.
This effect is exactly analogous to the heat effect that is associated with a
change at constant pressure and temperature: A// = H2 - H I . The variables//
and E are related by the potential of the system to expand or contract that is,
to the potential to be affected by PV work by the explicit function

H = E + PV
For a change,
A// = AE + A(/JV)
If the change is a chemical reaction at constant temperature and pressure,
A(PV) becomes PAV because the pressure remains constant, and it comes as a
result of the difference in the number of gaseous moles of products and reactants in the balanced chemical equation:
I

A(/>V) = PAV = (kn)RT

where An = n2 (gaseous moles of products) - n1 (gaseous moles of reactants).
For chemical reactions, then,
A// = AE + (bn)RT

222

Thermochemistry

This equation makes it simple to calculate enthalpies of reaction from values of

AE obtained at constant volume, and vice versa.

PROBLEM:

The combustion of C 2 H 5 OH a) in a bomb calorimeter at constant volume gives a

value of A = -326.1 kcal/mole. Calculate the value of A//.
SOLUTION:

The balanced chemical equation

C 2 H 5 OH U) + 30 2(fl) - 2C0 2(9) + 3H 2 0 (()
shows that A;; = 2 - 3 = -1. Therefore, at standard conditions (25.0C),
A// = AE + (An)KJ

( 1.987 molecal; K/\ /\10-

kcal\

- (298 K)
cal /

= -326.7 kcal (per mole of C 2 H 5 OH)

THE FIRST LAW OF THERMODYNAMICS

A concise summary of the principles of the last section is given by the first law
of thermodynamics, which states that any change in internal energy (AE) of a
system is just equal to the difference between the heat (Q) it absorbs and the
work (W) it performs:
AE = Q - W

In other words, energy cannot be created or destroyed; all energy must be

accounted for.
A "system" is any carefully defined object or collection of materials that is
under discussion or study. For example, it may be the substances in a chemical
reaction mixture, the contents of a calorimeter, a solid of prescribed dimensions
or amount, or a gas at a given temperature, pressure, and volume. Everything
in the lab or the universe that exchanges heat or work with the system is called
"the surroundings."
For a chemical reaction at constant volume, W = 0, so AE = Q. If the
reaction absorbs heat from the surroundings, Q is positive, and the reaction is
endothermic (AE is positive).
For a chemical reaction at constant pressure, Q = A//, and W = (&n)RT, so
A// = AE + (&n)RT. If the reaction absorbs heat from the surroundings, A// is

'roblems A

223

positive, and the reaction is endothermic; AE may be larger or smaller than A//
depending on the sign of Arc.

PROBLEMS A
1. Calculate the approximate specific heat of each of the following elements: (a)
S; (b) Zn; (c) La; (d) U; (e) Pb.
2. Calculate the resultant temperature when 150 g of water at 75.0C is mixed
with 75.0 g of water at 20.0C. (Assume no heat loss to container or surroundings.)
3. Calculate the resultant temperature when 50.0 g of silver metal at 150.0C is
mixed with 50.0 g of water at 20.0C. (Assume no heat loss to container or
surroundings.)
4. Suppose 150 ml of water at 50.0C, 25.0 g of ice at 0C, and 100 g of Cu at
100.0C are mixed together. Calculate the resultant temperature, assuming no
heat loss, and using the approximate specific heat of Cu.
5. Suppose 150 ml of water at 20.0C, 50.0 g of ice at 0C, and 70.0 g of Cu at
100.0C are mixed together. Calculate the resultant temperature, assuming no
heat loss, and using the approximate specific heat of Cu.
6. A Dewar flask (vacuum-jacketed bottle) is used as a calorimeter, and the
following data are obtained. Measurements in parts (a) and (b) are made to
obtain the heat capacity of the calorimeter, and parts (c) and (d) are performed
on an unknown metal.
(a) Calorimeter with 150.0 g of H2O has a temperature of 21.3C.
(b) When 35.0 ml of H2O at 99.5C are added to the calorimeter and water of
part (a), the resultant temperature is 35.6C.
(c) Calorimeter with 150.0 g of H2O has a temperature of 22.7C.
(d) A 50.3 g sample of metal at 99.5C added to the calorimeter and water of
(c) gives a resultant temperature of 24.3C.
Calculate the approximate atomic weight of the metal.
7. A 100.0 g sample of glycerol is put into the calorimeter calibrated in Problem
6, and its temperature is observed to be 20.5C. Then 45.7 g of iron at 165.0C
are added to the glycerol, giving a resultant temperature of 37.4C. Calculate
the specific heat of the glycerol. (Use the approximate specific heat of iron.)
8. Calculate the heat capacity of a calorimeter (Figure 14-1) that, when containing 300 ml of water, requires a current of 0.840 amp passing for 3 min 41 sec
through a 9.05 ohm immersed resistance in order to raise the water temperature from 22.376C to 23.363C.
9. Calculate the following quantities, using the calorimeter calibrated in Problem
8.
(a) The specific heat of a water-insoluble material. First, 38.5 g of a finely
divided sample are stirred with 250 ml of water; then a current of 0.695

