Chemistry & Chemi c a l R eac t ivi t y, 10th Edition

By John C. Kotz, Paul M. Treichel, John R. Townsend And David A. Treichel

Chapter 5: Principles of Chemical Reactivity: Energy

and Chemical Reactions - Thermochemistry

Chapter Outline
5.1 Energy: Some Basic Principles
5.2 Specific Heat Capacity: Heating and Cooling
5.3 Energy and Changes of State
5.4 The First Law of Thermodynamics
5.5 Enthalpy Changes for Chemical Reactions
5.6 Calorimetry
5.7 Enthalpy Calculations
5.8 Product- or Reactant-Favored Reactions and Thermodynamics

5.1 Energy: Some Basic Principles

Goals for Section 5.1

• Recognize and use the language of thermodynamics: the system and its
surroundings; exothermic and endothermic reactions.
• Describe the nature of energy transfers as heat.
• Understand the sign conventions of thermodynamics.

The importance of energy is evident in our daily lives—in heating and cooling our
homes, in powering our appliances, and in propelling our vehicles, among other
things. Most of the energy we use for these purposes is obtained by carrying out
chemical reactions, largely by burning fossil fuels. We use natural gas for heating,
coal and natural gas to generate most of our electric power, and fuels derived from
petroleum for automobiles and for heat. In addition, energy is required for living:
Chemical reactions in our bodies provide the energy for body functions, for movement,
and to maintain body temperature.

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In Chapter 1, we defined energy as the capacity to do work and stated that
energy could be divided into two basic categories: kinetic energy (the energy associated
with motion) and potential energy (the energy that results from an object’s
position, composition, or state). Chemists often use the term thermal energy
when referring to the kinetic energy of molecules. As you will soon see, thermal
energy is associated with the transfer of energy as heat between a hotter object and
a cooler one.

◀ The reaction of potassium and water. This reaction involves the transfer of energy between
the system and surroundings in the form of heat (thermal energy), work, and light.

One type of potential energy is chemical energy, the energy associated with the
forces holding atoms together as molecules or binding atoms and molecules together
as solids or liquids. In a chemical reaction, chemical energy (potential energy)
is converted to other forms of energy such as heat or light (kinetic energy).
Also in Chapter 1 you learned that, although energy can be converted from one
type into another, the total amount of energy is conserved. This is formally stated in
the law of conservation of energy: Energy can neither be created nor destroyed. Or,
stated differently, the total energy of the universe is constant. In order to understand the
importance of this law, we need to introduce some new terminology and carefully
consider the implications of a number of experiments.

Systems and Surroundings

In thermodynamics, the terms system and surroundings have precise and important
meanings. A system is defined as an object, or collection of objects, being studied
(Figure 5.1). The surroundings include everything outside the system that can exchange
energy and/or matter with the system. In the discussion that follows, we will
need to define systems precisely. If we are studying the energy evolved in a chemical
reaction carried out in solution, for example, the system might be defined as the
reactants, products, and solvent. The surroundings would be the reaction flask and
the air in the room and anything else in contact with the flask with which it might
exchange energy or matter. At the atomic level, the system could be a single atom or
molecule, and the surroundings would be the atoms or molecules in its vicinity. This
concept of a system and its surroundings applies to nonchemical situations as well.
To study the energy balance on our planet, we might choose to define Earth as the
system and outer space as the surroundings. On a cosmic level, the solar system
might be defined as the system being studied, and the rest of the galaxy would be
the surroundings. How the system and its surroundings for each situation are defined
depends on the information we are trying to obtain or convey.

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Directionality and Extent of Transfer of Heat: Thermal Equilibrium

Energy can be transferred between a system and its surroundings or between different
parts of the system. One way that energy can be transferred is as heat. Energy is
transferred as heat if two objects at different temperatures are brought into contact.
In Figure 5.2, for example, the beaker of water and the piece of metal being heated
in a Bunsen burner flame have different temperatures. When the hot metal is
plunged into the cold water, energy is transferred as heat from the metal to the water.
The thermal energy (molecular motion) of the water molecules increases, and
the thermal energy of the metal atoms decreases. Eventually, the two objects reach
the same temperature, and the system has reached thermal
equilibrium. The distinguishing feature of thermal equilibrium is that, on the macroscopic
scale, no further temperature change occurs; both the metal and water are at the same
temperature.

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Figure 5.3 Exothermic and endothermic processes. The symbol q represents the
energy transferred as heat, and the subscript sys refers to the system.

Submerging a hot metal bar in water and following the temperature change may
seem like a rather simple experiment with an obvious outcome. However, the experiment
illustrates two important principles:
• Energy transfer as heat will occur spontaneously from an object at a higher
temperature to an object at a lower temperature; the object whose temperature
increases gains thermal energy and the object whose temperature decreases
loses thermal energy.
• Transfer of energy as heat continues until both objects are at the same temperature
and thermal equilibrium is achieved.

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For the specific case where energy is transferred only as heat within an isolated
system (that is, a system that cannot transfer either energy or matter with its surroundings),
we can also say that the quantity of energy lost as heat by the hotter object and the quantity of
energy gained as heat by the cooler object are numerically equal. This is required by the law of
conservation of energy.
When energy is transferred as heat between a system and its surroundings, we describe
the directionality of this transfer as exothermic or endothermic (Figure 5.3).
• In an exothermic process, energy is transferred as heat from a system to its surroundings.
The energy of the system decreases and the energy of the surroundings
increases. We designate energy transferred as heat by the symbol q. For an
exothermic process, qsys < 0.
• An endothermic process is the opposite of an exothermic process. Energy is
transferred as heat from the surroundings to the system, increasing the energy
of the system and decreasing the energy of the surroundings. For an endothermic
process, qsys > 0.

5.2 Specific Heat Capacity: Heating and Cooling

Goal for Section 5.2

• Use specific heat capacity in calculations of energy transfers as heat involving
temperature changes.

When an object is heated or cooled, the quantity of energy transferred depends on

three things: the quantity of material, the magnitude of the temperature change, and
the identity, including the phase (g, ℓ, aq, or s), of the material gaining or losing
energy. To mathematically relate the quantity of energy transferred to the quantity
of material and the temperature change, for a given substance, we use the specific
heat capacity (C). This is defined as the energy transferred as heat that is
required to raise the temperature of 1 gram of a substance by one
kelvin. It has units of joules per gram per kelvin (J/g-K). A few specific heat capacities are
listed in Figure 5.4, and a longer list is given in Appendix D (Table 11).
Heat capacity can also be expressed on a per-mole basis. The amount of energy
that is transferred as heat in raising the temperature of one mole of a substance by
one kelvin is the molar heat capacity. For water, the molar heat capacity is 75.4 J/mol-K. The
molar heat capacity of metals at room temperature is always near 25 J/mol-K.

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Figure 5.4 Specific heat capacity. Metals have different values of specific heat capacity.
However, their molar heat capacities are all near 25 J/mol K.

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The energy gained or lost as heat when a given mass of a substance is warmed
or cooled can be calculated using Equation 5.1.

Here, q is the energy gained or lost as heat by a given mass of substance (m), C is the
specific heat capacity, and ΔT is the change in temperature, which is calculated as
the final temperature minus the initial temperature.

