160 CHEMISTRY

UNIT 6

THERMODYNAMICS

It is the only physical theory of universal content concerning

which I am convinced that, within the framework of the
applicability of its basic concepts, it will never be overthrown.
After studying this Unit, you will
be able to Albert Einstein
• explain the terms : system and
surroundings;
• discriminate between close,
open and isolated systems;
• explain internal energy, work Chemical energy stored by molecules can be released as heat
and heat; during chemical reactions when a fuel like methane, cooking
• state first law of gas or coal burns in air. The chemical energy may also be
thermodynamics and express
it mathematically; used to do mechanical work when a fuel burns in an engine
• calculate energy changes as
or to provide electrical energy through a galvanic cell like
work and heat contributions dry cell. Thus, various forms of energy are interrelated and
in chemical systems; under certain conditions, these may be transformed from
• explain state functions: U, H. one form into another. The study of these energy
• correlate ∆U and ∆H; transformations forms the subject matter of thermodynamics.
• measure experimentally ∆U The laws of thermodynamics deal with energy changes of
and ∆H; macroscopic systems involving a large number of molecules
• define standard states for ∆H; rather than microscopic systems containing a few molecules.
• calculate enthalpy changes for Thermodynamics is not concerned about how and at what
various types of reactions;
rate these energy transformations are carried out, but is
• state and apply Hess’s law of
based on initial and final states of a system undergoing the
constant heat summation;
change. Laws of thermodynamics apply only when a system
• differentiate between extensive
and intensive properties; is in equilibrium or moves from one equilibrium state to
• define spontaneous and non- another equilibrium state. Macroscopic properties like
spontaneous processes; pressure and temperature do not change with time for a
• explain entropy as a system in equilibrium state. In this unit, we would like to
thermodynamic state function answer some of the important questions through
and apply it for spontaneity; thermodynamics, like:
• explain Gibbs energy change
(∆G); and How do we determine the energy changes involved in a
• establish relationship between chemical reaction/process? Will it occur or not?
∆G and spontaneity, ∆G and
equilibrium constant.
What drives a chemical reaction/process?
To what extent do the chemical reactions proceed?

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THERMODYNAMICS 161

6.1 THERMODYNAMIC TERMS be real or imaginary. The wall that separates

the system from the surroundings is called
We are interested in chemical reactions and the
boundary. This is designed to allow us to
energy changes accompanying them. For this
control and keep track of all movements of
we need to know certain thermodynamic
matter and energy in or out of the system.
terms. These are discussed below.
6.1.2 Types of the System
6.1.1 The System and the Surroundings
We, further classify the systems according to
A system in thermodynamics refers to that
the movements of matter and energy in or out
part of universe in which observations are
of the system.
made and remaining universe constitutes the
surroundings. The surroundings include 1. Open System
everything other than the system. System and In an open system, there is exchange of energy
the surroundings together constitute the and matter between system and surroundings
universe . [Fig. 6.2 (a)]. The presence of reactants in an
The universe = The system + The surroundings open beaker is an example of an open system*.
However, the entire universe other than Here the boundary is an imaginary surface
the system is not affected by the changes enclosing the beaker and reactants.
taking place in the system. Therefore, for 2. Closed System
all practical purposes, the surroundings In a closed system, there is no exchange of
are that portion of the remaining universe matter, but exchange of energy is possible
which can interact with the system. between system and the surroundings
Usually, the region of space in the [Fig. 6.2 (b)]. The presence of reactants in a
neighbourhood of the system constitutes closed vessel made of conducting material e.g.,
its surroundings. copper or steel is an example of a closed
For example, if we are studying the system.
reaction between two substances A and B
kept in a beaker, the beaker containing the
reaction mixture is the system and the room
where the beaker is kept is the surroundings
(Fig. 6.1).

Fig. 6.1 System and the surroundings

Note that the system may be defined by
physical boundaries, like beaker or test tube,
or the system may simply be defined by a set
of Cartesian coordinates specifying a
particular volume in space. It is necessary to
think of the system as separated from the
surroundings by some sort of wall which may Fig. 6.2 Open, closed and isolated systems.

* We could have chosen only the reactants as system then walls of the beakers will act as boundary.

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162 CHEMISTRY

3. Isolated System of the system. It may be chemical, electrical,

In an isolated system, there is no exchange of mechanical or any other type of energy you
energy or matter between the system and the may think of, the sum of all these is the energy
surroundings [Fig. 6.2 (c)]. The presence of of the system. In thermodynamics, we call it
reactants in a thermos flask or any other closed the internal energy, U of the system, which may
insulated vessel is an example of an isolated change, when
system. • heat passes into or out of the system,
6.1.3 The State of the System • work is done on or by the system,
The system must be described in order to make • matter enters or leaves the system.
any useful calculations by specifying These systems are classified accordingly as
quantitatively each of the properties such as you have already studied in section 6.1.2.
its pressure (p), volume (V), and temperature
(T ) as well as the composition of the system. (a) Work
We need to describe the system by specifying Let us first examine a change in internal
it before and after the change. You would recall energy by doing work. We take a system
from your Physics course that the state of a containing some quantity of water in a thermos
system in mechanics is completely specified at flask or in an insulated beaker. This would not
a given instant of time, by the position and allow exchange of heat between the system
velocity of each mass point of the system. In and surroundings through its boundary and
thermodynamics, a different and much simpler we call this type of system as adiabatic. The
concept of the state of a system is introduced. manner in which the state of such a system
It does not need detailed knowledge of motion may be changed will be called adiabatic
of each particle because, we deal with average process. Adiabatic process is a process in
measurable properties of the system. We specify which there is no transfer of heat between the
the state of the system by state functions or system and surroundings. Here, the wall
state variables. separating the system and the surroundings
The state of a thermodynamic system is is called the adiabatic wall (Fig 6.3).
described by its measurable or macroscopic Let us bring the change in the internal
(bulk) properties. We can describe the state of energy of the system by doing some work on
a gas by quoting its pressure (p), volume (V),
temperature (T ), amount (n) etc. Variables like
p, V, T are called state variables or state
functions because their values depend only
on the state of the system and not on how it is
reached. In order to completely define the state
of a system it is not necessary to define all the
properties of the system; as only a certain
number of properties can be varied
independently. This number depends on the
nature of the system. Once these minimum
number of macroscopic properties are fixed,
others automatically have definite values.
Fig. 6.3 An adiabatic system which does not
The state of the surroundings can never
permit the transfer of heat through its
be completely specified; fortunately it is not
boundary.
necessary to do so.
6.1.4 The Internal Energy as a State it. Let us call the initial state of the system as
Function state A and its temperature as TA. Let the
internal energy of the system in state A be
When we talk about our chemical system called UA. We can change the state of the system
losing or gaining energy, we need to introduce in two different ways.
a quantity which represents the total energy

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THERMODYNAMICS 163

One way: We do some mechanical work, say the route taken. Volume of water in a pond,
1 kJ, by rotating a set of small paddles and for example, is a state function, because
thereby churning water. Let the new state be change in volume of its water is independent
called B state and its temperature, as TB. It is of the route by which water is filled in the
found that T B > T A and the change in pond, either by rain or by tubewell or by both.
temperature, ∆T = T B–TA. Let the internal (b) Heat
energy of the system in state B be UB and the
We can also change the internal energy of a
change in internal energy, ∆U =UB– UA.
system by transfer of heat from the
Second way: We now do an equal amount (i.e., surroundings to the system or vice-versa
1kJ) electrical work with the help of an without expenditure of work. This exchange
immersion rod and note down the temperature of energy, which is a result of temperature
change. We find that the change in temperature difference is called heat, q. Let us consider
is same as in the earlier case, say, TB – TA. bringing about the same change in temperature
(the same initial and final states as before in
In fact, the experiments in the above
section 6.1.4 (a) by transfer of heat through
manner were done by J. P. Joule between
thermally conducting walls instead of
1840–50 and he was able to show that a given
adiabatic walls (Fig. 6.4).
amount of work done on the system, no matter
how it was done (irrespective of path) produced
the same change of state, as measured by the
change in the temperature of the system.
So, it seems appropriate to define a
quantity, the internal energy U, whose value
is characteristic of the state of a system,
whereby the adiabatic work, wad required to
bring about a change of state is equal to the
difference between the value of U in one state
and that in another state, ∆U i.e.,
∆U = U 2 − U 1 = w ad
Fig. 6.4 A system which allows heat transfer
Therefore, internal energy, U, of the system
through its boundary.
is a state function.
By conventions of IUPAC in chemical We take water at temperature, TA in a
thermodynamics. The positive sign expresses container having thermally conducting walls,
that wad is positive when work is done on the say made up of copper and enclose it in a huge
system and the internal energy of system heat reservoir at temperature, TB. The heat
increases. Similarly, if the work is done by the absorbed by the system (water), q can be
system,wad will be negative because internal measured in terms of temperature difference ,
energy of the system decreases. TB – TA. In this case change in internal energy,
∆U= q, when no work is done at constant
Can you name some other familiar state
volume.
functions? Some of other familiar state
functions are V, p, and T. For example, if we By conventions of IUPAC in chemical
bring a change in temperature of the system thermodynamics. The q is positive, when
from 25°C to 35°C, the change in temperature heat is transferred from the surroundings to
is 35°C–25°C = +10°C, whether we go straight the system and the internal energy of the
up to 35°C or we cool the system for a few system increases and q is negative when
degrees, then take the system to the final heat is transferred from system to the
temperature. Thus, T is a state function and surroundings resulting in decrease of the
the change in temperature is independent of internal energy of the system..
* Earlier negative sign was assigned when the work is done on the system and positive sign when the work is done by the
system. This is still followed in physics books, although IUPAC has recommended the use of new sign convention.