224

Thermochemistry

(b)

(c)

(d)

(e)

amp for 8 mm 53 sec raises the temperature of the mixture from 24 605C
to 26 328C
The specific heat of a liquid First, 300 g of it are put in the calorimeter in
place of the water, then a current of 0 742 amp is passed for 3 mm 22 sec,
raising its temperature from 21 647C to 22 406C
The enthalpy change per mole of precipitated PbI2 when 25 0 ml of 6 00 vi
Nal are added with stirring to 300 ml of 0 250 M Pb(NO3)2 contained in the
calorimeter A current of 0 900 amp passing for 8 mm 18 sec through the
heater immersed in the reaction mixture causes a temperature rise only
0 750 of the rise observed for the reaction Also write the equation for the
reaction involved
The enthalpy change per mole of KBrO 3 when 15 0 g of solid KBrO 3 are
dissolved in 200 ml of water in the calorimeter This is the so called heat
of solution ' After the salt is dissolved, a current of 0 800 amp passing for
10 mm 38 sec is required in order to regain the initial temperature of the
water Also write the equation for this reaction
The enthalpy of fusion per mole of p-iodotoluene, C 7 H 7 I When 21 8 g of
p-iodotoluene are added to 200 ml of water in the calorimeter, the crystals
(being immiscible with water and also more dense) sink to the bottom As
current is passed through the heater, the temperature of the mixture rises
until the p-iodotoluene starts to melt, at this point, all of the electrical
energy is used for fusion and none for raising the temperature A current
of 0 820 amp passing for 4 mm 41 sec is required for the period in which
the temperature stays constant and before the temperature again begins to
rise, as both the water and the liquidp-iodotoluene rise above the melting
point of 34 0C Write the equation for the reaction '

10 A metal X, whose specific heat is 0 119 cal/g C, forms an oxide whose composition is 32 00% O
(a) What is the empirical formula of the oxide 9
(b) What is the exact atomic weight of the metal 0
11 A metal Y, whose specific heat is 0 0504 cal/g C, forms two chlorides, whose
compositions are 46 71% Cl and 59 42% Cl
(a) Find the formulas of the chlorides
(b) What is the exact atomic weight of the metal 9
12

(i) Use Table 14-1 to determine the standard enthalpy of reaction, in kcal,
for each of the following reactions
() Give the values of the standard enthalpies of reaction in kjoules
(in) Calculate the change in standard internal energy (A) for each of the
reactions
(a) FeO (s) + H 2(9) <=*Fe(s) + H 2 O (()
(b) 4NH 3(9 > + 502(s) ft 6H 2 0 (9) + 4NO (9)
(c) Zn (sl + 2HC1W> ? H 2(9) + ZnCl 2(M ,
(d) 2FeO (g) + J0 2(fl) ? Fe203(s)
(e) 3N0 2(91 + H20m ft 2HN0 3(M) + NO (S)
(f) 2N20(9) ft 2N 2(9) + 0 2(9)

13 Calculate the standard enthalpy change (per mole) for the following reactions
Also write the equation for the reaction in each case

Problems B

225

(a)
(b)
(c)
(d)
(e)

