1

5.1 THE NATURE OF THERMODYNAMICS
Thermodynamics is concerned with the relationship between the energy
changes that occur in chemical and physical processes. In effect, the laws
of thermodynamics are the embodiment of the totality of the experimental
facts concerning energy changes that occur in nature. The vast, diverse
body of experimental facts concerning these energy changes are
summarized in the statements of the three laws of thermodynamics.
These can be used to predict the direction in which a process would
proceed. Thus this science is of great importance to the chemist, since it
can predict whether or not a chemical reaction will proceed spontaneously
from a knowledge of the thermodynamic properties of the reactants and
products. If thermodynamics tells us that a prospective reaction is
favorable, then we are on a safe ground to try to find the proper
experimental conditions to make the reaction proceed. For example,
when gaseous H2 and O2 are mixed, thermodynamics tells us that H2O
should be formed, since H2O is more energetically stable than H2 and
O2. It is a well-known fact that at room temperature, a mixture of H2 and
O2 will not produce H2O. However, if the mixture is sparked, water is
produced with explosive violence, thereby proving the prediction
thermodynamics makes concerning this reaction. One limitation of
thermodynamics is that it does not give any indication of how fast the
reaction will proceed, i.e., in essence, the laws of thermodynamics do not
contain time as a variable. Thus thermodynamics is only interested in
where the system was initially and where it is after the completion of the
process. It does not care how the attainment of the final condition came
about or how long it takes to reach this condition. In the case of a
chemical reaction, for example, thermodynamics may tell us that the
reaction will go spontaneously, but it cannot tell us how long the reaction
will take to reach equilibrium or what the path of the reaction will be.
The latter two problems are dealt with in the study of chemical kinetics.
5.2 DEFINITION OF THERMODYNAMIC TERMS
Before developing the laws of thermodynamics, consideration will be
given to the definition of the terms commonly used in this field, since a
clear understanding of these definition and terms will aid immensely in the
discussions to follow.
ENERGY
Energy is usually defined as the capacity to do work. Kinetic energy,
potential energy, chemical energy, and thermal energy are forms of energy
particularly useful to the chemist.
Kinetic energy is defined as the energy produced by a moving object.
For an object of mass m moving at a velocity v, the kinetic energy is equal
to ½ mv
2
.
Potential energy is energy available by virtue of an object’s position.
For instance, because of its altitude, a rock at the top of a cliff has more
potential energy and will make a bigger splash if it falls into the water
below than a similar rock located part way down the cliff.
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Chemical energy can be considered a form of potential energy
because it is associated with the relative positions and the various attractive
and repulsive forces of atoms within a given substance.
Thermal energy is the energy associated with the random motion of
atoms and molecules. The thermal energy of a substance is related to its
temperature and quantity of matter in it. For example, the thermal energy
stored in a bathtub filled with water at 40 C is much more than the
thermal energy in a cup of coffee at 70 C.
HEAT
Heat can be defined as the transfer of thermal energy between two bodies
that are at different temperatures. Thus, we often speak of “heat flow” from
a hot object to a cold one, or “heat absorbed” when describing energy
changes that occur during a process.
UNITS FOR ENERGY
The SI unit for energy is the Joule, J. The calorie, cal, and the liter
atmosphere, L∙atm, are other common units for energy. The relationship
between different units of energy is as follows:
1 cal = 4.184 J
1 L∙atm = 101.29 J
SYSTEMS AND SURROUNDINGS
Thermodynamics is concerned with the results of studies of definite parts
of the universe, which are called systems. A thermodynamic system is a
part of the universe, which is arbitrarily set off from the rest of the
universe by definite boundaries for the purpose of experimental or
theoretical study. The remainder of the universe is then, in effect, the
surroundings of the system. Usually, however, the surroundings are
restricted to a region in the immediate vicinity of the system under
study. For example, a cylinder containing a gas is placed in a
thermostated water bath. In this case, the gas is the system under study
and the thermostat would be the surroundings; the boundaries of the
system, of course, are the walls of the cylinder. The boundaries of a
system can be fixed, as in the case of a rigid cylinder, or variable, as in
the case of a cylinder equipped with a movable piston. Systems can be
further subdivided into open and closed systems. An open system is
one that can exchange both energy and matter with its surroundings. A
closed system can exchange energy only with its surroundings, and the
amount of matter in the system is not changed by transfer across the
boundaries. For example, a beaker containing an aqueous salt solution
(the system) in a thermostated water bath (the surroundings) is an open
system, if more salt is added or if water is allowed to evaporate, and if heat
energy from the thermostat is allowed to transfer into or out of the
solution. However, this system becomes a closed system if the beaker is
covered and no change in concentration occurs and if heat energy can still
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pass into or out of the solution. Note that a system is still considered
closed if a chemical reaction occurs in the system, thereby changing the
amounts of the different constituents, but not the total amount of matter
in the system. A liquid in equilibrium with its vapor in a sealed tube is
another example of a closed system. Heat energy can be added to
cause more liquid to vaporize, but the total amount of matter is not
changed, since no vapor can escape. A system in which there is no
transfer of either energy or matter across the boundaries is called an
isolated system. Thus if the sealed tube containing liquid and vapor were
thermally insulated so that heat energy could not enter or leave, the
liquid-vapor system would be an isolated system (Figure 5.1).
Figure 5.1 (a) an open system, which allows the
exchange of both energy and matter with the
surroundings; (b) a closed system, which allows
the exchange of energy but not matter; and (c)
an isolated system, which allows neither energy
nor matter to be exchanged.
THERMODYNAMIC EQUILIBRIUM
A system is said to have attained a state of thermodynamic
equilibrium when it shows no further tendency to change its
properties with time.
The criterion for thermodynamic equilibrium requires that
three types of equilibrium exist simultaneously in a system. First
of all, the system must be in thermal equilibrium. This means
the temperature must be uniform throughout the system, and
al so, the system must be at the same temperature as its
surroundings, if it is not insulated from the surroundings. Any
temperature differences that exist will cause heat to flow from a
higher temperature to a lower one until the temperature becomes
uniform throughout the system. Second, the system must be i n
mechanical equilibrium. Mechanical equilibrium requires that
there be no macroscopic movement within the system itself, or from
the system to its surroundings. For example, consider a gas contained in a
cylinder equipped with a movable piston. If the piston is pushed in rapidly,
the rapid motion will set up pressure and temperature differences in the
gas, since the pressure and temperature in the region close to the piston
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will be much greater than in a region away from the piston. Hence, no
single pressure measurement will unambiguously describe the system. If
enough time is allowed to elapse, these differences will level out until the
pressure and temperature throughout the gas will become uniform and
constant. The system is then in mechanical equilibrium. In a system
where more than one substance is present, thermodynamic equilibrium
requires that the composition of the system remains constant with time.
For chemical reactions this means no net chemical change can occur, i.e.,
the system must be at chemical equilibrium. Of course, this equilibrium
is a dynamic one in which the forward and reverse reactions are
continually occurring at equal rates. Hence there is no net change in the
concentration of reactants or products at equilibrium.

FUNCTIONS OR VARIABLES OF STATE
Thermodynamics deals with changes that occur in the properties of sys-
tems when the system goes from one equilibrium state to another. Such a
change in the values of the properties of the system occurs in what is
called a process. In fact, thermodynamics is interested only in the values
of the properties, which the system possesses in its initial and final states.
It is not concerned with how the system arrived at the final state. Thus as
long as the values of property in the initial and final state are the
equilibrium values, the quantity of interest in thermodynamics is the
change in the value for the process. The change in the value is defined
as the difference in the value between the final and initial states. Thus for
a compression process, if P2 is the equilibrium pressure of the gas after
compression (final state) and P1, is the equilibrium pressure before
compression (initial state), then the change in pressure, P, for the
compression is
∆P = P2 – P1 (5-1)
The magnitude of P will be the same, whether the process was carried
out in one step or several steps, as long as P2 and P1 are equilibrium
values of the pressure for the two states. Not all variables of a system
possess this property of being independent of the paths taken between
states. The variables that do possess this property are called functions
or variables of state. They form an important class of variables that
arc very useful in thermodynamics. Pressure, temperature, and volume
are examples of state variables. Other very important state variables are
obtained from the laws of thermodynamics.
5.3 THE FIRST LAW OF THERMODYNAMICS
The First law is based on the observation that energy can neither be created
nor destroyed in any physical or chemical process. For example, a metal ball
of mass m held h m above the ground has potential energy given by
mgh. When the ball is dropped it loses potential energy but this potential
energy is converted into kinetic energy, ½mv
2
. The conservation of
mechanical energy requires that the total energy of the system, here
considered as the ball isolated from its surroundings, to be a constant.
5
Thus one can write for this system that the total energy ET is the sum of the
potential and kinetic energy or, mathematically,
ET = mgh + ½mv
2
(5-2)
Eventually, of course, the metal ball must strike the ground and come to rest.
What happened then to the potential energy that the ball possessed origi-
nally? It is well known that this energy is converted into heat energy upon
striking the ground. This example illustrates that even though energy cannot
be created or destroyed, it can be converted into other forms. In the above
example mechanical energy was converted into heat energy. The First
law of thermodynamics is not concerned with how much of one form of
energy is converted into another. However, it requires that, when all the
energy changes have been accounted for, the total energy of the system
before and after the change must be the same.
5.4 INTERNAL ENERGY OF A SYSTEM
The internal energy of a substance or system is the grand total of all the
different forms of energy that the substance can possess. These include all
the kinetic and potential energies that molecules of the substance can
possess due to translational, vibrational and rotational motions. It includes
potential energies due to the attractive and repulsive forces acting between
the molecules and atoms of the substance. Gravitational energy is usually
neglected, since it is very small relative to the other forms of energy. It is
obvious that the internal energy of a substance depends on its physical
state. Thus a substance in the gaseous state will have a greater internal
energy than when in the liquid or solid state since the gaseous molecules
will have greater translational, vibrational, and rotational motion. The
internal energy is an extensive property, since it will depend on the
amount of substance present (a property that does not depend on the
amount of substance present, like density, is called an intensive property).
The large number of energy terms that can contribute to the total internal
energy of a substance makes it impossible to determine the absolute value
of this quantity for a substance in a given state. However, as was
explained above, thermodynamics is interested only in the change in the
properties that occur during a process. Thus if the process takes the
system from an initial to a final state, where the internal energies are Ei
and Ef, respectively, then the change in internal energy E will be given
by
∆E = Ef – Ei ( 5-3)
It is this difference in internal energy that can be measured experimentally
from the change in properties that occurs in the process, even though the
absolute values of Ef and Ei are unknown. For example, consider the
process whereby a quantity of heat q is added to the system, and at the same
time the system performs work equal to w. Both q and w are, of course,
measurable quantities, i.e., their magnitudes are known. What is the
change in internal energy of the system for this process? The system
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initially had some indeterminate internal energy Ej and the addition of q
joules of heat must increase Ej by q. Thus for this step of the process, the
final internal energy E' is now
E' = Ei + q (5-4)
Now work is performed by the system, and this work must come from the
internal energy E' of the system. For instance, for a gas expanding against a
piston, the molecules of the gas perform work by pushing against the atmos-
phere. Because the expansion of a gas results in a decrease in the internal
energy, E’, of the system (Figure 5.2), work done by the system is assigned a
negative sign. This leads to a final state having Ef given by
Ef = E' + w (5-5)
FIGURE 5.2 Changes in the internal
energy of a system. The system absorbs
heat from the surroundings, and then
performs expansion work. Note that
expansion work, work done by the
system is assigned a negative sign. Ef =
Ei + q + w and ΔE = Ef  Ei = q + w.
The law of conservation of energy requires that the internal energy
of the final state be equal to the initial energy plus or minus any energy that
was gained or lost, respectively, by the system. This result is exactly what is
expressed in Eq. (5-5), as can be seen in a clearer fashion when the
expression for E' from Eq. (5-4) is used in Eq. (5-5),
Ef = Ei + q + w (5-6)
and using Eq. (5-3) one has for ∆E,
∆E= Ef – Ei = q + w (5-
7)
Equation (5-7) is the mathematical formulation of the First law of thermo-
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dynamics for energy changes involving heat and work only. q is assigned a
positive value when heat is added to the system, thus increasing its internal
energy in the final state. If heat were removed from the system, the internal
energy of the final state would be less than that of the initial state and
therefore q must have a negative sign in Eq. (5-7). Similarly, if work were
done on the system by an external source, for example, if a gas in a cylinder
were compressed by the application of an external force on the piston, this
would result in an increase in the internal energy of the final state and
therefore, w would take a positive sign in Eq. (5-7). Table 5.1 summarizes
the sign conventions for q and w.
Table 5.1 Sign Convention for Work and Heat
Process Sign
Work done by the system on the surroundings 
Work done on the system by the surroundings +
Heat absorbed by the surroundings from the system 
Heat absorbed by the system from the surroundings +
It was mentioned above that the internal energy depends only on the
physical state in which the system exists. Thus ∆E in Eq. (5-3) does not de-
pend on the process or path by which the system went from the initial to the
final state and only depends on the initial and final states. This means that
the internal energy is another state function. This fact leads to a very
important conclusion, that it is impossible to construct a machine that will
produce work indefinitely without the input of energy, the so-called
perpetual motion machine. Consider a process which takes a system from
state A to a higher energy state B by path 1, as is shown in Figure 5.3, and
involves an input of heat q1, and work done by the system equal to wl . Let
us imagine another process (path 2 in Figure 5.3), involving an input of heat
Figure 5.3 Energy changes in a cyclic process.
q2 and work done by the system equal to w2, which will take us back to
8
state A. The energy changes in these two processes are
∆E1 = EB – EA = q1 + w1 path I (5-8a)
and
∆E2 = EA – EB= q2 + w2 path 2 (5-8b)
The change in energy taken around the whole cycle ∆EA→A, i.e., from
state A through state B and back to state A, is given by the sum of the Eqs.
(5-8a) and (5-8b),
∆EA→A = ∆E1 + ∆E2 (5-9)
I f the f i rst l aw of thermodynami cs has to be obeyed then
E, and E2 should be equal in magnitude but opposite in sign. This
means that the net change for the cycle should be
∆EA→A = ∆E1 + ( –∆E2) = 0 (5-10)
Using Eqs. (5-8a) and (5-8b) for ∆E, and ∆E2 in Eq. (5-10), one obtains
q1 + w1 − w2 –q2 = 0
or
q2 – q1 = w1

– w2
The latter equation states that the net input of heat energy must just equal
the net work done by the system in a cyclic process. Only when this is true
will the cycle end up at a state with the same internal energy as it had orig-
inally. If it were possible to construct an engine that ran in a cycle in which
E2 > E1, then one could continually produce work from the engine
without an equivalent expenditure of energy.
WORK AND HEAT
While E is independent of the path, q and w can be different for different
paths. For example, if a gas expands against an external force, the work done
by the gas will depend on the magnitude of this force. Also, different quan-
tities of heat can be added or removed from the system. Thus in order to
reach the same final state, i.e., to expand the gas the same amount, different
quantities of work and heat can be involved. These correspond to the differ-
ent paths taken to reach the final state and the only restriction placed on the
different paths is that the sum (q + w) be the same for each path. Therefore,
q and w are not thermodynamic state functions, but their sum is a state
function which, of course, is E.
Let us look at systems in which the only work done is pressure-
volume (PV) work, i.e., mechanical work. From the fundamental definition of
work as a force acting through a distance, one has for the differential work
dw resulting from a force f acting through a differential distance dr,
dw = f dr (5-11)
The work done by the force in moving an object from r1 to r2 is given
by the definite integral,
9


·
2
1
r
r
dr f w
(5-12)
Consider the case of a gas pushing against a piston, as is shown in
Figure 5.4. The gas does work when it pushes against the external pressure,
Pext. The external force fext, by definition, equals (Pext) (A), where A is the
cross-sectional area of the piston. Using this value for f in Eq. (5-12), one
has for the work of expansion


− ·
2
1
r
r
ext
dr A P w (5-13)
where dr is the infinitesimal movement of the piston. The minus sign
in Equation (5-13) takes care of the convention for work. For gas
expansion dr > 0, so −PextAdr is a negative quantity. For gas
compression (work done on the system), dr < 0, and −PextAdr is a
positive quantity. The product Adr is equal to the infinitesimal change in
the volume dV, and therefore, one has