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(c) The general case Solution

Let us consider the general case in which a (i) ∆ U = w ad, wall is adiabatic
change of state is brought about both by
(ii) ∆ U = – q, thermally conducting walls
doing work and by transfer of heat. We write
change in internal energy for this case as: (iii) ∆ U = q – w, closed system.
∆U = q + w (6.1) 6.2 APPLICATIONS
For a given change in state, q and w can Many chemical reactions involve the generation
vary depending on how the change is carried of gases capable of doing mechanical work or
out. However, q +w = ∆U will depend only on the generation of heat. It is important for us to
initial and final state. It will be independent of quantify these changes and relate them to the
the way the change is carried out. If there is changes in the internal energy. Let us see how!
no transfer of energy as heat or as work
(isolated system) i.e., if w = 0 and q = 0, then 6.2.1 Work
∆ U = 0. First of all, let us concentrate on the nature of
The equation 6.1 i.e., ∆U = q + w is work a system can do. We will consider only
mathematical statement of the first law of mechanical work i.e., pressure-volume work.
thermodynamics, which states that
For understanding pressure-volume
The energy of an isolated system is work, let us consider a cylinder which
constant. contains one mole of an ideal gas fitted with a
It is commonly stated as the law of frictionless piston. Total volume of the gas is
conservation of energy i.e., energy can neither Vi and pressure of the gas inside is p. If
be created nor be destroyed. external pressure is pex which is greater than
p, piston is moved inward till the pressure
Note: There is considerable difference between inside becomes equal to pex. Let this change
the character of the thermodynamic property
energy and that of a mechanical property such
as volume. We can specify an unambiguous
(absolute) value for volume of a system in a
particular state, but not the absolute value of
the internal energy. However, we can measure
only the changes in the internal energy, ∆U of
the system.
Problem 6.1
Express the change in internal energy of
a system when
(i) No heat is absorbed by the system
from the surroundings, but work (w)
is done on the system. What type of
wall does the system have ?
(ii) No work is done on the system, but
q amount of heat is taken out from
the system and given to the
surroundings. What type of wall does
the system have?
(iii) w amount of work is done by the Fig. 6.5(a) Work done on an ideal gas in a
system and q amount of heat is cylinder when it is compressed by a
supplied to the system. What type of constant external pressure, p ex
system would it be? (in single step) is equal to the shaded
area.

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THERMODYNAMICS 165

be achieved in a single step and the final If the pressure is not constant but changes
volume be Vf . During this compression, during the process such that it is always
suppose piston moves a distance, l and is infinitesimally greater than the pressure of the
cross-sectional area of the piston is A gas, then, at each stage of compression, the
[Fig. 6.5(a)]. volume decreases by an infinitesimal amount,
then, volume change = l × A = ∆V = (Vf – Vi ) dV. In such a case we can calculate the work
done on the gas by the relation
force
We also know, pressure = Vf
area
Therefore, force on the piston = pex . A
w=− ∫p
Vi
ex dV ( 6.3)
If w is the work done on the system by Here, pex at each stage is equal to (pin + dp) in
movement of the piston then case of compression [Fig. 6.5(c)]. In an
w = force × distance = pex . A .l expansion process under similar conditions,
= pex . (–∆V) = – pex ∆V = – pex (Vf – Vi ) (6.2) the external pressure is always less than the
pressure of the system i.e., pex = (pin– dp). In
The negative sign of this expression is
general case we can write, pex = (pin + dp). Such
required to obtain conventional sign for w,
processes are called reversible processes.
which will be positive. It indicates that in case
A process or change is said to be
of compression work is done on the system.
reversible, if a change is brought out in
Here (Vf – Vi ) will be negative and negative
such a way that the process could, at any
multiplied by negative will be positive. Hence
moment, be reversed by an infinitesimal
the sign obtained for the work will be positive.
change. A reversible process proceeds
If the pressure is not constant at every
infinitely slowly by a series of equilibrium
stage of compression, but changes in number
states such that system and the
of finite steps, work done on the gas will be
surroundings are always in near
summed over all the steps and will be equal
equilibrium with each other. Processes
to − ∑ p ∆V [Fig. 6.5 (b)]

Fig. 6.5 (c) pV-plot when pressure is not constant

Fig. 6.5 (b) pV-plot when pressure is not constant and changes in infinite steps
and changes in finite steps during (reversible conditions) during
compression from initial volume, Vi to compression from initial volume, Vi to
final volume, Vf . Work done on the gas final volume, Vf . Work done on the gas
is represented by the shaded area. is represented by the shaded area.

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other than reversible processes are known Isothermal and free expansion of an
as irreversible processes. ideal gas
In chemistry, we face problems that can For isothermal (T = constant) expansion of an
be solved if we relate the work term to the ideal gas into vacuum ; w = 0 since pex = 0.
internal pressure of the system. We can Also, Joule determined experimentally that
relate work to internal pressure of the system q = 0; therefore, ∆U = 0
under reversible conditions by writing Equation 6.1, ∆ U = q + w can be
equation 6.3 as follows: expressed for isothermal irreversible and
Vf Vf reversible changes as follows:
w rev = − ∫p
Vi
ex dV = − ∫ (p
Vi
in ± dp ) dV 1. For isothermal irreversible change
q = – w = pex (Vf – Vi )
Since dp × dV is very small we can write 2. For isothermal reversible change
Vf
Vf
w rev = − ∫ pin dV (6.4) q = – w = nRT ln V
Vi i

Now, the pressure of the gas (pin which we Vf

can write as p now) can be expressed in terms = 2.303 nRT log
Vi
of its volume through gas equation. For n mol
3. For adiabatic change, q = 0,
of an ideal gas i.e., pV =nRT
∆U = wad
nRT
⇒p = Problem 6.2
V
Therefore, at constant temperature (isothermal Two litres of an ideal gas at a pressure of
process), 10 atm expands isothermally at 25 °C into
a vacuum until its total volume is 10 litres.
Vf
dV Vf How much heat is absorbed and how much
w rev = − ∫ nRT = −nRT ln work is done in the expansion ?
Vi
V Vi
Solution
Vf We have q = – w = pex (10 – 2) = 0(8) = 0
= – 2.303 nRT log (6.5) No work is done; no heat is absorbed.
Vi
Free expansion: Expansion of a gas in Problem 6.3
vacuum (pex = 0) is called free expansion. No Consider the same expansion, but this
work is done during free expansion of an ideal time against a constant external pressure
gas whether the process is reversible or of 1 atm.
irreversible (equation 6.2 and 6.3).
Solution
Now, we can write equation 6.1 in number
We have q = – w = pex (8) = 8 litre-atm
of ways depending on the type of processes.
Problem 6.4
Let us substitute w = – pex∆V (eq. 6.2) in
equation 6.1, and we get Consider the expansion given in problem
6.2, for 1 mol of an ideal gas conducted
∆U = q − pex ∆V reversibly.
If a process is carried out at constant volume
Solution
(∆V = 0), then Vf
∆U = qV We have q = – w = 2.303 nRT log
Vs 10
the subscript V in qV denotes that heat is = 2.303 × 1 × 0.8206 × 298 × log
2
supplied at constant volume.

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= 2.303 x 0.8206 x 298 x log 5 Remember ∆H = qp, heat absorbed by the

system at constant pressure.
= 2.303 x 0.8206 x 298 x 0.6990
∆H is negative for exothermic reactions
= 393.66 L atm
which evolve heat during the reaction and
6.2.2 Enthalpy, H ∆H is positive for endothermic reactions
which absorb heat from the surroundings.
(a) A Useful New State Function
At constant volume (∆V = 0), ∆U = qV,
We know that the heat absorbed at constant therefore equation 6.8 becomes
volume is equal to change in the internal
energy i.e., ∆U = q . But most of chemical ∆H = ∆U = q
V
V
reactions are carried out not at constant The difference between ∆H and ∆U is not
volume, but in flasks or test tubes under usually significant for systems consisting of
constant atmospheric pressure. We need to only solids and / or liquids. Solids and liquids
define another state function which may be do not suffer any significant volume changes
suitable under these conditions. upon heating. The difference, however,
We may write equation (6.1) as becomes significant when gases are involved.
∆U = qp – p∆V at constant pressure, where qp Let us consider a reaction involving gases. If
is heat absorbed by the system and –p ∆V VA is the total volume of the gaseous reactants,
represent expansion work done by the system. VB is the total volume of the gaseous products,
Let us represent the initial state by nA is the number of moles of gaseous reactants
subscript 1 and final state by 2 and nB is the number of moles of gaseous
products, all at constant pressure and
We can rewrite the above equation as
temperature, then using the ideal gas law, we
U2–U1 = qp – p (V2 – V1) write,
On rearranging, we get pVA = nART
qp = (U2 + pV2) – (U1 + pV1) (6.6)
and pVB = nBRT
Now we can define another thermodynamic
function, the enthalpy H [Greek word Thus, pVB – pVA = nBRT – nART = (nB–nA)RT
enthalpien, to warm or heat content] as :
or p (VB – VA) = (nB – nA) RT
H = U + pV (6.7)
so, equation (6.6) becomes or p ∆V = ∆ngRT (6.9)
qp= H2 – H1 = ∆H Here, ∆ng refers to the number of moles of
Although q is a path dependent function, gaseous products minus the number of moles
H is a state function because it depends on U, of gaseous reactants.
p and V, all of which are state functions. Substituting the value of p∆V from
Therefore, ∆H is independent of path. Hence, equation 6.9 in equation 6.8, we get
qp is also independent of path.
∆H = ∆U + ∆ngRT (6.10)
For finite changes at constant pressure, we
can write equation 6.7 as The equation 6.10 is useful for calculating
∆H from ∆U and vice versa.
∆H = ∆U + ∆pV
Since p is constant, we can write Problem 6.5
∆H = ∆U + p∆V (6.8) If water vapour is assumed to be a perfect
It is important to note that when heat is gas, molar enthalpy change for
absorbed by the system at constant pressure, vapourisation of 1 mol of water at 1bar
we are actually measuring changes in the and 100°C is 41kJ mol–1. Calculate the
enthalpy. internal energy change, when

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1 mol of water is vapourised at 1 bar

pressure and 100°C.
Solution
(i) The change H2O (l ) → H2O ( g )

∆H = ∆U + ∆n g RT Fig. 6.6(a) A gas at volume V and temperature T

or ∆U = ∆H – ∆n g RT , substituting the
values, we get
∆U = 41.00 kJ mol −1 − 1
× 8.3 J mol −1K −1 × 373 K
= 41.00 kJ mol-1 – 3.096 kJ mol-1 Fig. 6.6 (b) Partition, each part having half the
= 37.904 kJ mol–1 volume of the gas

