2

CHAPTER

Equilibrium and
Kinetics

In this chapter, we introduce the concept of stability and metastability using the
mechanical analog of a tilting rectangular block. We discuss the importance of
the indefinite existence of materials in the metastable state. After defining basic
thermodynamic functions, we also discuss the statistical nature of entropy and
the role of the high-energy fraction of atoms in the statistical distribution in
surmounting activation barriers for reactions in materials.

Units
SI units
Quantity Other units
Unit Symbol
Temperature T kelvin K °C, °F
Pressure P megapascal MPa atmosphere,
or or psi, kg/cm2,
meganewton MN m–2 dyne/cm2,
per square mm of Hg
metre
123 14444244443

Internal energy E
External energy PV
Enthalpy H
Gibbs free energy G joule per J mol–1 cal/mole,
Thermal energy RT mole cal/gm
Activation energy Q
Entropy S joule per mole J mol–1 K–1 cal/mole/°C,
Specific heat Cv, Cp per kelvin cal/gm/°C

Constants
Avogadro’s number N = 6.023 ´ 1023 mol–1
Boltzmann’s constant k = 1.380 ´ 10–23 J K–1
Gas constant R = 8.314 J mol–1 K–1

9
10 Equilibrium and Kinetics

2.1 Stability and Metastability

The concept of stability is easily understood by considering a mechanical

analog. In Fig. 2.1, a rectangular block of square cross-section is shown in

1
2
3
2 3
1 4
4
5

Fig. 2.1 Various positions of a tilting rectangular block illustrate the concept of
stability and metastability.

various tilted positions. In position 1, the block is resting on the square base; the
arrow from the centre of mass indicates the line along which the weight acts. In
position 2, the block is tilted slightly to the right, about one of its edges such
that the line along which the weight acts is still within the square base. The
centre of mass has moved up due to the tilt. In position 3, the tilt is increased to
such an extent that the line of force just falls on the periphery of the base. The
centre of mass is now at the maximum possible height from the base. Further
tilting lowers it. The line of force now falls outside the square base but within
the rectangular base, position 4. On coming to rest on the rectangular face,
position 5, the centre of mass is at the lowest possible position for all
configurations of the block.
The centres of mass for the various positions of the block are joined by a
curve. The potential energy of the block is measured by the height of the centre
of the mass from the base. Position 5 corresponds to the lowest potential energy
for all configurations and is correspondingly described as the most stable state
or simply the stable state. A system always tends to go towards the most stable
state. Position 3 has the maximum potential energy and is called an unstable
state. Positions 2 and 4 are also unstable states but do not have the maximum
energy. Position 1 is called a metastable state.
We can use this mechanical analogy to illustrate various equilibrium
configurations of a system. Figure 2.2 shows the potential energy of a system as
a function of configuration. The potential energy curve has two valleys and a
peak. At these positions, the curve has zero slope, that is, the energy does not
 Stability and Metastability 11

vary as a function of configuration for infinitesimally small perturbations. Such

configurations are called equilibrium configurations. Corresponding to the
terminology used for the tilting block, we have stable equilibrium, unstable
equilibrium and metastable equilibrium, see Fig. 2.2. Even though the potential
energy is a minimum in the metastable state, it is not the lowest for all
configurations of the system. Due to the valley position, after small
perturbations, the original configuration is restored in both stable and metastable
equilibrium. Such restoration does not occur in the case of unstable equilibrium.

Unstable

Activation barrier
Potential energy

Metastable

Stable

Configuration
Fig. 2.2 Potential energy as a function of the configuration coordinate.

A metastable state of existence is very common in materials. For example,

most metals at room temperature are stable only in the form of an oxide.
Oxygen is easily available in the surrounding air. Yet a metal may not combine
with oxygen at room temperature (except for a very thin film on the surface). It
may exist in the metastable metallic state for an indefinite period. This period
could be centuries, as is borne out by the unchanging state of some ancient
metallic statues and pillars. This fortunate set of circumstances enables us to use
metals in many engineering applications.
In the mechanical analogy we used, the block can be tilted and brought to
the most stable configuration starting from a metastable state by an external
supply of energy in the form of a hand push or a jiggling base. In materials, the
most common source of such energy is the thermal energy. As the temperature
of a solid is increased from 0 K, the atoms in the solid vibrate about their mean
positions with increasing amplitude. When the temperature is sufficiently high,
rotation of atoms (or small groups of atoms) also becomes possible in some
solids. The translational motion of atoms past one another is more characteristic
of liquids and gases. The energy associated with the vibrations, rotations and
translations aids in taking a material from a metastable state to a stable state. In
the above example of the oxidation of metals, at sufficiently high temperatures,
thermal energy will aid the chemical combination of the metal with the
surrounding oxygen, taking it from the metastable to the stable state. This, of
course, poses the problem of protecting metals against oxidation, when used at
high temperatures.
12 Equilibrium and Kinetics