Dissolving NH 3 in water
The burning (or rusting) of iron to give Fe2O3
Combustion of liquid C6H6
The reaction of metallic cadmium with dilute HC1
The evolution of H2S on mixing HC1 and Na 2 S solutions

14. The enthalpy of combustion of rhombic sulfur is -70.96 kcal/mole. The enthalpy of combustion of monoclinic sulfur is -70.88 kcal/mole. Calculate the
standard enthalpy and entropy of transition from rhombic to monoclinic sulfur.
15. Calculate the standard enthalpy and entropy of vaporization for C 2 H 5 OH at
25C.
16. Calculate the bond energies in the following gaseous molecules: (a) NO; (b)
H2O; (c) NH3; (d) PC15.
17. The observed heat of combustion at constant volume for sucrose
(Ci 2 H 22 O 11(s) ) at 25.0C is A = -1345 kcal/mole.
(a) Write the equation for the combustion reaction and calculate A// for the
reaction.
(b) Calculate the standard enthalpy of formation of sucrose.
(c) The overall metabolism of sucrose in your body is the same as the combustion reaction in the bomb calorimeter. Calculate how much heat is
produced in your body for every teaspoon of sugar (5.2 g) you eat and
metabolize. How much for every pound of sugar you eat?

PROBLEMS B
18. Calculate the approximate specific heat of each of the following elements: (a)
Pt; (b) P; (c) Sr; (d) As; (e) Au.
19. Calculate the resultant temperature when 250 g of water at 25.0C are mixed
with 100 g of water at 80.0C. (Assume no heat loss to container or surroundings.)
20. Calculate the resultant temperature when 100 g of lead metal at 200.0C are
mixed with 200 g of water at 20.0C. (Assume no heat loss to container or
surroundings.)
21. Suppose 200 ml of water at 55.0C, 35.0 g of ice at 0C, and 120 g of Zn at
100.0C are mixed. Calculate the resultant temperature, assuming no heat
loss, and using the approximate specific heat of Zn.
22. Suppose 200 ml of water at 15.0C, 60.0 g of ice at 0C, and 90.0 g of Cd at
125.0C are mixed. Calculate the resultant temperature, assuming no heat
loss, and using the approximate specific heat of Cd.

23. A metal X, whose specific heat is 0.112 cal/g C, forms an oxide whose composition is 27.90% O.
(a) What is the exact atomic weight of the metal?
(b) What is the formula of the oxide?

226

Thermochemistry

24. A metal Y, whose specific heat is 0.0312 cal/g C, forms two chlorides whose
compositions are 35.10% Cl and 15.25% Cl.
(a) What is the exact atomic weight of the metal?
(b) What are the formulas of the chlorides?
25. A Dewar flask (vacuum-jacketed bottle) is used as a calorimeter, and the
following data are obtained. Measurements in parts (a) and (b) are made to
obtain the heat capacity of the calorimeter, and parts (c) and (d) are performed
on an unknown metal.
(a) Calorimeter with 200 g of water has a temperature of 23.7C.
(b) When 50.0 g of water at 99.1C are added to the calorimeter and water in
(a), the resultant temperature is 36.0C.
(c) Calorimeter with 200 g of water has a temperature of 20.6C.
(d) A 91.5 g sample of metal at 99. PC added to the calorimeter and water in
(c) gives a resultant temperature of 21.5C.
Calculate the approximate atomic weight of the metal.
26. A 200 g sample of an unknown high-boiling liquid is put into the calorimeter
calibrated in Problem 25, and its temperature is observed to be 24.2C. Then
55.3 g of copper at 180.0C are added to the liquid in the calorimeter to give a
resultant temperature of 28.0C. Calculate the specific heat of the liquid. Use
the approximate specific heat of copper.
27. Calculate the heat capacity of a calorimeter (Figure 14-1) that, when containing 250 ml of water, requires a current of 0.650 amp passing for 5 min 25 sec
through the 8.35 ohm immersed resistance in order to raise the water temperature from 25.357C to 26.213C.
28. Compute the following quantities, using the calorimeter calibrated in Problem
27.
(a) The specific heat of an unknown metal. First, 40.0 g of a finely divided
sample are stirred with 220 ml of water; then a current of 0.720 amp for 12
min 24 sec raises the temperature from 25.265C to 27.880C.
(b) The specific heat of an unknown liquid. First, 250 g of it are placed in the
calorimeter in place of the water; then a current of 0.546 amp is passed for
4 min 45 sec, raising the temperature from 26.405C to 27.033C.
(c) The enthalpy change per mole of precipitated BaSO4 when 125 ml of 0.500
M BaCl2 solution are mixed in the calorimeter with 125 ml of 0.500 M
Na2SO4 solution. A current of 0.800 amp passing for 5 min 41 sec through
the heater immersed in the reaction mixture caused a temperature rise
1.500 times larger than that observed for the reaction. Also write the
equation for the reaction involved.
(d) The enthalpy change per mole of NH 4 NO 3 when 16.0 g of solid NH 4 NO 3
are dissolved in 250 ml of water in the calorimeter. This is the so-called
"heat of solution." After the salt is dissolved, a current of 1.555 amp
passing for 4 min 16 sec is required in order to regain the initial temperature of the water. Write the equation for this "reaction."
(e) The enthalpy of fusion per mole of diiodobenzene, C 6 H 4 I 2 . When 20.0 g of
diiodobenzene are added to 250 ml of water in the calorimeter, the crystals
(being immiscible with water and also more dense) sink to the bottom. As