(b) Extensive and Intensive Properties (c) Heat Capacity

In thermodynamics, a distinction is made In this sub-section, let us see how to measure
between extensive properties and intensive heat transferred to a system. This heat appears
properties. An extensive property is a as a rise in temperature of the system in case
property whose value depends on the of heat absorbed by the system.
quantity or size of matter present in the
The increase of temperature is proportional
system. For example, mass, volume,
to the heat transferred
internal energy, enthalpy, heat capacity, etc.
are extensive properties. q = coeff × ∆T
Those properties which do not depend The magnitude of the coefficient depends
on the quantity or size of matter present are on the size, composition and nature of the
known as intensive properties. For system. We can also write it as q = C ∆T
example temperature, density, pressure etc. The coefficient, C is called the heat capacity.
are intensive properties. A molar property,
Thus, we can measure the heat supplied
χm, is the value of an extensive property χ of
by monitoring the temperature rise, provided
the system for 1 mol of the substance. If n
χ we know the heat capacity.
is the amount of matter, χ m = is When C is large, a given amount of heat
n
independent of the amount of matter. Other results in only a small temperature rise. Water
examples are molar volume, Vm and molar has a large heat capacity i.e., a lot of energy is
heat capacity, Cm. Let us understand the needed to raise its temperature.
distinction between extensive and intensive C is directly proportional to amount of
properties by considering a gas enclosed in
substance. The molar heat capacity of a
a container of volume V and at temperature
substance, Cm =   , is the heat capacity for
T [Fig. 6.6(a)]. Let us make a partition such C
that volume is halved, each part [Fig. 6.6 n
(b)] now has one half of the original volume, one mole of the substance and is the quantity
V of heat needed to raise the temperature of
, but the temperature will still remain the one mole by one degree celsius (or one
2
same i.e., T. It is clear that volume is an kelvin). Specific heat, also called specific heat
extensive property and temperature is an capacity is the quantity of heat required to
intensive property. raise the temperature of one unit mass of a

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THERMODYNAMICS 169

substance by one degree celsius (or one i) at constant volume, qV

kelvin). For finding out the heat, q, required ii) at constant pressure, qp
to raise the temperatures of a sample, we
(a) ∆U Measurements
multiply the specific heat of the substance,
c, by the mass m, and temperatures change, For chemical reactions, heat absorbed at
∆T as constant volume, is measured in a bomb
calorimeter (Fig. 6.7). Here, a steel vessel (the
q = c × m × ∆T = C ∆T (6.11) bomb) is immersed in a water bath. The whole
(d) The Relationship between Cp and CV device is called calorimeter. The steel vessel is
for an Ideal Gas immersed in water bath to ensure that no heat
At constant volume, the heat capacity, C is is lost to the surroundings. A combustible
denoted by CV and at constant pressure, this substance is burnt in pure dioxygen supplied
is denoted by Cp . Let us find the relationship
between the two.
We can write equation for heat, q
at constant volume as qV = CV ∆T = ∆U

at constant pressure as qp = C p ∆T = ∆H
The difference between Cp and CV can be
derived for an ideal gas as:
For a mole of an ideal gas, ∆H = ∆U + ∆(pV )
= ∆U + ∆(RT )
= ∆U + R∆T
∴ ∆H = ∆U + R ∆T (6.12)
On putting the values of ∆H and ∆U,
we have
C p ∆T = CV ∆T + R∆T
C p = CV + R
Cp – CV = R (6.13) Fig. 6.7 Bomb calorimeter

in the steel bomb. Heat evolved during the

6.3 MEASUREMENT OF ∆ U AND ∆ H: reaction is transferred to the water around the
CALORIMETRY bomb and its temperature is monitored. Since
We can measure energy changes associated the bomb calorimeter is sealed, its volume does
with chemical or physical processes by an not change i.e., the energy changes associated
experimental technique called calorimetry. In with reactions are measured at constant
calorimetry, the process is carried out in a volume. Under these conditions, no work is
vessel called calorimeter, which is immersed done as the reaction is carried out at constant
in a known volume of a liquid. Knowing the volume in the bomb calorimeter. Even for
heat capacity of the liquid in which calorimeter reactions involving gases, there is no work
is immersed and the heat capacity of done as ∆V = 0. Temperature change of the
calorimeter, it is possible to determine the heat calorimeter produced by the completed
evolved in the process by measuring reaction is then converted to qV, by using the
temperature changes. Measurements are known heat capacity of the calorimeter with
made under two different conditions: the help of equation 6.11.

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(b) ∆H Measurements
of the bomb calorimeter is 20.7kJ/K,
Measurement of heat change at constant pressure what is the enthalpy change for the above
(generally under atmospheric pressure) can be reaction at 298 K and 1 atm?
done in a calorimeter shown in Fig. 6.8. We know
Solution
that ∆Η = qp (at constant p) and, therefore, heat
absorbed or evolved, qp at constant pressure is Suppose q is the quantity of heat from the
also called the heat of reaction or enthalpy of reaction mixture and CV is the heat capacity
reaction, ∆rH. of the calorimeter, then the quantity of heat
absorbed by the calorimeter.
In an exothermic reaction, heat is evolved,
q = CV × ∆T
and system loses heat to the surroundings.
Therefore, qp will be negative and ∆rH will also Quantity of heat from the reaction will
be negative. Similarly in an endothermic have the same magnitude but opposite
reaction, heat is absorbed, qp is positive and sign because the heat lost by the system
∆rH will be positive. (reaction mixture) is equal to the heat
gained by the calorimeter.
q = − CV × ∆T = − 20.7 kJ/K × (299 − 298) K
= − 20.7 kJ
(Here, negative sign indicates the
exothermic nature of the reaction)
Thus, ∆U for the combustion of the 1g of
graphite = – 20.7 kJK–1
For combustion of 1 mol of graphite,

12.0 g mol −1 × ( −20.7 kJ )

=
1g
= – 2.48 ×102 kJ mol–1 , Since ∆ ng = 0,
∆ H = ∆ U = – 2.48 ×102 kJ mol–1

6.4 ENTHALPY CHANGE, ∆ r H OF A

REACTION – REACTION ENTHALPY
In a chemical reaction, reactants are converted
into products and is represented by,
Fig. 6.8 Calorimeter for measuring heat changes Reactants → Products
at constant pressure (atmospheric The enthalpy change accompanying a
pressure). reaction is called the reaction enthalpy. The
enthalpy change of a chemical reaction, is given
Problem 6.6 by the symbol ∆rH
1g of graphite is burnt in a bomb ∆rH = (sum of enthalpies of products) – (sum
calorimeter in excess of oxygen at 298 K of enthalpies of reactants)
and 1 atmospheric pressure according to
the equation = ∑a H
i
i products − ∑ bi H reactants (6.14)
i
C (graphite) + O2 (g) → CO2 (g)
During the reaction, temperature rises Here symbol ∑ (sigma) is used for
from 298 K to 299 K. If the heat capacity summation and ai and bi are the stoichiometric

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THERMODYNAMICS 171

coefficients of the products and reactants ethanol at 298 K is pure liquid ethanol at
respectively in the balanced chemical 1 bar; standard state of solid iron at 500 K is
equation. For example, for the reaction pure iron at 1 bar. Usually data are taken
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) at 298 K.
∆r H = ∑ a i H Pr oducts − ∑ bi H reac tan ts Standard conditions are denoted by adding
i i
= [Hm (CO2 ,g) + 2Hm (H2O, l)]– [Hm (CH4 , g) the superscript 0 to the symbol ∆H, e.g., ∆H0
+ 2Hm (O2, g)] (b) Enthalpy Changes during Phase
where Hm is the molar enthalpy. Transformations
Enthalpy change is a very useful quantity. Phase transformations also involve energy
Knowledge of this quantity is required when
changes. Ice, for example, requires heat for
one needs to plan the heating or cooling
melting. Normally this melting takes place at
required to maintain an industrial chemical
constant pressure (atmospheric pressure) and
reaction at constant temperature. It is also
during phase change, temperature remains
required to calculate temperature dependence
constant (at 273 K).
of equilibrium constant.
0
H2O(s) → H2O(l); ∆fusH = 6.00 kJ moI–1
(a) Standard Enthalpy of Reactions 0
Here ∆fusH is enthalpy of fusion in standard
Enthalpy of a reaction depends on the
state. If water freezes, then process is reversed
conditions under which a reaction is carried
and equal amount of heat is given off to the
out. It is, therefore, necessary that we must
surroundings.
specify some standard conditions. The
standard enthalpy of reaction is the The enthalpy change that accompanies
enthalpy change for a reaction when all melting of one mole of a solid substance
the participating substances are in their in standard state is called standard
standard states. enthalpy of fusion or molar enthalpy of
The standard state of a substance at a fusion, ∆fusH 0.
specified temperature is its pure form at Melting of a solid is endothermic, so all
1 bar. For example, the standard state of liquid enthalpies of fusion are positive. Water requires

Table 6.1 Standard Enthalpy Changes of Fusion and Vaporisation

(Tf and Tb are melting and boiling points, respectively)

