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Principles of Reactivity
Energy and Chemical Reactions

Some chemical reactions begin as soon as the reactants come into contact and
continue until at least one reactant (the limiting reactant) is completely consumed.
If a candy Bear, which is mostly sugar, is dropped into hot, molten potassium
chlorate, the sugar reacts very vigorously with the potassium chlorate
C6H12O6(s) + 4KClO3(ℓ) → 6CO2(g) + 6H2O(g) + 4KCl(s)
Reducing agent Oxidizing agent

or, if aluminum and bromine are combined, they react rapidly with evolution of a
great deal of energy to give aluminum bromide.
Other reactions happen much more slowly, but reactants are still converted almost
completely to products. An example is the rusting of iron at room temperature.

Two questions about chemical reactions are important to chemists:

will a reaction occur? and, if it does, how fast will it go?

In this chapter we wish to investigate some aspects of the first question:

how can we predict? when a reaction will occur.
We begin by categorizing reactions as product- or reactant- favored systems.
If a system is product-favored, most of the reactants are eventually converted to
products without outside intervention, although ‘‘eventually’’ may last a very long
time. Product-favored reactions are also those that usually, but not always, evolve
energy. You already know something about product-favored reactions for example :
● Reactions that lead to a precipitate.
● Reactions in which an acid and a base combine to form water.
● Reactions that produce a gas, such as the decomposition of a metal carbonate in
acid
● Oxidation-reduction reactions, such as the combination of metals with oxygen or
halogens to give metal oxides and halides.
Some other reactions have virtually no tendency to occur by themselves.
We label these reactions as reactant-favored systems.

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For example, the splitting of NaCl into its elements
Reactant-favored reaction : 2NaCl(s) → 2Na(s) + Cl2(g)

is exactly the opposite of the product-favored reaction of sodium and chlorine

Product- favored reaction : 2Na(s) + Cl2(g) → 2NaCl(s)

The splitting of NaCl is therefore reactant-favored. Evidence of this is that deposits

of salt, NaCl, have existed on earth for millions of years without forming the
elements Na and Cl2.

What do we mean by outside intervention? Usually it is some flow of energy.

For example, at very high temperatures, small but significant quantities of NO can
be formed from air.
N2(g) + O2(g) → 2NO(g)

Such high-temperature conditions are found in power plants and automobile engines,
and a large number of such sources can produce enough NO and other nitrogen
oxides to cause significant air pollution problems.

Salt can be decomposed to its elements by providing heat to melt it and electric
energy to separate the ions and form the elements.
2NaCl(ℓ) → 2Na(ℓ) + Cl2(g)
In each case energy can cause a reactant-favored system to produce products.

Energy is a central idea when describing a reaction as product- or reactant- favored.

For this reason it is useful to know something about energy and its interactions with
matter.
The most common of these interactions is the transfer of energy as heat or thermal
energy when chemical reactions occur.
Transfer of heat is a major topic of thermodynamics, the science of heat and work
the subject of this chapter.
ENERGY : ITS FORMS AND UNITS

Just what is energy, and where does the energy we use come from?
Energy is defined as the capacity to do work, and work is something you
experience all the time.
If you climb a mountain, you do some work against the force of gravity as you carry
yourself and your equipment up the mountain’s side.
You can do this work because you have the energy or capacity to do so, the energy
having been provided by the food you have eaten.
Food energy is chemical energy-energy stored in chemical compounds and released
when the compounds undergo the chemical reactions of metabolism .

Energy can be assigned to one of two classes: kinetic or potential.

An object has kinetic energy because it is moving. Examples are :
● Thermal energy of atoms, molecules, or ions in motion at the sub-
microscopic level. All matter has thermal energy because, according to
the kinetic-molecular theory, the submicroscopic particles of matter are in constant
motion.
● Mechanical energy of a macroscopic object like a moving baseball or automobile.
● Electric energy of electrons moving through a conductor.
● Sound, which corresponds to compression and expansion of the spaces between
molecules.

Potential energy is energy that results from an object’s position. Examples are :
● Chemical potential energy resulting from attractions among electrons and atomic
nuclei in molecules
● Gravitational energy, such as that of a ball held well above the floor or that of
water at the top of a waterfall
● Electrostatic energy, such as that of positive and negative ions a small distance
apart.
Potential energy is stored energy—it can be converted into kinetic energy.
For example as water droplets fall over a waterfall, the potential energy of the water
is converted into kinetic energy, and the drops move faster and faster.
Similarly, kinetic energy can be converted to potential energy.
The kinetic energy of falling water can turn a turbine to produce electricity.
Temperature , Heat, and the Conservation of Energy

When you stand on a diving board, poised to dive into a swimming pool, you have
considerable potential energy because of your position above the water.
Once you jump off the board, some of that potential energy is converted
progressively into kinetic energy, which depends on your mass (m) and velocity (v).
Kinetic energy of a body in motion = ½ (mass) . (velocity)2 = ½ m.v2

During the dive, your mass is constant, whereas the force of gravity accelerates
your body to move faster and faster as you fall, so your velocity and kinetic energy
increase.
This happens at the expense of potential energy. At the moment you hit the water,
your velocity is abruptly reduced, and much of your kinetic energy is converted to
mechanical energy of the water, which splashes as your body moves it aside by
doing work on it. Eventually you float on the surface, and the water becomes still
again. If you could see them, however, you would find that the water molecules were
moving a little faster in the vicinity of your dive; that is, the temperature of the water
would be a little higher.

This series of energy conversions, from potential to kinetic, and from kinetic to heat,
illustrates the law of energy conservation, which states that energy can neither be
created nor destroyed the total energy of the universe is constant.
This law summarizes the results of a great many experiments in which heat, work,
and other forms of energy transfer have been measured and the total energy found
to be the same before and after an event.
The law of energy conservation is the reason we have been careful not to say that
when a lump of coal is burned, its energy has been used up.