− ·
2
1
V
V
ext
dV A P w
(5-14)
where V1 and V2 are the initial and final volume, respectively.
When the opposing external pressure is constant, like the
pressure exerted by the atmosphere, Equation (5-14) becomes
w = −PextΔV (5-15)
Figure 5.4 The work done by a gas in a
cylinder fitted with a movable weightless
piston as it expands against a constant
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external pressure from r1 to r2 is w = −PextΔV.
It is obvious that for an expansion process, dV is positive and for
compression dV is negative. Since Pext is always positive, w will be negative
when the gas does work against Pext (expansion) and will be positive when
work is done on the gas by Pext (compression). That the pressure used in
Eq. (5-14) is the external pressure of the surroundings and not the internal
pressure of the gas can be shown by the following example.
EXAMPLE 5.1
A certain gas aexpands in volume from 2.0 L to 6.0 L at constant
temperature. Calculate the work done by the gas if it expands (a) against
vacuum ad (b) against a constant pressure of 1.2 atm.
Solution
(a) Since the external pressure is zero, the work w done is
w = −PΔV
= −0(6.0 − 2.0) L
= 0
(b) The external, opposing pressure is 1.2 atm, so
w = −PΔV
= −(1.2 atm)(6.0 − 2.0) L
= −4.8 L.atm
To convert the answer to joules, we write
atm L 1
J 101.3
atm L 8 . 4

× ⋅ · w
= −4.9 × 10
2
J
WORK DONE BY VAPORIZATION OF LIQUIDS IN OPEN
CONTAINERS
An important example of a system involving PV work is the vaporization of a
liquid at its normal boiling point. When a liquid vaporizes in an open
container, the vapor can be considered to do work against a constant
pressure, against the atmospheric pressure in this case. At the normal boiling
point vapor of the liquid, the pressure of the vapor can be taken equal to the
constant external atmospheric pressure. One then has from Eq. (5-8) that
the work done in converting a given quantity of liquid, having a volume Vl
to a vapor, having a volume Vv , against a constant pressure, Patm, which is
equal to the vapor pressure Pv, is
w = −Pat m∆V = −Pv ( Vv – V1) (5-16)
But V1 << Vg and Vl can be neglected when compared to Vv. In addition, if the
vapor is assumed to behave ideally, one has Vv = nRT/Pv, where n is the
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number of moles of liquid that was converted to vapor and Pv is the equilib-
rium vapor pressure of the liquid at the temperature T. Using these
assumptions in Eq. (5-16), one obtains
nRT
P
nRT
P V P w
v
v v v
− ·

,
`

.
|
− · − ·
(5-17)
This equation shows that for the work done in the vaporization of a
given amount of liquid depends only on the temperature and is independent
of the pressure or volume.
Note that Equation (5-17) also applies to reactions carried out in
open containers, which are accompanied by the production of gaseous
product. This is illustrated in example 5.3
EXAMPLE 5.2
Calculate the work done in vaporizing 1 mole of H2O at 100°C assuming
ideality. 1 L∙atm = 101.3 J.
Solution
At 100°C, the normal boiling point, the vapor pressure of H2O is 1 atm. The
molar volume of H2O vapor at this temperature is given by
mol / L 6 . 30
K 273
K 373
mol
L
4 . 22 · × ·
v
V
In this case, Vv = ΔV.
The molar volume of the liquid is 0.018 L (1 mol H2O = 18 g = 18
mL = 0.018 L) and is negligible compared to the molar value of the vapor.
The work done in vaporizing 1 mole of water against a constant
pressure of 1 atm is given by
J 10 3.10 atm L 30.6 mol 1
mol
L
30.6 atm 1
3
× − · − · × × − · − · ΔV P w
atm
or alternately by using w = −PvΔV =−PvVv = nRT
J 10 3.10 K 373
mol K
J
8.314 mol 1
3
× − · ×

× − · w
The energy necessary to perform this PV work of vaporization comes
from the heat energy absorbed from the surroundings. However, more
energy must be absorbed from the surroundings than is necessary to
perform this PV work. This additional amount of heat must be supplied to
the system in order to separate the molecules from their neighbors in the
liquid. The quantity of heat necessary to vaporize 1 mole of H2O at 373 K is
obtained from its heat of vaporization, which is equal to 40.69 kJ/mol. The
change in the internal energy of a mole of water upon vaporization then is
given by Eq. (5-7) as
ΔE = EH2O(v) − EH2O(l) = q + w = 40.69 kJ + (−3.10 kJ) = 37.59 kJ
Thus the internal energy of the vapor is greater than that of the
liquid, as has been stated several times in this text, and this is due to the
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large amounts of heat necessary to vaporize the liquid compared to the PV
work done by the vapor.
EXAMPLE 5.3
Calculate the work done when 50 g of iron dissolves in hydrochloric acid
in (a) a closed vessel and (b) an open beaker at 25°C. Treat the hydrogen
gas as perfect and ignore the initial volume of the system.
Solution
The reaction is
Fe(s) + 2 HCl(aq) ÷→ FeCl2(aq) + H2(g)
In the course of reaction 1 mole of gas is generated for each mole
of iron consumed. The gas drives back the surrounding atmosphere and
thereby does the work –P∆V.
For (a) ∆V = 0 because the vessel is closed and cannot expand.
Therefore
w = –P∆V = 0
For (b) ∆V ≈ Vg, and the system expands until its pressure P is 1
atm. Then, we can use PVg = nH2RT.
Note also that the number of moles of hydrogen produced is equal
to the number of moles of iron consumed.
w = –P∆V ≈ –nH2RT = –nFeRT
K 298 K mol / J 314 . 8
mol / g 85 . 55
g 50
× ⋅ × · w
= 2.2 kJ
5.4 ENTHALPY
In most laboratory work in chemistry, reactions are carried out in open
flasks and therefore they occur at the constant pressure of the atmosphere.
For constant pressure processes in which pressure-volume work is the only
work done, Eq. (5-7) can be written, using Eq. (5-15) for w,
qp = ∆E + P ∆V (5-18)
where the subscript on q indicates that the heat change occurs at constant
pressure. If, however, the process is carried out at constant volume, ∆V is
zero and one obtains
qv = ∆E (5-
19)
i.e., the change in internal energy for a constant volume process, in which
no PV work is done, is equal to the heat absorbed or evolved by the sys-
tem. Because of the importance of constant pressure processes, it is con-
venient to define a new thermodynamic function, the enthalpy, given the
symbol H. The enthalpy is defined by the equation
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H = E + PV (5-20)
Since E, P, and V are all state functions, it follows that H is also a state
function and is therefore, independent of the path taken between initial and
final states of the system. One can write, from Eq. (5-18), for the change in
enthalpy ∆H,
∆H = ∆E + ∆( PV) (5-26)
Expanding the quantity ∆(PV) in the usual manner gives
∆H = ∆E + P∆V+ V∆P (5-27)
For a constant pressure process, ∆P = 0, and one has
∆H = ∆E + P∆V (5-28)
Substituting ∆E from Eq. (5-23) into Eq. (5-28) gives
∆H = qp – P∆V + P∆V = qp (5-29)
Thus one sees that the change in enthalpy for a constant pressure process,
in which the only work done is PV work, is equal to the heat absorbed or
evolved in the process. Since H = Hf – Hi , where Hf and Hi are
the enthalpies of the final and initial states, respectively, then when
heat is absorbed by the system, the positive value for H means that the
heat content of the final state is greater than that of the initial state. When
heat is evolved by the system, H has a negative sign and the heat content
of the final state is less than that of the initial state. Using qp and qv for
H and E, respectively, in Eq. (5-28), one obtains
qp = qv + P∆V (5-24)
It is obvious from this equation that the heat absorbed in a
constant pressure process is greater than the heat absorbed in a constant
volume process by an amount equal to the PV work done by the system.
This means more heat energy is required to raise a system to a given
energy state in a constant pressure process, as compared to a constant
volume process, because some of the heat goes into performing PV work.
5.5 MOLAR HEAT CAPACITY
The concepts of enthalpy and internal energy are useful in obtaining an
exact definition of heat capacities of gases. Two types of heat capacities
could be defined. These are Cv and Cp, the heat capacities at constant
volume and pressure, respectively. Using the definition of the molar heat
capacity as the heat energy necessary to raise the temperature of one mole
of gas through one degree, one has, using qv and qp as the heat absorbed in
the constant volume and pressure processes, respectively, needed to give an
increase in temperature of ∆T,

ΔT
q
C
v
v
· (5-25a)
and

ΔT
q
C
p
p
· (5-25b)
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Using Eqs. (5-19) and (5-23) in Eqs. (5-25a) and (5-25b), i.e., using ∆E
and ∆H for qv and qp, respectively, gives

ΔT
ΔE
C
v
·
(5-26a)
and

ΔT
H
C
p
Δ
· (5-26b)
Since qp > qv, as explained above, then Cp > Cv. The exact relationship
between Cp and Cv can be obtained as follows. Using Eq. (5-22) in (5-26b)
gives

ΔT
V P
ΔT
ΔE
ΔT
V P ΔE
ΔT
ΔH
C
p
Δ Δ
+ ·
+
· · (5-27)
The first term in the expression on the right is equal to Cv by Eq. (5-
26a). The second term is simply equal to R for one mole of an ideal gas.
(Show this.) Hence, one has
Cp = Cv + R (5-28)
Thus Cp is greater than Cv by R = 8.314 J/mol·K. This quantity is
simply the work done by the gas in pushing back the piston against a
constant pressure, i.e.
w = −P∆V = −R∆T and for ∆T = 1K, w = −R
Table 5.2 Molar Heat Capacities at 25°C and 1 atm
Cv ( J / mol · K) Cp ( J / mol · K)
He, Ne, Ar, Kr, Xe
12. 5 20. 78
H2
20. 53 28. 84
N2
21. 06 29. 37
CO2
28. 81 37. 12
H2 O( g)
16. 46 24. 77
NH3
27. 32 35. 63
CH4
27. 33 35. 64
5.7 THERMOCHEMISTRY
Up to now, consideration has been given only to energy changes in-
volved in physical processes. One of the most important applications of
15
the First law to chemistry is in the study of the heat changes that
occur in chemical reactions. This study forms the subject of
thermochemistry.
It was shown in the above discussions that ∆E and ∆H were
independent of the path taken in going from the initial to the final state
of a system. Thus for reactants going to products in a chemical
reaction, the only important consideration is the measurable
quantities qv (= ∆E) and qp (= ∆H), the heat changes involved in the
reaction occurring at constant volume and constant pressure,
respectively. The absolute values of the internal energies and
enthalpies of reactants and products are not required, since one is in-
terested only in the change in these values for the reaction. When
heat is evolved in a reaction, the final state (products) is lower in
energy and by the convention used before, q is negative. For a
constant pressure reaction (for instance, a reaction run in an open
beaker), qp, and. therefore. ∆H, is negative. This fact is indicated by
writing the reaction
Reactants ÷→ products ∆HT = –q J
where q is the heat evolved in the reaction at the absolute or Kelvin
temperature T. For example, the reaction of sulfur and oxygen gas to give
sulfur dioxide at 25°C is found to evolve 296.9 kJ for 1 mole of SO2
formed. This is written
S(s) + O2(g) ÷→ SO2(g) ∆H298 = –296.9 kJ
Note that the physical state of the reactants and products is
indicated. This is necessary since the internal energy and enthalpy of a
substance depends on its physical state, as was explained previously. Thus
the heat change for the above reaction would be more if SO2

were formed in
the liquid state because the conversion of liquid SO2 to gaseous SO2
requires the input of some energy in the form of heat.
5.8 STANDARD STATES
The specification of the physical state still leaves the state of the system
incompletely defined. For instance, sulfur can exist in two solid forms;
rhombic and monoclinic. Furthermore, the values of the enthalpy and the
internal energy will depend on the temperature and pressure for any given
physical state. In order to standardize the data on heats of reactions, it is
necessary that some reference point be established for the thermodynamic
states of the reactants and the products. The choice of this reference point
is purely arbitrary and is called the standard state of the substance. By
convention, the following standard states have been adopted. The standard
state of a gas is the pure gas at 1 atm; for a liquid it is the pure liquid at 1
atm; and for a solid it is the stable crystalline form existing at 1 atm. For
example, graphite and rhombic sulfur are chosen as the standard states of
carbon and sulfur, respectively. Although the standard state does not
specify a temperature, we will always understand, unless stated otherwise,
16
values measured at 25 C. Now that the standard state is defined, one is
free to choose any value as a reference point in order to tabulate
thermodynamic data. To this end, the most convenient choice is to
assign the value of zero to the chemical elements in their standard states.
Thus H = 0 for all chemical elements, the superscript zero indicating
that the elements are in their standard states. Hence, at 1 atm and 25°C,
solid rhombic sulfur, solid copper, liquid bromine, and gaseous oxygen all
have H = 0. The enthalpy changes are measured relative to the standard
states, as will be discussed in the next section.
5.9 STANDARD ENTHALPY OF REACTIONS
The enthalpy of a reaction is the enthalpy change, Hrxn that occurs during
the reaction. When the reaction occurs between the reactants, all in their
standard states, and products, also all in their standard states, the enthalpy
change is known as the standard enthalpy change of the reactions, H
rxn. For example, when at 1 atm pressure, 2 moles of carbon monoxide are
burned in oxygen to produce 2 moles of carbon dioxide, the standard
enthalpy change of the reaction is 565.8 kJ 
2 CO(g) + O2(g) ÷→ 2 CO2(g) H rxn = 565.8 kJ 
ENTHALPY OF COMBUSTION
The heat involved due to the complete combustion of 1 mole of a
hydrocarbon with oxygen is known as the enthalpy of combustion. As
an example, one mole of propane, C3H8(g),

is burned in O2(g) at 1 atm
and 25°C to give CO2(g) and H2O(l), and the heat evolved is found to be
2220 kJ/mol. Since all substances are at 1 atm and 25°C, they are in their
standard states, and the heat evolved is the standard enthalpy of
combustion. This change is expressed in an equation as
C3H8(g) + 5 O2(g) ÷→ 3 CO2(g) + 4 H2O(l) H = 2220kJ/mol
The experimental enthalpies of combustion for some other hydrocarbons
are given in Table 5.3.
TABLE 5.3 Enthalpies of Combustion for Hydrocarbons at
25°C
Hydrocarbon H (kJ/mol)
Methane, CH4(g) –890.36
Ethane, C2H6(g) –1559.88
Propane, C3H8(g) –2220.07
n-Butane, C4H10(g) –2878.51
Isobutane. C4H10)(g) –2871.65
Ethylene, C2H4(g) –1410.97
Acetylene, C2H2(g) –1299.63
Benzene, C6H6(l) –3267.62
17
5.10 HESS’S LAW
In 1840, Hess put forth the following empirical law: the overall heat
change at constant pressure or constant volume in a given chemical reaction
is the same regardless of whether it takes place in one direct step or in sev-
eral steps. Thus if compound B could be formed from A directly and it were
also possible to go from A to B through intermediates C and D, the enthalpy
change for the direct path would be the same as the sum of the enthalpy
changes involved in the intermediate reactions. This is shown schematically
in Figure 5.5, where the ∆H's are the enthalpy changes for the individual
reactions proceeding in the directions shown by the arrows. Hess's law re-
quires that ∆H4 = ∆H1 + ∆H2 + ∆H3. It can be shown that this result can
be derived from the First law. Thus since ∆H is a state function, the sum of
the ∆H's around the cycle, taken from A through C, D and B and back to A,
by the First law must be zero [see Eq. (5-10)]. This means