2.2 Basic Thermodynamic Functions

The concepts of equilibrium and kinetics are intimately associated with the basic
thermodynamic parameters. Pressure P and temperature T are familiar intensive
parameters. As opposed to these, we have extensive (or capacity) parameters,
which depend on the extent or quantity of the material that comprises the
system. The extensive thermodynamic functions are now described.
Internal energy E (also denoted by U) at temperature T is given by
T

E = E0 + Ô
0
Cv dT (2.1)

where E0 is the internal energy of the material at 0 K and Cv is the specific heat
at constant volume. The enthalpy or the heat content of a material H is defined
in a similar manner:
T

H = H0 + Ô0
C p dT (2.2)

where H0 is the enthaply at 0 K and Cp is the specific heat at constant pressure.

E and H are related through P and V, where V is the volume of the material:
H = E + PV (2.3)
PV represents the external energy as opposed to the internal energy and is equal
to the work done by the material at constant pressure in creating a volume V for
itself. For condensed systems like the liquid and the solid state, at atmospheric
pressure, the PV term is negligible so that E » H. This approximation can be
used in most of the problems concerning solid materials.
H0 represents the energy released when the individual atoms of the material
are brought together from the gaseous state to form a solid at 0 K. The gaseous
state (where there is no interaction between the atoms) is taken as the reference
zero energy state. To indicate that the system has lost energy, H0 is written with
a negative sign. As the temperature increases from 0 K, the material absorbs heat
from the surroundings and H increases. The solid melts on reaching the melting
point and a further quantity of heat DH called the enthalpy of fusion is added at
the melting temperature. When all the solid has melted, the temperature of the
liquid may further increase with the absorption of more energy.
All the energy that a system possesses is not available as work during a
chemical change. That part of the energy which can become available as work is
called the Gibbs free energy (or simply the Gibbs energy). The part which
cannot be released as work is called the bound energy. Another thermodynamic
function called entropy defines the relationship between the total energy and the
Gibbs energy. At constant pressure, the entropy S of a system is given by
T

S= Ô
0
C p dT/ T (2.4)
 Basic Thermodynamic Functions 13

The entropy of a material is zero at 0 K, in contrast to the enthalpy and the

internal energy terms, which have non-zero negative values at 0 K. The entropy
increases with increasing temperature. It is a measure of the thermal disorder
introduced in the solid, as it is heated above 0 K. The solid state is characterized
by the random vibrations of atoms about their mean positions. In the liquid state,
the atoms have more freedom and can also move past one another, resulting in
greater disorder. Correspondingly, the entropy increases when a solid melts at
constant temperature.

Example 2.1 Calculate the entropy increase when one mole of ice melts into
water at 0°C.

Solution The latent heat of fusion of ice, DH = 6.02 kJ mol–1

(80 cal/gm). This heat is absorbed at the constant temperature Tm (0°C). The
entropy increase in the process

heat added %H
DS = temperature Tm

= 6.02 ´ 103/273.15
= 22.04 J mol–1 K–1

In addition to thermal entropy, a system may also possess configurational

entropy, which is dependent on the configurations of the system. Following
Boltzmann’s definition, the configurational entropy can be written as
S = k ln w (2.5)
where k is Boltzmann’s constant and w is the number of different configurations
of equal potential energy in which the system can exist. The next section gives a
more detailed discussion of configurational and thermal entropies.
The Gibbs energy G is defined in terms of the enthalpy H and the entropy S:
G = H – TS (2.6)
As already pointed out, the free energy represents the available part of the
energy which can be converted to work. As the temperature increases, H
increases, but TS increases more rapidly than H and so G decreases with
increasing temperature (see Problem 2.3).
The Gibbs energy is used as a criterion of stability. The most stable state
of a material is that which has the minimum Gibbs energy. For a process to
occur spontaneously, the Gibbs energy must decrease during the process.
Changes in thermodynamic quantities are always defined as the final value
minus the initial value:
DG = Gfinal – Ginitial (2.7)
14 Equilibrium and Kinetics

Then, for a spontaneous process, the free energy change DG during the process
must be negative. At a constant temperature and pressure, we can write this
condition for a spontaneous change as
DG = (DH – T DS) < 0 (2.8)
Only if there is no change in the entropy of a system during a process, the
enthalpy change DH can be used in place of DG as a criterion of stability. In the
example of the tilting block, where no entropy change occurs during the tilt, we
were justified in defining the stable state as a state of lowest potential energy (or
enthalpy). In general, however, the entropy change may not be negligible.
Several chemical reactions are known to be endothermic, that is, they absorb
heat during the reaction making DH positive, however, they may occur
spontaneously, indicating that DG is negative. In such cases, T DS > DH.