What has been used up is an energy resource: the coal’s capacity to transfer heat
energy to its surroundings when it is burned. If the coal is burned in a power plant,
its chemical energy can be changed to an equal quantity of energy in other forms.
These are mainly electricity, which can be very useful, and thermal energy in the
gases going up the smoke - stack. It is not the coal’s energy, but rather its ability
to store energy and release it in a form that people can use that has been used up.
Thermal energy, or heat, is associated with temperature, but heat is not the same as
temperature.
Transferring energy by heating an object increases the object’s temperature, and
the temperature increase can be measured with a thermometer.
For example, when the thermometer is placed into hot water, heat is transferred
from the water to the thermometer. The increased energy of the mercury atoms
means that they are moving about more rapidly, which slightly increases the volume
of the spaces between the atoms. Consequently, the mercury expands (as most
substances do when heated), and the upper end of the column of mercury rises
higher in the thermometer tube.

Energy transfer, as heat, happens when two objects at different temperatures are
brought into contact.
Energy always transfers spontaneously from the hotter to the cooler object.
For example, a piece of metal being heated in a Bunsen burner flame and a beaker
containing cold water are two objects with different temperatures. When the hot
metal is plunged into the cold water, heat is transferred from the metal to the water
until the two objects reach the same temperature.

Two important aspects of thermal energy should be understood:

● The more energy an atom or molecule has, the faster it moves.
● The total thermal energy in an object is the sum of the individual energies of all
the atoms or molecules in that object.
The average speed of motion of atoms and molecules is related to the temperature.

The total thermal energy depends on temperature, the types of atoms or molecules,
and the number of them in a sample. For a given substance thermal energy depends
on temperature and the amount of substance.
Thus a cup of steaming coffee may contain less thermal energy than a bath - tub full
of warm water, even though the coffee is at a higher temperature.

Under most circumstances, objects in a given region, such as your room, are at about
the same temperature.
If an object such as a cup of coffee or tea is much hotter than this, it transfers energy
by heating the rest of the objects in your room until the hot coffee cools off (and
your room warms up a bit).
If an object, say a cold glass of ice water, is much cooler than its surroundings in
your room, heat is transferred to the water from everything else until it warms up
(and your room cools off a little).
Because the total amount of material in your room is much greater than in a cup of
coffee or tea or a glass of ice water, the room temperature changes very little. Heat
transfer occurs until everything is at the same temperature .

Energy Units

Some of the units in which energy is measured were originally designed to measure
heat.
A calorie was originally defined as the quantity of energy (transferred by heating)
that is required to raise the temperature of 1.00 g of pure liquid water by 1.00 degree
Celsius, from 14.5 ◌C ْ to 15.5 ◌C.
ْ
The calorie represents a very small quantity of heat, and because we often work with
larger quantities of matter, the kilocalorie (1000 calories) is used instead.
Most of us tend to think of heat as measured in calories, probably because we hear
about dieting or read breakfast cereal boxes.
Currently most chemists use the joule ( J), the SI unit of energy. One calorie is now
defined as equivalent to 4.184 J. The joule is preferred because it is derived directly
from the units used in the calculation of mechanical energy (i.e., potential and
kinetic energy). If a 2.0-kg object (about 4 pounds) is moving with a velocity of 1.0
meter per second (roughly 2 mph), the kinetic energy is

Kinetic energy = ½ m.v2 =½(2kg).(1m/s)2 = 1kg.m2/s2 = 1J

Like the calorie, the joule is often inconveniently small as a unit for many purposes
in chemistry and other sciences, and so the kilo joule (kJ), which is equivalent to
1000 joules, is often used. For example, burning peanuts may produce 40,000 J or
more per gram of peanut oil. Chemists find it more convenient to express large
numbers such as these in kilojoules, that is, as 40 kJ/g in this case.
SPECIFIC HEAT AND THERMAL ENERGY TRANSFER

In the 1770s Joseph Black studied the nature of heat and was the first to distinguish
clearly between the hotness ( or temperature) of an object and its heat capacity.

The specific heat capacity, C, of a substance is defined as the ratio of the heat
supplied to some mass of the substance (say, 1.00 g) to the consequent rise in the
substance’s temperature. Mathematically, we express this as
Specific heat capacity (C)=quantity of heat supplied/(mass of object).(temperature change)
C (J/g.K) = q (J) / m (g) . ∆T (K)
where the quantity of heat transferred by heating is symbolized by q.
In chemistry we shall use heat in units of joules, masses in grams, and temperatures
in kelvins. The specific heat of a substance, which is often just called its specific
heat, is therefore expressed in units of joules per grams times kelvins ( J/g . K).

Specific heat is determined by experiment. For example, it has been found that
60.5 joules is required to change the temperature of 25.0 g of ethylene glycol
(a compound used as antifreeze in automobile engines) by 1.00 K. This means
the specific heat of the compound is
Cethylene glycol = 60.5 J /(25 g) . (1 K) = 2.42 J/g.K
The specific heat of many substances have been determined experimentally.
The wide differences in the specific heat of substances can be used to distinguish
them from each other just as density can.
Water has one of the highest known values of specific heat.
For water, the specific heat is 4.184 J/g . K, whereas it is only about 0.45 J/ g . K
for iron or 0.84 J/g . K for common glass. That is, it takes about nine times as much
heat to raise the temperature of a gram of water 1 K as it does for iron, or about five
times as much heat is required to increase the temperature of a gram of water by the
same amount as a gram of glass.
The high specific heat of water also informs us that a considerable quantity of
thermal energy must be transferred out of the substance before it cools down
appreciably. For example,1.00 g of water must give up 4.18 J of thermal energy to
cool one kelvin, whereas 1.0 g of glass gives up only 0.84 J, or about one-fifth as
much thermal energy as water for the same temperature change.
The very high specific heat of water is important to all of us, because many joules
must be absorbed by a large body of water to raise its temperature just a degree or
so. Conversely, a great deal of energy must be lost before the temperature of the
water drops by more than a degree. Thus, a lake can store an enormous quantity
of energy, and so bodies of water have a profound influence on our weather.