0 · ∑
i
i
ΔH
= ∆H1 + ∆H2 + ∆H3 + (–∆H4) (5-29)
or
∆H4 = ∆H1 + ∆H2 + ∆H3
which is the same result predicted by Hess's law. In Eq. (5-29) the
sign of ∆H4 was reversed since in going around the cycle in a
counterclockwise manner, the reverse of the reaction path A ÷→ B was
traversed. If heat were evolved in going from A ÷→ B, the First law
requires that the same amount of heat be absorbed in the reverse
reaction. Thus ΔH is equal in magnitude but opposite in sign for the reverse
reaction.
Figure 5.5 Enthalpy changes in a cyclic process
The importance of Hess's law lies in the fact that the enthalpy
changes can be calculated for reactions that cannot be performed in the
laboratory. In order to obtain reliable H values for reactions, the reactions
must proceed rapidly and must go to completion. Many reactions are too
slow or involve the formation of side products and therefore do not meet
18
these criteria. Hess's law can be used to obtain H for these reactions.
For example, it is not possible to measure directly the heat evolved when
graphite is reacted with O2 to give CO, since it is impossible to prevent the
formation of CO2. However, the heat evolved in the complete combustion
of graphite to CO2 can be measured, as well as the heat evolved in the
combustion of CO to CO2
.
At 18°C, these reactions are
(1) C(graphite) + O2(g) ÷→ CO2(g) ∆Hrxn1 = –393.1 kJ
(2) CO(g) + ½O2(g) ÷→ CO2(g) ∆Hrxn2 = –282.9 kJ
In order to obtain ∆H for the reaction at 18°C
C( graphi te) + ½O2(g) ÷→ CO(g)
from the measured values of H for the above two reactions, reverse
reaction (2) and add to reaction (1). The same procedure must be followed
with the enthalpy changes for these reactions. Reversing the direction of
reaction (2) means the sign of Hrxn2 must be reversed, i.e., the reaction
CO2(g) ÷→ CO(g) + ½O2(g) requires the input of 282.9 kJ. The result then is
C(graphite) + ½O2(g) ÷→ CO(g) ∆Hrxn = –110.2 kJ
ENTHALPY OF FORMATION
When a mole of a given compound is formed in its standard state from its
elements, all in their standard states, the heat evolved or absorbed is known
as the standard enthalpy of formation of the compound,

f
ΔH
. As an
example, the formation of SO2(g) from its elements at 25°C and 1
atm evolves –296.90 kJ/mol of SO2(g) formed, and, therefore,

f
ΔH
= –
296.90 kJ/mol at 25°C and 1 atm.
S(rhombic) + O2(g) ÷→ SO2(g)

f
ΔH
= –296.90 kJ/mol
The heat evolved when 1 mole of methane gas is formed from
graphite and hydrogen gas at 25°C is –74.85 kJ/mol. This is repre-
sented by
C(graphite) + 2 H2(g) ÷→ CH4(g)

f
ΔH
= –74.7kJ/mol
A chemist is interested in the heat change accompanying a chemical
reaction, since the value of the equilibrium constant depends on it to a large
extent. One would like, therefore, to tabulate the H values for every
chemical reaction. However, this is too great an undertaking. The same goal
is achieved by determining the heat of formation of some chemical
species from its elements in their standard states,

f
ΔH
. For a general
reaction,
aA + bB + . . . ÷→ cC + dD + . . .
if

f
ΔH
for products and reactants are known, ∆H for the reaction can be
19
found from Hess's law in the form


rxn
ΔH =

i
i
n
i H (
f
) Δ

(products) —

j
nj
j H (
f
) Δ

(reactants) ( 5-30)
where ni are the coefficients of the products and nj are coefficients of the re-
actants, in the balanced chemical equation.
Now one can see why it is convenient to choose the enthalpy of the
elements in their standard states as zero. Since H for the process is the
difference in enthalpies of the product (final state) and reactants (initial
state), then for the formation of one mole of methane, CH4, under standard
state conditions, the measured value of the enthalpy change for the reaction
becomes

rxn
ΔH = (1 mol)
) , CH
4
g ( ΔH
f

– (1 mol)
) , ( ΔH
f
graphite C

– (1 mol)
) H
2
g , ( ΔH
f

The value obtained is equal to the enthalpy of formation of methane since Δ
) , ( H
f
graphite C

and Δ
) H
2
g , ( H
f

are assigned a value of zero.

rxn
ΔH =
) , CH
4
g ( ΔH
f

The enthalpy of formation for various compounds are shown in
Table 5.4.
TABLE 5.4 Enthalpies of Formation at 25°C
Substance

f
ΔH (kJ/mol)
H20(g) –241.8
H20(l) –285.8
HCI(g) –92.3
S02(g) –296.1
SO3 ( g) –395.2
NH3(g) –46.3
CO(g) –110.5
CO2(g) –393.5
CH4(g) –74.7
C2H2(g) +226.6
NO(g) +90.4
NO2(g) +33.85
Many compounds cannot be directly synthesized from their
elements. In some cases, the reaction proceeds too slowly, or side reactions
produce substances other than the desired compounds. In these cases

f
ΔH

can be determined by an indirect approach. As an example, consider the
formation of benzene, C6H6, from its elements at 25 C and 1 atm,
3H2(g) + 6C(graphite) ÷→ C6 H6 ( l)

f
ΔH
= ?
The enthalpy change in the written reaction cannot be determined
20
directly since the reaction of carbon and hydrogen results in a mixture of
hydrocarbons. However, one can obtain

f
ΔH
of benzene by noting that
benzene, like all organic compounds containing carbon and hydrogen can
be burned in oxygen to produce H2O and CO2, whose

f
ΔH
’s are known.
C6H6(l) + 15 O2(g) ÷→ 6 CO2(g) + 3 H2O(l)

rxn
ΔH = –3267.6 kJ
Now one can use the enthalpy of combustion of benzene, given
above, together with

f
ΔH
’s for CO2 and H2O to calculate the

f
ΔH
of
benzene

rxn
ΔH = (6 mol)
) , CO
2
g ( ΔH
f

+ (3 mol)
) , O H
2
l ( ΔH
f

– (1 mol)
l) , ( ΔH
6 f
H C
6


– (15 mol)
) O
2
g , ( ΔH
f

recalling that
) O
2
g , ( ΔH
f

is zero and rearranging for
l) , ( ΔH
6 f
H C
6

(1 mol) l) , ( ΔH
6 f
H C
6

= (6 mol) ) , CO
2
g ( ΔH
f

+ (3 mol) ) , O H
2
l ( ΔH
f



rxn
ΔH
= (6 mol)(–393.5 kJ/mol) + (3 mol)(–285.8 kJ/mol) – (–3267.6 kJ)

l) , ( ΔH
6 f
H C
6

= 49.2 kJ/mol
The following two examples show how

f
ΔH
could be used to calculate

rxn
ΔH .
EXAMPLE 5.4
Calculate the enthalpy of reaction at 25°C for the following reaction from
the standard heats of formation of reactants and products.
SO2(g) + 2 H2S(g) ÷→ 3 S(rhombic) + 2 H2O(l)
g) , ( ΔH
2 f
SO

= –296.1 kJ/mol, g) , ( ΔH
f
S H
2

= 20.2 kJ/mol, l) , ( ΔH
f
O H
2

=
–285.8 kJ/mol.
Solution
Using Eq. (5-30), one has

rxn
ΔH = (2 mol)
l) , ( ΔH
f
O H
2

+ (3 mol)(0) – (1 mol)
g) , ( ΔH
2 f
SO

– (2 mol)
g) , ( ΔH
f
S H
2

= (2 mol)(–285.8 kJ/mol) – (1 mol)(–296.1 kJ/mol) – (2 mol)(20.2 kJ/mol)
= – 234.5 kJ
EXAMPLE 5.5
Pentaborane-9, B5H9, is a colorless, highly reactive liquid that was
considered as a potential rocket fuel because it produces a large amount of
heat per gram when it explosively burns in oxygen. The idea was abandoned
because the solid B2O3 formed by the combustion is abrasive and would
quickly destroy the nozzle. The reaction is
2 B5H9(l) + 12 O2(g) ÷→ 5 B2O3(s) + 9 H2O(l)
21
The standard heat of formation at 25°C for B5H9, B2O3, and H2O are
respectively, 73.2 kJ/mol, −1263.6 kJ/mol, and −285.8 kJ/mol.
Calculate the heat liberated per gram of B5H9.
Solution
Using the given

f
ΔH
values, we write,

rxn
ΔH = (5 mol)

f
ΔH
( B2O3,s) + (9 mol)

f
ΔH
(H2O,l) (2 mol) 

f
ΔH
(B5H9,l) − 0
= (5 mol)(−1263.6 kJ/mol) + (9 mol)(−285.8 kJ/mol) −
(2 mol)(73.2 kJ/mol) − 0
= −9036.6 kJ
This is the amount of heat released for every two moles of
pentaborane-9. The heat released per gram of pentaborane-9 is
Heat released per gram of B5H9 =
9 5 9 5
9 5
H B mol 2
kJ 6 9036
H B g 12 63
H B mol 1 .
.

×
= −71.58 kJ/g 9 5
H B
Note that compounds with positive

f
ΔH
values release more heat during
combustion and are less stable than those with negative

f
ΔH
values.
5.11 RELATIONSHIP BETWEEN THE HEATS OF REACTION AT
CONSTANT PRESSURE AND CONSTANT VOLUME
Reactions occurring at constant pressure are the most common reactions in
chemical work since they consist of reactions occurring in open vessels in
which PV work is done by the system. However, a number of reactions are
performed under conditions of constant volume. For instance, the addition
of hydrogen to unsaturated hydrocarbons is usually performed in a rigid,
closed vessel known as a Paar bomb. Using Eq. (5-22)
∆H = ∆E + P∆V
one can see that if there is no net change in volume during a reaction, ∆V =
0 and ∆H = ∆E. Two main types of reactions correspond to this
condition. One type includes reactions involving only liquids and solids. In
this case, ∆V is negligibly small and P∆V is usually negligible in comparison
to ∆E. The second type includes reactions in which the number of moles of
gaseous products equals the number of moles of gaseous reactant, thus
resulting in no net increase in volume, and ∆V is essentially zero.
Let us consider the case where there is a change in the number of
moles of gaseous substances during the reaction. In this case P∆V will be a
significant quantity and must be taken into account in Eq. (5-22).
Assuming the gases to behave ideally, one can write for P∆V
P∆V = ∆nRT (5-31)
where ∆n represents the number of moles of gaseous product minus the
number of moles of gaseous reactants. Substituting Eq. (5-31) into (5-22)
gives
22
∆H = ∆E + ∆nRT (5-32)
This equation gives the relationship between the heats of reaction at constant
pressure and at constant volume for a reaction involving PV work only.
EXAMPLE 5.6
Calculate the heat change for the combustion of n-pentane when the
reaction is run in a Paar bomb at 25°C. The reaction is
C5 H1 2 ( l ) + 8O2 ( g) ÷→ 5 CO2(g) + 6 H2O(l)

rxn
ΔH = –3536. 2 kJ
Solution
The value of

rxn
ΔH is –3536. 2 kJ. The value of ∆n is (5 – 8) = –3 moles,
and using Eq. (5-32), one has for the constant volume reaction
∆E = ∆H –∆nRT
= ( ) K 298 K mol / J 314 . 8 mol 3 – – J 10 5362 . 3 –
6
× ⋅ × ×
= –3. 5362 × 10
6
J + 7.43 × 10
3
J
= –3. 53 J
Notice that the difference between ∆E and ∆H is very small.
5.12 BOND ENERGIES
In many cases it is desired to obtain an estimate of

rxn
ΔH for a reaction in
which

f
ΔH
for a reactant or product is not known and cannot be
experimentally determined. Consequently, one cannot use Eq. (5-30) to
obtain ∆H for the reaction. A way around this problem can be found in
the use of bond energies, which as you will see, yields good estimates
of

f
ΔH
that can be used to calculate

rxn
ΔH . It will be seen that this
procedure presupposes a knowledge of the structure of the
compound and therefore, does not strictly belong in a discussion
of classical thermodynamics.
MEASUREMENT OF BOND ENERGIES
The bond energies of simple molecules such as H2, O2, and C12 are usually
measured spectroscopically. That is, the light that is emitted by the
molecules when they are energized (excited) by a flame or an electric arc is
analyzed, and the amount of energy needed to break the bond is computed.
For more complex molecules, thermochemical data can be used to calculate
bond energies in a Hess's law kind of calculation. We will use the standard
heat of formation of methane, CH4, to illustrate how this is accomplished.
However, before we can attempt such a calculation, we must take a
moment to define a new thermochemical quantity that we will call the
atomization energy, symbolized Hat o m. This is the amount of energy that
is needed to rupture all the chemical bonds in one mole of gaseous molecules
to give gaseous atoms as products. For example, the change corresponding
to the atomization of methane is
23
CH4(g) ÷→ C(g) + 4 H(g)
and the enthalpy change for the process is Hat o m. For this particular
molecule, Hat o m corresponds to the total amount of energy needed to
break all the C—H bonds in one mole of CH4; therefore, division of
Hat o m by 4 would give the average C—H bond energy in methane,
expressed in kJ/mol (or kcal/mol).
4 H(g) + C(g)

2 H2(g) + C(s) ÷→ CH4(g)
Figure 5.6. Two paths for the formation of methane from
its
elements in their standard states. Steps 1, 2, and 3 of the
upper path involve the formation of gaseous atoms of the
elements and the formation of the bonds in CH4.
Figure 5.6 shows how we can use the standard heat of formation,

f
ΔH
to calculate the atomization energy. Across the bottom we have the
chemical equation for the formation of CH4 from its elements. The enthalpy
change for this reaction, of course, is

f
ΔH
. In this figure we also can see an
alternative three-step path that leads to CH4(g). One step is the breaking of
H—H bonds in the H2 molecules to give gaseous hydrogen atoms, another is
the vaporization of carbon to give gaseous carbon atoms, and the third is
the combination of the gaseous atoms to form CH4 molecules. These
changes are labeled 1, 2, and 3 in the Figure.
Since H is a state function, the net enthalpy change from one state
to another is the same regardless of the path that we follow. This means
that the sum of the enthalpy changes along the upper path must be the
same as the enthalpy change along the lower path,

f
ΔH
. Perhaps this can
be more easily seen in Hess's-law terms if we write the changes along
the upper path in the form of thermochemical equations.
Steps 1 and 2 have enthalpy changes that are called standard
heats of formation of gaseous atoms. Values for these quantities
have been measured for many of the elements and some of them are
given in Table 5.5. Note that for diatomic gaseous molecules these
values are exactly half the bond energy in the molecule. Step 3 is the
opposite of atomization, and its enthalpy change will therefore be the
negative of Hat o m ( recal l that i f we reverse a reacti on, we change
the si gn of i ts H) .
(Step 1) 2 H2(g) ÷→ 4 H(g)

1
ΔH = 4

f
ΔH
[H(g)]
1 2 3
24
(Step 2) C(s) ÷→ C(g)

2
ΔH
=

f
ΔH
[C(g)]
(Step 3) 4H( g ) + C( g ) ÷→ CH 4 ( g )

3
ΔH
= – H atom
2H2(g) + C(s) ÷→ CH4(g)

ΔH
=

f
ΔH
[CH4(g)]
Notice that by adding the first three equations, we get the
equation for the formation of CH4 from its elements in their standard
states. This means that adding the

ΔH
values of the first three equations
should give

f
ΔH
for CH4.

1
ΔH +

2
ΔH
+

3
ΔH
=

f
ΔH
[CH4(g)]
Let’s substitute for

1
ΔH ,

2
ΔH
, and

3
ΔH
, and then solve for Hatom. First,
we substitute for the

ΔH
quantities.
(4 mol)

f
ΔH
[H(g)] + (1 mol)

f
ΔH
[C(g)] + (– Hatom) = (1 mol)

f
ΔH
[CH4(g)]
Next, we solve for (– Hatom)
– Hatom = (1 mol)

f
ΔH
[CH4(g)] – (4 mol)

f
ΔH
[H(g)] – (1 mol)

f
ΔH
[C(g)]
Changing sign and rearranging the right side of the equation gives
Hatom = (4 mol)

f
ΔH
[H(g)] + (1 mol)

f
ΔH
[C(g)] – (1 mol)

f
ΔH
[CH4(g)]
Now all we need are values for the

f
ΔH
’s on the right side. From Table 5.5
we obtain

f
ΔH
[H(g)] and

f
ΔH
[C(g)], and the value of

f
ΔH
[CH4(g)] as
already seen is equal to 74.8 kJ/mol obtained from 5.3. 


f
ΔH
[H(g)] = 218.0 kJ/mol


f
ΔH
[C(g)] = 715.0 kJ/mol


f
ΔH
[CH4(g)] = –74.8 kJ/mol
Substituting these values gives
Hatom = 1662 kJ/mol (rounded)
and division by 4 gives an estimate of the average C—H bond energy in this
molecule.
bond H C mol kJ 5 415
4
mol kJ 1662
energy Bond − · · / .
/
Table 5.5 Standard Heats of
Formation of
Gaseous Atoms from the
Elements.

f
ΔH
atom kJ/mol kcal/mol*
C 715.0 170.9
N 472.7 113.0
O 249.2 59.6
H 218.0 52.1
F 79.9 18.9
25
Cl 121.0 28.9
Br 111.9 26.7
S 274.7 65.7
* 1 cal = 4.184 J
This value is quite close to the value in Table 5.6, which is an average of C
—H bond energies in many different compounds. The other bond energies in
Table 5.6 are also based on thermochemical data and were obtained by
similar calculations.
Table 5.6 Average Bond Energies in Polyatomic
Molecules
Bond Energy Bond Energy
Bond kJ/mol Bond kJ/mol
H–N 391 C–H 413
C–C 413 C–N 292
C–O 351 C=N 615
C=O 715 C≡N 891
C–C 348 C–F 439
C=C 615 C–Cl 328
C≡C 812 H–O 464
UESES OF BOND ENERGIES
An amazing thing about covalent bond energies is that they are very
nearly the same in many different compounds. This suggests, for
example, that a C—H bond is very nearly the same in CH4 as it is in a
large number of other compounds that contain this kind of bond. That
alone is very useful information, because it explains why molecules
having similar bonds behave in similar ways. If the properties of a
particular kind of bond varied much from compound to compound, this
would not be true.
Because the bond energy doesn't vary much from compound to
compound, we can use tabulated bond energies to estimate the heats of
formation of substances. This is illustrated in Example 5.7.
EXAMPLE 5.7
Use the bond energies in Table 5.5 and 5.6 to estimate the heat of formation
of methanol vapor, CH3OH(g).
Solution
We solve this problem in much the same way that we calculated the
bond energy of methane in the discussion above. We setup two paths from
the elements to the compound, as shown in the Figure shown below. The
lower path has an enthalpy change corresponding to

f
ΔH
[CH3OH(g)], while
the upper path takes us to the gaseous elements and then through the
26
energy released when the bonds in the molecule are formed. This latter energy
can be computed from the bond energies in Table 5.6. As before, the sum of
the energy changes along the upper path must be the same as the energy
change along the lower path, and this permits us to compute

f
ΔH
[CH3OH(g)].
C(g) + 4 H(g) + O(g)

C(s) + 2 H2(g) + 1/2O2(g) ÷→ CH3OH(g)
Steps 1, 2, and 3 involve the
,
formation of the gaseous atoms from the
elements, and their enthalpy changes are taken from Table 5.5.