Calculating a change in temperature using Equation 5.2 will give a result with an
algebraic sign that indicates the direction of energy transfer. For example, we can use
the specific heat capacity of copper, 0.385 J/g ⋅ K, to calculate the energy that must
be transferred from the surroundings to a 10.0-g sample of copper if the metal’s
temperature is raised from 298 K (25 °C) to 598 K (325 °C).

Notice that the answer has a positive sign. This indicates that the energy of the
sample of copper has increased by 1160 J, which is in accord with energy being transferred
as heat to the copper (the system) from the surroundings.

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The relationship between energy, mass, and specific heat capacity has numerous
implications. The high specific heat capacity of liquid water, 4.184 J/g ⋅
K, is a major reason that large bodies of water have a profound influence on
climate. In spring, lakes warm up more slowly than the air. In autumn, the energy
transferred by a large lake as it cools moderates the drop in air temperature.
The relevance of specific heat capacity is also illustrated when food is wrapped
in aluminum foil (specific heat capacity 0.897 J/g ⋅ K) and heated in an oven.
You can remove the foil with your fingers after taking the food from the oven.
The food and the aluminum foil are very hot, but the small mass of aluminum
foil used and its low specific heat capacity result in only a small quantity of energy
being transferred to your fingers (which have a larger mass and a higher
specific heat capacity).

A practical example of knowing

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about specific heat capacity. If
you are careful, it is possible to
remove the salmon from the grill
by grasping the edges of the
aluminum foil with unprotected
hands. Due to the small quantity
of aluminum and its low specific
heat capacity, only a small
quantity of energy is transferred.

Check Your Understanding

You did an experiment in which you found that 59.8 J was required to raise the temperature
of 25.0 g of ethylene glycol (a compound used as antifreeze in automobile engines) by
1.00 K. Calculate the specific heat capacity of ethylene glycol from these data.

Quantitative Aspects of Energy Transferred as Heat

Specific heat capacity is a characteristic intensive property of a pure substance. It can
be determined experimentally by accurately measuring temperature changes that
occur when energy is transferred as heat from the substance to a known quantity of

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water (whose specific heat capacity is known).
Suppose a 55.0-g piece of metal is heated in boiling water to 99.8 °C and then
dropped into cool water in an insulated beaker (Figure 5.5). Assume the beaker
contains 225 g of water and its initial temperature (before the metal was dropped
in) was 21.0 °C. The final temperature of the metal and water is 23.1 °C. What is
the specific heat capacity of the metal? Here are the important aspects of this
experiment.
• Let’s define the metal and the water as the system and the beaker and environment
as the surroundings and assume that energy as heat is transferred only
within the system. (This means that energy is not transferred between the system
and the surroundings. This assumption is good, but not perfect; for a more
accurate result, we would also want to account for any energy transfer to the
surroundings.)

Figure 5.5 Transfer of energy as heat. When energy is transferred as heat from a hot
metal to cool water, the thermal energy of the metal decreases and that of the water
increases. The value of qmetal is thus negative and the value of qwater is positive.

• The water and the metal end up at the same temperature. (Tfinal is the same for
both.)
• We will also assume energy is transferred only as heat within the system.
• The energy transferred as heat from the metal to the water, qmetal, has a negative

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value because the temperature of the metal decreases. Conversely, qwater has a
positive value because its temperature increases.
• The values of qwater and qmetal are numerically equal but are opposite in sign.
Because of the law of conservation of energy, in an isolated system the sum of the
energy changes within the system must be zero. If energy is transferred only as heat, then

where the quantities q1, q2, and so on represent the energies transferred as heat for
the individual parts of the system. For this specific problem, there are thermal energy
changes associated with the two components of the system, water and metal,
qwater and qmetal; thus

Each of these quantities is related individually to specific heat capacities, masses,

and changes of temperature, as defined by Equation 5.1. Thus

The specific heat capacity of the metal, Cmetal , is the unknown in this problem. Using
the specific heat capacity of water (4.184 J/g ⋅ K) and converting Celsius to kelvin
temperatures gives

EXAMPLE 5.2
Using Specific Heat Capacity
Problem In an experiment like that in Figure 5.5, an 88.5-g piece of iron whose temperature
is 78.8 °C (352.0 K) is placed in a beaker containing 244 g of water at 18.8 °C
(292.0 K). When thermal equilibrium is reached, what is the final temperature? (Assume no
energy is transferred to warm the beaker and its surroundings.)
What Do You Know? Iron cools and the water warms until thermal equilibrium is
reached. The energies associated with the two changes are determined by the specific
heat capacities, masses, and temperature changes for each species. If we define the system
as the iron and water, the sum of these two energy quantities will be zero. The final
temperature is the unknown in this problem. Masses and initial temperatures are given;
the specific heat capacities of iron and water can be found in Appendix D or Figure 5.4.

Strategy The sum of the two energy quantities, qFe and qwater , is zero (qFe + qwater = 0).
Each energy quantity is defined using Equation 5.1; the value of ΔT in each is Tfinal − Tinitial.
We can use either kelvin or Celsius temperatures (Problem Solving Tip 5.1). Substitute the

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given information into Equation 5.3 and solve.

Check Your Understanding

A 15.5-g piece of chromium, heated to 100.0 °C, is dropped into 55.5 g of water at
16.5 °C. The final temperature of the metal and the water is 18.9 °C. What is the specific
heat capacity of chromium? (Assume no energy is lost to the container or to the surrounding
air.)

5.3 Energy and Changes of State

Goal for Section 5.3
• Use heat of fusion and heat of vaporization to calculate the energy transferred as
heat in changes of state.
A change of state refers to changes between the three states of matter: solid, liquid,
and gas. When a solid melts, its atoms, molecules, or ions move about vigorously
enough to break free of the attractive forces holding them in rigid positions in the
solid lattice. When a liquid boils, the particles move much farther apart from one
another, to distances at which attractive forces are minimal. In both cases, energy
must be furnished to overcome attractive forces among the particles.
The energy transferred as heat that is required to convert a substance from a
solid at its melting point to a liquid is called the heat of fusion. The energy transferred
as heat to convert a liquid at its boiling point to a vapor is called the heat
of vaporization. Values for a few common substances are given in Appendix D
(Table 12).
It is important to recognize that temperature is constant throughout a change of state
(Figures 5.6). During a change of state, the added energy is used to overcome the
forces holding one molecule to another, not to increase the temperature.
For water, the heat of fusion at 0 °C is 333 J/g, and the heat of vaporization at

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100 °C is 2256 J/g. These values can be used to calculate the energy required for a
given mass of water to melt or evaporate, respectively. For example, the energy required
to convert 500. g of water from the liquid to gaseous state at 100 °C is

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Figure 5.6 Contrast between a change of state and an increase in temperature as a result
of adding energy

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In contrast, to melt the same mass of ice to form liquid water at 0 °C requires only
167 kJ.

Figure 5.7 gives a profile of the energy changes occurring as 500. g of ice at
−50 °C is converted to water vapor at 200 °C. This involves a series of steps:
(1) warming ice to 0 °C, (2) conversion to liquid water at 0 °C, (3) warming
liquid water to 100 °C, (4) evaporation at 100 °C, and (5) warming the water
vapor to 200 °C. Each step requires the input of energy. The energy transferred as
heat to raise the temperature of solid, liquid, and vapor can be calculated with
Equation 5.1, using the specific heat capacities of ice, liquid water, and water
vapor (which are different), and the energies for the changes of state can be calculated
using heats of fusion and vaporization. These calculations are shown in
Example 5.3.