The equation defining specific heat informs us that the larger the specific heat, the
more thermal energy a substance can store. Furthermore, substances with a high
specific heat often cool down more slowly than those with a smaller specific heat.
If you wrap some bread in aluminum foil and heat it in an oven, you know you can
remove the foil after taking the bread from the oven without burning your fingers,
even though the bread is very hot. This is also the reason that a chain of fast food
restaurants warns you that the filling of an apple pie can be much warmer than the
paper wrapper or the pie crust .

Knowing the specific heat of a substance allows you to calculate the heat transferred
to or from that substance if the mass of substance and its temperature change are also
known. Conversely, you can calculate the temperature change that should occur
when a given quantity of heat is transferred to or from a sample of known mass.
The equation that defines specific heat allows you to do this, but it may be more
convenient to rewrite it in the following form
Heat transferred = (specific heat).(mass).(temperature change of substance)
q = ( C in J/g.K ).( m in g ).( ∆T in K )
For example, the thermal energy required to warm a 10.0 g piece of copper from 25
ْ (298 K) to 325 ◌ْ C (598 K) is
◌C
q = 10 g x 0.385 J/g.K x (598 – 298)K = 1160 J

To this point, we have emphasized only the quantity of heat transferred.

Equation, however, allows a demonstration not only of the quantity of heat but also
the direction in which it is transferred. When ΔT is determined as in the previous
calculation, that is, as : ∆T = Final temperature – Initial temperature
it has an algebraic sign: positive (+) for T increase (Tf > Ti) and negative (-) for a
decrease (Tf < Ti). If the temperature of the substance increases, ΔT has a positive
(+) sign and so does q. This means heat was transferred to the substance(as in the
example of heating a piece of copper).
The opposite case, a decrease in the temperature of the substance, means ΔT has a
negative (-) sign and does q ; heat was transferred from the substance.

Let us find the number of joules of heat energy transferred from a cup of coffee to
your body and the surrounding air if the temperature of a cup of coffee held in your
hand drops from 60.0 ◌C ْ (333.2 K) to 37.0 ◌C
ْ (310.2 K) (normal body
temperature).
Assume the coffee has a mass of 250. g; also assume the specific heat of coffee is the
same as water. The quantity of heat transferred can be obtained from Equation.
Heat transferred = q = 4.184 J/g.K x (250 g) x (310 – 333)K = 24100 J = 24.1 kJ
Notice that the final answer has a negative value. In this case heat energy is
transferred from the coffee to the surroundings, and the temperature of the coffee
decreases.
Units of Specific Heat
In this textbook we have given specific heat values in units of J/g . K. This means
that units of joules are divided by units of grams and kelvins. An alternative method
of writing this is J g-1 K-1. Recall that 1/10 is the same as 10-1, so 1/g is the same
as g-1, for example.
Specific heat values given in handbooks of chemistry are often molar specific heat.
For example, liquid water has a specific heat of 4.184 J/g . K, or 75.4 J/mol . K.
4.184 J/g.K x 18 g/mol = 75.4 J/mol.K
E X E R C I S E 6.3 Using Specific Heat
If 24.1 kJ is used to warm a piece of aluminum with a mass of 250. g, what is the
ْ
final temperature of the aluminum if its initial temperature is 5.0 ◌C. The specific
heat of aluminum is 0.902 J/g . K.

Using the Concept of Energy Conservation

In Example 6.3 you learned that the thermal energy transferred from a hot piece of
metal was equal to the thermal energy transferred to the water.
We expressed this as qmetal =-qwater, where the negative sign reflects the fact that qmetal
has a negative value (qmetal = -9820 J).
Another way to look at this is to write the equation as qmetal + qwater = 0.
This tells us that net value of the energy transferred must be zero; energy must be
conserved.
ENERGY AND CHANGES OF STATE

So far we have described transfers of energy that occur between objects as a result of
temperature differences. But energy transfers also occur when matter is transformed
from one form to another in the course of a physical or chemical change.
When a solid melts, its atoms, molecules, or ions move about vigorously enough to
break free of the constraints imposed by their neighbors in the solid. When a liquid
boils, particles move much farther apart from one another. In both cases attractive
forces among the particles must be overcome, which requires an input of energy.

Joseph Black was the first to recognize that heat is associated with changes of state,
which always take place at constant temperature. The quantity of heat required to
ْ is 333 J/g and is called the heat of fusion of the ice. (500 kJ)
melt ice at 0 ◌C
required to raise the temperature of a 1.00-kg block of iron from 0 ◌Cْ to 1100 ◌C,
ْ at
which it glows red hot, leads only to the melting of 1.50 kg of ice, at which point the
ْ
ice and the melted water both have a temperature of 0 ◌C.
3
500 x 10 J x 1 g / 333 J = 1.5 kg ice melted

The quantity of heat required to convert liquid water to vapor, called the heat of
ْ
vaporization, is 2260 J/g at 100 ◌C.
What quantity of water can be vaporized if 500. kJ of heat is transferred to water at
ْ ? Only 221 grams
100 ◌C
500 x 103 J x 1 g / 2260 J = 221 g water vaporized

Heat transfer to an object can lead to a temperature or a phase

change (or both).
Here the same quantity of heat (500 kJ) has been transferred to a
one-kilogram block of iron at 0 ◌C ْ as has been transferred to a
ْ
two-kilogram block of ice at 0 ◌C.
The temperature of the iron block has increased by
1100 K and makes the block red hot. On the other hand, this
quantity of heat has led only to the melting of 1.5 kg of ice, and
ْ
the ice and melted water are still at 0 ◌C.
 Figure 6.9
A graph illustrating the
quantity of heat absorbed
and the consequence
temperature change as
500. g of water is warmed
ْ to 200 ◌C.
from -50 ◌C ْ
The graph also Illustrates
the heat evolved when steam
ْ is cooled to -50 ◌C.
at 200 ◌C ْ

Figure 6.9 illustrates the quantity of heat absorbed and the consequent temperature
change as 500. g of water is warmed from -50 ◌C ْ to 200 ◌C.
ْ First, the temperature
ْ
of the ice increases as heat is added. On reaching 0 ◌C, however, the temperature
remains constant as sufficient heat is absorbed to melt the ice to liquid water.
When all the ice has melted, the liquid absorbs heat and is warmed to 100 ◌C, ْ the
boiling point of water. The temperature is again constant as heat is absorbed to
completely convert the liquid to vapor, that is, to steam. Any further heat absorbed
ْ
heats the steam to 200 ◌C.

