Unit 5

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 Albert Einstein

able to
• explain the terms : system and
surroundings;
• discriminate between close, open
and isolated systems;
Chemical energy stored by molecules can be released as
• explain internal energy, work and
heat; heat during chemical reactions when a fuel like methane,
• state first law of thermodynamics cooking gas or coal burns in air. The chemical energy may
and express it mathematically; also be used to do mechanical work when a fuel burns
• calculate energy changes as in an engine or to provide electrical energy through a
work and heat contributions in galvanic cell like dry cell. Thus, various forms of energy
chemical systems;
are interrelated and under certain conditions, these may
• explain state functions: U, H.
be transformed from one form into another. The study
• correlate ∆U and ∆H;
of these energy transformations forms the subject matter
• measure experimentally ∆U and
∆H; of thermodynamics. The laws of thermodynamics deal
• define standard states for ∆H; with energy changes of macroscopic systems involving
• calculate enthalpy changes for a large number of molecules rather than microscopic
various types of reactions; systems containing a few molecules. Thermodynamics is
• state and apply Hess’s law of not concerned about how and at what rate these energy
constant heat summation; transformations are carried out, but is based on initial and
• differentiate between extensive final states of a system undergoing the change. Laws of
and intensive properties;
thermodynamics apply only when a system is in equilibrium
• define spontaneous and non-
spontaneous processes;
or moves from one equilibrium state to another equilibrium
• e x p l a i n e n t r o p y a s a
state. Macroscopic properties like pressure and temperature
thermodynamic state function do not change with time for a system in equilibrium state.
and apply it for spontaneity; In this unit, we would like to answer some of the important
• explain Gibbs energy change (∆G); questions through thermodynamics, like:
and
How do we determine the energy changes involved in a
• establish relationship between
∆G and spontaneity, ∆G and chemical reaction/process? Will it occur or not?
equilibrium constant. What drives a chemical reaction/process?
To what extent do the chemical reactions proceed?

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 THERMODYNAMICS 137

5.1 Thermodynamic terms the system from the surroundings is called

We are interested in chemical reactions and boundary. This is designed to allow us to
the energy changes accompanying them. For control and keep track of all movements of
this we need to know certain thermodynamic matter and energy in or out of the system.
terms. These are discussed below.
5.1.2 Types of the System
5.1.1 The System and the Surroundings We, further classify the systems according
A system in thermodynamics refers to that to the movements of matter and energy in or
part of universe in which observations are out of the system.
made and remaining universe constitutes
the surroundings. The surroundings include 1. Open System
everything other than the system. System In an open system, there is exchange of energy
and the surroundings together constitute the and matter between system and surroundings
universe. [Fig. 5.2 (a)]. The presence of reactants in an
The universe = The system + The surroundings open beaker is an example of an open system*.
Here the boundary is an imaginary surface
However, the entire universe other than enclosing the beaker and reactants.
the system is not affected by the changes
taking place in the system. Therefore, for all 2. Closed System
practical purposes, the surroundings are that In a closed system, there is no exchange of
portion of the remaining universe which can matter, but exchange of energy is possible
interact with the system. Usually, the region between system and the surroundings
of space in the neighbourhood of the system [Fig. 5.2 (b)]. The presence of reactants in a
constitutes its surroundings. closed vessel made of conducting material
For example, if we are studying the e.g., copper or steel is an example of a closed
reaction between two substances A and B system.
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. 5.1).