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172 CHEMISTRY

heat for evaporation. At constant temperature

Solution
of its boiling point Tb and at constant pressure:
0 0
We can represent the process of
H2O(l) → H2O(g); ∆vapH = + 40.79 kJ moI–1 ∆vapH evaporation as
is the standard enthalpy of vaporisation.
Amount of heat required to vaporize H 2O(1) 
vaporisation
→ H2 O(g)
1mol 1mol
one mole of a liquid at constant
temperature and under standard pressure No. of moles in 18 g H2O(l) is
(1bar) is called its standard enthalpy of 18g
vaporization or molar enthalpy of = = 1mol
18 g mol −1
vaporization, ∆vapH 0.
Heat supplied to evaporate18g water at
Sublimation is direct conversion of a solid 0
298 K = n × ∆vap H
into its vapour. Solid CO2 or ‘dry ice’ sublimes
0 = (1 mol) × (44.01 kJ mol–1)
at 195K with ∆ sub H =25.2 kJ mol –1 ;
naphthalene sublimes slowly and for this = 44.01 kJ
∆sub H0 = 73.0 kJ mol–1 . (assuming steam behaving as an ideal
gas).
Standard enthalpy of sublimation,
0 ∆vapU = ∆vap H V − p ∆V = ∆vap H V − ∆n g RT
∆subH is the change in enthalpy when one
mole of a solid substance sublimes at a
constant temperature and under standard ∆vap H V − ∆n g RT = 44.01 kJ
pressure (1bar). − (1)(8.314 JK −1 mol −1 )(298K )(10 −3 kJ J −1 )
The magnitude of the enthalpy change ∆vapU V = 44.01 kJ − 2.48 kJ
depends on the strength of the intermolecular
= 41.53 kJ
interactions in the substance undergoing the
phase transfomations. For example, the strong Problem 6.8
hydrogen bonds between water molecules hold
Assuming the water vapour to be a perfect
them tightly in liquid phase. For an organic
gas, calculate the internal energy change
liquid, such as acetone, the intermolecular when 1 mol of water at 100°C and 1 bar
dipole-dipole interactions are significantly pressure is converted to ice at 0°C. Given
weaker. Thus, it requires less heat to vaporise the enthalpy of fusion of ice is 6.00 kJ mol-
1 mol of acetone than it does to vaporize 1 mol 1
heat capacity of water is 4.2 J/g°C
of water. Table 6.1 gives values of standard The change take place as follows:
enthalpy changes of fusion and vaporisation Step - 1 1 mol H2O (l, 100°C) à 1
for some substances. mol (l, 0°C) Enthalpy
change ∆H1
Problem 6.7
Step - 2 1 mol H2O (l, 0°C) à 1 mol
A swimmer coming out from a pool is H2O( S, 0°C) Enthalpy
covered with a film of water weighing change ∆H2
about 18g. How much heat must be Total enthalpy change will be -
supplied to evaporate this water at
∆H = ∆H1 + ∆H2
298 K ? Calculate the internal energy of
vaporisation at 298K. ∆H1 = - (18 x 4.2 x 100) J mol-1
∆vap H 0 for water = - 7560 J mol-1 = - 7.56 k J mol-1
at 298K= 44.01kJ mol–1 ∆H2 = - 6.00 kJ mol-1

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THERMODYNAMICS 173

∆f H ) at 298K of a
y
Table 6.2 Standard Molar Enthalpies of Formation (∆
Few Selected Substances

Therefore, aggregation (also known as reference

states) is called Standard Molar Enthalpy
∆H = - 7.56 kJ mol-1 + (-6.00 kJ mol-1)
= -13.56 kJ mol-1 of Formation. Its symbol is ∆f H 0, where
the subscript ‘ f ’ indicates that one mole of
There is negligible change in the volume
the compound in question has been formed
during the change form liquid to solid
in its standard state from its elements in their
state.
most stable states of aggregation. The reference
Therefore, p∆v = ∆ng RT = 0 state of an element is its most stable state of
∆H = ∆U = - 13.56kJ mol-1 aggregation at 25°C and 1 bar pressure.
For example, the reference state of dihydrogen
(c) Standard Enthalpy of Formation is H2 gas and those of dioxygen, carbon and
The standard enthalpy change for the sulphur are O 2 gas, C graphite and S rhombic
formation of one mole of a compound from respectively. Some reactions with standard
its elements in their most stable states of molar enthalpies of formation are as follows.

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H2(g) + ½O2 (g) → H2O(1); Here, we can make use of standard enthalpy
∆f H = –285.8 kJ mol
0 –1 of formation and calculate the enthalpy
change for the reaction. The following general
C (graphite, s) + 2H2(g) → Ch4 (g); equation can be used for the enthalpy change
∆f H0 = –74.81 kJ mol–1 calculation.
2C (graphite, s)+3H2 (g)+ ½O2(g) → C2H5OH(1); ∆rH0 = ∑ ai ∆f H0 (products) – ∑ bi ∆f H0 (reactants)
∆f H0 = – 277.7kJ mol–1
i i

(6.15)
It is important to understand that a where a and b represent the coefficients of the
standard molar enthalpy of formation, ∆f H ,
0 products and reactants in the balanced
0 equation. Let us apply the above equation for
is just a special case of ∆rH , where one mole
decomposition of calcium carbonate. Here,
of a compound is formed from its constituent
coefficients ‘a’ and ‘b’ are 1 each. Therefore,
elements, as in the above three equations,
where 1 mol of each, water, methane and ∆rH0 = ∆f H0 = [CaO(s)]+ ∆f H0 [CO2(g)]
ethanol is formed. In contrast, the enthalpy – ∆f H0 = [CaCO3(s)]
change for an exothermic reaction: =1 (–635.1 kJ mol–1) + 1(–393.5 kJ mol–1)
CaO(s) + CO2(g) → CaCo3(s); –1(–1206.9 kJ mol–1)
∆rH0 = – 178.3kJ mol–1 = 178.3 kJ mol–1
is not an enthalpy of formation of calcium Thus, the decomposition of CaCO3 (s) is an
carbonate, since calcium carbonate has been endothermic process and you have to heat it
formed from other compounds, and not from for getting the desired products.
its constituent elements. Also, for the reaction (d) Thermochemical Equations
given below, enthalpy change is not standard A balanced chemical equation together with
0
enthalpy of formation, ∆fH for HBr(g). the value of its ∆rH is called a thermochemical
H2(g) + Br2(l) → 2HBr(g); equation. We specify the physical state
∆r H0 = – 178.3kJ mol–1 (alongwith allotropic state) of the substance in
Here two moles, instead of one mole of the an equation. For example:
product is formed from the elements, i.e., . C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l);
∆r H0 = 2∆f H0
∆rH0 = – 1367 kJ mol–1
Therefore, by dividing all coefficients in the
The above equation describes the
balanced equation by 2, expression for
combustion of liquid ethanol at constant
enthalpy of formation of HBr (g) is written as
temperature and pressure. The negative sign
½H2(g) + ½Br2(1) → HBr(g); of enthalpy change indicates that this is an
∆f H0 = – 36.4 kJ mol–1 exothermic reaction.
Standard enthalpies of formation of some
common substances are given in Table 6.2. It would be necessary to remember the
By convention, standard enthalpy for following conventions regarding thermo-
formation, ∆f H 0, of an element in reference chemical equations.
state, i.e., its most stable state of aggregation 1. The coefficients in a balanced thermo-
is taken as zero. chemical equation refer to the number of
Suppose, you are a chemical engineer and moles (never molecules) of reactants and
want to know how much heat is required to products involved in the reaction.
decompose calcium carbonate to lime and 0
2. The numerical value of ∆rH refers to the
carbon dioxide, with all the substances in their number of moles of substances specified
standard state. by an equation. Standard enthalpy change
CaCO3(s) → CaO(s) + CO2(g); ∆r H0 = ? 0
∆rH will have units as kJ mol–1.

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THERMODYNAMICS 175

To illustrate the concept, let us consider (e) Hess’s Law of Constant Heat
the calculation of heat of reaction for the Summation
following reaction : We know that enthalpy is a state function,
therefore the change in enthalpy is
Fe2 O3 (s ) + 3H2 ( g ) → 2Fe ( s) + 3H2 O ( l ) ,
independent of the path between initial state
From the Table (6.2) of standard enthalpy of (reactants) and final state (products). In other
formation (∆f H 0), we find : words, enthalpy change for a reaction is the
∆f H 0 (H2O,l) = –285.83 kJ mol–1; same whether it occurs in one step or in a
series of steps. This may be stated as follows
∆f H 0 (Fe2O3,s) = – 824.2 kJ mol–1;
in the form of Hess’s Law.
Also ∆f H 0 (Fe, s) = 0 and
If a reaction takes place in several steps
∆f H 0 (H2, g) = 0 as per convention then its standard reaction enthalpy is the
Then, sum of the standard enthalpies of the
∆f H 10 = 3(–285.83 kJ mol–1) intermediate reactions into which the
overall reaction may be divided at the same
– 1(– 824.2 kJ mol–1)
temperature.
= (–857.5 + 824.2) kJ mol–1
Let us understand the importance of this
= –33.3 kJ mol–1 law with the help of an example.
Note that the coefficients used in these Consider the enthalpy change for the
calculations are pure numbers, which are reaction
equal to the respective stoichiometric
coefficients. The unit for ∆ r H
0
is 1
C (graphite,s) + O (g) → CO (g); ∆r H 0 = ?
–1
kJ mol , which means per mole of reaction. 2 2
Once we balance the chemical equation in a Although CO(g) is the major product, some
particular way, as above, this defines the mole CO2 gas is always produced in this reaction.
of reaction. If we had balanced the equation Therefore, we cannot measure enthalpy change
differently, for example, for the above reaction directly. However, if we
1 3 3 can find some other reactions involving related
Fe2 O3 (s ) + H2 ( g ) → Fe ( s) + H 2O ( l ) species, it is possible to calculate the enthalpy
2 2 2
change for the above reaction.
then this amount of reaction would be one
0 Let us consider the following reactions:
mole of reaction and ∆rH would be
3
C (graphite,s) + O2 (g) → CO2 (g);
∆f H 20 = (–285.83 kJ mol–1) ∆r H 0 = – 393.5 kJ mol–1 (i)
2

1 1
– (–824.2 kJ mol–1) CO (g) + O (g) → CO2 (g)
2 2 2
= (– 428.7 + 412.1) kJ mol–1 ∆r H 0 = – 283.0 kJ mol–1 (ii)
= –16.6 kJ mol–1 = ½ ∆r H 10 We can combine the above two reactions
It shows that enthalpy is an extensive quantity. in such a way so as to obtain the desired
reaction. To get one mole of CO(g) on the right,
3. When a chemical equation is reversed, the
0 we reverse equation (ii). In this, heat is
value of ∆rH is reversed in sign. For
example absorbed instead of being released, so we
0
change sign of ∆rH value
N2(g) + 3H2 (g) → 2NH3 (g);
∆r H 0 = – 91.8 kJ. mol–1 1
CO2 (g) → CO (g) + O (g);
2NH3(g) → N2(g) + 3H2 (g); 2 2
∆r H 0 = + 91.8 kJ mol–1 ∆r H 0 = + 283.0 kJ mol–1 (iii)

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Adding equation (i) and (iii), we get the Similarly, combustion of glucose gives out
desired equation, 2802.0 kJ/mol of heat, for which the overall
equation is :
1
C (graphite, s) + O2 ( g ) → CO ( g ) ; C6 H12 O6 ( g ) + 6O2 ( g ) → 6CO2 ( g ) + 6H 2 O(1);
2
∆C H 0 = – 2802.0 kJ mol–1
for which ∆r H 0
= (– 393.5 + 283.0)
Our body also generates energy from food
= – 110.5 kJ mol–1 by the same overall process as combustion,
In general, if enthalpy of an overall reaction although the final products are produced after
A→B along one route is ∆rH and ∆rH1, ∆rH2, a series of complex bio-chemical reactions
∆rH3..... representing enthalpies of reactions involving enzymes.
leading to same product, B along another
Problem 6.9
route,then we have
The combustion of one mole of benzene
∆rH = ∆rH1 + ∆rH2 + ∆rH3 ... (6.16)
takes place at 298 K and 1 atm. After
It can be represented as: combustion, CO2(g) and H2O (1) are
produced and 3267.0 kJ of heat is
∆rH liberated. Calculate the standard
A B 0
enthalpy of formation, ∆f H of benzene.
∆H1 ∆rH3 Standard enthalpies of formation of
CO2(g) and H2 O(l) are –393.5 kJ mol–1
C D
∆rH2 and – 285.83 kJ mol–1 respectively.