Figure 5.7 Energy transfer

as heat and the temperature
change as 500. g of water
warms from −50 °C to 200 °C
(at 1 atm).

EXAMPLE 5.3

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Energy and Changes of State
Problem Calculate the energy needed to convert 500. g of ice at −50.0 °C to steam at
200.0 °C (Figure 5.7). The heat of fusion of water is 333 J/g, and the heat of vaporization is
2256 J/g. The specific heat capacities of ice, liquid water, and water vapor are given in
Appendix D.
What Do You Know? The overall process of converting ice at −50 °C to steam at
200 °C involves both temperature changes and changes of state; all require input of energy
as heat. Recall that melting occurs at 0 °C and boiling at 100 °C (at 1 atm pressure).
You know the mass of the water and will need the specific heat capacities of ice, liquid
water, and steam from Appendix D. The heat of fusion of water (333 J/g), and the heat of
vaporization (2256 J/g) are given.
Strategy The problem is broken down into a series of steps:
Step 1: Warm the ice from −50 °C to 0 °C.
Step 2: Melt the ice at 0 °C.
Step 3: Raise the temperature of the liquid water from 0 °C to 100 °C.
Step 4: Evaporate the water at 100 °C.
Step 5: Raise the temperature of the steam from 100 °C to 200 °C.
Use Equation 5.1 and the specific heat capacities of solid, liquid, and gaseous water to
calculate the energy transferred as heat associated with the temperature changes. Use the
heats of fusion and of vaporization to calculate the energy transferred as heat associated
with changes of state. The total energy transferred as heat is the sum of the energies of the
individual steps.

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Check Your Understanding
Calculate the amount of energy necessary to raise the temperature of 1.00 L of ethanol
(d = 0.7849 g/cm3) from 25.0 °C to its boiling point (78.3 °C) and then to vaporize the liquid.
(Cethanol = 2.44 J/g ⋅ K; heat of vaporization at 78.3 °C = 38.56 kJ/mol.)

EXAMPLE 5.4
Change of State
Problem What is the minimum mass of ice at 0 °C that must be added to the contents
of a can of diet cola (340. mL) to cool the cola from 20.5 °C to 0.0 °C? Assume that the
specific heat capacity and density of diet cola are the same as for water.
What Do You Know? The final temperature is 0 °C. Melting ice requires energy as
heat, and cooling the cola evolves energy as heat. The sum of the energy changes for the
two components in the system is zero; that is, the two energy changes (melting ice, cooling
cola) will be the same magnitude but opposite in sign. (You also need to assume there
is no transfer of energy between the surroundings and the system.) You will need the
density and specific heat capacity of water (Appendix D).

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Strategy Assuming only energy changes within the system, qcola + qice = 0. The energy
evolved as the cola cools, qcola, is calculated using Equation 5.1. The initial temperature
is 20.5 °C and the final temperature is 0 °C. The mass of cola is calculated from the
volume and density. The energy as heat required to melt the ice, qice, is determined from
the heat of fusion (333 J/g). The mass of ice is the unknown.

Check Your Understanding

To make a glass of iced tea, you pour 250 mL of tea, whose temperature is 18.2 °C, into
a glass containing five ice cubes. Each cube has a mass of 15 g. What quantity of ice will
melt, and how much ice will remain floating in the tea? Assume iced tea has a density of
1.0 g/mL and a specific heat capacity of 4.2 J/g ⋅ K, that energy is transferred only as heat
within the system, ice is at 0.0 °C, and no energy is transferred between system and
surroundings.

5.4 The First Law of Thermodynamics

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Goals for Section 5.4
• Recognize how energy transferred as heat and work done on or by a system
contributes to changes in the internal energy of a system.
• Calculate the work done by a system by the expansion of a gas against a constant
pressure.
• Calculate changes in enthalpy and internal energy.
• Recognize state functions whose values are determined only by the state of the
system and not by the pathway by which the state was achieved.
Recall that thermodynamics is the science of heat and work . To this point, we have
only considered energy being transferred as heat, but now we need to broaden the discussion
to include work. Work done by a system or on a system will also affect the
energy in the system. If a system does work on its surroundings, energy must be
expended by the system, and the system’s energy will decrease. Conversely, if work
is done by the surroundings on a system, the energy of the system will increase.
A system doing work on its surroundings is illustrated in Figure 5.8. A small
quantity of dry ice, solid CO2, is sealed inside a plastic bag, and a weight (a book)
is placed on top of the bag. When energy is transferred as heat from the surroundings
to the dry ice, the dry ice changes directly from solid to gas at −78 °C in a
process called sublimation:

As sublimation proceeds, gaseous CO2 expands within the plastic bag, lifting the
book against the force of gravity. The system (the CO2 inside the bag) is expending
energy to do this work.
Even if the book had not been on top of the plastic bag, work would have
been done by the expanding gas because the gas must push back the atmosphere
when it expands. Instead of raising a book, the expanding gas moves a part of the
atmosphere.
Now let us think about this example in terms of thermodynamics. First, we
must identify the system and the surroundings. The system is the CO2, initially a
solid and later a gas. The surroundings consist of objects that exchange energy with

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Figure 5.8 Energy changes in a physical process (a phase change as solid CO2 changes to CO2 gas).

the system. This includes the plastic bag, the book, the table-top, and the surrounding
air. Sublimation requires energy, which is transferred as heat to the system (the
CO2) from the surroundings. At the same time, the system does work on the surroundings
by lifting the book. An energy balance for the system will include both quantities, energy transferred as heat and
energy transferred as work.
This example can be generalized. For any system, we can identify energy transfers
both as heat and as work between the system and surroundings. The change in
energy for a system is given explicitly by Equation 5.4,

[some times ΔE is used in place of ΔU]

which is a mathematical statement of the first law of thermodynamics: The energy

change for a system (ΔU) is the sum of the energy transferred as heat (q) between
the system and its surroundings and the energy transferred as work (w) between the
system and its surroundings.
The equation defining the first law of thermodynamics is just a restatement of
the general principle of conservation of energy. Because energy is conserved, we
must be able to account for any change in the energy of the system. All energy
transfers between a system and its surroundings occur by the processes of heat and

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work. Equation 5.4 thus states that the change in the energy of the system is exactly
equal to the sum of the energy transfers (heat and/or work) from or to the
surroundings.
The quantity U ( or E) in Equation 5.4 has a formal name—internal energy.

The internal energy in a chemical system is the sum of the potential

and kinetic energies inside the system, that is, the energies of the
atoms, molecules, or ions in the system.

The potential energy here is the energy associated with the attractive and repulsive
forces between all the nuclei and electrons in the system. It includes the energy associated
with bonds in molecules, forces between ions, and forces between molecules.
The kinetic energy is the energy of motion of the atoms, ions, and molecules
in the system. Actual values of internal energy are rarely determined or needed. Instead,
in most instances, we are interested in the change in internal energy, a measurable
quantity. In fact, Equation 5.4 tells us how to determine ΔU: Measure the energy
transferred as heat and work to or from the system.
The sign conventions for Equation 5.4 are important and are outlined in the
following table.