ENTHALPY

Carbon dioxide undergoes a change of state from solid to gas, a process called
ْ
sublimation, at -78 ◌C: CO2(s, -78oC) → CO2(g, -78oC)
heat
To describe the change from solid to gas in thermodynamic terms, we first need to
extend the earlier discussion of heat as energy transferred between objects.
In thermodynamics one of the ‘‘objects’’ is usually of primary concern. It may be a
substance involved in a change of state or substances undergoing a reaction. It is
called the system.
The other ‘‘object’’ is called the surroundings and includes everything outside the
system that can exchange energy with the system.
A system may be contained within an actual physical boundary, such as a flask or
a cell in your body. Alternatively, the boundary may be purely imaginary.

Suppose our system consists of solid and gaseous CO2 at -78 ◌C, ْ that the
ْ
surroundings are also at -78 ◌C, and that one mole CO2 (solid) is transformed into
one mole CO2 (gas). Just as the potential energy of a ball is greater when it is farther
above the earth, which attracts it, the potential energy of a CO2 molecule is greater
when it is farther from another CO2 molecule, again because an attractive force must
be overcome when the two are separated. Thus, the energy of a mole of CO2(g) is
greater than the energy of a mole of CO2(s). Where does this energy come from? That
depends on the circumstances.
Let us begin with the case in which CO2(s) and CO2(g) are inside a rigid container for
one molecule to escape from solid to gas can be supplied by neighboring molecules
which consequently vibrate a little less about their position in the crystal lattice.

Phase Change Direction of Heat Transfer - Sign of qv(system) -Type of Change

‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
CO2(solid)→CO2(gas) Surrounding →System Positive Endothermic
CO2(gas)→CO2(solid) System→ Surrounding Negative Exothermic

As more and more molecules escape, the motion of remaining solid-state molecules
diminishes more and more, which would lead to a lowering of the temperature.
Atoms and molecules in the surroundings (the rigid container) are in contact with
CO2 molecules in the solid, however, and energy exchange can occur.

As soon as the temperature of the solid CO2 drops slightly below the temperature
of the surroundings, more energy transfers into the solid CO2 than transfers out, and
ْ
the temperature of the solid CO2 is restored to -78 ◌C. For the temperature not to
ْ
drop below -78 ◌C, the heat transfer from the surroundings must exactly equal the
energy required to overcome attractive forces as solid CO2sublimes.

What we have just described is transfer of energy as heat from the surroundings to
the system while the process CO2 (s) → CO2 (g) takes place.
In such a case the temperature of the system at first decreases, but then thermal
energy is transferred from the surroundings and constant temperature is maintained.
When heat must be transferred into a system to maintain constant temperature as a
process occurs, the process is said to be endothermic.

In contrast, the reverse process, converting CO2 gas to solid CO2 (dry ice), is an
exothermic process; heat is transferred out of the sample of CO2 to the surroundings
when some of the CO2(g) condenses to a solid.

In summary, when the endothermic process CO2(s)→ CO2(g) occurs inside a rigid
container, the only exchange of energy is the heat transferred into the system.
Thus, by conservation of energy, the heat absorbed at constant volume, qv, must
equal the change in the energy of the system, ΔE.
If the process does not occur in a rigid container the situation is a bit more
complicated, because two occur, not just one.

Crushed dry ice has been placed in the plastic bag.

(c) The bag has been closed. Some dry ice has sublimed , converting solid CO2 at -78 ◌C ْ to
gaseous CO2 at -78 ◌C.ْ The gas has filled the bag and has done work by raising a book that has
been placed on the bag.
(d) A similar experiment but without the book. The expanding CO2 in this case has pushed aside
the air that formerly occupied the space taken up by the inflated bag. Pushing aside the
atmosphere requires work, just as raising a book does.

As shown in Figure 6.11c, CO2 (s) vaporizing into a flexible container can raise a
book above a table top. Raising a book is an example of doing work. Not only is
energy transferred into the solid CO2 as heat, but energy is also transferred out of the
CO2 gas as work.
Work is done whenever something is caused to move against an opposing force.
In this case the gas has to work against the weight of the book to raise it.

Because energy is now transferred in two ways between system and surroundings,
it is no longer true that ΔE = q.
Energy transferred in or out of the system by work, symbolized by w, must also be
taken into account.
The change in energy of the system is now:
∆E = q + W
That is, the energy of the system is changed by the quantity of energy transferred as
heat and by the quantity of energy transferred by work. This is a statement of the
first law of thermodynamics, also called the law of energy conservation.
Another way of saying the same thing is that the total amount of energy in the
universe is constant.
Energy may be transferred as work or heat, but no energy can be lost, nor can heat
or work be obtained from nothing. All the energy transferred between a system and
its surroundings must be accounted for as heat and work. [This is true as long as no
other energy transfer, such as the radiant energy of a glowing light stick is involved.]

The first law is important in all aspects of our lives; it plays a central role in our
models of weather, in designing a power plant, or in understanding why diet and
exercise together lead to weight loss.
Even if the book had not been on top of the plastic bag in Figure 6.11c, work would
have been done by the expanding gas.
This is because whenever a gas expands into the atmosphere it has to push back the
atmosphere itself. Instead of raising a book, the expanding gas moves a part of the
atmosphere.
For the process shown in Figure 6.11d, the energy transferred from the surroundings
has two effects: (1) it overcomes the forces holding the molecules together in the
ْ
solid state at -78 ◌C, and (2) it does work on the atmosphere as the gas expands.
The energy that allowed the system to perform work on its surroundings had to come
from somewhere, and that ‘‘somewhere’’ was the energy, q, transferred as heat to
the system from its surroundings. The system converted part of that heat into work.
Therefore, the first law of thermodynamics tells us that the energy change, ΔE, for
the CO2 system must be less than q.
The reason for this is that heat is transferred into the system from its surroundings (q
has a positive sign), and work is done by the system on the surroundings (w has a
negative sign). That is,
ΔE = q + w = (q, positive number) + (w, negative number) and so: ΔE < q
In plants and animals, as well as in the laboratory, reactions usually occur at equals a
quantity called the enthalpy change, symbolized by ΔH (‘‘delta H’’).
Thus, ΔH = qp = heat transferred to or from a system at constant pressure.
Because ΔE = q + w, then at constant pressure ΔE = ΔH +w, showing that ΔH
accounts for all the energy transferred except the amount that does the work of
pushing back the atmosphere (which is usually small compared with ΔH).
Even if pressure is not constant,

ΔH = (enthalpy of the system at the end) - (enthalpy of the system at the start)
= Hfinal ‫ ــــ‬Hinitial

Figure 6.13
Enthalpy diagram for
the Interco version of
solid CO2 and CO2 gas
at constant pressure.