1
ΔH = 1 mol ×

f
ΔH
[C(g)] = 1 mol × 715.0 kJ/mol = 715.0 kJ

2
ΔH
= = 4 mol ×

f
ΔH
[H(g)] = 4 mol × (218.0 kJ/mol) = 872.0 kJ

3
ΔH
= 1 mol ×

f
ΔH
[O (g)] = 1 mol × (249.2 kJ/mol) = 249.2 0
Adding these values gives a total energy input for the first three steps of 1836.2
kJ. In other words, the net

ΔH
for the first three steps is +1836.2 kJ.
The formation of the CH3OH molecule from the gaseous atoms is
exothermic—energy is always released when atoms become joined by a
covalent bond. In this molecule we can count three C—H bonds, one C —O
bond, and one O—H bond. Their formation releases energy equal to their
bond energies, which we obtain from Table 5.6.
Bond Energy
(kJ)
3(C—H) 3 × (413 kJ/mol) = 1239
C —O 351
O—H 464
Adding these together gives a total of 2054 kJ.

ΔH
for this step is therefore
—2054 kJ (because it is exothermic). Now we can compute the total
enthalpy change for the upper path.


ΔH
= (+ 1836 kJ) + (–2054 kJ)


ΔH
= –218 kJ
The value just calculated must be equal to the

ΔH
for the lower path
of the Figure, which is

f
ΔH
for CH3OH(g). Experimentally, it has been found
that

f
ΔH
for this molecule (in the vapor state) is –201 kJ/mol. At first glance,
the agreement doesn't seem very good, but on a relative basis the calculated
value (–218 kJ) differs from the experimental one by only about 8%.
Comparisons between measured and calculated bond energies
1 2 3 4
27
have sometimes helped chemists understand unusual properties of
some substances. Consider, for example, the case of benzene, C6H6.
This molecule has its six carbon atoms arranged in a hexagonal ring,
and bonded to each carbon is one of the hydrogen atoms. One of the
Lewis structures that we

can draw for the molecule is
Benzene, however, doesn't behave chemically as if this is its
structure. It doesn't undergo reactions that are typical of hydrocarbons
with carbon -carbon double bonds, and the ring structure has a great
tendency to remain intact during chemical reactions. This Lewis structure
is inadequate in other ways, too. You learned that the bond length is
related to the number of electron pairs that are shared between two
bonded atoms. On that basis we would anticipate that some of the carbon
- carbon bonds in benzene should be longer than others. Actually, they
are all the same, and to account for this we say that the actual structure
of benzene is a resonance hybrid. The resonance structures that are
drawn to represent the hybrid are
If we used either one of these Lewis structures as if it really existed
in an attempt to calculate the heat of formation of C6H6, just as in
Example 5.7, the value we would obtain is about +230 kJ/mol.
However, the experimentally measured

f
ΔH
for C6H6 is only about +84
kJ/mol. The difference between the calculated and experimental values
is much too large to be just experimental error, and it means that the
actual molecule is more stable than we computed it to be by about 146
kJ/mol. In general, it is found that for molecules for which resonance
is used to explain equality of bond lengths—as in benzene here and
in molecules such as S02 and

S03, the actual

f
ΔH
is more exothermic
(less endothermic) than the

f
ΔH
calculated using tabulated bond
energies. In other words, resonance leads to an additional stabilization
of the molecule, and the energy difference between the calculated and
actual

f
ΔH
is called the resonance energy or stabilization energy.
28
5.13 DEPENDENCE OF HEAT CAPACITY AND OF ENTHALPY OF
REACTION ON TEMPERATURE
Experiments with gases have shown that while the heat capacity of a mon-
atomic gas is independent of temperature, except at extremely law
temperatures, the heat capacities of polyatomic molecules (gases, liquids,
and solids) increases with increasing temperature. Heat capacity equations
are often of the form
Cp = a + bT + cT
2
+ dT
3
(5-33a)
or
Cp = a + bT + cT
– 2
( 5-33b)
where a, b, and c are empirically determined constants for a given
substance. Using Eq. (5-26b) in the differential form
dH = CpdT (5-34)
and substituting the expression for Cp from Eq. (5-33a and 5-33b) into Eq. (5-
34), one obtains an expression for the change in enthalpy, dH, of a
substance in some phase for a change in temperature dT
dH = ( a + bT + cT
2
+ dT
3
) dT (5-35a)
or
dH = ( a + bT + cT
– 2
) dT ( 5-35b)
If one wants to determine the change in enthalpy ∆H for a process in which
the temperature changes from T1 to T2 (which is the heat qp necessary
to raise the temperature of a compound in the same phase from T1 to T2 at
constant pressure, one integrates Eq. (5-35a and 5-35b) between the
temperature T1 and T2. Thus


+ + + · ·
2
1
1 2
T
T
3 2
T T
dT ) dT cT bT (a H – H ΔH
(5-36)
and
( ) ( ) ( )
4
1
4
2
3
1
3
2
2
1
2
2 1 2
– –
3

2
) – ( T T
4
d
T T
c
T T
b
T T a ΔH + + + ·
(5-
37)
or


+ + · ·
2
1
1 2
T
T
–2
T T
dT ) cT bT (a H – H ΔH
(5-38)
and

( )

,
`

.
|
− + ·
1 2
2
1
2
2 1 2
1 1
2 T

T
c T – T
b
) T – a(T ΔH
(5-39)
If either the temperature change or the change in heat capacity over the tem-
perature range is small, i.e., b and c in Eq. (5-33a or 5-33b) are small, then
29
Cp can be taken equal to the constant value a. In this case, Cp is independent
of temperature, and integration of Eq. (5-36 or 5-38) gives
∆H = HT 2

– HT1 = Cp( T2 – T1) (5-40)
The heat capacities at constant pressure as a function of
temperature for various gases are given in Table 5.7.
EXAMPLE 5.8
Calculate the heat necessary to raise the temperature of 2 moles of gaseous
C12 from 500 K to 1000 K at constant pressure.
Solution
The expression for Cl2 of Cl2 as a function of temperature is obtained from
Table 5.7. Using this in Eq. (5-36), one has for one mole of gas

· ·
1000
500
p p
dT C q ΔH

× × + ·
1000
500
–2 5 3 –
dT ) T 10 –2.85 T 10 0.67 (37.03
( )
,
`

.
|
× +
×
+ ·
500
1
1000
1
10 85 2 500 ( 1000 (
2
10 67 . 0
500 1000 03 7 3 ΔH
5 2 2
3 –
– . ) – ) ) – ( .
∆H = 18515 + 251.25 + 285 = 19051J/mol
Since two moles of Cl2

were involved, ∆H is twice this value or
38102 J. If Cp had been taken as constant and equal to 37.03 J/mol·K
over this temperature range, Eq. (5-50) would give ∆H = 18515
J/mol, which is much lower than the correct value. Obviously, the
vibrational and rotational moles of motion in C12 are contributing to the
heat capacity to an appreciable extent over this temperature range.
TABLE 5.7 Heat Capacities at Constant Pressure as a
Function of T for Some Gases, liquids, and solids.
Cp(J/mol·K) = a + bT + cT
– 2*
Gases a b × 10
3
c × 10
–5
He, Ne, Ar, Kr, Xe 20.7
8
0 0
H2 27.2
8
3.26 0.5
0
O2 29.9
6
4.18 –1.67
N2 28.5
8
3.77 –0.50
30
F2 34.5
6
2.51 –3.51
Cl2 37.0
3
0.67 –2.85
Br2 37.3
2
0.50 –1.26
CO2 44.2
2
8.79 –8.62
H2O 30.5
4
10.2
9
0
NH3 29.7
5
25.1
0
–1.55
CH4 23.6
4
47.8
6
–1.92
Liquids (Tmelt→Tboil)
H2O 75.7
8
0 0
Solids
C(graphite) 16.8
6
4.77 –8.54
Cu 22.6
4
6.28 0
I2 40.1
2
49.7
9
0
NaCl 45.9
4
16.3
2
0
*Positive exponent means you use negative exponent in the
expression; e.g. if b × 10
3
= 123.0, then b = 123.0 × 10
–3
5.14 ENTHALPY CHANGE OF A REACTION AT ANY TEMPERATURE
The heat capacities of reactants and products can be used to calculate the
enthalpy change for a given reaction at some temperature T2 from a knowl-
edge of the enthalpy change for the reaction at some other temperature T1.
A calculation of this type is very useful since it eliminates the necessity of
experimentally determining ∆H for the reaction at every temperature. Let
us see how this calculation is performed. Consider the reaction
aA + bB ÷→ cC + dD
At T1, the enthalpy change is measured to be ∆H1. One now would like to
know the enthalpy change at temperature T2, where T2 > T1. This result can
be obtained by considering the cyclic process shown in Figure 5.7.
(aA + bB) at T2 ∆H2 cC + dD) at T2

31
∆H’ ∆H”

(aA + bB) at T1 ∆H1 (cC + dD) at T1
Figure 5.7. Alternative paths for converting reactants to
products.
1. The reaction aA + bB ÷→ cC + dD at T1 is performed and the
enthalpy change is ∆H1.
2. The reactants aA + bB are now raised from T1 to T2, the enthalpy
change for this process is given by Eq. (5-36) as

·
2
1
T
T
s) p(reactant
dT C ' ΔH
where
Cp(reactants) = aCp(A) + bCp(B)
3. Next, the reaction aA + bB ÷→ cC + dD at T2 is performed. The
enthalpy change for this step is ∆H2.
4. Finally, the products are lowered in temperature from T2 to T1.
The enthalpy change is

·
1
2
T
T
) p(products
dT C " ΔH
where
Cp(products) = cCp(C) + dCp(D)
Referring to Figure 5.7, we see that since ∆H is independent of path
∆H1 = ∆H’ + ∆H2 + ∆H”
Now H2 is the only unknown, so
H2 = H1 – H” – H’

dT C – dT C ΔH ΔH
2
1
1
2
T
T
s) p(reactant
T
T
) p(products – 1 2
∫ ∫
·
(5-41)
We can change the sign of the second term on the right-hand side of this
equation if we reverse the limits of integration. Thus

dT C – dT C ΔH ΔH
2
1
2
1
T
T
s) p(reactant
T
T
) p(products 1 2
∫ ∫
+
·
(5-42)
32
The expression can be made more compact if we define
∆Cp = Cp(products) – Cp(reactants)
= cCp(C) + dCp(d) – aCp(A) – bCp(B)
The integrals can be combined to give


+
·
2
1
1
T
T
p 2
dT ΔC ΔH ΔH
(5-43)

( ) ( ) [ ]

+ + ·
+
2
1
T
T
p p p 1 2
dT bCp(B) p(A) aC – (d) dC (C) cC ΔH ΔH
(5-44)
We see now that the difference in ∆H at the two temperatures depends
on the difference of the heat capacities of the products and reactants. Often
this heat-capacity difference is very small, and ∆H is virtually independent of
temperature, particularly over small temperature ranges.
If the heat capacities reactants and products do not change
appreciably over the temperature range T1 to T2, then we can write
∆H2 = ∆H1 + ∆Cp∆T (5-45)
On the other hand, if the heat capacities change appreciably over
the temperature range T1 to T2, then the empirical expressions for Cp as a
function of T for each substance must be used in Eq. (5-44) in a manner
exactly analogous to that used in Example 5-8.
EXAMPLE 5.9
The hydrogenation of methyl chloride was studied at 248°C (521 K). It was
found that at that temperature ∆H521 = –82.32 kJ. Calculate

298
ΔH
by
using Cp values reported at 400 K. Cp(CH4(g)) = 41.28 J/mol·K, Cp(HCl(g) =
29.11 J/mol·K, Cp(CH3Cl(g) = 48.46 J/mol·K, and Cp(H2(g) = 28.56
J/mol·K.
Solution

298
ΔH
is related to
521
ΔH by Eq. (5-45)

298
ΔH
=
521
ΔH + Cp T
For the reaction
CH3Cl + H2 ÷→ CH4 + HCl
∆Cp = Cp(products) – Cp(reactants)
= (1 mol)( 41.28 J/mol·K) + (1mol)( 29.11 J/mol·K)
– (1 mol)( 48.46 J/mol·K) – (1 mol)( 28.56 J/mol·K)
33
= –6.63 J/K
and so

298
ΔH
=
521
ΔH + Cp(298 – 521)
= –82.32 10
3
J + (–6.63 J/K)(298 K – 521 K)
= –82.32 10
3
J + (– 6.63 J/K)(–223K)
= –80.84 kJ
Comment: We see that the reaction would be nearly 2% less exothermic if
it were to run at 298 K.
EXAMPLE 5.10
One method for producing ethanol on an industrial scale is the direct
hydration of ethylene
C2H4(g) + H2O(g) ÷→ C2H5OH(g)

298
ΔH = –42.92 kJ
Calculate

50
ΔH .
The Cp functions of the form a + bT + cT
2
+ dT
3
in J/K · mol are
Cp(C2H5OH) = 19.9 + 20.95×10
– 2
T – 10.37×10
– 5
T
2
+ 20.04×10
– 9
T
3
Cp(C2H4) = 3.95 + 15.63×10
– 2
T – 8.338×10
– 5
T
2
+ 17.66×10
– 9
T
3
Cp(H2O) = 32.22 + 0.192×10
– 2
T + 1.054×10
– 5
T
2
– 3.594×10
– 9
T
3
Solution
The relationship between

298
ΔH and

50
ΔH is given by Eq. (5-43), (5-44)

+
·
50
298
p 298 50
dT ΔC ΔH ΔH
 
For the given reaction ∆Cp is
∆Cp = (1 mol) Cp(C2H5OH) – (1mol) Cp(C2H4) – (1 mol) Cp(H2O)
= ∆a + ∆bT + ∆cT
2
+ ∆dT
3
= –16.29 + (5.125×10
– 2
T ) – (3.088×10
– 5
T
2
) + (5.979×10
– 9
T
3
)
where ∆a = (19.9 – 3.95 – 32.22 = –16.29, ∆b = (20.95 ×10
– 2
) T – (15.63 ×
10
– 2
) T – 0.192 ×10
– 2
) T = 15.13 ×10
– 2
T and so on.
( )
∫ ∫
× + × × + ·
50
298
3 –9 2 –5 –2
50
298
p
dT ) T 10 (5.979 ) T 10 –(3.088 T) 10 (5.13 –16.29 dT ΔC
34
( )
( ) ( )
4 4
9 –
3 3
2 5 –
2 2
2 –
) 298 ( – ) 50 (
4
) 10 979 . 5 (
) 298 ( – ) 50 (
3
) 10 088 . 3 (