2.3 The Statistical Nature of Entropy

The entropy of a system has been defined by Eqs. (2.4) and (2.5). The meaning
of these equations can be understood with reference to physical processes.
Taking the configurational entropy first, consider the arrangement of equal
numbers of white and black spheres on 16 sites shown in Fig. 2.3. Four possible
configurations of these spheres are shown. In Figs. 2.3(a) and 2.3(b), the
arrangement is disordered and random. In Fig. 2.3(c), every white sphere is
surrounded by black spheres and every black sphere is surrounded by white
spheres. In Fig. 2.3(d), all white spheres are separated from the black spheres. It
is easy to calculate the total number w of such distinguishable configurations
that we can have with these spheres. For generality, if we call the total number
of sites as N and the number of white spheres as n, the number of black spheres
is (N – n), and it is easily seen that
N!
w= (2.9)
( N  n)! n !
For the above example, substituting N = 16 and n = 8, we obtain w = 12 870.
Among these, only two arrangements shown in Figs. 2.3(c) and 2.3(d) are
perfectly ordered and are thus very unlikely to occur in a random choice. The
probability of the system existing in a disordered configuration is almost unity.

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

Fig. 2.3 Some possible arrangements of 16 spheres, eight of which are white and
the other eight are black.
 The Statistical Nature of Entropy 15

Equation (2.5) states that the configurational entropy increases as the

logarithm of w. One mole of a solid contains more than 1023 atoms. If we mix
two different kinds of atoms randomly in a solid, we end up with an extremely
large number of distinguishable configurations and an appreciable amount of
configurational entropy. Since w can never be less than one, the configurational
entropy is either zero or positive. It is zero for an absolutely pure solid,
consisting of the same kind of atoms on all its sites or for a perfectly ordered
solid like a compound.
Consider a mole of atomic sites N in a solid. Let n atoms of B and (N – n)
atoms of A be mixed randomly on these sites. The configurational entropy is
zero before mixing. The increase in entropy due to mixing is given by
N!
DS = Sfinal – Sinitial = k ln (2.10)
( N  n)! n !
The following Stirling’s approximation is valid for n  1:
ln n! = n ln n – n (2.11)
Combining Eqs. (2.10) and (2.11), we obtain
DS = k [N ln N – (N – n) ln (N – n) – n ln n)] (2.12)
Equation (2.4) gives the thermal part of entropy as a function of temperature.
At 0 K, we can visualize the atoms of a solid to be at rest, so that there is no
disorder due to temperature and, consequently, the entropy is zero. As the
temperature increases, the atoms begin to vibrate about their mean positions in the
solid with increasing frequency and amplitude. The atoms can be considered to
oscillate in three modes corresponding to the three orthogonal directions. For
many solids above room temperature, the frequency of these oscillations reaches a
constant value, about 1013 s –1. In contrast, the amplitude of the oscillations
continues to increase with increasing temperature. The average energy per atom
per mode of oscillation is called the thermal energy and is equal to kT, where T is
the temperature in kelvin and k is Boltzmann’s constant equal to 1.380 ´ 10–23 J
K–1. For one mole of atoms, the thermal energy becomes
NkT = RT (2.13)
where N is Avogadro’s number and R is the gas constant given by
R = Nk = 6.023 ´ 1023 ´ 1.380 ´ 10–23 = 8.314 J mol–1 K–1
All the atoms of a solid do not vibrate with the same amplitude and energy at
any instant. The vibrating atoms interact with their neighbours and, as a very
large number of atoms are involved, the interaction effects are very complex.
Consequently, the vibrational energy of any particular atom fluctuates about the
average value in a random and irregular way. In other words, there is a statistical
distribution of vibrational energies between the atoms. This distribution is the
source of the thermal disorder. The entropy given by Eq. (2.4) should be
associated with this distribution. The thermal entropy arises from the vibrational
energy distribution in a solid, while the configurational entropy arises from the
distribution in the configurational arrangements.
16 Equilibrium and Kinetics

In the vibrational energy distribution, the fraction of atoms that possess

energy equal to or greater than E is given by the Maxwell-Boltzmann equation:
n/N = exp (–E/kT ) (2.14)
where n is the number of such atoms and N is the total number of atoms in the
solid. The exponential term on the right side, which is a fraction, also gives the
probability that any given atom will have energy equal to or greater than E. The
Maxwell-Boltzmann equation is basic to the understanding of the equilibrium
and kinetic processes in materials.

Example 2.2 Find the fraction of atoms with energy equal to or greater than
1 eV in a solid (i) at room temperature (300 K) and (ii) at 1500 K.