If the enthalpy of the final system is greater than that of the initial system (as when
ْ
solid CO2 changes to CO2 vapor at -78 ◌C), the enthalpy has increased, and the
process has a positive ΔH; qp must also be positive and the process is endothermic.
Conversely, if the enthalpy of the final system is less than that of the initial system,
heat has transferred out of the system, and ΔH is negative; the process is exothermic.
Another endothermic process is the evaporation of water to water vapor at 25 ◌C. ْ
The evaporation of one mole of water requires 44 kJ.
H2O(ℓ) → H2O(g) ; ∆Hv = + 44 kJ/mol (change is endothermic)
44 kJ of heat energy transferred from surrounding to the liquid water .

But what about water vapor condensing to form liquid again?

If 44.0 kJ of heat energy is required to break the attractions between H2O molecules
in one mole of the liquid so they can move into the gas phase, the same quantity of
energy (44.0 kJ per mole) is regained when the molecules in the vapor condense to
form the liquid. Condensation of water is exothermic; 44.0 kJ per mole is transferred
from the water to the surroundings when a mole of H2O molecules condenses to
liquid: H2O(g) → H2O(ℓ) ; ∆Hc = - 44 kJ (change is exothermic)
44 kJ of heat energy transferred to surrounding from the vapor water .

Some key ideas that apply to all of thermodynamics may be summarized here.
● When heat transfer occurs (at constant pressure) from a system to its surroundings,
as when a vapor condenses to a liquid or solid, the process is exothermic with
respect to the system and ΔH(qp) has a negative value. Conversely, when heat is
absorbed from the surroundings, as when a solid or liquid changes to a vapor, the
process is endothermic with respect to the system and ΔH(qp) has a positive value.
● For changes that are the reverse of each other, the ΔH values are numerically the
same, but their signs are opposite.
Thus, for evaporation of water, ΔH=+44.0 kJ/mol, whereas for the condensation of
water ΔH=-44.0 kJ/mol.
● The change in energy or enthalpy is directly proportional to the quantity of
material undergoing a change. If two moles of water are evaporated, twice as much
heat energy or 88.0 kJ is required.

● The value of ΔH is always associated with a balanced equation for which the
coefficients are read as moles, so that the equation shows the macroscopic amount
of material to which the value of ΔH applies. Thus, for the evaporation of
two moles of water :
2H2O(ℓ) → 2H2O(g) ; ∆H = 88 kJ
ENTHALPY CHANGES FOR CHEMICAL REACTIONS

The enthalpy change can be determined for any physical or chemical change.
For a chemical reaction the products represent the ‘‘final system’’ and the reactants
the ‘‘initial system.’’ Therefore, ∆H = Hproducts – Hreactants
Like changes of state, chemical reactions can be exothermic or endothermic.
Many reactions [such as the Al + Br2 reaction and the reactions of elements with air]
are exothermic.

To learn more about enthalpy changes that accompany chemical reactions, consider
the decomposition of one mole of water vapor to its elements.

H2O(g) → H2(g) + ½O2(g) ; ∆H = +242 kJ/mol (change endothermic)

Decomposition of 1 mol water vapor requires 242 kJ of energy to be transferred

in from surrounding .

(Note that to write an equation for the decomposition of one mole of H2O, it is
necessary to use a fractional coefficient for O2. This is acceptable in thermo-
chemistry because coefficients are always taken to mean moles and not molecules.)

The left side of Figure 6.14 shows that the enthalpy of the products of this reaction
is greater than that of the reactants.

Figure 6.14
Enthalpy diagram for the
Interco version of water
vapor, H2O(g), liquid water,
H2O(ℓ), and the elements.
Water vapor would have to absorb 242 kJ of energy (at constant pressure) from the
surroundings as it decomposes to its elements. That is, the enthalpy change for the
endothermic decomposition of water is ΔH=+242 kJ per mole of water.
The decomposition of water can be reversed; hydrogen and oxygen can combine to
form water.
The quantity of heat energy involved in this oxidation reduction reaction (Fig. 6.14)
H2(g) + ½O2(g) → H2O(g) ; ∆H=-242kJ/mol (change is exothermic)
is the same as for the decomposition reaction except that the combination of the
elements is exothermic. That is, ΔH =-242 kJ per mole of water vapor formed.

As in the case of phase changes, some key ideas about enthalpy changes for
reactions can be summarized:
● When heat is evolved or transferred (at p=const.) to the surroundings by an
exothermic reaction, ΔH has a negative value. Conversely, when heat is absorbed
from the surroundings by an endothermic reaction, ΔH has a positive value.
● For chemical reactions that are the reverse of each other, the ∆H values are
numerically the same, but their signs are opposite.
● The change in energy or enthalpy is directly proportional to the quantity of
material undergoing a change. If 2 moles of water are decomposed, twice as
much heat energy, or 484 kJ, is required.
● In thermodynamics, the value of ΔH is always associated with a balanced
equation for which the coefficients are read as moles, so that the equation shows
the macroscopic amount of material to which the value of ΔH applies.
Thus, for the decomposition of 2 moles of water vapor
H2O(g) → 2H2(g) + O2(g) ; ∆H=+484 kJ

Because energy is transferred when a substance undergoes a change of state, the

quantity of energy associated with a chemical reaction must depend on the physical
state (solid, liquid, or gas) of the reactants and products.