Fig. 5.1  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
be real or imaginary. The wall that separates Fig. 5.2 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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 138 chemIstry

3. Isolated System a quantity which represents the total energy

In an isolated system, there is no exchange of the system. It may be chemical, electrical,
of energy or matter between the system and mechanical or any other type of energy you
the surroundings [Fig. 5.2 (c)]. The presence may think of, the sum of all these is the energy
of reactants in a thermos flask or any other of the system. In thermodynamics, we call it
closed insulated vessel is an example of an the internal energy, U of the system, which
isolated system. may change, when
• heat passes into or out of the system,
5.1.3 The State of the System • work is done on or by the system,
The system must be described in order to
• matter enters or leaves the system.
make any useful calculations by specifying
quantitatively each of the properties such as These systems are classified accordingly
its pressure (p), volume (V), and temperature as you have already studied in section 5.1.2.
(T ) as well as the composition of the system.
(a) Work
We need to describe the system by specifying
it before and after the change. You would Let us first examine a change in internal energy
recall from your Physics course that the by doing work. We take a system containing
state of a system in mechanics is completely some quantity of water in a thermos flask
specified at a given instant of time, by the or in an insulated beaker. This would not
position and velocity of each mass point of allow exchange of heat between the system
the system. In thermodynamics, a different and surroundings through its boundary and
and much simpler concept of the state of a we call this type of system as adiabatic. The
system is introduced. It does not need detailed manner in which the state of such a system
knowledge of motion of each particle because, may be changed will be called adiabatic
we deal with average measurable properties of process. Adiabatic process is a process in
the system. We specify the state of the system which there is no transfer of heat between
by state functions or state variables. the system and surroundings. Here, the wall
The state of a thermodynamic system is separating the system and the surroundings
described by its measurable or macroscopic is called the adiabatic wall (Fig. 5.3).
(bulk) properties. We can describe the state
of 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, Fig. 5.3 An adiabatic system which does not
others automatically have definite values. permit the transfer of heat through its
The state of the surroundings can never boundary.
be completely specified; fortunately it is not Let us bring the change in the internal
necessary to do so. energy of the system by doing some work on
it. Let us call the initial state of the system
5.1.4 The Internal Energy as a State as state A and its temperature as TA. Let
Function the internal energy of the system in state A
When we talk about our chemical system be called UA. We can change the state of the
losing or gaining energy, we need to introduce system in two different ways.

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 THERMODYNAMICS 139

One way: We do some mechanical work, say the route taken. Volume of water in a pond, for
1 kJ, by rotating a set of small paddles and example, is a state function, because change
thereby churning water. Let the new state in volume of its water is independent of the
be called B state and its temperature, as route by which water is filled in the pond,
TB. It is found that TB > TA and the change either by rain or by tubewell or by both.
in temperature, ∆T = TB–TA. Let the internal (b) Heat
energy of the system in state B be UB and the
change in internal energy, ∆U =UB– UA. We can also change the internal energy
of a system by transfer of heat from the
Second way: We now do an equal amount
surroundings to the system or vice-versa
(i.e., 1kJ) electrical work with the help of an
immersion rod and note down the temperature without expenditure of work. This exchange
change. We find that the change in temperature of energy, which is a result of temperature
is same as in the earlier case, say, TB – TA. difference is called heat, q. Let us consider
bringing about the same change in temperature
In fact, the experiments in the above (the same initial and final states as before
manner were done by J. P. Joule between in section 5.1.4 (a) by transfer of heat
1840–50 and he was able to show that a through thermally conducting walls instead
given amount of work done on the system, of adiabatic walls (Fig. 5.4).
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 =U2 –U1= wad
Fig. 5.4 A system which allows heat transfer
Therefore, internal energy, U, of the through its boundary.
system 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
system and the internal energy of system huge heat reservoir at temperature, TB. The
increases. Similarly, if the work is done by the heat 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 heat
from 25°C to 35°C, the change in temperature is transferred from the surroundings to the
is 35°C–25°C = +10°C, whether we go straight system and the internal energy of the system
up to 35°C or we cool the system for a few increases and q is negative when heat is
degrees, then take the system to the final transferred from system to the surroundings
temperature. Thus, T is a state function and resulting in decrease of the internal energy of
the change in temperature is independent 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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 140 chemIstry

(c) The general case

Solution
Let us consider the general case in which
a change of state is brought about both by (i) ∆ U = w ad, wall is adiabatic
doing work and by transfer of heat. We write (ii) ∆ U = – q, thermally conducting
change in internal energy for this case as: walls
∆U = q + w (5.1) (iii) ∆ U = q – w, closed system.