The work in the example involving the sublimation of CO2 (Figure 5.8) is of a
specific type, called P –V (pressure–volume) work. It is the work (w) associated with
a change in volume (ΔV) that occurs against a resisting external pressure (P). For a
system in which the external pressure is constant, the value of P –V work can be
calculated using Equation 5.5,

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To calculate this work in units of joules, the pressure is measured in pascals (1 Pa =
1 kg/m ⋅ s2) and the volume change is measured in cubic meters (m3).
In a constant-volume process, ΔV = 0. This means the energy transferred as
work will also be zero. Thus, the change in internal energy of the system under
constant-volume conditions is equal only to the energy transferred as heat (qv).

Enthalpy
Most experiments in a chemical laboratory are carried out in beakers or flasks open
to the atmosphere, where the external pressure is constant. Similarly, chemical processes
that occur in living systems are open to the atmosphere. Because so many
processes in chemistry and biology are carried out under conditions of constant
pressure, it is useful to have a specific measure of the energy transferred as heat under
this circumstance.

Under conditions of constant pressure,

where the subscript p indicates conditions of constant pressure. If the only type of
work that occurs is P –V work, then

Rearranging this gives

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We now introduce a new thermodynamic function called enthalpy, H, which is
defined as

The change in enthalpy for a system at constant pressure would be calculated from
the following equation:

Thus,

For a system where the only type of work possible is P –V work, the change in enthalpy,
ΔH, is equal to the energy transferred as heat at constant pressure, qp. The
directionality of energy transfer (under conditions of constant pressure) is indicated
by the sign of ΔH.
• Negative values of ΔH: energy is transferred as heat from the system to the surroundings
(exothermic process).
• Positive values of ΔH: energy is transferred as heat from the surroundings to the
system (endothermic process).
Under conditions of constant pressure and where the only type of work possible
is P –V work, ΔU (= qp − PΔV) and ΔH (= qp) differ by PΔV (the energy transferred
to or from the system as work). We observe that in many processes—such as the
melting of ice—the volume change, ΔV, is small, and hence the amount of energy
transferred as work is small. Under these circumstances, ΔU and ΔH have almost the
same value. The amount of energy transferred as work will be significant, however,
when the volume change is large, as when gases are formed or consumed. Thus, ΔU
and ΔH have significantly different values for processes such as the evaporation or
condensation of water, the sublimation of CO2, and chemical reactions in which the
number of moles of gas changes.

Example 5.5
Energy and Work
Problem Nitrogen gas (1.50 L) is confined in a cylinder under constant atmospheric
pressure (1.01 × 105 pascals). The gas expands to a volume of 2.18 L when 882 J of energy
is transferred as heat from the surroundings to the gas. What is the change in internal
energy of the gas?
What Do You Know? Energy as heat (882 J) is transferred at constant pressure
into the system; thus, qp = +882 J. The system does work on the surroundings when the
gas expands from 1.50 L to 2.18 L under a constant pressure of 1.01 × 105 pascals, thereby
transferring some energy back to the surroundings.

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Strategy Calculate the work done by the system using wp = −P(ΔV). The unit of work
is joules, provided that SI units are used for pressure and volume. The pressure is given in
SI units (pascals, Pa, where 1 Pa = 1 kg/(m.s ). To calculate work, the volume must be
2

converted to m3 (1 m3 = 1000 L). The change in internal energy of the gas is the sum of the
enthalpy change of the gas and the work done by the gas on the surroundings

(ΔU =qp + wp).

State Functions
Internal energy and enthalpy share a significant characteristic—namely, changes in
these quantities depend only on the initial and final states. They do not depend on
the path taken on going from the initial state to the final state. No matter how you
go from reactants to products in a reaction the values of ΔH and ΔU are always the
same. A quantity that has this property is called a state function.
Many commonly measured quantities, such as the pressure of a gas, the volume
of a gas or liquid, and the temperature of a substance are state functions. For example,
if the final temperature of a substance is 75 °C and its initial temperature
was 25 °C, the change in temperature, ΔT, is calculated as Tfinal − Tinitial = 75 °C
− 25 °C = 50 °C. It does not matter if the substance was heated directly from 25 °C
to 75 °C or if the substance was heated from 25 °C to 95 °C and then cooled to

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75 °C; the overall change in temperature is still the same, 50 °C.
Not all quantities are state functions; some depend on the pathway taken to get
from the initial condition to the final condition. For instance, distance traveled is
not a state function (Figure 5.9). The travel distance from New York City to Denver
depends on the route taken. Nor is the elapsed time of travel between these two
locations a state function. In contrast, a change in altitude is a state function; in going
from New York City (at sea level) to Denver (1600 m above sea level), there is
an altitude change of 1600 m, regardless of the route followed.
Significantly, in the expansion of a gas, neither the energy transferred as heat nor
the energy transferred as work individually is a state function. However, their sum,
the change in internal energy, ΔU, is. The value of ΔU is fixed by Uinitial and Ufinal. A
transition between the initial and final states can be accomplished by different
routes having different values of q and w, but the sum of q and w for each path must
always give the same ΔU.

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5.5 Enthalpy Changes for Chemical Reactions
Goal for Section 5.5
• Understand and use the enthalpy change for the conversion of reactants to
products in their standard states, ΔrH°.
Enthalpy changes accompany chemical reactions. For example, the standard reaction
enthalpy, ΔrH °, for the decomposition of water vapor to hydrogen and oxygen
at 25 °C is +241.8 kJ/mol-rxn.

H2O(g) → H2(g) + 1⁄2 O2(g) ΔrH° = +241.8 kJ/mol-rxn

The positive sign of ΔrH° indicates that the decomposition is an endothermic process.
There are several important things to know about ΔrH°.
• The designation of ΔrH° as a “standard enthalpy change” (where the superscript °

26
indicates standard conditions) means that the pure, unmixed reactants in their
standard states have formed pure, unmixed products in their standard states. The
standard state of an element or a compound is defined as the most stable form of
the substance in the physical state that exists at a pressure of 1 bar and at a specified
temperature. [Most sources report standard reaction enthalpies at 25 °C (298 K).]
• The “per mol-rxn” designation in the units for ΔrH° means this is the enthalpy
change for a “mole of reaction” (where rxn is an abbreviation for reaction). One
mole of reaction is said to have occurred when a chemical reaction occurs exactly
in the amounts specified by the coefficients of the balanced chemical equation.
For example, for the reaction H2O(g) → H2(g) + 1/2 O2(g), a mole of
reaction has occurred when 1 mol of water vapor has been converted completely
to 1 mol of H2 and 1/2 mol of O2 gas.
Now consider the opposite reaction, the combination of hydrogen and oxygen
to form 1 mol of water. The magnitude of the enthalpy change for this reaction is
the same as that for the decomposition reaction, but the sign of ΔrH° is reversed.
The exothermic formation of 1 mol of water vapor from 1 mol of H2 and 1/2 mol
of O2 transfers 241.8 kJ to the surroundings (Figure 5.10).

The value of ΔrH° depends on the chemical equation used. Let us write the
equation for the formation of water again but without a fractional coefficient for O 2.

The value of ΔrH° for 1 mol of this reaction, the formation of 2 mol of water, is twice
the value for the formation of 1 mol of water.
It is important to identify the states of reactants and products in a reaction because
the magnitude of ΔrH° depends on whether they are solids, liquids, or gases. For the
formation of 1 mol of liquid water from the elements, the enthalpy change is −285.8 kJ.