6.5 ENTHALPIES FOR DIFFERENT TYPES Solution

OF REACTIONS The formation reaction of benezene is
It is convenient to give name to enthalpies given by :
specifying the types of reactions. 6C (graphite ) + 3H2 ( g ) → C6 H6 ( l ) ;
(a) Standard Enthalpy of Combustion ∆f H 0 = ? ... (i)
(symbol : ∆cH 0)
The enthalpy of combustion of 1 mol of
Combustion reactions are exothermic in benzene is :
nature. These are important in industry,
15
rocketry, and other walks of life. Standard C 6 H6 ( l ) + O2 → 6CO2 ( g ) + 3H2 O ( l ) ;
enthalpy of combustion is defined as the 2
enthalpy change per mole (or per unit amount) ∆C H 0 = – 3267 kJ mol–1... (ii)
of a substance, when it undergoes combustion The enthalpy of formation of 1 mol of
and all the reactants and products being in CO2(g) :
their standard states at the specified
temperature. C ( graphite ) + O2 ( g ) → CO2 ( g ) ;
Cooking gas in cylinders contains mostly ∆f H 0 = – 393.5 kJ mol–1... (iii)
butane (C4H10). During complete combustion The enthalpy of formation of 1 mol of
of one mole of butane, 2658 kJ of heat is H2O(l) is :
released. We can write the thermochemical
1
reactions for this as: H2 ( g ) + O 2 ( g ) → H2 O ( l ) ;
2
13 ∆C H 0 = – 285.83 kJ mol–1... (iv)
C4 H10 ( g ) + O2 ( g ) → 4CO2 ( g ) + 5H2 O(1);
2
multiplying eqn. (iii) by 6 and eqn. (iv)
∆C H 0 = – 2658.0 kJ mol–1 by 3 we get:

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THERMODYNAMICS 177

In this case, the enthalpy of atomization is

6C ( graphite ) + 6O2 ( g ) → 6CO2 (g ) ; same as the enthalpy of sublimation.
∆f H 0 = – 2361 kJ mol–1
(c) Bond Enthalpy (symbol: ∆bondH 0 )
3
3 H2 ( g ) + O2 ( g ) → 3H 2 O (1) ; Chemical reactions involve the breaking and
2 making of chemical bonds. Energy is required
∆f H 0 = – 857.49 kJ mol–1 to break a bond and energy is released when
Summing up the above two equations : a bond is formed. It is possible to relate heat
of reaction to changes in energy associated
15
6C ( graphite ) + 3H2 ( g ) + O2 ( g ) → 6CO2 ( g ) with breaking and making of chemical bonds.
2 With reference to the enthalpy changes
+ 3 H2 O ( l ) ; associated with chemical bonds, two different
terms are used in thermodynamics.
∆f H 0 = – 3218.49 kJ mol–1... (v)
(i) Bond dissociation enthalpy
Reversing equation (ii);
(ii) Mean bond enthalpy
15
6CO2 ( g ) + 3H2 O ( l ) → C6 H6 ( l ) + O2 ; Let us discuss these terms with reference
2 to diatomic and polyatomic molecules.
∆f H 0 = – 3267.0 kJ mol–1... (vi) Diatomic Molecules: Consider the following
Adding equations (v) and (vi), we get process in which the bonds in one mole of
dihydrogen gas (H2) are broken:
6C ( graphite ) + 3H2 (g ) → C6 H6 ( l ) ; 0
H2(g) → 2H(g) ; ∆H–HH = 435.0 kJ mol
–1

∆f H 0 = – 48.51 kJ mol–1... (iv) The enthalpy change involved in this process

is the bond dissociation enthalpy of H–H bond.
The bond dissociation enthalpy is the change
(b) Enthalpy of Atomization in enthalpy when one mole of covalent bonds
(symbol: ∆aH 0 ) of a gaseous covalent compound is broken to
Consider the following example of atomization form products in the gas phase.
of dihydrogen Note that it is the same as the enthalpy of
0
H2(g) → 2H(g); ∆aH = 435.0 kJ mol
–1
atomization of dihydrogen. This is true for all
You can see that H atoms are formed by diatomic molecules. For example:
breaking H–H bonds in dihydrogen. The 0
Cl2(g) → 2Cl(g) ; ∆Cl–ClH = 242 kJ mol
–1

enthalpy change in this process is known as 0

O2(g) → 2O(g) ; ∆O=OH = 428 kJ mol
–1
enthalpy of atomization, ∆ aH 0. It is the
enthalpy change on breaking one mole of In the case of polyatomic molecules, bond
bonds completely to obtain atoms in the gas dissociation enthalpy is different for different
phase. bonds within the same molecule.
In case of diatomic molecules, like Polyatomic Molecules: Let us now consider
dihydrogen (given above), the enthalpy of a polyatomic molecule like methane, CH4. The
atomization is also the bond dissociation overall thermochemical equation for its
enthalpy. The other examples of enthalpy of atomization reaction is given below:
atomization can be CH4 ( g ) → C(g ) + 4H( g );
0
CH4(g) → C(g) + 4H(g); ∆aH = 1665 kJ mol
–1
∆a H 0 = 1665 kJ mol–1
Note that the products are only atoms of C
In methane, all the four C – H bonds are
and H in gaseous phase. Now see the following
identical in bond length and energy. However,
reaction: the energies required to break the individual
0
Na(s) → Na(g) ; ∆aH = 108.4 kJ mol
–1
C – H bonds in each successive step differ :

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178 CHEMISTRY

CH4(g) → CH3(g)+H(g);∆bond H0 = +427 kJ mol–1 given in Table 6.3. The reaction enthalpies are
CH3(g) → CH2(g)+H(g);∆bond H = +439 kJ mol
0 –1 very important quantities as these arise from
the changes that accompany the breaking of
CH2(g) → CH(g)+H(g);∆bond H0 = +452 kJ mol–1 old bonds and formation of the new bonds.
CH(g) → C(g)+H(g);∆bond H0 = +347 kJ mol–1 We can predict enthalpy of a reaction in gas
Therefore, phase, if we know different bond enthalpies.
The standard enthalpy of reaction, ∆rH0 is
CH4(g) → C(g)+4H(g);∆a H0 = 1665 kJ mol–1 related to bond enthalpies of the reactants and
In such cases we use mean bond enthalpy products in gas phase reactions as:
of C – H bond.
0
For example in CH4, ∆C–HH is calculated as: ∆r H 0 = ∑ bond enthalpiesreactants
0
∆C–HH = ¼ (∆a H0) = ¼ (1665 kJ mol–1) − ∑ bond enthalpies products
= 416 kJ mol–1 (6.17)**
We find that mean C–H bond enthalpy in This relationship is particularly more
methane is 416 kJ/mol. It has been found that useful when the required values of ∆f H0 are
mean C–H bond enthalpies differ slightly from not available. The net enthalpy change of a
compound to compound, as in reaction is the amount of energy required to
CH3CH2Cl,CH3NO2, etc, but it does not differ break all the bonds in the reactant molecules
in a great deal*. Using Hess’s law, bond minus the amount of energy required to break
enthalpies can be calculated. Bond enthalpy all the bonds in the product molecules.
values of some single and multiple bonds are Remember that this relationship is
–1
Table 6.3(a) Some Mean Single Bond Enthalpies in kJ mol at 298 K

H C N O F Si P S Cl Br I
435.8 414 389 464 569 293 318 339 431 368 297 H
347 293 351 439 289 264 259 330 276 238 C
159 201 272 - 209 - 201 243 - N
138 184 368 351 - 205 - 201 O
155 540 490 327 255 197 - F
176 213 226 360 289 213 Si
213 230 331 272 213 P
213 251 213 - S
243 218 209 Cl
192 180 Br
151 I
–1
Table 6.3(b) Some Mean Multiple Bond Enthalpies in kJ mol at 298 K

N=N 418 C=C 611 O=O 498

N≡N 946 C≡ C 837
C=N 615 C=O 741
C≡N 891 C≡O 1070

* Note that symbol used for bond dissociation enthalpy and mean bond enthalpy is the same.
** If we use enthalpy of bond formation, (∆f H bond
0 ), which is the enthalpy change when one mole of a particular type of

bond is formed from gaseous atom, then ∆f H 0 = ∑ ∆f H 0 bonds of products – ∑ ∆f H 0 bonds of reactants

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THERMODYNAMICS 179

approximate and is valid when all substances

2. Na( g ) → Na + ( g ) + e −1 ( g ) , the ionization of
(reactants and products) in the reaction are in
gaseous state. sodium atoms, ionization enthalpy
∆iH0 = 496 kJ mol–1
(d) Lattice Enthalpy
1
3. Cl2 ( g ) → Cl( g ) , the dissociation of
The lattice enthalpy of an ionic compound is 2
the enthalpy change which occurs when one chlorine, the reaction enthalpy is half the
mole of an ionic compound dissociates into its bond dissociation enthalpy.
ions in gaseous state.
1
Na + Cl − ( s) → Na + ( g ) + Cl − ( g ) ;
0 –1
∆bondH = 121 kJ mol
2
0
∆latticeH = +788 kJ mol–1
4. Cl( g ) + e −1 ( g ) → Cl( g ) electron gained by
Since it is impossible to determine lattice
enthalpies directly by experiment, we use an chlorine atoms. The electron gain enthalpy,
indirect method where we construct an ∆egH 0 = – 348.6 kJ mol –1.
You have learnt about ionization enthalpy
enthalpy diagram called a Born-Haber Cycle
(Fig. 6.9). and electron gain enthalpy in Unit 3. In
fact, these terms have been taken from
Let us now calculate the lattice enthalpy
thermodynamics. Earlier terms, ionization
of Na+Cl–(s) by following steps given below :
energy and electron affinity were in
1. Na(s) → Na( g ) , sublimation of sodium practice in place of the above terms (see
0
metal, ∆subH = 108.4 kJ mol–1 the box for justification).