For a given change in state, q and w can 5.2 Applications

vary depending on how the change is carried Many chemical reactions involve the generation
out. However, q +w = ∆U will depend only on of gases capable of doing mechanical work or
initial and final state. It will be independent the generation of heat. It is important for us
of the way the change is carried out. If there to quantify these changes and relate them
is no transfer of energy as heat or as work to the changes in the internal energy. Let us
(isolated system) i.e., if w = 0 and q = 0, then see how!
∆ U = 0.
The equation 5.1 i.e., ∆U = q + w is 5.2.1 Work
mathematical statement of the first law of First of all, let us concentrate on the nature of
thermodynamics, which states that work a system can do. We will consider only
The energy of an isolated system is mechanical work i.e., pressure-volume work.
constant. For understanding pressure-volume
It is commonly stated as the law of conservation work, let us consider a cylinder which
of energy i.e., energy can neither be created contains one mole of an ideal gas fitted with
nor be destroyed. a frictionless piston. Total volume of the gas
is Vi and pressure of the gas inside is p. If
Note: There is considerable difference between
external pressure is pex which is greater than
the character of the thermodynamic property
p, piston is moved inward till the pressure
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 5.1
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. 5.5 (a) Work done on an ideal gas in a
cylinder when it is compressed by
system and q amount of heat is
a constant external pressure, p ex
supplied to the system. What type
(in single step) is equal to the shaded
of system would it be? area.

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 THERMODYNAMICS 141

inside becomes equal to pex. Let this change If the pressure is not constant but
be achieved in a single step and the final changes during the process such that it
volume be V f . During this compression, is always infinitesimally greater than the
suppose piston moves a distance, l and pressure of the gas, then, at each stage of
is cross-sectional area of the piston is A compression, the volume decreases by an
[Fig. 5.5(a)]. infinitesimal amount, dV. In such a case we
then, volume change = l × A = ∆V = (Vf – Vi ) can calculate the work done on the gas by the
We also know, pressure = relation
Vf
Therefore, force on the piston = pex . A
If w is the work done on the system by
w p
Vi
ex dV (5.3)
movement of the piston then
w = force × distance = pex . A .l Here, pex at each stage is equal to (pin + dp)
in case of compression [Fig. 5.5(c)]. In an
= pex . (–∆V) = – pex ∆V = – pex (Vf – Vi ) (5.2)
expansion process under similar conditions,
The negative sign of this expression is the external pressure is always less than the
required to obtain conventional sign for w, pressure of the system i.e., pex = (pin– dp). In
which will be positive. It indicates that in case general case we can write, pex = (pin + dp). Such
of compression work is done on the system. processes are called reversible processes.
Here (Vf – Vi ) will be negative and negative
A process or change is said to be
multiplied by negative will be positive. Hence
reversible, if a change is brought out in such a
the sign obtained for the work will be positive.
way that the process could, at any moment,
If the pressure is not constant at every be reversed by an infinitesimal change.
stage of compression, but changes in number A reversible process proceeds infinitely
of finite steps, work done on the gas will be slowly by a series of equilibrium states
summed over all the steps and will be equal such that system and the surroundings are
to – Σ р ∆V [Fig. 5.5 (b)] always in near equilibrium with each other.

Fig. 5.5 (c) pV-plot when pressure is not constant

Fig. 5.5 (b) pV-plot when pressure is not constant and changes in infinite steps (reversible
and changes in finite steps during conditions) during compression from
compression from initial volume, Vi to initial volume, Vi to final volume, Vf .
final volume, Vf . Work done on the gas Work done on the gas is represented
is represented by the shaded area. by the shaded area.