For example, the decomposition of one mole of liquid water to H2 and O2

H2O(ℓ) → H2(g) + ½O2(g) ; ∆H=+286 kJ/mol

requires more energy than the decomposition of one mole of water vapor, as shown
in Figure 6.14.
The heat of vaporization, 44 kJ/mol, must be added to the enthalpy change for the
decomposition of H2O(g) to give the value for the decomposition of H2O(ℓ).

Enthalpy changes for reactions have many practical applications. For instance,
when enthalpies of combustion are known, the quantity of heat transferred by the
combustion of a given mass of a fuel such as propane, C3H8, can be calculated.

Suppose you are designing a heating system, and you want to know how much
heat is provided by burning 454 grams (1 pound) of propane gas in a furnace.
The exothermic reaction that occurs is
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(ℓ) ; ∆H = -2220 kJ/mol
and the enthalpy change is ΔH=-2220 kJ per mole propane burned.
How much heat is transferred to the surroundings by burning 454 g of C3H8 gas?
The first step is to find the number of moles of propane present in the sample.
N = W/M =454 g / 44 g.mol-1 = 10.3 mol
Then you can multiply by the amount of heat transferred per mole of gas.
10.3 mol x 2220 kJ/mol = 22900kJ0.3

This is a substantial quantity of energy when you compare it with the fact that, when
your body completely ‘‘burns’’ 454 g of milk, only about 1400 kJ is evolved, in part
because milk is largely water.

HESS’S LAW

Knowing how much heat is transferred as a chemical process occurs is very

important.
First of all, the direction of heat transfer is an important clue that helps predict in
which direction a chemical reaction will go because, at room temperature, most
exothermic reactions are product-favored.
Second, we can use ΔH to calculate the heat obtainable when a fuel is burned, as
was done.
Third, when reactions are carried out on a larger scale, as in a chemical plant.
We therefore want to know ΔH values for as many reactions as possible.
For many reactions direct experimental measurements can be made by using a
device called a calorimeter, but for many other reactions this is not a simple task.
Besides, it would be very time-consuming to measure values for every conceivable
reaction, and it would take a great deal of space to tabulate so many values.
Fortunately there is a better way. It is based on the fact that mass and energy are
conserved in chemical reactions.

Energy conservation is the basis of Hess’s law, which states that, if a reaction is
the sum of two or more other reactions, then ΔH for the overall process must be
the sum of the ΔH values of the constituent reactions.

For example, as illustrated in the preceding section (see Figure 6.14) for the
decomposition of liquid water into the elements H2(g) and O2(g) (with all substances
at 25 ◌C), ْ the two successive changes are (1) the vaporization of liquid water and
(2) the decomposition of water vapor to the elements (with all substances at 25 ◌C). ْ
The equation and the ΔH value for the overall process can be found by adding the
equations and the ΔH value for the overall process can be found by adding the
equations and the ΔH values for the two steps:
(1) H2O(ℓ) → H2O(g) ; ∆H1= +44 kJ/mol
(2) H2O(g) → H2(g) + ½O2(g) ; ∆H2 = +242 kJ/mol
‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
(1)+(2) H2O(ℓ) → H2(g) + ½O2(g) ; ∆H3 = +286 kJ/mol
Here, H2O(g) is a product of the first reaction and a reactant in the second.
Thus, as in adding two algebraic equations in which the same quantity or term
appears on both sides of the equation , H2O(g) can be canceled out. The net result
is an equation for the overall reaction and its associated enthalpy change.

Hess’s law is useful because it enables us to find the enthalpy change for a reaction
or state change that cannot be measured conveniently.
Suppose you want to know the enthalpy change for the formation of carbon
monoxide, CO, from the elements, solid carbon (as graphite) and oxygen gas.
C(s) + ½O2(g) → CO(g) ; ∆H1 = ?
Experimentally this is not easy to do; it is difficult to keep the carbon from burning
completely to carbon dioxide.

The way to solve this is to recognize that we can more easily determine by
experiments the enthalpy change for the conversion of carbon to CO2 and for the
conversion of CO to CO2.
C(s) + O2(g) → CO2(g) ; ∆H3 = -394 kJ/mol
CO(g) + ½O2(g) → CO2(g) ; ∆H2 = -283 kJ/mol

Figure 6.15 One mole of carbon dioxide can be

formed from carbon and oxygen in a direct reaction
(ΔHnet=-393.5 kJ) or in two steps.
Hess’s law states that the sum of the enthalpy
changes for the two steps must equal that for the
direct reaction.
That is, ΔH1 + ΔH2 = ΔHnet.
Knowing any two of these values,
therefore, allows us to calculate the third.

As the diagram in Figure 6.15 makes clear, the formation of CO is the first of two
steps in going from carbon to carbon dioxide. We know the enthalpy change for the
second step (ΔH2), and we know the enthalpy change for the net reaction (ΔHnet).

Using Hess’s law, therefore, we can solve for the enthalpy change for the first step
(ΔH1). This can be done readily, because ΔH for the net reaction is the sum of the
ΔH values for the first and second steps.
C(s) + ½O2(g) → CO(g) ; ∆H1 = ?
CO(g) + ½O2(g → CO2(g) ; ∆H2 = -283 kJ/mol
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
C(s) + O2(g) → CO2(g) ; ∆H3 = -394 kJ/mol
∆H3 = ∆H1 + ∆H2
∆H1 = -394 – (-283) = -111 kJ/mol
E X A M P L E 6.6 Using Hess’s Law

Suppose we want to know the enthalpy change for the formation of methane , CH4,
from solid carbon (as graphite) and hydrogen gas.
C(s) + 2H2(g) → CH4(g) ; ∆H = ?