Ionization Energy and Electron Affinity

Ionization energy and electron affinity are
defined at absolute zero. At any other
temperature, heat capacities for the
reactants and the products have to be
taken into account. Enthalpies of reactions
for
+ –
M(g) → M (g) +e (for ionization)
– –
M(g) + e → M (g) (for electron gain)
at temperature, T is
T
0
∆rH (T ) = ∆rH (0) + 0
∫∆C
0
r
0
P
dT

The value of C p for each species in the

above reaction is 5/2 R (CV = 3/2R)
So, ∆rCp0 = + 5/2 R (for ionization)
0
∆rCp = – 5/2 R (for electron gain)
Therefore,
0
∆rH (ionization enthalpy)
= E0 (ionization energy) + 5/2 RT
0
∆rH (electron gain enthalpy)
= – A( electron affinity) – 5/2 RT

+ − + −
5. Na ( g ) + Cl ( g ) → Na Cl ( s )
Fig. 6.9 Enthalpy diagram for lattice enthalpy The sequence of steps is shown in Fig. 6.9,
of NaCl and is known as a Born-Haber cycle. The

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0
importance of the cycle is that, the sum of The enthalpy of solution of AB(s), ∆solH , in
the enthalpy changes round a cycle is water is, therefore, determined by the selective
0
zero. A p p l y i n g H e s s ’ s l a w , w e g e t , values of the lattice enthalpy,∆latticeH and
0
0
∆latticeH = 411.2 + 108.4 + 121 + 496 – 348.6 enthalpy of hydration of ions, ∆hydH as
0 0 0
0 ∆sol H = ∆latticeH + ∆hydH
∆latticeH = + 788kJ 0
For most of the ionic compounds, ∆sol H is
for NaCl(s) d Na+(g) + Cl–(g)
positive and the dissociation process is
Internal energy is smaller by 2RT ( because endothermic. Therefore the solubility of most
∆ng = 2) and is equal to + 783 kJ mol–1. salts in water increases with rise of
Now we use the value of lattice enthalpy to temperature. If the lattice enthalpy is very
calculate enthalpy of solution from the high, the dissolution of the compound may not
expression: take place at all. Why do many fluorides tend
0 0 0 to be less soluble than the corresponding
∆solH = ∆latticeH + ∆hydH
chlorides? Estimates of the magnitudes of
For one mole of NaCl(s),
enthalpy changes may be made by using tables
lattice enthalpy = + 788 kJ mol–1
0 of bond energies (enthalpies) and lattice
and ∆hydH = – 784 kJ mol –1( from the
energies (enthalpies).
literature)
0
∆sol H = + 788 kJ mol –1 – 784 kJ mol –1 (f) Enthalpy of Dilution
= + 4 kJ mol–1 It is known that enthalpy of solution is the
The dissolution of NaCl(s) is accompanied enthalpy change associated with the addition
by very little heat change. of a specified amount of solute to the specified
amount of solvent at a constant temperature
(e) Enthalpy of Solution (symbol : ∆solH0 )
and pressure. This argument can be applied
Enthalpy of solution of a substance is the to any solvent with slight modification.
enthalpy change when one mole of it dissolves Enthalpy change for dissolving one mole of
in a specified amount of solvent. The enthalpy gaseous hydrogen chloride in 10 mol of water
of solution at infinite dilution is the enthalpy can be represented by the following equation.
change observed on dissolving the substance For convenience we will use the symbol aq. for
in an infinite amount of solvent when the water
interactions between the ions (or solute
molecules) are negligible. HCl(g) + 10 aq. → HCl.10 aq.
When an ionic compound dissolves in a ∆H = –69.01 kJ / mol
solvent, the ions leave their ordered positions on Let us consider the following set of enthalpy
the crystal lattice. These are now more free in changes:
solution. But solvation of these ions (hydration
(S-1) HCl(g) + 25 aq. → HCl.25 aq.
in case solvent is water) also occurs at the same
∆H = –72.03 kJ / mol
time. This is shown diagrammatically, for an
ionic compound, AB (s) (S-2) HCl(g) + 40 aq. → HCl.40 aq.
∆H = –72.79 kJ / mol
(S-3) HCl(g) + ∞ aq. → HCl. ∞ aq.
∆H = –74.85 kJ / mol
The values of ∆H show general dependence
of the enthalpy of solution on amount of solvent.
As more and more solvent is used, the enthalpy
of solution approaches a limiting value, i.e, the
value in infinitely dilute solution. For
hydrochloric acid this value of ∆H is given
above in equation (S-3).

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THERMODYNAMICS 181

If we subtract the first equation (equation between them, it is at an extremely slow rate.
S-1) from the second equation (equation S-2) It is still called spontaneous reaction. So
in the above set of equations, we obtain– spontaneity means ‘having the potential to
HCl.25 aq. + 15 aq. → HCl.40 aq. proceed without the assistance of external
∆H = [ –72.79 – (–72.03)] kJ / mol agency’. However, it does not tell about the
= – 0.76 kJ / mol rate of the reaction or process. Another aspect
of spontaneous reaction or process, as we see
This value (–0.76kJ/mol) of ∆H is enthalpy
is that these cannot reverse their direction on
of dilution. It is the heat withdrawn from the
their own. We may summarise it as follows:
surroundings when additional solvent is
added to the solution. The enthalpy of dilution A spontaneous process is an
of a solution is dependent on the original irreversible process and may only be
concentration of the solution and the amount reversed by some external agency.
of solvent added. (a) Is Decrease in Enthalpy a Criterion
for Spontaneity ?
6.6 SPONTANEITY
If we examine the phenomenon like flow of
The first law of thermodynamics tells us about
water down hill or fall of a stone on to the
the relationship between the heat absorbed
ground, we find that there is a net decrease in
and the work performed on or by a system. It
potential energy in the direction of change. By
puts no restrictions on the direction of heat
analogy, we may be tempted to state that a
flow. However, the flow of heat is unidirectional
chemical reaction is spontaneous in a given
from higher temperature to lower
direction, because decrease in energy has
temperature. In fact, all naturally occurring
taken place, as in the case of exothermic
processes whether chemical or physical will
reactions. For example:
tend to proceed spontaneously in one
direction only. For example, a gas expanding 1 3
to fill the available volume, burning carbon N2(g) + H2(g) = NH3(g) ;
2 2
in dioxygen giving carbon dioxide. 0
∆r H = – 46.1 kJ mol–1
But heat will not flow from colder body to
1 1
warmer body on its own, the gas in a container H2(g) + Cl2(g) = HCl (g) ;
will not spontaneously contract into one 2 2
corner or carbon dioxide will not form carbon ∆r H0 = – 92.32 kJ mol–1
and dioxygen spontaneously. These and many 1
other spontaneously occurring changes show H2(g) + O (g) → H2O(l) ;
2 2
unidirectional change. We may ask ‘what is the 0
∆r H = –285.8 kJ mol–1
driving force of spontaneously occurring
The decrease in enthalpy in passing from
changes ? What determines the direction of a
reactants to products may be shown for any
spontaneous change ? In this section, we shall
exothermic reaction on an enthalpy diagram
establish some criterion for these processes
as shown in Fig. 6.10(a).
whether these will take place or not.
Thus, the postulate that driving force for a
Let us first understand what do we mean
chemical reaction may be due to decrease in
by spontaneous reaction or change ? You may
energy sounds ‘reasonable’ as the basis of
think by your common observation that
evidence so far !
spontaneous reaction is one which occurs
immediately when contact is made between Now let us examine the following reactions:
1
the reactants. Take the case of combination of N (g) + O2(g) → NO2(g);
hydrogen and oxygen. These gases may be 2 2 0
∆r H = +33.2 kJ mol–1
mixed at room temperature and left for many
years without observing any perceptible C(graphite, s) + 2 S(l) → CS2(l);
0
change. Although the reaction is taking place ∆r H = +128.5 kJ mol–1

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Fig. 6.10 (a) Enthalpy diagram for exothermic

reactions
These reactions though endothermic, are
spontaneous. The increase in enthalpy may
be represented on an enthalpy diagram as
shown in Fig. 6.10(b).

Fig. 6.11 Diffusion of two gases

respectively and separated by a movable

partition [Fig. 6.11 (a)]. When the partition is
withdrawn [Fig.6.11( b)], the gases begin to
diffuse into each other and after a period of
time, diffusion will be complete.
Let us examine the process. Before
partition, if we were to pick up the gas
molecules from left container, we would be
Fig. 6.10 (b) Enthalpy diagram for endothermic sure that these will be molecules of gas A and
reactions similarly if we were to pick up the gas
molecules from right container, we would be
Therefore, it becomes obvious that while
sure that these will be molecules of gas B. But,
decrease in enthalpy may be a contributory
if we were to pick up molecules from container
factor for spontaneity, but it is not true for all
when partition is removed, we are not sure
cases.
whether the molecules picked are of gas A or
(b) Entropy and Spontaneity gas B. We say that the system has become less
Then, what drives the spontaneous process in predictable or more chaotic.
a given direction ? Let us examine such a case We may now formulate another postulate:
in which ∆H = 0 i.e., there is no change in in an isolated system, there is always a
enthalpy, but still the process is spontaneous. tendency for the systems’ energy to become
Let us consider diffusion of two gases into more disordered or chaotic and this could be
each other in a closed container which is a criterion for spontaneous change !
isolated from the surroundings as shown in At this point, we introduce another
Fig. 6.11. thermodynamic function, entropy denoted as
The two gases, say, gas A and gas B are S. The above mentioned disorder is the
represented by black dots and white dots manifestation of entropy. To form a mental