) 298 ( – ) 50 (
2
) 10 13 . 5 (
) 298 – 50 )( 29 . 16 (–
×
+
×
×
+ ·
T
= 4039.92 – 2211,54 + 271.11 – 11.78
= 2087.71

50
ΔH =

298
ΔH + 2087.71
= – 45.756 kJ + 2.088 kJ = – 43.668 kJ
Notice that, like in the previous Exercise, at approximately 250°C
lower termperature, the reaction is only slightly less exothermic, and for
practical purposes ∆H can be considered insensitive to temperature over a
few hundred degrees temperature change.
5.15 THE SECOND LAW OF THERMODYNAMICS: FEASIBILITY OF
ENERGY CHANGE
The Second law is formulated in order to complete the generalization of
the experimental facts concerned with the way in which energy forms can be
interconverted. The First law is only concerned with energy balance, i.e., if
one form of energy is created during a process, an equal quantity of energy,
either in the same form or in a different form, must be used up. For example,
when two metal bars at different temperatures are brought together, q
calories of heat will flow from the bar at the higher temperature to the one
at the lower temperature until thermal equilibrium is established. The
reverse process can be considered to occur also, i.e., –q calories of heat can
be lost by one bar and gained by the second, thus restoring the system (the
two bars) to its original state. Neither process violates the First law since
all energy changes are accounted for. However, the second process violates
our knowledge, based on numerous observations, that a bar of metal at a
uniform temperature can never, without some external help, become hotter
at one end and colder at the other. Hence our experience places restrictions
on how processes involving energy changes can occur that are not
considered in the First law. These restrictions are formulated into expres-
sions of the Second law.
As can be seen from the example just given, the Second law is concerned
with the feasibility of an energy change occurring. Thus the Second law
states that heat can never flow from a colder to a hotter body without some
outside aid.
5.16 SPONTANEOUS PROCESSES AND ENTROPY
One of the main objectives in studying thermodynamics, as far as
chemists are concerned, is to he able to predict whether or not a
reaction will occur when reactants are brought together under a
special set of conditions (for example, at a certain temperature,
pressure, and concentration). This knowledge is important whether
35
one is synthesizing compounds in a research laboratory,
manufacturing chemicals on an industrial scale, or trying to
understand the intricate biological processes in a cell. A reaction that
does occur under the given set of conditions is called a spontaneous
reaction. If a reaction does not occur under specified conditions, it is
said to be nonspontaneous. We observe spontaneous physical and
chemical processes every day, including many of the following examples:
•A waterfall runs downhill, but never up, spontaneously.
•A lump of sugar spontaneously dissolves in a cup of coffee, but
dissolved sugar does not spontaneously reappear in its original form.
•Water freezes spontaneously below 0°C, and ice melts
spontaneously above 0°C (at 1 atm).
•Heat flows from a hotter object to a colder one, but the reverse
never happens spontaneously.
•The expansion of a gas in an evacuated bulb is a spontaneous process.
The reverse process, that is, the gathering of all the molecules into
one bulb, is not spontaneous.
•A piece of sodium metal reacts violently with water to form sodium
hydroxide and hydrogen gas. However, hydrogen gas does not react
with sodium hydroxide to form water and sodium.
•Iron exposed to water and oxygen forms rust, but rust does not
spontaneously change back to iron.
These examples show that processes that occur spontaneously in
one direction cannot, under the same conditions, also take place
spontaneously in the opposite direction. If we assume that spontaneous
processes occur so as to decrease the energy of a system, we can explain
why a ball rolls downhill. Similarly, a large number of exothermic
reactions are spontaneous. An example is the combustion of methane:
CH4( g ) + 2 O2 (g)

÷→

CO2( g ) + 2 H2 O(l)


ΔH
= –890.4 kJ
Another example is the acid-base neutralization reaction:
H
+
(aq) + OH

(aq) ÷→ H2O(l)

ΔH
= –56.2 kJ
But consider a solid-to-liquid phase transition such as
H20(s) ÷→ H2O(l)

ΔH
= 6.01 kJ
In this case, the assumption that spontaneous processes always decrease a
system's energy fails. Experience tells us that ice melts spontaneously
above 0 C even though the process is endothermic. Another example that
contradicts our assumption is the dissolution of ammonium nitrate in
water:
NH4NO3(s) ÷→
+
4
NH
(aq) +

3
NO
(aq)

ΔH
= 25 kJ
This process is spontaneous, and yet it is also endothermic. The
decomposition of mercury(II) oxide is an endothermic reaction that is
nonspontaneous at room temperature, but it becomes spontaneous when
the temperature is raised:
36
2HgO(s) ÷→ 2Hg(l) + O2(g)

ΔH
= 90.7 kJ
From a study of the examples mentioned and many more cases,
we come to the following conclusion: Exothermicity favors the
spontaneity of a reaction but does not guarantee it. Just as it is possible
for an endothermic reaction to be spontaneous, it is possible for an
exothermic reaction to be nonspontaneous. In other words, we cannot
decide whether or not a chemical reaction will occur spontaneously
solely on the basis of energy changes in the system. To make this kind of
prediction we need another thermodynamic quantity, which turns out to be
entropy.
5.17 ENTROPY
In order to predict the spontaneity of a process, we need to know two things
about the system. One is the change in enthalpy, which is nearly
equivalent to E for most processes. The other is entropy (S), which is
a measure of the randomness or disorder of a system. The greater the
disorder of a system, the greater its entropy. Conversely, the more ordered a
system, the smaller its entropy. One way to illustrate order and disorder is
with a deck of playing cards. A new deck of cards is arranged in an
ordered fashion (the cards are from ace to king and the suits are in the
order of spades to hearts to diamonds to clubs). Once the deck has been
shuffled, the cards are no longer in sequence by number or by suit. It is
possible, but extremely unlikely, that by reshuffling the cards we can
restore the original order. There are many ways for the cards to be Out
of sequence but only one way for them to he ordered according to our
definition.
For any substance, the particles in the solid state are more
ordered than those in the liquid state, which in turn are more ordered
than those in the gaseous state. So for the same molar amount of a
substance, we can write
Ssolid < Sliquid << Sgas
In other words, entropy describes the extent to which atoms,
molecules, or ions are distributed in a disorderly fashion in a given region
in space.
One way to conceptualize order and disorder is in terms of
probability. A probable event is one that can happen in many ways, and an
improbable event is one that can happen in only one or a few ways. An
ordered state has a low probability of occurring and a small entropy, while a
disordered state has a high probability of occurring and a large entropy.
As we will see, it is possible to determine the absolute entropy of a
substance, something we cannot do for energy or enthalpy. Standard
entropy is the absolute entropy of a substance at 1 atm and 25°C. It is this
value that is generally used in calculations. (Recall that the standard state
refers only to 1 atm. The reason for specifying 25°C is that many processes
are carried out at room temperature.) Table 5.7 lists standard entropies of a
37
few elements and compounds; A more extensive listing can be found in
Appendices of General Chemistry books. The units of entropy are J/K or
J/K∙mol for 1 mole of the substance. We use joules rather than kilojoules
because entropy values are typically quite small. Entropies of elements and
compounds are all positive (that is, S° > 0). By contrast, the standard
enthalpy of formation (

f
ΔH
) for elements in their stable form is zero,
and for compounds it may be positive or negative.
Referring to Table 5.8, we can make the following observations.
The entropy of water vapor is greater than the entropy of liquid water,
because a mole of water has a much smaller volume in the liquid state
than it does in

the gaseous state. In other words, water molecules are
more ordered in the liquid state because there is less space for them
to occupy. Similarly, bromine vapor has a higher entropy value
than liquid bromine, and iodine vapor has a greater entropy value
than solid iodine. For different substances in the same phase, the
molecular complexity and molar mass determine which ones have
higher entropy values. Both diamond and graphite are solids, for ex-
ample, but diamond has the more ordered structure. Therefore, di-
amond has a smaller entropy value than graphite. Both neon and
helium are monatomic gases, but neon has a greater entropy value
than helium because its molar mass is Greater.
Table 5.8 Standard Entropy Values (S
°) for Selected Substances.
Substance S°(J/K·mol)
H2O(l) 69.9
H2O(g) 188.7
Br2(l) 152.3
Br2(g) 245.3
I2(s) 116.7
I2(g) 260.6
C(diamond) 2.44
C(graphite) 5.69
He(g) 126.1
Ne(g) 146.2
Like energy and enthalpy, entropy is a state function. Consider
a certain process in which a system changes from some initial state
to some final state. The entropy change for the process, ∆S, is
∆S = Sf – Si (5-46)
where Sf and Si are the entropies of the system in the final and
initial states, respectively. If the change results in an increase in
randomness, or disorder, then Sf > Si or ∆S > 0. Thus, both melting
and vaporization processes have ∆S > 0. The solution process usually
leads to an increase in entropy. The following example deals with the
entropy changes of a system resulting from physical changes.
38
EXAMPLE 5.11
Predict whether the entropy change is greater than or less than
zero for each of the following processes: (a) freezing ethanol, (b)
evaporating a beaker of liquid bromine at room temperature, (c)
dissolving sucrose in water, (d) cooling nitrogen gas from 80°C to
20°C.
Answer
(a) This is a liquid-to-solid phase transition. The system becomes
more ordered, so that ∆S < 0.
(b) This is a liquid-to-vapor phase transition. The system
becomes more disordered, and ∆S > 0.
(c) A solution is invariably more disordered than its components (the
solute and solvent). Therefore, ∆S > 0.
(d) Cooling decreases molecular motion; therefore, ∆S < 0.
PRACTICE EXERCISE
How does the entropy of a system change for each of the following
processes? (a) condensing water vapor, (b) forming sucrose
crystals from a supersaturated solution, (c) heating hydrogen gas
from 60°C to 80°C, (d) subliming dry ice
5.18 THE SECOND LAW OF THERMODYNAMI CS STATED
I N TERMS OF ENTROPY
The connect i on bet ween ent ropy and t he spont anei t y of a
r eact i on i s expressed by t he second law of thermodynamics:
The entropy of the universe increases in a spontaneous process and
remains unchanged in an equilibrium process. Since the universe is made
up of the system and the surroundings, the entropy change in the
universe (∆Suniv) for any process is the sum of the entropy changes in
the system (∆Ssys) and in the surroundings (∆Ssurr). Mathematically,
we can express the second law of thermodynamics as follows:
For a spontaneous process: ∆Suniv = ∆Ssys + ∆Ssurr > 0 (5-47)
For an equilibrium process: ∆Suniv = ∆Ssys + ∆Ssurr = 0 (5-48)
For a spontaneous process, the second law says that ∆Suniv must be
greater than zero, but it does not place a restriction on either ∆Ssys or
∆Ssurr. Thus it is possible for either ∆Ssys or ∆Ssurr to be negative, as
long as the sum of these two quantities is greater than zero. For an
equilibrium process, ∆Suniv is zero. In this case ∆Ssys and ∆Ssurr must be
equal in magnitude, but opposite in sign. What if for some process we
find that ∆Suniv is negative'? What this means is that the process is not
spontaneous in the direction described. Rather, it is spontaneous in the
opposite direction.
ENTROPY CHANGES IN THE SYSTEM
To calculate ∆Suniv we need to know both ∆Ssys and ∆Ssurr. Let us focus first
39
on ∆Ssys Suppose that the system is represented by the following reaction:
aA + bB ÷→ cC + dD
As is the case for the enthalpy of a reaction, the standard entropy of
reaction

rxn
ΔS
is given by


rxn
ΔS
= [cS (C) + dS (D)] – [aS (A) + bS (B) (5-
49)
or, in general, using Σ to represent summation and m and n for the
stoichiometric coefficients in the reaction,


rxn
ΔS
= Σn S (productd) – ΣmS (reactants) (5-
50)
The standard entropy values of a large number of compounds have been
measured in J/K∙mol. To calculate

rxn
ΔS
(which is ∆Ssys), we look up their
values in an Appendix and proceed according to the following example.
EXAMPLE 5.12
From the absolute entropy values the chemicals taking part in the
reactions given below, calculate the standard entropy changes for the
following reactions at 25°C. S°

(CaO) = 39.8 J/K∙mol, S°(C02) =
213.6J/K∙mol, S°(CaCO3) = 92.9 J/K∙mol, S°

(NH3) =193 J/K∙mol, S°(N2)
=192 J/K∙mol, S°(H2) = 131 J/K∙mol, S°(HCl) = 187 J/K∙mol, S°(Cl2) = 223
J/K∙mol.
(a) CaCO3(s) ÷→ CaO(s) + CO2(g)
(b) N2(g) + 3H2(g) ÷→ 2NH3(g)
(c) H2(g) + C12(g) ÷→ 2HCI(g)
Answer
We can calculate ∆S° by using Equation (5-60).
(a)

rxn
ΔS
= [S°

(CaO) + S°

(C02)] – [S°

(CaCO3)]
= [(1 mol)(39.8 J/K∙mol) + (1 mol)(213.6J/K∙mol)]
– (1 mol)(92.9 J/K∙mol)
= 160.5 J/K
Thus, when I mol e of CaCO3 decomposes to form 1 mole of CaO
and I mol e of gaseous CO2, there is an increase in entropy equal to 160.5
J/K.
(b)

rxn
ΔS
= [2S°

(NH3)] – [S°

(N2) + 3S°

(H2)]
= (2 mol)(193 J/K∙mol) – [(1 mol)(192 J/K∙mol)
+ (3 mol)(131 J/K∙mol)]
= –199 J/K
This result shows that when I mole of gaseous nitrogen reacts
with 3 moles of gaseous hydrogen to form 2 moles of gaseous
ammonia, there is a decrease in entropy equal to –199 J/K.
40
(c)

rxn
ΔS
= [2S°

(HCl)] – [S°

(H2) + S°

(Cl2)]
= (2 mol)(187 J/K∙mol) – [(1 mol)(I 31 J/K∙mol)
+ (1 mol)(223 J/K∙mol)]
= 20 J/K
Thus the formation of 2 moles of gaseous HCl from 1 mole of
gaseous H2 and 1 mole of gaseous C12 results in a small increase in
entropy equal to 20 J/K.
The results of Example 12 are consistent with results
observed for many other reactions. Taken together, they support the
following general rules:
• If a reaction produces more gas molecules than it consumes
[Example 12(a)], S°

is positive.
• If the total number of gas molecules diminishes ]Example
12(b)], S°

is negative.
• If there is no net change in the total number of gas
molecules ]Example 12(c)], then S°

may be positive or negative,
but will he relatively small numerically.
These conclusions make sense, given that gases invariably
have greater entropy than liquids and solids. For reactions involving
only liquids and solids, predicting the sign of S° is more difficult,
but in many such cases an increase in the total number of molecules
and/or ions is accompanied by an increase in entropy.
The following example shows how knowing the nature of
reactants and products makes it possible to predict entropy changes.
EXAMPLE 5.14
Predict whether the entropy change of the system in each of the
following reactions is positive or negative.
(a)2 H2(g) + O2(g) ÷→ 2 H2O(l)
(b)NH4Cl(s) ÷→ NH3(g) + HCl(g)
(c)H2(g) + Br2(g) ÷→ 2 HBr(g)
Answer
(a) Two gases combine to form a liquid. Therefore, S is negative.
(b) Since the solid is converted to two gaseous products, S is positive.
(c) We see that the same number of moles of gas is involved in the
reactants as in the product. Therefore we cannot predict the sign of S,
but we know the change must be quite small.
PRACTICE EXERCISE
Discuss qualitatively the sign of the entropy change expected for each of the
following processes:
(a)I2(g) ÷→ 2 I(g)
(b)2 Zn( s ) + 02(g) ÷→ 2 ZnO(s)
(c)N2(g) + O2(g) ÷→ 2 NO(g)
41
ENTROPY CHANGES IN THE SURROUNDINGS
Next we see how the ∆Ssurr is calculated. When an exothermic process
takes place in the system, the heat transferred to the surroundings
enhances motion of the molecules in the surroundings.
Consequently, there is an increase in disorder at the molecular level,
and the entropy of the surroundings increases. Conversely, an
endothermic process in the system absorbs heat from the
surroundings and so decreases the entropy of the surroundings
because molecular motion decreases. For constant-pressure
processes the heat change i s equal to the enthalpy change of the
system, ∆Ssys. Therefore, the change in entropy of the surroundings, ∆Ssurr
is proportional to
∆Ssurr ∝ –∆Ssys
The minus sign is used because if the process is exothermic, ∆Ssys
is negative and ∆Ssurr is a positive quantity, indicating an increase in
entropy. On the other hand, for an endothermic process, ∆Ssys is
positive and the negative sign ensures that the entropy of the
surroundings decreases.
The change in entropy for a given amount of heat also depends on the
temperature. If the temperature of the surroundings is high, the
molecules are already quite energetic. Therefore, the absorption of heat
from an exothermic process in the system will have relatively little
impact on molecular motion and the resulting increase in entropy will be
small. However, if the temperature of the surroundings is low, then the
addition of the same amount of heat will cause a more drastic increase in
molecular motion and hence a larger increase in entropy. By analogy,
someone coughing in a crowded restaurant will not disturb too many
people, but someone coughing in a library definitely will. From the
inverse relationship between ∆Ssurr and temperature T (in Kelvins)—that
is, the higher the temperature, the smaller the ∆Ssurr and vice versa—we
can rewrite the above relationship as

T
ΔH –
ΔS
sys
surr
· (5-61)
Let us now apply the procedure for calculating ∆Ssys and

∆Ssurr

to
the synthesis of ammonia and ask whether the reaction is spontaneous at
25°C:
N2(g) + 3 H2(g) ÷→ 2 NH3(g) ∆H° = –92.6 kJ
From Example 12(b) we have ∆Ssys = –199 J/K, and substituting ∆Hsys