The enthalpy change for the direct combination of the elements would be extremely
difficult to measure in the laboratory.
We can measure ΔH, however, when the elements and methane burn in oxygen .
(1) C(s) + O2(g) → CO2(g) ; ∆H = -394 kJ/mol
(2) H2(g) + ½O2(g) → H2O(ℓ) ; ∆H = -286 kJ/mol
(3) CH4(g) + 2O2(g) → CO2(g) + 2H2O(ℓ) ; ∆H = -890 kJ/mol

Solution
The three reactions (1, 2, and 3), as they are now written, cannot be added together
to obtain the equation for the formation of CH4 from its elements. CH4 should be a
product, but it is a reactant in equation (3). The solution to this is to reverse equation
(3). At the same time, the sign of ΔH for the reaction is reversed.
If a reaction is exothermic in one direction (the combustion of methane evolves
energy), its reverse must be endothermic.
(3)' CO2(g) + 2H2O(g) → CH4(g) + 2O2(g) ; ∆H = -∆H3 = +890kJ/mol
Next, we see that two moles of H2O(ℓ) is required as a product, whereas equation
(2) is written for only one mole of water. We therefore multiply the stoichiometric
coefficients in (2) by 2 and multiply the value of ΔH by 2.
2(2) 2H2(g) + O2(g) → 2H2O(ℓ) ; 2∆H2 = 2mol(-286kJ/mol)= -572 kJ
With these modifications, we can add the three equations to give the equation for the
formation of methane from its elements.
(1) C(s) + O2(g) → CO2(g) ; ∆H = -394 kJ/mol
2(2) 2H2(g) + O2(g) → 2H2O(ℓ) ; ∆H = -572 kJ/mol
(3)' CO2(g) + 2H2O(ℓ) → CH4(g) + 2O2(g) ; ∆H = +890 kJ/mol
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
C(s) + 2H2(g) → CH4(g) ; ∆Hnet = -75 kJ/mol

The solution to this problem is shown diagrammatically in Figure 6.16.

Figure 6.16
Methane may be formed
directly from the elements.
Alternatively, the carbon
may be burned to CO2 (g)
and the hydrogen burned to
water.
Then CO2 and H2O are
combined to form CH4 (and
the O2 used in the
combustion is returned).
Hess’s law states that the
enthalpy change for the
direct reaction (ΔHnet) is the
sum of the enthalpy changes
along the alternative path (ΔHnet = ∆H1+2∆H2+(-ΔH3).
See Example 6.6 for a more complete designation of the ∆H values.

STATE FUNCTIONS
Hess’s law works because the enthalpy change for a reaction is a state function,
a quantity whose value is determined only by the state of the system.
The enthalpy change for a chemical or physical change does not depend on the path
you choose to go from the initial conditions to the final conditions. No matter how
you go from reactants to products in a reaction the net heat evolved or required (at
constant pressure) is always the same.
This point is illustrated in Figure 6.15 for the formation of CO2 from its elements
and in Figure 6.16 for the formation of methane.
For the reaction
C(s) + 2H2(g) → CH4(g) ; ∆Hnet = -75 kJ/mol

the enthalpy change for the direct reaction (ΔHdirect=-74.8 kJ) is the same as the sum
of the enthalpy changes along the indirect pathway that goes through carbon dioxide
and water.
Many commonly measured quantities, such as the pressure of a gas, the volume
of a gas or liquid, the temperature of a substance, and the size of your bank account,
are state functions.
The volume of a balloon is also a state function. You can blow up a balloon to a
large volume and then let some air out to arrive at the desired volume. Alternatively,
you can blow up the balloon in stages, adding tiny amounts of air at each stage.
The final volume does not depend on how you got there .

An infinite number of ways exist for how to arrive at the final state, but the final
value depends only on the size of the balloon, and not on the path taken from the
initial to the final state.
Because enthalpy is a state function, in principle there is an absolute enthalpy for
the reactants (Hinitial = Hreactants) and for the products (Hfinal = Hproducts).
The difference between these enthalpies is the change for the system.
ΔHreaction = Hfinal - Hinitial = Hproducts - Hreactants

Because the reaction starts and finishes at the same place no matter which pathway
is chosen, ΔHreaction must always be independent of pathway.
Unlike volume, temperature, pressure, or energy, however, the absolute enthalpy
of a substance is not usually determined, only its change in a chemical or physical
process.
The thermal energy evolved or required in a chemical process, for example, is a
reflection of the difference in enthalpy between the reactants and products.
We determine only whether the enthalpy of the products is greater than or less than
that of the reactants by some amount.
STANDARD ENTHALPIES OF FORMATION

Hess’s law makes it possible for us to tabulate ΔH values for a few reactions and

to derive a great many other ΔH values by adding together appropriate ones as

described.

Because ΔH values depend on temperature and pressure, it is necessary to specify

both of these when a table of data is made.
ْ are specified, although other
Usually a pressure of 1 bar and a temperature of 25 ◌C
conditions of temperature are used.

The standard state of an element or a compound is the most stable form of the
substance in the physical state in which it exists at 1 bar and the specified
temperature.

Thus, at 25 ◌C ْ and a pressure of 1 bar, the standard state for hydrogen is the gaseous
state, H2(g), and for sodium chloride, it is the solid state, NaCl(s).
ْ
For carbon, which can exist in any one of three solid states at 1 bar and 25 ◌C, the
most stable form, graphite, is selected as the standard.

When a reaction occurs with all the reactants and products in their standard states
under standard conditions, the observed, or calculated, enthalpy change is known as
the standard enthalpy change of reaction, ΔH ◌, ْ where the superscript ◌ْ ◌ْ
indicates standard conditions.
All the reactions we have discussed to this point have followed this convention,
so all the ΔH values should have ◌ْ attached.

The standard enthalpy change of a reaction for the formation of one mole of a
compound directly from its elements is called the standard molar enthalpy of
formation, ΔH ْ◌ f , where the subscript f indicates that one mole of the compound
in question has been formed in its standard state from its elements, also in their
standard states.

Some of the reactions already discussed define standard molar enthalpies of

formation.
H2(g) + ½O2(g) → H2O(ℓ) ; ∆Hfo = -286 kJ/mol
C(s) + 2H2(g) → CH4(g) ; ∆Hfo = -75 kJ/mol
As another example, the following equation shows that 277.7 kJ is evolved if
graphite, the standard state form for carbon, is combined with gaseous hydrogen
and oxygen to form one mole of ethanol at 298 K.
2C(graphite) + 3H2(g) + ½O2(g) → C2H5OH(ℓ) ; ∆Hof= -278 kJ/mol
Finally, it is important to understand that a standard molar enthalpy of formation
(ΔH ْ◌ f) is just a special case of an enthalpy change for a reaction.