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THERMODYNAMICS 183

picture, one can think of entropy as a measure qrev

of the degree of randomness or disorder in the ∆S = (6.18)
T
system. The greater the disorder in an isolated
system, the higher is the entropy. As far as a The total entropy change ( ∆Stotal) for the
chemical reaction is concerned, this entropy system and surroundings of a spontaneous
change can be attributed to rearrangement of process is given by
atoms or ions from one pattern in the reactants ∆Stotal = ∆Ssystem + ∆Ssurr > 0 (6.19)
to another (in the products). If the structure
of the products is very much disordered than When a system is in equilibrium, the
that of the reactants, there will be a resultant entropy is maximum, and the change in
increase in entropy. The change in entropy entropy, ∆S = 0.
accompanying a chemical reaction may be We can say that entropy for a spontaneous
estimated qualitatively by a consideration of process increases till it reaches maximum and
the structures of the species taking part in the at equilibrium the change in entropy is zero.
reaction. Decrease of regularity in structure Since entropy is a state property, we can
would mean increase in entropy. For a given calculate the change in entropy of a reversible
substance, the crystalline solid state is the process by
state of lowest entropy (most ordered), The
gaseous state is state of highest entropy. qsys ,rev
∆Ssys =
Now let us try to quantify entropy. One way T
to calculate the degree of disorder or chaotic We find that both for reversible and
distribution of energy among molecules would irreversible expansion for an ideal gas, under
be through statistical method which is beyond isothermal conditions, ∆U = 0, but ∆Stotal i.e.,
the scope of this treatment. Other way would
∆Ssys + ∆Ssurr is not zero for irreversible
be to relate this process to the heat involved in
a process which would make entropy a process. Thus, ∆U does not discriminate
thermodynamic concept. Entropy, like any between reversible and irreversible process,
other thermodynamic property such as whereas ∆S does.
internal energy U and enthalpy H is a state
Problem 6.10
function and ∆S is independent of path.
Predict in which of the following, entropy
Whenever heat is added to the system, it
increases/decreases :
increases molecular motions causing
increased randomness in the system. Thus (i) A liquid crystallizes into a solid.
heat (q) has randomising influence on the (ii) Temperature of a crystalline solid is
system. Can we then equate ∆S with q ? Wait ! raised from 0 K to 115 K.
Experience suggests us that the distribution
of heat also depends on the temperature at ( iii ) 2NaHCO3 ( s) → Na 2 CO3 ( s) +
which heat is added to the system. A system CO2 (g ) + H2 O (g )
at higher temperature has greater randomness
in it than one at lower temperature. Thus, (iv) H2 ( g ) → 2 H ( g )
temperature is the measure of average
chaotic motion of particles in the system. Solution
Heat added to a system at lower temperature (i) After freezing, the molecules attain an
causes greater randomness than when the ordered state and therefore, entropy
same quantity of heat is added to it at higher decreases.
temperature. This suggests that the entropy (ii) At 0 K, the contituent particles are
change is inversely proportional to the static and entropy is minimum. If
temperature. ∆S is related with q and T for a temperature is raised to 115 K, these
reversible reaction as :

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184 CHEMISTRY

begin to move and oscillate about their = 4980.6 JK–1 mol–1

equilibrium positions in the lattice and This shows that the above reaction is
system becomes more disordered, spontaneous.
therefore entropy increases.
(iii) Reactant, NaHCO3 is a solid and it (c) Gibbs Energy and Spontaneity
has low entropy. Among products
We have seen that for a system, it is the total
there are one solid and two gases.
entropy change, ∆S total which decides the
Therefore, the products represent a
spontaneity of the process. But most of the
condition of higher entropy.
chemical reactions fall into the category of
(iv) Here one molecule gives two atoms either closed systems or open systems.
i.e., number of particles increases Therefore, for most of the chemical reactions
leading to more disordered state. there are changes in both enthalpy and
Two moles of H atoms have higher entropy. It is clear from the discussion in
entropy than one mole of dihydrogen previous sections that neither decrease in
molecule. enthalpy nor increase in entropy alone can
Problem 6.11 determine the direction of spontaneous change
For oxidation of iron, for these systems.
For this purpose, we define a new
4Fe ( s) + 3O 2 ( g ) → 2Fe2 O 3 ( s) thermodynamic function the Gibbs energy or
entropy change is – 549.4 JK–1mol–1at Gibbs function, G, as
298 K. Inspite of negative entropy change G = H – TS (6.20)
of this reaction, why is the reaction Gibbs function, G is an extensive property
spontaneous? and a state function.
0
(∆ r H for this reaction is The change in Gibbs energy for the system,
3 –1
–1648 × 10 J mol ) ∆Gsys can be written as
Solution
∆Gsys = ∆H sys − T ∆Ssys − Ssys ∆T
One decides the spontaneity of a reaction
by considering At constant temperature, ∆T = 0

( )
∆Stotal ∆Ssys + ∆Ssurr . For calculating ∴ ∆G sys = ∆H sys − T ∆Ssys

∆S surr, we have to consider the heat Usually the subscript ‘system’ is dropped
absorbed by the surroundings which is and we simply write this equation as
equal to – ∆rH . At temperature T, entropy
0
∆G = ∆H − T ∆S (6.21)
change of the surroundings is
Thus, Gibbs energy change = enthalpy
change – temperature × entropy change, and
is referred to as the Gibbs equation, one of the

=−
( −1648 ×10 3
J mol −1 ) most important equations in chemistry. Here,
we have considered both terms together for
298 K spontaneity: energy (in terms of ∆H) and
= 5530 JK–1mol–1 entropy (∆S, a measure of disorder) as
indicated earlier. Dimensionally if we analyse,
Thus, total entropy change for this
we find that ∆G has units of energy because,
reaction
both ∆H and the T∆S are energy terms, since
∆r Stotal = 5530 JK –1mol –1 + T∆S = (K) (J/K) = J.
( −549.4 JK –1
mol –1 ) Now let us consider how ∆G is related to
reaction spontaneity.

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THERMODYNAMICS 185

We know, can be ‘small’ in which case T must be large.

∆Stotal = ∆Ssys + ∆Ssurr (b) The positive entropy change of the system
can be ’large’, in which case T may be small.
If the system is in thermal equilibrium with
the surrounding, then the temperature of the The former is one of the reasons why reactions
surrounding is same as that of the system. are often carried out at high temperature.
Also, increase in enthalpy of the surrounding Table 6.4 summarises the effect of temperature
is equal to decrease in the enthalpy of the on spontaneity of reactions.
system.
(d) Entropy and Second Law of
Therefore, entropy change of Thermodynamics
surroundings,
We know that for an isolated system the
∆H surr ∆H sys change in energy remains constant. Therefore,
∆Ssurr = =− increase in entropy in such systems is the
T T
natural direction of a spontaneous change.
This, in fact is the second law of
 ∆H sys 
∆Stotal = ∆Ssys +  − thermodynamics. Like first law of
 T  thermodynamics, second law can also be
Rearranging the above equation: stated in several ways. The second law of
thermodynamics explains why spontaneous
T∆Stotal = T∆Ssys – ∆Hsys exothermic reactions are so common. In
For spontaneous process, ∆Stotal > 0 , so exothermic reactions heat released by the
reaction increases the disorder of the
T∆Ssys – ∆Hsys > Ο
surroundings and overall entropy change is
( )
⇒ − ∆H sys − T ∆Ssys > 0 positive which makes the reaction
spontaneous.
Using equation 6.21, the above equation can
(e) Absolute Entropy and Third Law of
be written as
Thermodynamics
–∆G > O
Molecules of a substance may move in a
∆G = ∆H − T ∆S < 0 (6.22) straight line in any direction, they may spin
like a top and the bonds in the molecules may
∆Hsys is the enthalpy change of a reaction,
T∆Ssys is the energy which is not available to stretch and compress. These motions of the
do useful work. So ∆G is the net energy molecule are called translational, rotational
available to do useful work and is thus a and vibrational motion respectively. When
measure of the ‘free energy’. For this reason, it temperature of the system rises, these motions
is also known as the free energy of the reaction. become more vigorous and entropy increases.
On the other hand when temperature is
∆G gives a criteria for spontaneity at lowered, the entropy decreases. The entropy
constant pressure and temperature. of any pure crystalline substance
(i) If ∆G is negative (< 0), the process is approaches zero as the temperature
spontaneous. approaches absolute zero. This is called
third law of thermodynamics. This is so
(ii) If ∆G is positive (> 0), the process is non because there is perfect order in a crystal at
spontaneous. absolute zero. The statement is confined to
Note : If a reaction has a positive enthalpy pure crystalline solids because theoretical
change and positive entropy change, it can be arguments and practical evidences have
spontaneous when T∆S is large enough to shown that entropy of solutions and super
outweigh ∆H. This can happen in two ways; cooled liquids is not zero at 0 K. The
(a) The positive entropy change of the system importance of the third law lies in the fact that

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it permits the calculation of absolute values proceed with a decrease in free energy, which
of entropy of pure substance from thermal seems impossible. It is possible only if at
data alone. For a pure substance, this can be equilibrium the free energy of the system is
q minimum. If it is not, the system would
done by summing rev increments from 0 K spontaneously change to configuration of
T
lower free energy.
to 298 K. Standard entropies can be used to
calculate standard entropy changes by a So, the criterion for equilibrium
A + B l C + D ; is
Hess’s law type of calculation.
∆rG = 0
6.7 GIBBS ENERGY CHANGE AND Gibbs energy for a reaction in which all
EQUILIBRIUM reactants and products are in standard state,
0
We have seen how a knowledge of the sign and ∆rG is related to the equilibrium constant of
magnitude of the free energy change of a the reaction as follows:
0
chemical reaction allows: 0 = ∆rG + RT ln K
0
(i) Prediction of the spontaneity of the or ∆rG = – RT ln K
chemical reaction. 0
or ∆rG = – 2.303 RT log K (6.23)
(ii) Prediction of the useful work that could We also know that
be extracted from it. (6.24)
So far we have considered free energy For strongly endothermic reactions, the
changes in irreversible reactions. Let us now 0
value of ∆rH may be large and positive. In
examine the free energy changes in reversible such a case, value of K will be much smaller
reactions. than 1 and the reaction is unlikely to form
‘Reversible’ under strict thermodynamic much product. In case of exothermic
sense is a special way of carrying out a reactions, ∆rH0 is large and negative, and ∆rG0
process such that system is at all times in is likely to be large and negative too. In such
perfect equilibrium with its surroundings. cases, K will be much larger than 1. We may
When applied to a chemical reaction, the expect strongly exothermic reactions to have
term ‘reversible’ indicates that a given a large K, and hence can go to near
0 0
reaction can proceed in either direction completion. ∆rG also depends upon ∆rS , if
simultaneously, so that a dynamic the changes in the entropy of reaction is also
equilibrium is set up. This means that the taken into account, the value of K or extent
reactions in both the directions should of chemical reaction will also be affected,
Table 6.4 Effect of Temperature on Spontaneity of Reactions

0 0 0
∆rH ∆rS ∆rG Description*

– + – Reaction spontaneous at all temperatures

– – – (at low T ) Reaction spontaneous at low temperature
– – + (at high T ) Reaction nonspontaneous at high temperature
+ + + (at low T ) Reaction nonspontaneous at low temperature
+ + – (at high T ) Reaction spontaneous at high temperature
+ – + (at all T ) Reaction nonspontaneous at all temperatures

* The term low temperature and high temperature are relative. For a particular reaction, high temperature could even
mean room temperature.