Solution (i) At 300 K, thermal energy kT = 1.380 ´ 10–23 ´ 300 J

One electron volt is the kinetic energy acquired by an electron (having a charge
of 1.6 ´ 10–19 coulomb) falling through a potential of 1 V:
1 eV = 1.6 ´ 10–19 C ´ 1 V
= 1.6 ´ 10–19 J
So, kT = 1.38 ´ 10–23 ´ 300/(1.6 ´ 10–19) eV
= 0.026 eV
n/N = exp (–1/0.026) = exp (–38.5)
= 10–16.70 = 2 ´ 10–17
(ii) At 1500 K, kT = 0.129 eV
n/N = exp (–7.75) = 4.3 ´ 10–4
With a five-fold increase in temperature, the fraction of the highly energetic
atoms has increased by about 13 orders of magnitude.

2.4 The Kinetics of Thermally Activated Processes

Arrhenius first measured the rate of a chemical reaction as a function of

temperature. He found that the rate is an exponential function of temperature
according to the following equation:

È Q Ø
Rate = A exp É 
Ê RT ÙÚ
(2.15)

where A is a pre-exponential constant and Q is called the activation energy. In

Fig. 2.4, the logarithm of the rate of a reaction is plotted as a function of the
 The Kinetics of Thermally Activated Processes 17

1
log rate

–1

–3

1.4 1.5 1.6 1.7 1.8

1/T ´ 103, K–1
Fig. 2.4 The Arrhenius plot for the reaction: I2 + H2 U 2HI.

reciprocal of temperature. Such a plot is called the Arrhenius plot. The straight
line relationship is evident. The slope of the straight line is equal to –Q/R and
the intercept on the y-axis is the logarithm of A. This exponential dependence of
a reaction rate on temperature can be justified as follows: Consider a reaction
between different atomic species A, B and C. Let atom A interact with molecule
BC to produce molecule AB and atom C:
A + BC ® AB + C
For this reaction to go in the forward direction as indicated, A and BC must
come into contact, the bond between B and C must be broken and the bond
between A and B must be formed. This usually involves an intermediate step
through which the reaction has to proceed:
A + BC ® (ABC)* ® AB + C
The complex species (ABC)* forms in the intermediate step. The exact nature of
this complex is not a matter of concern to us here. The important point is that
this complex has a high energy. The energy variation along the path of the
reaction is shown schematically in Fig. 2.5. The activated complex is at the peak

Activated complex (ABC)*

DH *
Energy

Reactants
A + BC
Products
AB + C

Reaction path
Fig. 2.5 Energy variation along the reaction path. The activation barrier is DH*.
18 Summary

of this energy curve. This figure can be compared with the potential energy
variation, when the rectangular block is tilted. The activated complex here
corresponds to the unstable position of the tilting block.
For the reaction to occur, the reacting species A and BC must first form the
activated complex, that is, they must reach the energy peak. Once the activated
state is reached, the reaction can instantly proceed to the final step. Just one out
of the 1013 vibrations that occur every second can take the reaction down the
energy hill to the final product AB and C.
The average thermal energy of an atom is insufficient to surmount a typical
activation barrier, which has a height of 1 eV. The average thermal energy of any
mode reaches 1 eV, only at an extremely high temperature, 12 000 K. Yet many
processes in materials that are dependent on thermal energy proceed vigorously
at much lower temperatures. This dilemma is resolved by considering the
Maxwell-Boltzmann energy distribution. Equation (2.14) tells us that there is
always a small fraction of species with energies much greater than the average.
We then have to rely on this small fraction to surmount the activation barrier.
The small fraction of atoms, which has energy equal to or greater than the
activation barrier DH*, would reach the final state at the very start, thus making
the reaction to proceed in the forward direction by a small amount. The
consequent depletion that occurs in the number of the high energy species is
replenished immediately, with the restoration of the equilibrium statistical
distribution. The reaction thus continues as a function of time. The rate of the
reaction is proportional to the number of species n with energy equal to or
greater than that of the activation barrier, as well as to the vibrational frequency
n. The vibrational frequency determines the rate of the final step from the
activated state to the product species.

È %H * Ø
Rate µ nn µ Nn exp É kT Ù (2.16)
Ê Ú

where N is the total number of species. The similarity in form of this equation
with the Arrhenius equation (2.15) is evident. The height of the barrier DH* is to
be equated to the experimental activation energy Q. The vibrational frequency n
and the total number of species N form part of the pre-exponential term A.

SUMMARY

1. The concept of stability and metastability can be understood with reference

to various positions of a rectangular block.
2. As we tilt the block from the metastable position to the stable position, we
pass through the high-energy unstable state.