( –
92. 6 kJ) in Equation (5-51), we obtain

K 311
K 298
J 1000 6 92
ΔS ·
×
·
) . (– –
surr
The change in entropy of the universe is
42
∆Suni v = ∆Ssys + ∆Ssurr
= –199 J/K + 311 J/K
= 112 J/K
Because ∆Suni v is positive, we predict that the reaction is
spontaneous at 25°C. It is important to keep in mind that just
because a reaction is spontaneous does not mean that it will occur
at an observable rate. The synthesis of ammonia is, in fact, extremely
slow at room temperature. Thermodynamics can tell us whether a
reaction will occur spontaneously under specific conditions, but it
does not say how fast it will occur.
5.19 PHASE TRANSITIONS
Since during a phase transition there is a change in molecular order,
there should be a change in entropy. At the temperature at which a
phase transition occurs (the melting point or boiling point) two phases
exist at equilibrium. If a system is at equilibrium, then there is no
tendency for spontaneous change in either direction. Under constant
pressure conditions Equation (5-48) becomes
∆Ssys = –∆Ssurr

T
ΔH
T
ΔH –
– ΔS
sys sys
sys
·

,
`

.
|
·
(5-52)
The change in entropy as a result of vaporization, fusion, and
sublimation can be written as

sub
sub
sub
boil
vap
vap
fus
fus
fus
T
ΔH
ΔS ;
T
ΔH
ΔS ;
T
ΔH
ΔS · · ·
(5-53)
where ∆Hfus, ∆Hvap, and ∆Hsub are the heats of fusion, vaporization, and
sublimation, respectively, and Tfus, Tboil, and Tsub are the fusion, boiling,
and sublimation temperatures, respectively.
As an example, let us first consider the ice-water equilibrium. For
the ice ÷→ water transition, ∆Hsys is the molar heat of fusion, equal to
6010 J/mol and T is the normal melting point. The entropy change is
therefore
mol K / J 0 . 22
K 273
mol / J 6010
⋅ ·
Thus when 1 mole of ice melts at 0°C, there is an increase in
entropy of 22.0 J/K. The increase in entropy is consistent with the increase
in disorder from solid to liquid. Conversely, for the water ÷→ ice transition,
the decrease in entropy is given by
mol K / J 0 . 22 –
K 273
mol / J 6010 –
⋅ ·
43
In the laboratory we normally carry out unidirectional phase
changes, that is, either ice to water or water to ice. We can calculate
entropy change in each case using the equation ∆S = ∆H/T as long as the
temperature remains at 0°C. The same procedure can be applied to the
water-steam transition. In this case ∆H is the heat of vaporization and T is
the boiling point of water. Example 5.14 examines the phase transitions in
benzene.
EXAMPLE 5.14
The molar heats of fusion and vaporization of benzene are 10.9 kJ/mol and
31.0 kJ/mol, respectively. Calculate the entropy changes for the solid
liquid and liquid ÷→ vapor transitions for benzene. At 1 atm pressure,
benzene melts at 5.5°C and boils at 80.1°C.
Solution
At the melting point, the system is at equilibrium. Therefore ∆S, the
entropy of fusion is given by
fus
fus
fus
T
ΔH
ΔS ·
K 273 5 5
kJ 1 J 1000 mol kJ 9 10
) . (
) / ( ) / . (
ΔS
fus
+
·
= 39.1 J/K · mol
Similarly, at the boiling point we have
K 273 1 80
kJ 1 J 1000 mol kJ 0 32
) . (
) / ( ) / . (
ΔS
vap
+
·
= 87.8 J/K · mol
Comment Since vaporization creates more disorder than the melting
process, ∆Svap > ∆ Sf us.
5.20 ENTROPY CHANGES WHEN A SUBSTANCE IS HEATED
IRREVERSIBLY AT CONSTANT PRESSURE.
To obtain the change of entropy as a substance is heated
irreversibly, it is necessary to discover a reversible path between
the same initial and final temperatures. Since S is a State function,
S is the same for the irreversible as for the reversible process.
Therefore, the equations at constant pressure are

∫ ∫
· ·
2
1
2
1
T
T
p
T
T
sys
dT
T
C
T
dH
ΔS
(5-54)
Assuming Cp is independent of temperature, we can write
1
2
ln
T
T
C ΔS
p
·
44
If the system is heated very slowly the change in the surroundings
is equal and opposite in sign to that for the system, and
Ssys + Ssurr = Suni v = 0
The entropy changes for temperature changes at constant volume
are analogous to those at constant pressure except that Cv replaces
Cp.

1
2
v
T
T
v
T
T
sys
T
T
C dT
T
C
T
dE
ΔS
2
1
2
1
ln · · ·
∫ ∫
(5-65)
Again for a reversible change, the entropy change for the system plus
surroundings is zero.
5.21 THE THIRD LAW OF THERMODYNAMICS AND ABSOLUTE
ENTROPY
Finally it is appropriate to consider the third law of thermodynamics
briefly in connection with the determination of entropy values. So
far we have related entropy to molecular disorder—the greater the
disorder or freedom of motion of the atoms or molecules in a system,
the greater the entropy of the system. The most ordered arrangement
of any substance with the least freedom of atomic or molecular
motion is a perfect crystalline substance at absolute zero (0 K). It
follows, therefore, that the lowest entropy any substance can attain is
that of a perfect crystal at absolute zero. According to the third law
of thermodynamics, the entropy of a perfect cr
y
stalline substance is
zero at the absolute zero of temperature. As the temperature increases,
the freedom of motion also increases. Thus the entropy of any
substance at a temperature above 0 K is greater than zero. Note also
that if the crystal is impure or if it has defects, then its entropy is
greater than zero even at 0 K because it would not be perfectly ordered.
The important point about the third law of thermodynamics is
that it allows us to determine the absolute entropies of substances.
Starting with the knowledge that the entropy of a pure crystalline
substance is zero at 0 K, we can measure the increase in entropy of
the substance when it is heated to, say, 298 K. The change in
entropy, ∆S, is given by
∆S = Sf – Si
= Sf
since Si is zero. The entropy of the substance at 298 K, then, is
given by ∆S or Sf , which is called the absolute entropy because this is
the true value and not a value derived using some arbitrary reference.
Thus the entropy values quoted so far are all absolute entropies. In
contrast, we cannot have the absolute energy or enthalpy of a sub-
stance because the zero of energy or enthalpy is undefined.
45
For a constant pressure process, provided there is no change in the
phase of the substance, the entropy change of a chemical substance is
given by


· ·
T
0
p
f
dT
T
C
S ΔS
(5-56)
Hence, to determine the absolute entropy value of some chemical
substance at temperature T one must express the heat capacity of the
substance as a function of T (i.e., Cp = a + bT + cT
2
+ dT
3
) and then
determi ne the entropy value either numerically by the integration of Eq
(5-56), or graphically by determining the area under the curve for the
graph of Cp/T vs T (Figure 5.8).
Firure 5.8
It should be realized that if the crystalline substance melts and then
turns into a gas before it reaches 298°K, the calculation of the standard
entropy given by Eq. (5-56) should be modified so as to include the
entropy change on fusion and vaporization given by Eq. (5-53), and the
entropy changes due to heating to 298°K. Thus Eq. (5-56) becomes
∫ ∫ ∫
+ + + + · ·
298
T
p
v
v
T
T
p
f
f
T
0
p
v
v
f
f
dT
T
(g) C
T
ΔH
dT
T
(l) C
T
ΔH
dT
T
(s) C
S ΔS

(5-57)
If we try to calculate the entropy from 0 to 298 using this equation,
with Cp dependent on temperature, we get the following for the first,
third and the fifth term

( )
2
1
2
1
2
1
ln S ΔS
T
T
–2
T
T
–2
T
T
p
T
2c
bT T a dT
T
cT bT a
dT
T
C
]
]
]

− + ·
+ +
· · ·
∫ ∫

This obviously does not work for a change in temperature from 0 K
to Tf because at 0 K, we have lnT term which goes to infinity. One
approach to overcome this complication is to measure values of Cp
down to a few Kelvins, and then use Debye theory of heat capacity
of solids at low temperatures,
46

1 3
mol K J

p
/ kT C ⋅ ·
(5-58)
Notice that Equation (5-58) contains only one constant, k, which
can be determined from a value of Cp in the region below 20 K. The
integral for the entropy then becomes
∫ ∫ ∫
· · ·
1 1 1
T
0
2
T
0
3 T
0
p
dT T k dT
T
T k
dT
T
(s) C
ΔS
EXAMPLE 5.15
The molar Cp of a solid at 10 K is 0.43 J/K∙mol. What is the entropy of the
solid at that temperature?
Solution
Cp at 10 K is described by the Debye Equation

1 3
mol K J

p
/ kT C ⋅ ·
The value of k in the above Equation is
mol K J 10 3 4
K) (10
mol J/K 0.43 mol K J 43 0
4
3 3
⋅ × ·

·

·

/ .
T
/ .
k
The entropy of the solid at 10 K is
dT T k d
T
T
k dT
T
C
S S
T T T
p
∫ ∫ ∫
· + · + ·
0
2
0
3
0
T 0 (0) 
[ ]
3 3
) K 0 (
3
1
− · T k S
Substituting
[ ]
3 3 4
) K 0 ( ) K 10 ( mol K J 10 3 4
3
1
− ⋅ × ·

) / . ( S
S = 0.14 J/K∙mol
Figure 5.9 shows the change (increase) in entropy of a
substance with temperature. At absolute zero, it has a zero entropy
value (assuming that it is a perfect crystalline substance). As it is heated,
its entropy increases gradually because of greater molecular motion
(described by the first term of Eq. (5-57). At the melting point, there is a
sizable increase in entropy as the more random liquid state is formed.
Further heating increases the entropy of the liquid again due to enhanced
molecular motion (third term of Eq. 5-57)). At the boiling point there is a
large increase in entropy as a result of the liquid to gas transition. Beyond
that temperature, the entropy of the gas continues to rise with increasing
temperature (Fifth term of Eq. (5-57)). The entropy change of the overall
process from 0 K to T2 is the sum of the five terms in Eq. (5-57).
As another example, consider the calculation of absolute entropy of
methylammonium chloride, CH3NH3Cl, which undergoes phase transitions
47
involving three allotropic forms between 0 K and 298 K. Heat capacities for
this solid in its various allotropic forms have been determined very precisely
down to 12 K.

Figure 5.9 Entropy increase of a substance as the
temperature rises from absolute zero
Solid methylammonium chloride exist in the β form from 0 K up to
220.4 K, in the γ form from 220.4 to 264.5 K, and in the α form from 264.5
K to 298 K. In the following equations, Cp is the heat capacity of the β form,
Cp’ of the γ form, and Cp” of the α form. One can calculate the entropy by
integrating Equation (5-64) for each allotrope in the temperature region in
which it is most stable and then adding the two entropies of transition to
the integral thus obtained. The details at a pressure of 1 atm are as follows:
a) CH3NH3Cl(s, β, 0 K) ⇒ CH3NH3Cl(s, β, 12.04 K)
( ) Equation) Debye mol K J 0.280 dT T k dT
T
C
ΔS
–1 –1
12.04
0
2
12.04
0
p
1
⋅ ⋅ · · ·
∫ ∫
b) CH3NH3Cl(s, β, 12.04 K) ⇒ CH3NH3Cl(s, β, 220.4 K)
–1 –1
220.4
12.04
p
2
mol K J 93.4 dT
T
C
ΔS ⋅ ⋅ · ·

c) CH3NH3Cl(s, β, 220.4 K) ⇒ CH3NH3Cl(s, γ, 220.4 K)
1 – 1 –
3
mol K J 07 . 8 ⋅ ⋅ · ·
T
ΔH
ΔS

48
d) CH3NH3Cl(s, γ, 220.4 K) ⇒ CH3NH3Cl(s, γ, 264.5 K)
–1 –1
264.5
220.4
p
4
mol K J 15.4 dT
T
' C
ΔS ⋅ ⋅ · ·


e) CH3NH3Cl(s, γ, 264.5 K) ⇒ CH3NH3Cl(s, α, 264.5 K)
1 – 1 –
5
mol K J 7 . 10 ⋅ ⋅ · ·
T'
ΔH'
ΔS
f) CH3NH3Cl(s, α, 264.5 K) ⇒ CH3NH3Cl(s, α, 298 K)
–1 –1
298
264.5
p
6
mol K J 10.7 dT
T
" C
ΔS ⋅ ⋅ · ·

Addition of steps (a) through (f) gives
g) CH3NH3Cl(s, β, 0 K) ⇒ CH3NH3Cl(s, α, 298 K)
∆S = S° = ∆S1 + ∆S1 + ∆S2 + ∆S3 + ∆S4 + ∆S5 + ∆S6 = 138.6
1 – 1 –
mol K J ⋅ ⋅
Thus for methylammonium chloride, CH3NH3Cl, the absolute entropy, S°,
=138.6
1 – 1 –
mol K J ⋅ ⋅ .
5.22 VARIATION OF THE ENTROPY CHANGE OF A REACTION WITH
TEMPERATURE
Recall that entropy, like enthalpy, is a State function and arguments used to
develop ∆Hrxn at any temperature apply to develop an equation similar to
Equation (5-43) shown below

+
·
2
1
1
T
T
p 2
dT ΔC ΔH ΔH
The equation for calculating ∆Srxn at a temperature T2 from a knowledge of ∆
Srxn at T1 is


+
·
2
1
1
T
T
p
2
dT
T
ΔC
ΔS ΔS (5-59)
5.23 GI BBS FREE ENERGY
The second law of thermodynamics tells us that a spontaneous reaction
increases the entropy of the Universe; that is, ∆Suniv > 0. In order to
determine the sign of ∆Suniv, for a reaction, however, we would need to
calculate both ∆Ssys and ∆Ssurr. However, we are usually concerned only
with what happens in a particular system, and the calculation of ∆Ssurr can
be quite difficult. Therefore, we generally rely on another thermo-
dynamic function to help us determine whether a reaction will occur
spontaneously if we consider only the system itself.
49
From Equation (5-47), we know that for a spontaneous process, we
have
∆Suniv = ∆Ssys + ∆Ssurr > 0
Substituting –∆Hsys /T for ∆Ssurr, we write
∆Suniv = ∆Ssys



0 >
T
ΔH
sys
Multiplying both sides of the equation by T gives
T∆Suniv = –∆Hsys + T∆Ssys > 0
Now we have a criterion for a spontaneous reaction that is expressed
only in terms of the properties of the system (∆Hsys and ∆Ssys) and we can
ignore the surroundings. For convenience, we can change the above
equation, multiplying it throughout by –1 and replacing the > sign with <:
–T∆Suniv = ∆Hsys – T∆Ssys < 0
This equation says that for a process carried out at temperature T, if the
changes in enthalpy and entropy of the system are such that ∆Hsys – T∆
Ssys is less than zero, the process must be spontaneous.
In order to express the spontaneity of a reaction more directly, we
can use another thermodynamic function called Gibbs

free energy (G), or
simply free energy:
G = H – TS (5-60)
All quantities in Equation (5-60) pertain to the system, and T is the
temperature of the system. You can see that G has units of energy (both
H and TS are in energy units). Like H and S, G is a state function.
The change in free energy (∆G) of a system for a constant-
temperature process is
∆G = ∆H – T∆S (5-61)
In this context free energy is the energy available to do work. Thus, if a
particular reaction is accompanied by a release of usable energy (that is, if
∆G is negative), this fact alone guarantees that it is spontaneous, and
there is no need to worry about what happens to the rest of the universe.
Note that we have merely organized the expression for the entropy
change of the universe, eliminating ∆Suniv, and equating the free-energy
change of the system (∆G) with –T∆Suniv, so that we can focus on changes
in the system. We can now summarize the conditions for spontaneity
and equilibrium at constant temperature and pressure in terms of ∆
G as follows:
∆G < 0 The reaction is spontaneous in the forward direction.
∆G > 0 The reaction is nonspontaneous. The reaction
is spontaneous in the opposite direction.
∆G = 0 The system is at equilibrium. There is no net change.