Notice that this value is not the same as ΔrH° for the formation of 1 mol of water vapor
from hydrogen and oxygen. The difference between the two values is equal to the enthalpy
change for the condensation of 1 mol of water vapor to 1 mol of liquid water.
These examples illustrate several general features of enthalpy changes for chemical
reactions.
• Enthalpy changes are specific to the reaction being carried out. The identities of
reactants and products and their states (s, ℓ, g) are important, as are the
amounts of reactants and products.
• The enthalpy change depends on the number of moles of reaction, that is, the
number of times the reaction as written is carried out.

27
• ΔrH° has a negative value for an exothermic reaction; it has a positive value for
an endothermic reaction.
• Values of ΔrH° are numerically the same, but opposite in sign, for chemical reactions
that are the reverse of each other.
Standard reaction enthalpies can be used to calculate the energy transferred as
heat under conditions of constant pressure for any given mass of a reactant or product.
Suppose you want to know the energy transferred to the surroundings as heat if
454 g of propane, C3H8, is burned (at constant pressure), given the equation for the
exothermic combustion and the enthalpy change for the reaction.

Two steps are needed. First, find the amount of propane present in the sample:

Second, use ΔrH° to determine ΔH° for this amount of propane:

28
EXAMPLE 5.6
Calculating the Enthalpy Change for a Reaction
Problem Sucrose (table sugar, C12H22O11) can be oxidized to CO2 and H2O, and the
enthalpy change for the reaction can be measured.

What is the enthalpy change when 5.00 g of sugar is burned under conditions of constant
pressure?

What Do You Know? The balanced equation for the combustion and the value of
ΔrH° are given. Also, the mass of sugar is given.
Strategy First determine the amount (mol) of sucrose in 5.00 g, and then use this with
the value given for the enthalpy change for the oxidation of 1 mol of sucrose.

29
5.6 Calorimetry
Goal for Section 5.6
• Describe how to measure and calculate the quantity of energy transferred as heat
in a reaction by calorimetry.

The energy evolved or absorbed as heat in a chemical or physical process can be measured
by calorimetry. The apparatus used in this kind of experiment is a calorimeter.

Constant-Pressure Calorimetry, Measuring 𝚫H

A constant-pressure calorimeter can be used to measure the amount of energy transferred

as heat under constant-pressure conditions, that is, the enthalpy change for a
chemical reaction.
The constant-pressure calorimeter used in general chemistry laboratories is often
a “coffee-cup calorimeter.” This inexpensive device consists of two nested Styrofoam
coffee cups with a loose-fitting lid and a thermometer (Figure 5.11) or
thermocouple. Styrofoam, a fairly good insulator, minimizes energy transfer as heat
between the system and the surroundings. The reaction is carried out in solution in
the cup. If the reaction is exothermic, it releases energy as heat to the solution, and
the temperature of the solution rises. If the reaction is endothermic, energy is absorbed
as heat from the solution, and a decrease in the temperature of the solution
will be seen. The change in temperature of the solution is measured. Knowing the
mass and specific heat capacity of the solution and the temperature change, the
enthalpy change for the reaction can be calculated.
In this type of calorimetry experiment, it is convenient to define the chemicals
and the solution as the system. The surroundings are the cup and everything beyond
the cup. As noted above, we assume there is no energy transfer to the cup or beyond
and that energy is transferred only as heat within the system. Two energy changes
occur within the system. One is the change that takes place as the chemical reaction
occurs, either releasing the potential energy stored in the reactants or absorbing energy and converting it to potential
energy stored in the products. We label this energy as qr. The other energy change is the energy gained or lost as
heat by the solution
(qsolution). Based on the law of conservation of energy,

30
Figure 5.11 A coffee-cup calorimeter. A chemical reaction produces a change in temperature
of the solution in the calorimeter. The Styrofoam container is fairly effective in preventing the
transfer of energy as heat between the solution and its surroundings. Because the cup is open to
the atmosphere, this is a constant pressure measurement.

The value of qsolution can be calculated from the specific heat capacity, mass, and
change in temperature of the solution. The quantity of energy evolved or absorbed
as heat for the reaction (qr) is the unknown in the equation.
The accuracy of a calorimetry experiment depends on the accuracy of the measured
quantities (temperature, mass, specific heat capacity). In addition, it depends
on how closely the assumption is followed that there is no energy transfer beyond
the solution. A coffee-cup calorimeter is a simple apparatus, and the results obtained
with it are not highly accurate, largely because this assumption is poorly met. In research
laboratories, calorimeters are used that more effectively limit the energy transfer
between system and surroundings. In addition, it is also possible to correct for the
minimal energy transfer that does occur between the system and the surroundings.

EXAMPLE 5.7
Using a Coffee-Cup Calorimeter
Problem You place 0.0500 g of magnesium chips in a coffee-cup calorimeter and then
add 100.0 mL of 1.00 M HCl. The reaction that occurs is

Mg(s) + 2HCl(aq) → H2(g) + MgCl2(aq)

The temperature of the solution increases from 22.21 °C (295.36 K) to 24.46 °C (297.61 K).
What is the enthalpy change for the reaction per mole of Mg? Assume that the specific

31
heat capacity of the solution is 4.20 J/g.K, the density of the HCl solution is 1.00 g/mL, and
that no energy as heat is lost to the surroundings.
What Do You Know? You know that energy is evolved as heat in this reaction
because the temperature of the solution rises. The sum of the energy evolved as heat in the
reaction, qr, and the energy absorbed as heat by the solution, qsolution, will be zero, that is,
qr + qsolution = 0.
The value of qsolution can be calculated from data given; qr is the unknown.
Strategy Solving the problem has four steps.
Step 1: Calculate the amount of magnesium.
Step 2: Calculate qsolution from the values of the mass, specific heat capacity, and ΔT using
Equation 5.1.
Step 3: Calculate qr , assuming no energy transfer as heat occurs beyond the solution, that
is,

qr + qsolution = 0.

Step 4: Use the value of qr and the amount of Mg to calculate the enthalpy change per mole
of Mg.

32
33
34
Constant-Volume Calorimetry, Measuring 𝚫E

Constant-volume calorimetry is often used to evaluate the energy released by the

combustion of fuels and the caloric value of foods. A weighed sample of a combustible
solid or liquid is placed inside a “bomb,” often a cylinder about the size of a
large fruit juice can with thick steel walls and ends (Figure 5.12). The bomb is
placed in a water-filled container with well-insulated walls. After filling the bomb
with pure oxygen, the sample is ignited, usually by an electric spark. The heat generated by the
combustion reaction warms the system. The bomb, its contents,
and the water are defined as the system. Assessment of energy transfers as heat
within the system shows that

qr + qbomb + qwater = 0

where qr is the energy released as heat by the reaction, qbomb is the energy involved
in heating the calorimeter bomb, and qwater is the energy involved in heating the
water in the calorimeter. Because the volume does not change in a constant-volume
calorimeter, energy transfer as work does not occur. Therefore, the energy transferred
as heat at constant volume (qv) is equal to the change in internal energy, ΔU.

Calorimetry, 𝚫U, and 𝚫H. The two types of calorimetry (constant volume and constant
pressure) highlight the differences between enthalpy and internal energy. The energy transferred
as heat at constant pressure, qp, is, by definition, ΔH, whereas the energy transferred as heat at
constant volume, qv , is ΔU.