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 142 chemIstry

Processes other than reversible processes Isothermal and free expansion of an

are known as irreversible processes. ideal gas
In chemistry, we face problems that can For isothermal (T = constant) expansion of
be solved if we relate the work term to the an 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 5.3 as follows: Equation 5.1, can be
Vf Vf
expressed for isothermal irreversible and
reversible changes as follows:
w rev   
Vi
pex 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

w rev    pin dV (5.4) q = – w = nRT ln

Vi

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

can write as p now) can be expressed in terms = 2.303 nRT log V
i
of its volume through gas equation. For n mol For adiabatic change, q = 0,
of an ideal gas i.e., pV =nRT
∆U = wad
nRT
p  Problem 5.2
V
Two litres of an ideal gas at a pressure of 10
Therefore, at constant temperature atm expands isothermally at 25 °C into a
(isothermal process), vacuum until its total volume is 10 litres.
Vf How much heat is absorbed and how
dV Vf
w rev    nRT  nRT ln much work is done in the expansion ?
V Vi
Vi
Solution
Vf We have q = – w = pex (10 – 2) = 0(8) = 0
= – 2.303 nRT log (5.5) No work is done; no heat is absorbed.
Vi
Problem 5.3
Free expansion: Expansion of a gas in
Consider the same expansion, but
vacuum (pex = 0) is called free expansion.
this time against a constant external
No work is done during free expansion of an pressure of 1 atm.
ideal gas whether the process is reversible or
irreversible (equation 5.2 and 5.3). Solution
Now, we can write equation 5.1 in number We have q = – w = pex (8) = 8 litre-atm
of ways depending on the type of processes. Problem 5.4
Let us substitute w = – pex∆V (eq. 5.2) in
Consider the expansion given in problem
equation 5.1, and we get 5.2, 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
We have q = – w = 2.303 nRT log
∆U = qV Vs
the subscript V in qV denotes that heat is = 2.303 × 1 × 0.8206 × 298 × log 10
supplied at constant volume. 2

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 THERMODYNAMICS 143

Remember ∆H = qp, heat absorbed by the

= 2.303 x 0.8206 x 298 x log 5 system at constant pressure.
= 2.303 x 0.8206 x 298 x 0.6990
= 393.66 L atm ∆H is negative for exothermic reactions
which evolve heat during the reaction and
∆H is positive for endothermic reactions
5.2.2 Enthalpy, H
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 5.8 becomes
volume is equal to change in the internal
∆H = ∆U = qV
energy i.e., ∆U = qV. But most of chemical
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
constant atmospheric pressure. We need to of only solids and / or liquids. Solids and
define another state function which may be liquids do not suffer any significant volume
suitable under these conditions. changes upon heating. The difference,
however, becomes significant when gases are
We may write equation (5.1) as
involved. Let us consider a reaction involving
∆U = qp – p∆V at constant pressure, where
gases. If VA is the total volume of the gaseous
qp is heat absorbed by the system and –p ∆V
reactants, VB is the total volume of the gaseous
represent expansion work done by the system.
products, nA is the number of moles of gaseous
Let us represent the initial state by
reactants and nB is the number of moles of
subscript 1 and final state by 2
gaseous products, all at constant pressure
We can rewrite the above equation as and temperature, then using the ideal gas
U2–U1 = qp – p (V2 – V1) law, we write,
On rearranging, we get pVA = nART
qp = (U2 + pV2) – (U1 + pV1) (5.6) 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 (5.7)
or p ∆V = ∆ngRT (5.9)
so, equation (5.6) becomes
qp= H2 – H1 = ∆H Here, ∆ng refers to the number of moles of
gaseous products minus the number of moles
Although q is a path dependent function,
of gaseous reactants.
H is a state function because it depends on
U, p and V, all of which are state functions. Substituting the value of p∆V from
Therefore, ∆H is independent of path. Hence, equation 5.9 in equation 5.8, we get
qp is also independent of path. ∆H = ∆U + ∆ngRT (5.10)
For finite changes at constant pressure, The equation 5.10 is useful for calculating
we can write equation 5.7 as ∆H from ∆U and vice versa.
∆H = ∆U + ∆pV
Since p is constant, we can write Problem 5.5
∆H = ∆U + p∆V (5.8) If water vapour is assumed to be a
perfect gas, molar enthalpy change for
It is important to note that when heat is vapourisation of 1 mol of water at 1bar
absorbed by the system at constant pressure, and 100°C is 41kJ mol–1. Calculate the
we are actually measuring changes in the internal energy change, when
enthalpy.