STANDARD FREE-ENERGY CHANGES
50
The standard free-energy of reaction (

rxn
ΔG
) is the free-energy change for
a reaction when it occurs under standard-state conditions, when
reactants in

their standard states are converted to products in their
standard states. Table 5.9 summarizes the conventions used by
chemists to define the standard states of pure substances as well as
solutions.
Table 5.9 Conventions for Standard
States
State of Matter Standard State
Gas 1 atm pressure
Liquid Pure liquid
Solid Pure solid
Elements*

f
ΔG
(element) = 0
Solution 1 molar
concentration
*The most stable allotropic form at 25°C and
1 atm.
To calculate

rxn
ΔG
we start with the equation
aA + bB ÷→ cC + dD
The standard free-energy change for this reaction is given by

rxn
ΔG = [c

f
ΔG
(c) + d

f
ΔG
(D)] – [a

f
ΔG
(A) + b

f
ΔG
(B)]
or, in general,


rxn
ΔG
= Σn

f
ΔG
( product s) – Σn

f
ΔG
( react ant s) ( 5- 62)
where n and m are stoichiometric coefficients. The term

f
ΔG
is the
standard free energy of formation of a compound, that is, the free-energy
change that occurs when 1 mole of the compound is synthesized from its
elements in their standard states. For the combustion of graphite:
C(graphite) + O2(g) ÷→ CO2(g)
the standard free-energy change [from Equation (5-62)] is

rxn
ΔG
= (1 mol)

f
ΔG
(CO2) – [(1 mol)

f
ΔG
(C, graphite) + (1 mol)

f
ΔG
(O2)]
As in the case of the standard enthalpy of formation,
we define the standard free energy of formation of any element in
its stable form as zero. Thus

f
ΔG
(C, graphite) = 0 and

f
ΔG
(O2) = 0
Therefore the standard free-energy change for the reaction in this
case is numerically equal to the standard free energy of formation of CO2:

rxn
ΔG
=

f
ΔG
(CO2)
Note that

rxn
ΔG

is in kJ, but

f
ΔG
is in kJ/mol.

f
ΔG
for a number of
compounds can be found in the Appendices of most General Chemistry
51
textbooks. Calculations of standard free-energy changes are
handled as shown in the following example.
EXAMPLE 5.16
Calculate the standard free-energy changes for the following reactions at
25°C.
(a)CH4(g) + 2 O2(g) ÷→ CO2(g) + 2 H2O(l)
(b)2 MgO(s) ÷→ 2 Mg(s) + O2(g)
Solution
(a) According to Equation (5-62), we write

rxn
ΔG
= [(1 mol)

f
ΔG
(CO2) + (2 mol)

f
ΔG
(H2O) – [(1 mol)

f
ΔG
(CH4)
+ (2 mol)

f
ΔG
(O2)]
We insert the appropriate values from an Appendix:

rxn
ΔG
= [(1 mol)(-394.4 kJ/mol) + (2 mol)(–237.2 kJ/mol)] –
[(1 mol)(–50.8 kJ/mol) + (2 mol)(0 kJ/mol)]
= –818.0 kJ
(b) The equation is

rxn
ΔG
= [(2 mol)

f
ΔG
(Mg) + (1 mol)

f
ΔG
(O2)] − [(2mol)

f
ΔG
(MgO)]
From data taken from an Appendix we write

rxn
ΔG
= [(2 mol)(0 kJ/mol) + (1 mol)(0 kJ/mol)] – [(2 mol)(–569.6 kJ/mol]
= 1139 kJ
In the preceding example the large negative value of

rxn
ΔG
for the
combustion of methane in (a) means that the reaction is a spontaneous
process under standard-state conditions, whereas the decomposition of
MgO in (b) is nonspontaneous because

rxn
ΔG
is a large, positive quantity.
Remember, however, that a large, negative

rxn
ΔG
does not tell us
anything about the actual rate of the spontaneous process; a mixture
of CH4 and O2 at 25°C could sit unchanged for quite some time in the
absence of a spark or flame.
APPLICATIONS OF EQUATION (5-61)
In order to predict the sign of ∆G, according to Equation (5-61) we need
to know both ∆H and ∆S. A negative ∆H (an exothermic reaction) and a
positive ∆S (a reaction that results in an increase in disorder of the
system) tend to make ∆G negative, although temperature may
influence the direction of a spontaneous reaction. The four possible
outcomes of this relationship are:
• If both ∆H and ∆S are positive, then ∆G will be negative only when
the T∆S term is greater in magnitude than ∆H. This condition is met
when T is large.
• If ∆H is positive and ∆S is negative, ∆G will always be positive,
regardless of temperature.
52
• If ∆H is negative and ∆S is positive, then ∆G will always be negative
regardless of temperature.
• If ∆H is negative and ∆S is negative, then ∆G will be negative only
when T∆S is smaller in magnitude than ∆H. This condition is met when
T is small.
The temperatures that will cause ∆G to be negative for the first
and last cases depend on the actual values of ∆H and ∆S of the
system. Table 5.10 summarizes the effects of the possibilities just
described.
We will now consider two specific applications of Equation (5.61).
TABLE 5.10 Factors Affecting the Sign of ∆G in the Relationship ∆G =
∆H – T∆S
H S G Example
+ +
Reaction proceeds spontaneously at high
temperatures. At low temperatures,
reaction is spontaneous in the reverse
direction.
H2(g) + I2(g)÷→2HI(g)
+ –
∆G is always positive. Reaction is
spontaneous in the reverse direction at all
temperatures.
3O2(g)÷→2O3(g)
– +
∆G is always negative. Reaction
proceeds spontaneously at all tempe-
ratures.
2H2O2(l)÷→2H2O(l)+O2(g)
– –
Reaction proceeds spontaneously at low
temperatures. At high temperatures,
the reverse reaction becomes
spontaneous.
NH3(g)+HCl(g)÷→NH4Cl(s)
TEMPERATURE AND CHEMICAL REACTION
Calcium oxide (CaO), also called quicklime, is an extremely valuable
inorganic substance used in steelmaking, production of calcium metal,
the paper industry, water treatment, and pollution control. It is
prepared by decomposing limestone (CaCO3) in a kiln at a high
temperature:
CaCO3(s) ÷→ CaO(s) + CO2(g)
The reaction is reversible, and CaO readily combines with CO2 to
form CaCO3. The pressure of CO2 in equilibrium with CaCO3 and
CaO increases with temperature. In the industrial preparation of
quicklime, the system is never maintained at equilibrium; rather, CO2
is constantly removed from the kiln to shift the equilibrium from
53
left to right, promoting the formation of calcium oxide.
The important information for the practical chemist is the
temperature at which the decomposition of CaCO3 becomes
appreciable (that is, the temperature at which the reaction becomes
spontaneous). We can make a reliable estimate of that temperature
as follows. First we calculate ∆H° and ∆S° for the reaction at 25°C,
using the data available in an Appendix. To determine ∆H° we apply
Equation (5.30):
H = [

f
ΔH
(CaO) +

f
ΔH
(CO2)] – [

f
ΔH
(CaCO3)]
=[(1 mol)(–635.6 kJ/mol) + (1 mol)(–393.5 kJ/mol)]
– [(1 mol)(–1206.9 kJ/mol)]
= 177.8 kJ
Next we apply Equation (5-59) to find ∆S°
∆S° = [S°(CaO) + S°(CO2)] – [S° (CaCO3)]
= [(1 mol)(39.8 J/K∙mol) + (1 mol)(213.6 J/K∙mol)l
– [(1 mol)(92.9 J/K∙mol)]
= 160.5 J/K
For reactions carried out under standard-state conditions, Equation (5-
71) takes the form
∆G° = ∆H° – T∆S°
so we obtain
∆G° = 177.8 kJ — (298 K)(160.5 J/K) (1 kJ/1000J)
= 130.0 kJ
Since ∆G is a large positive quantity, we conclude that the reaction is not
favored at 25°C (or 298 K). In order to make ∆G° negative, we first
have to find the temperature at which ∆G° is zero; that is,
0 = ∆H° – T∆S°



ΔS
ΔH
T ·

K / J 5 . 160
) kJ 1 / J 1000 ( ) kJ 8 . 177 (
· T
= 1108 K or 835°C
At a temperature higher than 835°C, ∆G becomes negative,
indicating that the decomposition is spontaneous. For example, at
840°C, or 1113 K,
∆G° = ∆H° – T∆S°
= 177.8 kJ – (1113 K)(160.5 J/K)(1kJ/1000 J)
= –0.8 kJ
Two points are worth making about such a calculation.
First, we used the ∆H° and ∆S° values at 25°C to calculate changes
54
that occur at a much higher temperature. Since both ∆H° and ∆S°
change with temperature, this approach will not give us an accurate
value of ∆G°, but it is good enough for rough estimates. Second, the
standard state does not specify temperature, therefore we can use
the symbol ∆G°. Third, we should not be misled into thinking that
nothing happens below 835°C and that at 835°C CaCO3 suddenly
begins to decompose. The fact that ∆G° is a positive value at some
temperature below 835°C does not mean that no CO2 is produced,
but rather that the pressure of the CO2 gas formed at that
temperature will be below 1 atm (its standard-state value). In fact,
the pressure of CO2 at first increases very slowly with temperature;
however, it becomes easily measurable above 700°C. The significance
of 835°C is that this is the temperature at which the equilibrium
pressure of CO2 reaches 1 atm. Above 835°C, the equilibrium
pressure of CO2 exceeds 1 atm.
If a system is at equilibrium, then there is no tendency for spontaneous
change in either direction. The condition ∆G = 0 applies to any phase
transition.
PHASE TRANSITIONS
At the temperature at which a phase transition occurs (the melting point or
boiling point), ∆G = 0 so Equation (5-61) becomes
0 = ∆H – T∆S
T
ΔH
ΔS ·
where ∆H is ∆Hfus, ∆Hvap, or ∆Hsub; the heat of fusion, vaporization, or
sublimation, and T is Tfus, Tboil, or Tsub; the fusion, boiling, or sublimation
temperature.
Notice that the above equation is the same as Equation (5-53) and
can be applied to calculate entropy changes during phase transitions.
(See Example 5.14).
5.24 FREE ENERGY AND CHEMICAL EQUILIBRIUM
Suppose we start a reaction in solution with all the reactants in their
standard states (that is, all at 1 M concentration). As soon as the reaction
starts, the standard-state condition no longer exists for the reactants or the
products since their concentrations are different from 1 M. Under conditions
that are not standard state, we must use ∆G rather than ∆G° to predict the
direction of the reaction. The relationship between ∆G and ∆G° is
∆G = ∆G° + RT l n Q (5-63)
where R is the gas constant (8.314 J/K∙mol), T is the absolute temperature
of the reaction, and Q is the reaction quotient, that is, a number equal to
the ratio of product concentrations, each raised to the power of its
stoichioinctric coefficient at some point other than equilibrium. We see that
∆G depends on two quantities: ∆G° and RT l n Q. For a given reaction at
55
temperature T the value of ∆G° i s fixed but that of RT l n Q is not, because
Q varies according to the composition of the reacting mixture. Let us
consider two special cases:
Case 1: If ∆G° i s a large negative value, the RT l n Q term will not become
positive enough to match the ∆G° term until a significant amount of
product has formed.
Case 2: If ∆G° is a large positive value, the RT l n Q term will be more
negative than ∆G° is positive only as long as very little product formation
has occurred and the concentration of the reactant is high relative to that of
the product.
At equilibrium, by definition, ∆G = 0 and Q = K, where K is the
equilibrium constant. Thus
0 = ∆G° + RT l n K
or
∆G° = –RT ln K (5-64)
In this equation, Kp is used for gases and Kc for reactions in
solution. Note that the larger the K is, the more negative ∆G° is. For
chemists, Equation (5-74) is one of the most important equations in
thermodynamics because it allows us to find the equilibrium constant of a
reaction if we know the change in standard free energy and vice versa.
It is significant that Equation (5-64) relates the equilibrium constant
to the standard free energy change ∆G° rather than to the actual free energy
change ∆G. The actual free energy of the system changes as the reaction
proceeds and becomes zero at equilibrium. On the other hand, both ∆G°
and K are constants for a particular reaction at a given temperature. In fact,
if ∆G° < 0. the products are favored over reactants at equilibrium.
Conversely, if ∆G° > 0, there will be more reactants than products at
equilibrium. Table 5.11 summarizes the three possible relations between ∆G
° and K, as predicted by Equation (5-64).
For reactions having very large or very small equilibrium constants,
it is generally very difficult, if not impossible, to measue the K values by
monitoring the concentrations of all the reacting species. Consider, for
example, the formation of nitric oxide fro molecular nitrogen and molecular
oxygen:
N2(g) + O2(g) ⇄ 2 NO(g)
At 25°C, the equilibrium constant Kc is
31 –
2 2
2
c
10 0 . 4
] O [ ] N [
] NO [
× · · K
The very small value of Kc means that the concentration of NO at
equilibrium will be exceedingly low. In such a case the equilibrium constant
is more conveniently obtained from ∆G°. (as we have seen, ∆G° can be
calculated from ∆H° and ∆S°.) On the other hand, the equilibrium constant
56
for the formation of hydrogen iodide from molecular hydrogen and
molecular iodine is near unity at room temperature:
H2(g) + I2(g) ⇄ 2 HI(g)
For this reaction it is easier to measure K and then calculate ∆G
using Equation (5-64) than to measure ∆H and S .
Table 5.11 Relation between G and K as Predicted by the
Equation G = –RT ln K
K ln K G Comments
> 1 Positive Negati
ve
Products are favored over reactants at
euilibrium.
= 1 0 0 Products and reactants are equally favored at
equilibrium.
< 1 Negativ
e
Positiv
e
Reactants are favored over products at
equilibrium.
It is important to remember when solving Equation (5-64) that
the unit of ∆G° is J or kJ and those of RT ln K are J/mol. The
reason for the difference is that in deriving Equation (5-64), the unit
"mol" was absorbed into the logarithmic term (ln K). Thus in using
this equation, we will add (1 mol) to the RT ln K term to make the
units consistent on both sides of the equation. The following
examples illustrate the use of Equations (5-63) and (5-64).
EXAMPLE 5.17
Using data listed in an Appendix, calculate the equilibrium constant
(Kp) for the following reaction at 25°C:
2 H2O(l) ⇄ 2 H2(g) + O2(g)
Solution
According to Equation (5-62)

rxn
ΔG
= [2

f
ΔG
(H2) +

f
ΔG
(O2)] – [2

f
ΔG
(H2O)]
= [(2 mol)(0 kJ/mol) + (1 mol)(0 kJ/mol)]
– [(2 mol)(–237.2 kJ/mol)]
= 474.4 kJ
Using Equation (5-64)

rxn
ΔG
= –RT ln Kp
p
K ln ) K 298 )( mol K / J 314 . 8 ( ) mol 1 (
kJ 1
J 1000
kJ 4 . 474 ⋅ · ×
ln Kp = –191.5
Kp = e
–191.5
=7 × 10
-84
57
Comment This extremely small equilibrium constant is consistent
with the fact that water does not decompose into hydrogen and
oxygen gases at 25°C. Thus a large positive ∆G° favors reactants
over products at equilibrium. Note that we have added the (1
mol) term on the right side of Equation (5-64) here to make the
units consistent.
EXAMPLE 5.18
Using the solubility product of silver chloride at 25°C (1.6 × 10
–10
),
calculate ∆G° for the process
AgCl(s) ⇄ Ag
+
(aq) + Cl

(aq)
Solution
Because this is a heterogeneous equilibrium, the solubility product is the
equilibrium constant.
Ksp = [Ag
+
][CI

] = 1.6 × 10
–10
Using Equation (5-64) we obtain
∆G
°
= –(1 mol)(8.314 J/K∙mol)(298 K) ln 1.6 × 10
–10
= 5.6 × 10
4
J = 56 kJ
Comment The large, positive ∆G indicates that AgCI is slightly
soluble and that the equilibrium lies mostly to the left.