Problems B

227

current is passed through the heater, the temperature of the mixture rises
until the dnodobenzene starts to melt, at this point, all of the electrical
energy is used for fusion and none for raising the temperature A current
of 0 500 amp passing for 6 mm 49 sec is required for the period in which
the temperature stays constant and before the temperature again begins to
rise, as both the water and the liquid dnodobenzene rise above the melting
point of 27C Write the equation for the "reaction "
29

(;) Use Table 14-1 to determine the standard enthalpy of reaction (in kcal)
for each of the accompanying reactions
00 Give the values of the standard enthalpies of reaction in kjoules
(in) Calculate the change in standard internal energy (AE) for each of the
reactions
(a) C (s) + H 2 0 (s) ? H 2(fll + C0 (fl)
(b) C 6 H 6(() + 7i02(9l ? 6C02(9l + 3H20((1
(c) 2K (S) + H 2 SO 4(M) <=* K 2 SO 4(M) + H 2(9)
(d) N 2 0 (9) + H 2(91 ^ H 2 O U) + N 2(9)
(e) NH 3(0) * iN 2(fl) + liH2(9)
(f) 2H 2 S (fl) + 30 2(fl) +* 2H20U1 + 2S0 2(fl)

30 Calculate the standard enthalpy change (per mole) for the following reactions
Also write the equation for the reaction in each case
(a) Dissolving HC1 in water
(b) Combustion of C4H10 vapor
(c) Combustion of liquid C 2 H 5 OH
(d) The production of PC15 from PC13
(e) The reaction of metallic zinc with dilute H2SO4
31 The enthalpy of combustion of diamond is 94 50 kcal/mole The enthalpy of
combustion of graphite is -9405 kcal/mole What is the standard enthalpy
and entropy of transition from diamond to graphite 9
32 Calculate the standard enthalpy and entropy of vaporization of C6H6 at
250C
33 Calculate the bond energies in the following gaseous molecules (a) CO, (b)
CO 2 , (c) SO2, (d) NaCl The enthalpy of sublimation of NaCl is A// = +54 70
kcal/mole, and the standard enthalpy of formation of NaCl,,, is A// = -98 23
kcal/mole
34 The observed heat of combustion at constant volume of a common fat,
glyceryl tnoleate (C 57 Hi 04 O 6(s) ) at 25 0C is A = 7986 kcal/mole
(a) Write the equation for the combustion reaction and calculate A// for the
reaction
(b) Calculate the standard enthalpy of formation of glyceryl tnoleate
(c) The overall metabolism of this fat in your body is the same as the combus
tion reaction in the bomb calorimeter Calculate how much heat is produced in your body for every ounce of this fat that you eat and metabolize
How much heat energy would your body produce while getting rid of one
pound of this fat 9