35
Figure 5.12 Constant-volume calorimeter. A combustible sample is burned in pure oxygen
in a sealed metal container or “bomb,” that is inside a water-filled container. Energy transferred as heat from the
reaction warms the bomb and the water surrounding it. By measuring the increase in temperature, the energy
transferred as heat in the reaction can be determined.

EXAMPLE 5.8
Constant-Volume Calorimetry
Problem Octane, C8H18, a primary constituent of gasoline, burns in air:

C8H18(ℓ) + 25/2 O2(g) → 8 CO2(g) + 9 H2O(ℓ)

A 1.00-g sample of octane is burned in a constant-volume calorimeter similar to that

shown in Figure 5.12. The calorimeter is in an insulated container with 1.20 kg of water. The
temperature of the water and the bomb rises from 25.00 °C (298.15 K) to 33.20 °C
(306.35 K). The heat required to raise the bomb’s temperature (its heat capacity), Cbomb , is
837 J/K. (a) What is the heat of combustion per gram of octane? (b) What is the heat of

36
combustion per mole of octane?

What Do You Know? There are energy changes for the three components of this
system: the energy evolved in the reaction, qr; the energy absorbed by the water, qwater;
and the energy absorbed by the calorimeter, qbomb. You know the following: the molar
mass of octane, masses of the sample and the calorimeter water, Tinitial, Tfinal, Cbomb, and
Cwater . You can assume no energy loss to the surroundings.

Strategy
• The sum of all the energies transferred as heat in the system = qr + qbomb + qwater = 0.
The first term, qr, is the unknown. The second and third terms in the equation can be
calculated from the data given: qbomb is calculated from the bomb’s heat capacity and
ΔT, and qwater is determined from the specific heat capacity, mass, and ΔT for water.
• The value of qr is the energy evolved in the combustion of 1.00 g of octane. Use this
and the molar mass of octane (114.2 g/mol) to calculate the energy evolved as heat
per mole of octane.

37
38
5.7 Enthalpy Calculations
Goals for Section 5.7
• Apply Hess’s law to find the enthalpy change, Δr H°, for a reaction.
• Know how to draw and interpret energy level diagrams.
• Use standard molar enthalpies of formation, Δf H°, to calculate the enthalpy
change for a reaction, Δr H°.
Enthalpy changes for an enormous number of chemical and physical processes are
available on the World Wide Web and in reference books. This section outlines how
to use these data.

Hess’s Law

39
The enthalpy change for a reaction can be measured by calorimetry for many, but
not all, chemical processes. Consider, for example, the oxidation of carbon to form
carbon monoxide.

C(s) + 1/2 O2(g) → CO(g)

The primary product of the reaction is CO2 and not CO, even if a deficiency of oxygen
is used. As soon as CO is formed, it will react with O2 to form CO2. It is not
possible to measure the change in enthalpy for this reaction by calorimetry because
the reaction cannot be carried out in a way that allows CO to be the sole product.
The enthalpy change for the reaction forming CO(g) from C(s) and O2(g) can
be determined indirectly, however, from enthalpy changes for other reactions for
which values of ΔrH° can be measured. The calculation is based on Hess’s law,
which states that if a reaction is the sum of two or more other reactions, ΔrH° for the
overall process is the sum of the ΔrH° values of those reactions.
The oxidation of C(s) to CO(g) can be determined indirectly from thermochemical
data obtained from two reactions that can be studied by calorimetry. These
reactions are the oxidation of CO(g) and the oxidation of C(s), both of which form
CO2(g) as the sole product.

The equations above can be manipulated so that when added together they yield the
desired net equation. To have CO(g) appear as a product in the net equation, Equation
1 is reversed. The sign of the standard enthalpy change is also reversed (Section
5.5). Equation 2 contains C(s) on the correct side of the equation and in the
correct stoichiometric amount; it is left unchanged. Adding these two equations
gives the equation for the oxidation of C(s) to CO(g).

Hess’s law tells us that the enthalpy change for the overall reaction (ΔrH°3) will
equal the sum of the enthalpy changes for reactions 1′ and 2.

40
Hess’s law also applies to physical processes. The enthalpy change for the reaction
of H2(g) and O2(g) to form 1 mol of H2O vapor is different from the enthalpy
change to form 1 mol of liquid H2O. The difference is the negative of the enthalpy of
vaporization of water, ΔrH°2 (= −ΔvapH°) as shown in the following analysis

Energy Level Diagrams

When using Hess’s law, it is often helpful to represent enthalpy data schematically
in an energy level diagram. In such drawings, the various substances being studied—
the reactants and products in a chemical reaction, for example—are placed on an
arbitrary energy scale. The relative enthalpy of each substance is given by its position
on the vertical axis, and numerical differences in enthalpy between them are shown
by vertical arrows. Such diagrams can give us a visual perspective on the magnitude
and direction of enthalpy changes and show how the enthalpies of the substances
are related.
Energy level diagrams that summarize the two examples of Hess’s law discussed
earlier are shown in Figure 5.13. In Figure 5.13a, the elements C(s) and O2(g) are at
the highest enthalpy. The reaction of carbon and oxygen to form CO2(g) lowers the
enthalpy by 393.5 kJ. This can occur either in a single step, shown on the left in
Figure 5.13a, or in two steps via initial formation of CO(g), as shown on the right.
Similarly, in Figure 5.13b, the mixture of H2(g) and O2(g) is at the highest enthalpy.
Both liquid and gaseous water have lower enthalpies, with the difference between
the two being the enthalpy of vaporization.

41
Figure 5.13. Energy level diagrams.
(a) Relating enthalpy changes in the formation of CO2(g).
(b) Relating enthalpy changes in the formation of H2O(ℓ). Enthalpy changes associated with
changes between energy levels are given alongside the vertical arrows.

The enthalpy change for a reaction is a state function; that is, the enthalpy change
from reactants to products does not depend on the path taken. Energy diagrams illustrate
this point. Chemists often want to know the enthalpy change for one step
of a reaction. If we know the overall enthalpy change, and the enthalpy changes for
all the steps but one, then the unknown change can be calculated.

EXAMPLE 5.9
Using Hess’s Law
Problem Suppose you want to know the enthalpy change for the formation of methane,
CH4, from solid carbon (as graphite) and hydrogen gas:

42
The enthalpy change for this reaction cannot be measured in the laboratory because the
reaction is very slow. We can, however, measure enthalpy changes for the combustion of
carbon, hydrogen, and methane.

Use this information to calculate ΔrH° for the formation of methane from its elements.

What Do You Know? This is a Hess’s law problem. You need to adjust the three
equations so they can be added together to give the desired equation,

C(s) + 2 H2(g) → CH4(g).

When an adjustment in an equation is made, you also need to adjust the enthalpy
change.

Strategy The three reactions (1, 2, and 3), as written, cannot be added together to
obtain the equation for the formation of CH4 from its elements. Methane, CH4, is a product
in the reaction for which we wish to calculate ΔrH°, but it is a reactant in Equation 3. Water
appears in two of these equations although it is not a component of the reaction forming
CH4 from carbon and hydrogen. To use Hess’s law to solve this problem, you first have to
manipulate the equations and adjust ΔrH° values accordingly before adding equations.
Recall, from Section 5.5, that writing an equation in the reverse direction reverses the sign
of ΔrH° and that doubling the amount of reactants and products doubles the value of ΔrH°.
Adjustments to Equations 2 and 3 will produce new equations that, along with Equation 1,
can be combined to give the desired net reaction.