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THERMODYNAMICS 187

0
depending upon whether ∆rS is positive or
negative. ( –13.6 × 10 3
J mol –1 )
2.303 (8.314 JK ) (298 K )
= –1 –1
Using equation (6.24), mol
0
(i) It is possible to obtain an estimate of ∆G = 2.38
V 0
from the measurement of ∆H and ∆S , Hence K = antilog 2.38 = 2.4 × 102.
and then calculate K at any temperature
for economic yields of the products. Problem 6.14
(ii) If K is measured directly in the At 60°C, dinitrogen tetroxide is 50
0
laboratory, value of ∆G at any other per cent dissociated. Calculate the
temperature can be calculated. standard free energy change at this
Using equation (6.24), temperature and at one atmosphere.

Solution
N2O4(g) 2NO2(g)
Problem 6.12
If N 2O4 is 50% dissociated, the mole
Calculate ∆rG 0 for conversion of oxygen
fraction of both the substances is given
to ozone, 3/2 O2(g) → O3(g) at 298 K. if Kp
for this conversion is 2.47 × 10 –29. by
Solution 1 − 0.5 2 × 0.5
xN = : x NO2 =
We know ∆rG 0 = – 2.303 RT log Kp and
2 O4
1 + 0.5 1 + 0.5
R = 8.314 JK–1 mol–1
0.5
Therefore, ∆rG =
0
pN = × 1 atm, p NO =
2 O4 1.5 2
– 2.303 (8.314 J K–1 mol–1)
× (298 K) (log 2.47 × 10–29) 1
× 1 atm.
= 163000 J mol–1 1.5
= 163 kJ mol–1. The equilibrium constant Kp is given by
Problem 6.13
(p )
2
Find out the value of equilibrium constant NO2 1.5
Kp = =
for the following reaction at 298 K. p N 2O 4 (1.5)2 (0.5 )

= 1.33 atm.
0 Since
Standard Gibbs energy change, ∆rG at 0
the given temperature is –13.6 kJ mol–1. ∆rG = –RT ln Kp
0
Solution ∆rG = (– 8.314 JK–1 mol–1) × (333 K)
× (2.303) × (0.1239)
We know, log K = –1
= – 763.8 kJ mol

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SUMMARY

Thermodynamics deals with energy changes in chemical or physical processes and enables us
to study these changes quantitatively and to make useful predictions. For these purposes, we
divide the universe into the system and the surroundings. Chemical or physical processes
lead to evolution or absorption of heat (q), part of which may be converted into work (w). These
quantities are related through the first law of thermodynamics via ∆U = q + w. ∆U, change in
internal energy, depends on initial and final states only and is a state function, whereas q and
w depend on the path and are not the state functions. We follow sign conventions of q and w by
giving the positive sign to these quantities when these are added to the system. We can measure
the transfer of heat from one system to another which causes the change in temperature. The
magnitude of rise in temperature depends on the heat capacity (C) of a substance. Therefore,
heat absorbed or evolved is q = C∆T. Work can be measured by w = –pex∆V, in case of expansion
of gases. Under reversible process, we can put pex = p for infinitesimal changes in the volume
making wrev = – p dV. In this condition, we can use gas equation, pV = nRT.
At constant volume, w = 0, then ∆U = qV , heat transfer at constant volume. But in study of
chemical reactions, we usually have constant pressure. We define another state function
enthalpy. Enthalpy change, ∆H = ∆U + ∆ngRT, can be found directly from the heat changes at
constant pressure, ∆H = qp.
There are varieties of enthalpy changes. Changes of phase such as melting, vaporization
and sublimation usually occur at constant temperature and can be characterized by enthalpy
changes which are always positive. Enthalpy of formation, combustion and other enthalpy
changes can be calculated using Hess’s law. Enthalpy change for chemical reactions can be
determined by

∆r H = ∑ (a ∆
i f ) (
H products − ∑ bi ∆ f H reactions )
f i

and in gaseous state by

0
∆rH = Σ bond enthalpies of the reactants – Σ bond enthalpies of the products
First law of thermodynamics does not guide us about the direction of chemical reactions
i.e., what is the driving force of a chemical reaction. For isolated systems,
∆U = 0. We define another state function, S, entropy for this purpose. Entropy is a measure of
disorder or randomness. For a spontaneous change, total entropy change is positive. Therefore,
for an isolated system, ∆U = 0, ∆S > 0, so entropy change distinguishes a spontaneous change,
while energy change does not. Entropy changes can be measured by the equation
q rev q rev
∆S = for a reversible process. is independent of path.
T T
Chemical reactions are generally carried at constant pressure, so we define another state
function Gibbs energy, G, which is related to entropy and enthalpy changes of the system by
the equation:
∆rG = ∆rH – T ∆rS
For a spontaneous change, ∆Gsys < 0 and at equilibrium, ∆Gsys = 0.
Standard Gibbs energy change is related to equilibrium constant by
0
∆rG = – RT ln K.
0
K can be calculated from this equation, if we know ∆ rG which can be found from
. Temperature is an important factor in the equation. Many reactions which
are non-spontaneous at low temperature, are made spontaneous at high temperature for systems
having positive entropy of reaction.

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THERMODYNAMICS 189

EXERCISES

6.1 Choose the correct answer. A thermodynamic state function is a quantity

(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.
6.2 For the process to occur under adiabatic conditions, the correct condition is:
(i) ∆T = 0
(ii) ∆p = 0
(iii) q = 0
(iv) w=0
6.3 The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) < 0
(iv) different for each element
0 0
6.4 ∆U of combustion of methane is – X kJ mol–1. The value of ∆H is
(i) = ∆U 0
(ii) > ∆U 0
0
(iii) < ∆U
(iv) =0
6.5 The enthalpy of combustion of methane, graphite and dihydrogen at 298 K
are, –890.3 kJ mol–1 –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy
of formation of CH4(g) will be
(i) –74.8 kJ mol–1 (ii) –52.27 kJ mol–1
(iii) +74.8 kJ mol–1 (iv) +52.26 kJ mol–1.
6.6 A reaction, A + B → C + D + q is found to have a positive entropy change. The
reaction will be
(i) possible at high temperature
(ii) possible only at low temperature
(iii) not possible at any temperature
(v) possible at any temperature
6.7 In a process, 701 J of heat is absorbed by a system and 394 J of work is done
by the system. What is the change in internal energy for the process?
6.8 The reaction of cyanamide, NH2CN (s), with dioxygen was carried out in a bomb
calorimeter, and ∆U was found to be –742.7 kJ mol–1 at 298 K. Calculate enthalpy
change for the reaction at 298 K.

3
NH2CN(g) + O (g) → N2(g) + CO2(g) + H2O(l)
2 2

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6.9 Calculate the number of kJ of heat necessary to raise the temperature of

60.0 g of aluminium from 35°C to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1.
6.10 Calculate the enthalpy change on freezing of 1.0 mol of water at10.0°C to ice at
–10.0°C. ∆fusH = 6.03 kJ mol–1 at 0°C.
Cp [H2O(l)] = 75.3 J mol–1 K–1
Cp [H2O(s)] = 36.8 J mol–1 K–1
6.11 Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat
released upon formation of 35.2 g of CO2 from carbon and dioxygen gas.
6.12 Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are –110, – 393, 81
and 9.7 kJ mol–1 respectively. Find the value of ∆rH for the reaction:
N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
6.13 Given
0
N2(g) + 3H2(g) → 2NH3(g) ; ∆rH = –92.4 kJ mol–1
What is the standard enthalpy of formation of NH3 gas?
6.14 Calculate the standard enthalpy of formation of CH3OH(l) from the following
data:

3
CH3OH (l) + O (g) → CO2(g) + 2H2O(l) ; ∆rH 0 = –726 kJ mol–1
2 2
0
C(graphite) + O2(g) → CO2(g) ; ∆cH = –393 kJ mol–1

1 0
H2(g) + O (g) → H2O(l) ; ∆f H = –286 kJ mol–1.
2 2
6.15 Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
0
∆vapH (CCl4) = 30.5 kJ mol–1.
0
∆fH (CCl4) = –135.5 kJ mol–1.
0 0
∆aH (C) = 715.0 kJ mol–1 , where ∆aH is enthalpy of atomisation
0
∆aH (Cl2) = 242 kJ mol–1
6.16 For an isolated system, ∆U = 0, what will be ∆S ?
6.17 For the reaction at 298 K,
2A + B → C
∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1
At what temperature will the reaction become spontaneous considering ∆H
and ∆S to be constant over the temperature range.
6.18 For the reaction,
2 Cl(g) → Cl2(g), what are the signs of ∆H and ∆S ?
6.19 For the reaction
2 A(g) + B(g) → 2D(g)
0 0
∆U = –10.5 kJ and ∆S = –44.1 JK–1.
0
Calculate ∆G for the reaction, and predict whether the reaction may occur
spontaneously.

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0
6.20 The equilibrium constant for a reaction is 10. What will be the value of ∆G ?
R = 8.314 JK–1 mol–1, T = 300 K.
6.21 Comment on the thermodynamic stability of NO(g), given

1 1 0
N (g) + O (g) → NO(g) ; ∆rH = 90 kJ mol–1
2 2 2 2

1 0
NO(g) + O (g) → NO2(g) : ∆rH = –74 kJ mol–1
2 2
6.22 Calculate the entropy change in surroundings when 1.00 mol of H2O(l) is formed
0
under standard conditions. ∆f H = –286 kJ mol–1.

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