In contrast with the three previous reactions, the enthalpy change for the following
reaction is not an enthalpy of formation; calcium carbonate has been formed from
other compounds, not directly from its elements.

CaO(s) + CO2(g) → CaCO3(s) ; ∆Horxn= -178 kJ/mol

Therefore, the enthalpy change is given the more general symbol of ΔH ◌ْ rxn.
The enthalpy change for the following reaction is also not a standard enthalpy
of formation.
P4(s) + 6Cl2(g) → 4PCl3(ℓ) ; ∆Horxn= -1279 kJ
Here a compound has been formed from its elements, but more than one mole of
the compound has been formed, and so ΔH ◌ْ rxn = 4 ΔH ْ◌ f [PCl3(ℓ)].

Standard enthalpies of formation for the elements in their standard states are zero,
because forming an element in its standard state from the same element in its
standard state involves no chemical or physical change.

Be sure to notice also that most ΔH ْ◌ f values are negative. That is, the process of
forming most compounds from their elements is exothermic.

Recall that we previously stated that at room temperature most exothermic reactions
are product-favored.

Thus, forming compounds from their elements (under standard conditions) is

generally a product-favored process.
Reactions of oxygen with metals are usually exothermic and product-favored

2Al(s) + 3/2O2(g) → Al2O3(s) ; ∆Hof= -1675 kJ/mol

and carbon generally combines with other elements in reactions with negative
enthalpy changes.

C(s) + O2(g) → CO2(g) ; ∆Hof= -394 kJ/mol

2C(s) + 3H2(g) + ½O2(g) → C2H5OH(ℓ) ; ∆Hof= -1676 kJ

One important exception to our general observation is ethyne (commonly called

acetylene), a compound with a strongly endothermic standard enthalpy of formation.
2C(s) + H2(g) → C2H2(g) ; ∆Hof= +227 kJ/mol

It is interesting that acetylene is a good fuel and that it is the starting point for
manufacturing many other carbon-containing compounds.

DETERMINING ENTHALPIES OF REACTION

Calorimetry
The heat evolved by a chemical reaction can be determined by a technique called
calorimetry.
When finding heats of combustion or the
caloric value of foods, the measurement
is often done in a combustion calorimeter
(Figure 6.17).

Figure 6.17 A combustion calorimeter.

A combustible sample is burned in pure
oxygen in a steel ‘‘bomb.’’
The heat generated by the reaction warms
the bomb and the water surrounding it.
By measuring the temperature increase,
the heat evolved by the reaction can be
determined .
A weighed sample of a combustible solid or liquid is placed in a dish that is encased
in a ‘‘bomb,’’ a cylinder about the size of a large fruit juice can with heavy steel
walls and ends .

The bomb is then placed in a water-filled container with well-insulated walls.

After filling the bomb with pure oxygen, the mixture of oxygen and sample is
ignited, usually by an electric spark. The heat generated when the sample burns
warms the bomb and the water around it, with both coming to the same temperature.
In this configuration, the oxygen and the compound represent the system, and the
bomb and water around it are the surroundings.
From the law of energy conservation, we can say that Heat transferred from the
system = heat transferred into the surroundings Heat evolved by the reaction = heat
absorbed by water and bomb
qreaction = - (qwater + qbomb)

where qreaction has a negative value because the combustion reaction is exothermic .
The temperature change of the water, which is also equal to the change for the bomb,
is measured.
Using these experimental measurements, the total quantity of heat absorbed by the
water and the bomb (qwater + qbomb) can be calculated from the specific heat of the
bomb and the water.
According to the previous equation, this total gives the heat evolved by combustion
of the compound.

Because the bomb is rigid, the heat transfer is measured at constant volume and is
therefore equivalent to DE, the change in energy. As explained earlier (see Section
6.4), ΔE = qv , whereas the change in enthalpy is the heat evolved or required at
constant pressure, that is, ΔH = qp.
Because ΔE and ΔH are related in a relatively simple way, however, ΔH values can
be calculated from ΔE values found in bomb calorimetry experiments.
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Using Hess’s Law

What experiments would you do to find the standard enthalpy of formation of solid
calcium hydroxide?
Ca(s) + O2(g) + H2(g) → Ca(OH)2(s) ; ∆Hof = ?
We know from experience that the enthalpy change for the reaction cannot be
measured directly in any convenient manner. It is therefore necessary to break
down the formation of calcium hydroxide into a series of reactions that can be
added together to give the equation for the formation of solid Ca(OH)2 from the
elements and whose enthalpy changes can be determined in a calorimeter
● Calcium is a metal and so reacts with oxygen to produce the oxide, CaO.

Ca(s) + ½O2(g) → CaO(s) ; ∆Horxn= ∆Hof = -635 kJ/mol

The enthalpy change for this reaction can be determined in a calorimeter (or found
ْ values).
in a table of ΔH ◌f

ْ for the formation of water from hydrogen and oxygen is well known.
●ΔH ◌f

H2(g) + ½O2(g) → H2O(ℓ) ; ∆Horxn= ∆Hof = -286 kJ/mol

● CaO is a basic oxide; it reacts with water to give calcium hydroxide, Ca(OH)2(s).

CaO(s) + H2O(ℓ) → Ca(OH)2(s) ; ∆Horxn= -65 kJ/mol

Once CaO has been formed from the direct reaction of the metal with oxygen, the
enthalpy change for its reaction with water can be determined in a calorimeter.
Adding the three reactions above together, we see that they give us the enthalpy of
formation of solid Ca(OH)2.

Ca(s) + ½O2(g) → CaO(s) ; ∆Hof = -635 kJ/mol

H2(g) + ½O2(g) → H2O(ℓ) ; ∆Hof = -286 kJ/mol
CaO(s) + H2O(ℓ) → Ca(OH)2(s) ; ∆Horxn= -65 kJ/mol

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