43
44
45
Standard Enthalpies of Formation
Calorimetry and the application of Hess’s law have made available a great many
ΔrH° values for chemical reactions. The table in Appendix L, for example, lists standard
molar enthalpies of formation, 𝚫fH°. The standard molar enthalpy of formation is
the enthalpy change for the formation of 1 mol of a compound directly from its component
elements in their standard states.

Several examples of standard molar enthalpies of formation will be helpful to

illustrate this definition.

ΔfH° for NaCl(s): At 25 °C and a pressure of 1 bar, Na is a solid, and Cl2 is a

gas. The standard enthalpy of formation of NaCl(s) is defined as the enthalpy
change that occurs when 1 mol of NaCl(s) is formed from 1 mol of Na(s) and
1⁄2 mol of Cl2(g):

Notice that a fraction is required as the coefficient for the chlorine gas in this equation
because the definition of Δf H° specifies the formation of one mole of NaCl(s).

Δf H° for NaCl(aq): The standard enthalpy of formation for an aqueous solution

of a compound refers to the enthalpy change for the formation of a 1 mol/L solution
of the compound starting with the elements. It is thus the enthalpy of formation of
NaCl(s) plus the enthalpy change that occurs when the substance dissolves in water.

Δf H° for C2H5OH(ℓ): At 25 °C and 1 bar, the standard states of the elements

are C(s, graphite), H2(g), and O2(g). The standard enthalpy of formation of
C2H5OH(ℓ) is defined as the enthalpy change that occurs when 1 mol of C2H5OH(ℓ)
is formed from 2 mol of C(s), 3 mol of H2(g), and 1/2 mol of O2(g).

Notice that the reaction defining the enthalpy of formation for liquid ethanol
is not a reaction a chemist can carry out in the laboratory. This illustrates an important

46
point: The enthalpy of formation of a compound does not necessarily
correspond to a reaction that can be carried out.
Appendix L lists values of Δf H° for some common substances, and a review of
these values leads to some important observations.

• The standard enthalpy of formation for an element in its standard state is zero.

• Most Δf H° values are negative, indicating that formation of most compounds

from the elements is exothermic. Very few values are positive, and these represent
compounds that are unstable with respect to decomposition to the elements.
(One example is NO(g) with Δf H° = +90.29 kJ/mol.)

• Values of Δf H° can often be used to compare the stabilities of related compounds.

Consider the values of Δf H° for the hydrogen halides. Hydrogen fluoride, HF,
is the most stable of these compounds with respect to decomposition to the
elements, whereas HI is the least stable (as indicated by Δf H° of HF being the
most negative value and that of HI being the most positive).

Enthalpy Change for a Reaction

Using standard molar enthalpies of formation and Equation 5.6, it is possible to
calculate the enthalpy change for a reaction under standard conditions

In this equation, the symbol Σ (the Greek capital letter sigma) means “take the
sum.” To find ΔrH°, add up the molar enthalpies of formation of the products, each
multiplied by its stoichiometric coefficient n, and subtract from this the sum of the
molar enthalpies of formation of the reactants, each multiplied by its stoichiometric

47
coefficient. This equation is a logical consequence of the definition of Δf H° and
Hess’s law (see A Closer Look: Hess’s Law and Equation 5.6, page 256 or below).

Suppose you want to know how much energy is required to decompose 1 mol
of calcium carbonate (limestone) to calcium oxide (lime) and carbon dioxide under
standard conditions:

You would use the following enthalpies of formation (from Appendix L):

and then use Equation 5.6 to find the standard enthalpy change for the reaction, ΔrH°.

The decomposition of limestone to lime and CO2 is endothermic. That is, energy
(179.0 kJ) must be supplied to decompose 1 mol of CaCO3(s) to CaO(s) and CO2(g).

48
EXAMPLE 5.10
Using Enthalpies of Formation
Problem Nitroglycerin, C3H5(NO3)3 , is a powerful explosive that forms four different
gases when detonated:

Calculate the enthalpy change that occurs when 10.0 g of nitroglycerin is detonated. The
standard enthalpy of formation of nitroglycerin, Δf H°, is −364 kJ/mol. Use Appendix L to
find other ΔfH° values that are needed.

What Do You Know? From Appendix L,

49
ΔfH°[CO2(g)] = −393.5 kJ/mol,
ΔfH°[H2O(g)] = −241.8 kJ/mol, and
ΔfH° = 0 for N2(g) and O2(g).

The mass and ΔfH° for nitroglycerin are also given.

Strategy Substitute the enthalpy of formation values for products and reactants into
Equation 5.6 to determine the enthalpy change for 1 mol of reaction. This represents the
enthalpy change for detonation of 2 mol of nitroglycerin. Determine the amount (mol)
represented by 10.0 g of nitroglycerin, then use this value with ΔrH° and the relationship
between moles of nitroglycerin and moles of reaction to obtain the answer.

The problem asks for the enthalpy change using 10.0 g of nitroglycerin. You next need to
determine the amount of nitroglycerin in 10.0 g.

The enthalpy change for the detonation of 0.04403 mol of nitroglycerin is

50
5.8 Product- or Reactant-Favored Reactions and Thermodynamics
An extensive study of thermodynamics will ultimately provide answers to four questions.

• How do we measure and calculate the energy changes associated with physical
changes and chemical reactions?

• What is the relationship between energy changes, heat, and work?

• How can we determine whether a chemical reaction is product-favored or

reactant-favored at equilibrium?

• How can we determine whether a chemical reaction or physical process will occur
spontaneously, that is, without outside intervention?

The first two questions were addressed in this chapter, but the other two questions
still remain. They will be considered in detail in Chapter 18.

We can, however, set the stage for consideration of these issues. In Chapter 3,
we learned that chemical reactions proceed toward equilibrium, and spontaneous
changes occur in a way that allows a system to approach equilibrium. Reactions in
which reactants are largely converted to products when equilibrium is reached are
said to be product-favored at equilibrium. Reactions in which only small amounts of
products are present at equilibrium are called reactant-favored at equilibrium
(pages 128–130).

Look back at the many chemical reactions that we have seen. For example, all

51
combustion reactions are exothermic, and the oxidation of iron (Figure 5.14) is
clearly exothermic.

The reaction has a negative value for ΔrH°, and it is also product-
favored at equilibrium.

Conversely, the decomposition of calcium carbonate is endothermic.

The decomposition of CaCO3 proceeds to an equilibrium that favors the

reactants; that is, it is reactant-favored at equilibrium.

Are all exothermic reactions product-favored at equilibrium and all endothermic

reactions reactant-favored at equilibrium?

From these examples, we might formulate that idea as a hypothesis that can be tested by
experiment and by examination of other examples. You would find that in most cases,

 product-favored reactions have negative values of ΔrH°

 reactant-favored reactions have positive values of ΔrH°.

But this is not always true; there are exceptions. Clearly, a further discussion of thermodynamics
must be tied to the concept of equilibrium. This relationship, and the complete discussion of the
third and fourth questions, will be presented in Chapter 18.