As another example, let us consider the decomposition of isopropyl
alcohol into acetone and hydrogen gas in the presence of a suitable catalyst:
(CH3)2CHOH(g) ⇄ (CH3)2CO(g) + H2(g)
At 452.2 K and a total pressue, P, of 0.564 atm , the equilibrium constant of
this reaction, K, is equal to 0.444. Equation (5-64) can be used to calculate
the standard free energy change whatever the total pressure is, as long as
the system is at equilibrium.
ΔG° = −(1 mol)(8.314 J/K∙mol)(452.2 K) ln 0.444 = 3.05 × 10
3
J
The positive value of ΔG° does not imply that the reaction under
consideration may not proceed spontaneously under any conditions. ΔG°
refers to the reaction
(CH3)2CHOH(g. P = 1 atm) ⇄ (CH3)2CO(g, P = 1 atm) + H2(g, P = 1 atm)
where each substance is in its standard state; that is, at a partial pressure
of 1 atm. The positive value of ΔG° only means that the reaction will not
proceed spontaneously under these conditions. However, if we were to start
with isopropyl alcohol at a partial pressure of 1 atm and no acetone or
hydrogen, the alcohol would decompose spontaneously at 452.2 K and more
than 50% dissociation could occur. Yields can be made even better is one of
the products is removed continuously (Le Chatelier’s principle)
We also might calculate ΔG for one set of conditions with the
substances not all in their standard states; for example,
58
(CH3)2CHOH(g, P = 1 atm) ⇄(CH3)2CO(g, P = 0.100 atm) + H2(g, P = 0.100 atm)
For this calculation we refer to Equation (5-63), which relates ΔG to ΔG° and
the non-equilibrium partial pressures
∆G = ∆G° + RT l n Q
Applied to our reaction, we get
CHOH
CO
ln
2
) (CH
H
2
) (CH
3
2 3
P
P P
RT ΔG + ·

= 3053 J + (1 mol)(8.314 J/K∙mol)(452.2 K) ×
00 . 1
) 100 . 0 (
ln
2
= −15.5 × 10
3
J
Thus, if one is considering a given reaction in connection with the
preparation of some substance, it is important not to be misled by positive
value of ΔG°, because ΔG° refers to the reaction under standard conditions,
when the pressures of each of the component gases is 1 atm and solutions
have a concentration of 1 M. It is quite possible that appreciable yields can
be obtained even though a reaction will not go to completion. Such was the
decomposition of isopropyl alcohol. Only when ΔG° has a very large positive
value, perhaps greater than 50 kJ, one can be assured without calculations
of the equilibrium constant that no significant transformation would occur.
EXAMPLE 5.19
The standard free-energy change for the reaction
N2(g) + 3 H2(g) ⇄ 2 NH3(g)
is –33.2 kJ and the equilibrium constant Kp is 6.59 × 10
5
at 25°C. In a
certain experiment, the initial pressures are PH2 = 0.250 atm, PN2 = 0.870
atm, and PNH3 = 12.9 atm. Calculate ∆G for the reaction at these pressures,
and predict the direction of reaction.
Solution
Equation (7-73) can be written as
∆G = ∆G° + RT ln Qp

2
2
3
N
3
H
2
NH
ln
P P
P
RT ΔG + ·

=
) 870 . 0 ( ) 250 . 0 (
) 9 . 12 (
ln ) K 298 )( mol K / J 314 . 8 )( mol 1 ( J 1000 2 . 33 –
3
2
× ⋅ + ×
=
4
10 1.22 ln K) mol)(298 J/K mol)(8.314 (1 J 000 1 2 . 33 – × × ⋅ + ×
59
= –33.2 × 10
3
J + 23.3 × 10
3
J
= –9.9 × 10
3
J = –9.9 kJ
Since ∆G is negative, the net reaction proceeds from left to right.
Comment Notice that Qp is smaller than it with Kp. This is to be expected
considering the very high pressure of ammonia relative to the reacting gases
(Le Chatelier’s principle).
TEMPERATURE DEPENDENCE OF EQUILIBRIA
While Le Chatelier’s principle provides a qualitative guide for predicting how
equilibria are affected by changes in temperature, we can obtain a
quantitative relation between K and T by using the thermodynamic concepts
available to us. To derive an expression, we combine two fundamental
relations: Eqs. (5.61) and (5-64)
ΔG = ΔH  TΔS
ΔG =  RT ln K

R
S
RT
H
K
 

+

− · ln (5-65)
This equation says that if we accept the approximation that ΔH and ΔS
are constants independent of temperature, then lnK becomes linearly
dependent on 1/T. According to Equation (5-65), for an exothermic reaction
K increases as T increases. These facts are consistent with the qualitative
conclusions based on Le Chatelier’s principle.
Not only does the sign of ΔH indicate the direction in which K
changes; for a given temperature variation, the magnitude of ΔH
determines how rapidly K changes as a function of temperature. According
to Equation (5-65), plotting lnK as a function of 1/T should give a straight
line whose slope is  ΔH /R, Thus the more negative ΔH is, the faster lnK
should decrease as T increases, and vice versa (Figure 5.9).
60
Figure 5.9 lnK versus 1/T for (a) exothermic
reaction with ΔH = 40.0 kJ; (b) endothermic
reaction with ΔH = 85 kJ.
Another form of Equation (5-65) that is particularly useful for
numerical calculations can be obtained by writing
R
S
RT
H
K
 

+

− ·
1
1
ln ,
R
S
RT
H
K
 

+

− ·
2
2
ln
and then subtracting the first of these expressions from the second. The
result is

,
`

.
|


− ·
1 2 1
2
1 1
ln
T T R
H
K
K

(5-66)
Equation (5-66) shows that if we know the value of ΔH and of the
equilibrium constant at one temperature, we can calculate K at any other
temperature. Also, if we measure K at two different temperatures, we can
calculate ΔH by Equation (5-66). Thus, it is possible to obtain ΔH for a
reaction without ever doing a calorimetric experiment.
EXAMPLE 5.20
For the reaction
NO(g) + 1/2O2(g) ⇄ NO2(g)
ΔG° = −34.9 kJ and ΔH° = −56.5 kJ at 298 K. Calculate the equilibrium
constant at 298 K and ay 598 K.
Solution
K RT ΔG
rxn
ln − ·

RT
ΔG
K
rxn

− · ln
RT
ΔG
rxn
e K


·
K = 1.28 × 10
6
To find the equilibrium constant at 598 K, we cannot use Equation
(5-64) since we do not know ΔG° at that temperature. However, we can use
Equation (5-66):

,
`

.
|
− − ·
1 2 1
2
1 1 Δ
ln
T T R
H
K
K

,
`

.
|


× −
− ·
×
298
1
598
1
mol J/K 8.314
) J 10 65 . 5 (
10 28 . 1
ln
4
6
2
K

,
`

.
|


× −
− · × −
298
1
598
1
mol J/K 8.314
) J 10 65 . 5 (
) 10 28 . 1 ln( ln
4
6
2
K
K2 = 14.4
The equilibrium constant of this exothermic reaction is smaller at
the higher temperatue, which is consistent with Le Chatelier’s principle.
61
COMMON UNITS AND CONVERSION FACTORS FOR
THERMODYNAMICS
1 cal = 4.184 J
1 L∙atm = 24.21 cal
1 L∙atm = 101.29 J
1 atm = 1.01325 × 10
5
N∙m
–2
(Newton meter
–2
)
1 atm = 760 mm Hg
1 atm = 101,325 Pa (Pascal)
1 torr = 1.000 mm Hg
1 torr = 133.32 Pa
1 J = 1 kg∙m
2
∙s
–2
1 N (Newton) = kg∙m∙s
–2
1 Pa = N∙m
–2
1 Pa = kg∙m
–1
∙s
–2
1 J = kg∙m
2
∙s
–2
0°C = 273.15 K (Kelvin)
R (gas constant) = 8.31433 J∙K
–1
∙mol
–1
R = 1.9872 cal∙K
–1
∙mol
–1
R = 0.082053 L∙K
–1
∙mol
–1
F (Faraday constant) = 9.64870 × 10
4
C∙mol
–1
(coulombs mole
–1
)
F = 2.3061 × 10
4
cal∙V
–1
∙mol
–1
1 eV (electron volt) = 1.601 × 10
–19
J
62
PROBLEMS
I. CaCO
3
(s) decomposes according to
CaCO
3
(s) ÷→ CaO(s) + CO
2
(g) ∆H = 42.4 kcal/mol
Calculate ∆E at 950°C by assuming that the change in volume of the solid is
negligible. R = 1.987 cal/mol.K.
II. Using the chemical equations given below, calculate the standard enthalpy, ∆H°, of
the following reaction
HCOOH(l) ÷→ CO(g) + H
2
O(l)
C(s) + ½O
2
(g) ÷→ CO(g) ∆H°
f
= –26.4 kcal/mol
H
2
(g) + ½O
2
(g) ÷→ H
2
O(l) ∆H°
f
= –68.3 kcal/mol
H
2
(g) + O
2
(g) + C(s) ÷→ HCOOH(l) ∆H°
f
= –97.5 kcal/mol
III. Predict whether the following reactions take place spontaneously: a) at 298 K and 1
atm, b) at 800 K and 1 atm
SO
3
(g) + NO(g) ÷→ SO
2
(g) + NO
2
(g)
∆H° = 9.98 kcal/mol; ∆S° = 0.01369 kcal/mol. Assume ∆H° and ∆S° do not vary
with temperature.
IV. Using the following equations, calculate the standard free energy of formation, ∆G°
f
for ozone at 298 K.
3/2 O
2
(g) ÷→ O
3
(g)
Given:
∆H°
f
(O
3
) = 34.0 kcal/mol
S°(O
3
) = 56.8 cal/mol.K
S°(O
2
) = 49.0 cal/mol.K
V. Calculate ∆G° and K
p
for the reaction
NO(g) + O
3
(g) ⇄ NO
2
(g) + O
2
(g)
Given:
∆G°
f
(NO
2
gas) = 12.39 kcal/mol at 298 K
∆G°
f
(O
2
gas) = 0
∆G°
f
(NO gas) = 20.72 kcal/mol at 298 K
∆G°
f
(O
3
gas) = 39.0 kcal/mol at 298 K
R = 1.987 cal/mol.K
VI. Calculate K
p
and K
c
at 25°C for the following equilibrium:
NO(g) + ½O
2
(g) ⇄ NO
2
(g)
Given:
∆G°
f
(NO
2
gas) = 12.39 kcal/mol at 298 K
63
∆G°
f
(NO gas) = 20.72 kcal/mol
R = 1.987 cal/mol.K
R = 0.0821 L.atm/mol.K
VII. Calculate ∆G° and ∆H° for the following reaction
SO2(g) + ½O
2
(g) ÷→ SO
3
(g)
Assuming that ∆H° and ∆S° are independent of temperature, calculate the
equilibrium constant at 298 K and 600 K.
Given:
∆G°
f
(SO
2
gas) = –71.79 kcal/mol
∆H°
f
(SO
2
gas) = –70.96 kcal/mol
∆G°
f
(SO
3
gas) = –88.52 kcal/mol
∆H°
f
(SO
3
gas) = –94.45 kcal/mol
VIII. The enthalpies of the following reactions are for 0°C and 1 atm:
N
2
(g) + 3H
2
(g) ÷→ 2NH
3
(g) ∆H
1
= –24.4 kcal
N
2
(g) + O
2
(g) ÷→ 2NO(g) ∆H
2
= +43.14 kcal
H
2
(g) + ½O
2
(g) ÷→ H
2
O(g) ∆H
3
= –57.9 kcal
The molar heat capacities at constant pressure for N
2
, H
2
, and NH
3
respectively are:
C
p
(N
2
) = 6.94 cal/mol.K
C
p
(H
2
) = 6.90 cal/mol.K
C
p
(NH
3
) = 8.63 cal/mol.K
a. Calculate the standard enthalpy of formation for NH
3
at 298 K.
b. Calculate for 0°C and 1 atm, the enthalpy for the oxidation reaction of
NH
3
(g):
2NH
3
(g) + 5/2 O
2
(g) ÷→ 2NO(g) + 3H
2
O(g)
IX. Calculate the bond energy C—H in CH
4
using the following data:
CH
4
(g) + 2O
2
(g) ÷→ CO
2
(g) + 2H
2
O(l) ∆H° = –890.5 kJ
CO
2
(g) ÷→ C
(graphite)
+ O
2
(g) ∆H° = +392.0 kJ
2H
2
O(l) ÷→ 2H
2
(g) + O
2
(g) ∆H° = +570.1 kJ
H
2
(g) ÷→ 2H(g) ∆H° = +435.75 kJ
C
(graphite)
÷→ C(g) ∆H° = +715.5 kJ
X. Consider the following equilibrium in aqueous solution:
A ⇄ B + H
2
O ∆H° = 22134 J
with [A] = 4[B] at 25°C.
64
a. Calculate the equilibrium constant of the above reaction at 50°C (assume
that ∆H and ∆S are independent of temperature).
b. Calculate ∆E°, ∆G°, and ∆S°.
XI. Calculate the standard enthalpy of formation of gaseous benzene, g) , (
6 6
H C ΔH
f

,
by the following two methods and comment on the significant difference in the
values obtained ascribing the difference to the correct energy factor.
Method a: Use a Hess diagram and the following data:

f
ΔH
[H(g)] = 218.0 kJ/mol or H—H bond energy = 2 218.0 kJ/mol,

f
ΔH
[C(g)] = 715.0 kJ/mol
Average CC bond energy = 615 kJ/mol
Average C—C bond energy = 348 kJ/mol
Average C—H bond energy = 413 kJ/mol
Method b: Use
) , CO2 g ( ΔH
f

= –393.5 kJ/mol,
) , O H2 l ( ΔH
f

= –285.8
kJ/mol, and the enthalpy of combustion of benzene
C6H6(g) + 15 O2(g) ÷→ 6 CO2(g) + 3 H2O(l)

comb
ΔH = –3302.4 kJ/mo
XII. For which of the following processes would S have a negative value?
a) 2 Fe2O3(s) ÷→ 4 Fe(s) + 3 O2(g)
b) Mg
2+
(aq) + 2 OH

(aq) ÷→ Mg(OH)2(s)
c) 3 H2(g) + 3 C2H4(g) ÷→ 3 C2H6(g)
XIII. The standard molar entropy of NH3(g) is 192.45 J/ mol · K at 298 K and its heat
capacity is given by c = a + bT + cT
2
where a = 29.75 J/ mol · K b = 25. 1 ×10
– 3
J/ mol · K and c = –1. 55 × 10
− 5
J/ mol · K.
d) Cal cul at e t he change i n t he st andard mol ar ent ropy, S, from
25ºC at 500ºC.
e) Calculate the standard molar entropy of NH3(g) at 500ºC.
XIV. Make use of the following data on methanol, CH3OH, and a) calculate the entropy
change when 1 mole of liquid methanol at 25°C is heated to its normal boiling point
and then completely evaporated at that temperature. b) Calculate the entropy of 1
mole of gaseous methanol at its boiling point.
Given:
S° for liquid methanol at 25°C = 126.8 J/K·mol
Boiling point of methanol = 64.6°C
ΔHvap =35.25 J/mol
Cp (J/K·mol) = 15.15 + 0.10 × 10
−3
T − 29.50 × 10
−6
T
2
XV. Ethyl hydroperoxide (CH3CH2-O-O-H) in the gaseous state is rumored to have a
value of

f
ΔH = 140.0 kJ/mol. Use the data given below to prove that the value is
feasible.

f
ΔH [C(g)] = 715.0 kJ/mol
65

f
ΔH [H(g)] = 218.0 kJ/mol

f
ΔH [O(g)] = 249.2 kJ/mol
Average bond energies in polyatomic molecules
Bond type C-H C-C C-O O-O O-H
KJ/mol 413 348 351 146 464
XVI. Using a flow calorimeter, a chemist studied the hydrogenation of methyl chloride
CH3Cl(g) + H2(g) ÷→ CH4(g) + HCl(g)
and found that at 248°C (541 K),

521
ΔH = –82.32 kJ/mol. Make the adjustment to
the standard temperature (298 k) so that this result could be incorporated into tables
of standard data. Cp values at 400 K for this calculation are as follows:
Cp(CH4(g)) = 41,28 J/mol K,
Cp(HCl(g)) = 29.11 J/mol K,
Cp(CH3Cl(g)) = 48.46 J/mol K,
Cp(H2(g)) = 28.56 J/mol K,
XVII. Given the following ∆H°rxn values, expressed as per mol of reactant:
NH3(g) ÷→ N2(g) + H2(g) ∆H°1 = + 46.19 kJ ⋅ mol
–1
N2O4(g) ÷→ 2NO2(g) ∆H°2 = + 58.04 kJ ⋅ mol
–1
2 NH3(g) ÷→ N2H4(l) + H2(g) ∆H°3 = + 142.8 kJ ⋅ mol
–1
2NO2(g) + 2H2(g) ÷→ N2(g) + 2H2O2(g) ∆H°4 = – 551.36 kJ ⋅ mol

Calculate ∆H°rxn at 298 K for the following reaction
N2O4(g) + N2H4(l) ÷→ 2N2(g) + 2H2O2(l)
XVIII. Given the thermodynamics data listed in the table below for the following reaction:
4 HCl(g) + O2(g) ÷→ 2 H2O(g) + 2 Cl2(g)
O2(g) Cl2(g) H2O(g) HCl(g)
∆H

f
(kJ/mol)
0 0 –241.81 –92.31
S
o
(J/K · mol) 205 223 189 187
Cp (J/ K · mol)
30.0+1.1×10
–3
T 36.9+3.0×10
–3
T 30.0++2.1×10
–3
T 26.5+1.0×10
–3
T
a. Calculate at T1 = 298 K the standard enthalpy change,

rxn
ΔH , and the
change in the standard entropy,

rxn
ΔS .
b. Calculate at T1 = 298 K the internal energy change,

rxn
ΔE . R = 8.314 J/ K
· mol
c. Calculate at T1 = 298 K the standard free energy change,

rxn
ΔG , and
comment on the significance of the value obtained. Calculate the
equilibrium constant (Kp) for the reaction at 298 K.
66
d. Determine the value of

rxn
ΔH at T2 = 500 K. Comment briefly on the
significance of the value obtained in relation to the value at T1 (i.e. if it is
consistent with any principal in chemistry.
e. Determine the value of

rxn
ΔS at T2 = 500 K. Comment briefly on the
significance of the value obtained in relation to the value at T1.
XIX. Using data given below, calculate the standard enthalpy of formation of gaseous
acetaldehyde, CH3COH.
Standard enthalpy of sublimation for carbon is
C(s) ÷→ C(g)

sub
ΔH = 718 kJ/mol
Bond Dissociation Energies of Diatomic Molecules and Average Bond Energies for
Bonds in Polyatomic Molecules in kJ/mol
C—H C—C C
=
O H—H O
=
O
+414 +347 +745 +436.4 +498.7

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