Applyi ng Chemical Principles

52
5.1 Gunpowder
Gunpowder has been used in fireworks, explosives, and firearms for over one thousand years.
Until the late 1800s, gunpowder was a mixture of saltpeter (KNO3), charcoal (largely C),
and sulfur. Today, this mixture is known as black powder. A simplified version of the reaction
occurring when it explodes is the following:

Although black powder was used for hundreds of years, it has some disadvantages as a
propellant: it produces a large quantity of white smoke, and the residues from the reaction are
corrosive.

Modern firearms use smokeless powders. These powders are primarily composed of
nitrocellulose (also known as guncotton) or a mixture of nitrocellulose and nitroglycerin.
Nitrocellulose is the product of the reaction of cotton (cellulose, with an empirical formula of
C6H10O5) with nitric acid. The fully nitrated product has the empirical formula C 6H7(NO3)3O2.
Decomposition of nitrocellulose and nitroglycerin releases more energy than the comparable
mass of black powder. Just as important, this is a better propellant because all of the products are
gaseous.

Black gunpowder. Black gunpowder has been known for over 1000 years. This photo shows one
of the disadvantages of black powder: the great amount of smoke produced.

53
Questions:
1. The standard enthalpies of formation of KNO3(s) and K2S(s) are −494.6 kJ/mol and −376.6
kJ/mol, respectively.
a) Determine the standard enthalpy change for the reaction of black powder according to the
balanced equation on the previous page.

b) Determine the enthalpy change that occurs when 1.00 g of black powder decomposes
according to the stoichiometry of the balanced equation above. (Even though black
powder is a mixture, assume that we can designate 1 mol of black powder as consisting
of exactly 2 mol of KNO3, 3 mol of C, and 1 mol of S.)

2. The enthalpy of reaction of guncotton depends on the degree of nitration of the cellulose. For a
particular sample, when 0.725 g of guncotton is decomposed in a bomb calorimeter, the
temperature of the system increases by 1.32 K. Assuming the bomb has a heat capacity of 691
J/K and the calorimeter contains 1.200 kg of water, what is the energy of
reaction per gram of guncotton?

3. The decomposition of nitroglycerin (C3H5N3O9) produces carbon dioxide, nitrogen, water, and
oxygen gases.
a. Write a balanced chemical equation for the decomposition
of nitroglycerin.
b. If the decomposition of 1.00 g nitroglycerin releases 6.23 kJ/g of energy in the form of heat,
what is the standard molar enthalpy of formation of nitroglycerin?

Reference:
J. Kelly, Gunpowder, Alchemy, Bombards, and Pyrotechnics:
The History of the Explosive That Changed the World, Basic
Books, New York, 2004.

5.2 The Fuel Controversy—Alcohol and Gasoline

54
It is clear that supplies of fossil fuels are declining and their prices are increasing, just as the
nations of the Earth have ever greater energy needs. One way to alleviate impending shortages,
and move away from a reliance of fossil fuels, is to use renewable fuels from biological sources.
Therefore, there has been a movement to replace some fraction of the gasoline sold with ethanol
(C2H5OH). In 2007, the U.S. Congress passed an energy bill stating that ethanol production
should be 20.5 billion gallons a year by 2015, up from about 4.7 billion gallons in 2007. The
actual ethanol production in 2016 was about 14.9 billion gallons. Most ethanol-containing fuels
currently used in the United States are a mixture of 10% ethanol and 90% gasoline (E10).
A small fraction of fuel is sold as E85—a blend of gasoline with 51–85% ethanol. However, this
can only be used in vehicles with engines designed for fuels with a high ethanol content
(so-called “flexible fuel” engines). In 2016 there were about 2700 E85 stations in the U.S., and
over 17 million vehicles were equipped to use it.

Is a goal of replacing gasoline completely with ethanol reasonable? This is a lofty goal, given
that present gasoline consumption in the U.S. is about 140 billion gallons annually. Heretofore,
ethanol was obtained from the fermentation of corn. The problem is that even if all of the corn
grown in the U.S. is converted to ethanol, the supply will still be inadequate. It is clear that there
must be more emphasis on ways to derive ethanol from other sources, such as cellulose from
cornstalks and various grasses.

Beyond this, there are other problems associated with ethanol. One is that it cannot be distributed
through a pipeline system as gasoline can. Any water in the pipeline is miscible with ethanol,
which causes the fuel value to decline.

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Ethanol available at a service station. E85 fuel is a blend of gasoline with 51–85% ethanol. Be
aware that you can only use E85 in vehicles designed for the fuel. In an ordinary vehicle,
the ethanol leads to deterioration of seals in the engine and fuel system.

Chapter Goals Revisited

The goals for this chapter are keyed to specific Study Questions to
help you organize your review.

5.1 E nergy: Some Basic Principles

• Recognize and use the language of thermodynamics: the system and its
surroundings; exothermic and endothermic reactions. 1, 3, 4, 67.
• Describe the nature of energy transfers as heat. 2.
• Understand the sign conventions of thermodynamics. 3, 4.

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5.2 Specific Heat Capacity: Heating and Cooling
• Use specific heat capacity in calculations of energy transfers as heat
involving temperature changes. 7–16, 75, 93, 94.

5.3 E nergy and Changes of State

• Use enthalpy (heat) of fusion and enthalpy (heat) of vaporization to
calculate the energy transferred as heat in changes of state. 17–24, 76–80.

5.4 The First Law of Thermodynamics

• Recognize how energy transferred as heat and work done on or by a
system contributes to changes in the internal energy of a system. 70.
• Calculate the work done by a system by the expansion of a gas against a
constant pressure. 25–28, 119.
• Calculate changes in enthalpy and internal energy. 29–32, 120.
• Recognize state functions whose values are determined only by the state
of the system and not by the pathway by which the state was achieved.
102.

5.5 E nthalpy Changes for Chemical Reactions

• Understand and use the enthalpy change for the conversion of reactants
to products in their standard states at constant pressure, ΔrH°. 33–36.

5.6 Calorimetry
• Describe how to measure and calculate the quantity of energy transferred
as heat in a reaction by calorimetry. 37–48, 97, 98.

5.7 Enthalpy Calculations

• Apply Hess’s law to find the enthalpy change, ΔrH°, for a reaction. 49–52,
81, 87, 116.
• Know how to draw and interpret energy level diagrams. 61, 62, 81, 82, 87,
111, 115.
• Use standard molar enthalpies of formation, ΔfH°, to calculate the
enthalpy change for a reaction, Δr H°. 55–59, 62, 83–86.

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Equation 5.1 (page 232)
The energy transferred as heat when the temperature of
a substance changes. Calculated from the specific heat capacity (C), mass (m), and
change in temperature (ΔT).

Equation 5.2 (page 232)

Temperature changes are always calculated as final temperature
minus initial temperature.

Equation 5.3 (page 235)

If no energy is transferred between a system and its surroundings
and if energy is transferred within the system only as heat, the sum of the
thermal energy changes within the system equals zero.

Equation 5.4 (page 241)

The first law of thermodynamics: The change in internal
energy (ΔU) in a system is the sum of the energy transferred as heat (q) and the
energy transferred as work (w).

Equation 5.5 (page 242)

P –V work (w) at constant pressure is the product of pressure
(P) and change in volume (ΔV)

Equation 5.6 (page 255)

This equation is used to calculate the standard enthalpy change of a reaction (ΔrH °) when the
enthalpies of formation (Δf H°) of all of the reactants and products are known. The parameter n
is the stoichiometric coefficient of each product or reactant in the balanced chemical equation.

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