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 144 chemIstry

1 mol of water is vapourised at 1 bar

pressure and 100°C.
Solution
(i) The change H2O (l ) → H2O (g)
∆H = ∆U + ∆ngRT Fig. 5.6(a) A gas at volume V and temperature T
or ∆U = ∆H – ∆ngRT, substituting the
values, we get
∆U = 41.00 kJ mol–1 – 1
× 8.3 J mol–1 K–1 × 373 K
= 41.00 kJ mol-1 – 3.096 kJ mol-1
= 37.904 kJ mol–1 Fig. 5.6 (b) Partition, each part having half the
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
properties. An extensive property is a appears as a rise in temperature of the system
property whose value depends on the quantity in case of heat absorbed by the system.
or size of matter present in the system. For The increase of temperature is proportional
example, mass, volume, internal energy, to the heat transferred
enthalpy, heat capacity, etc. are extensive
q  coeff  T
properties.
The magnitude of the coefficient depends
Those properties which do not depend on the size, composition and nature of the
on the quantity or size of matter present system. We can also write it as q = C ∆T
are known as intensive properties. For
example temperature, density, pressure etc. The coefficient, C is called the heat
are intensive properties. A molar property, capacity.
χm, is the value of an extensive property χ of Thus, we can measure the heat supplied
the system for 1 mol of the substance. If n is by monitoring the temperature rise, provided
 we know the heat capacity.
the amount of matter,  m  n is independent When C is large, a given amount of heat
of the amount of matter. Other examples are results in only a small temperature rise. Water
molar volume, Vm and molar heat capacity, has a large heat capacity i.e., a lot of energy
C m . Let us understand the distinction is needed to raise its temperature.
between extensive and intensive properties by
C is directly proportional to amount of
considering a gas enclosed in a container of
substance. The molar heat capacity of a
volume V and at temperature T [Fig. 5.6(a)].
Let us make a partition such that volume substance, Cm =  C  , is the heat capacity
is halved, each part [Fig. 5.6 (b)] now has n
for one mole of the substance and is
one half of the original volume, V , but the
2 the quantity of heat needed to raise the
temperature will still remain the same i.e., T. temperature of one mole by one degree
It is clear that volume is an extensive property celsius (or one kelvin). Specific heat, also
and temperature is an intensive property. called specific heat capacity is the quantity

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 THERMODYNAMICS 145

of heat required to raise the temperature of i) at constant volume, qV

one unit mass of a substance by one degree ii) at constant pressure, qp
celsius (or one kelvin). For finding out the
heat, q, required to raise the temperatures (a) ∆U Measurements
of a sample, we multiply the specific heat For chemical reactions, heat absorbed at
of the substance, c, by the mass m, and constant volume, is measured in a bomb
temperatures change, ∆T as calorimeter (Fig. 5.7). Here, a steel vessel (the
q  c  m  T  C T (5.11) bomb) is immersed in a water bath. The whole
device is called calorimeter. The steel vessel is
(d) The Relationship between Cp and CV
immersed in water bath to ensure that no heat
for an Ideal Gas
is lost to the surroundings. A combustible
At constant volume, the heat capacity, C is
denoted by CV and at constant pressure, this
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 (5.12)
On putting the values of ∆H and ∆U,
we have
C p T  CV T  RT
C p  CV  R Fig. 5.7 Bomb calorimeter

Cp – CV = R (5.13) substance is burnt in pure dioxygen supplied

in the steel bomb. Heat evolved during the
5.3 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
with chemical or physical processes by an does not change i.e., the energy changes
experimental technique called calorimetry. associated with reactions are measured at
In calorimetry, the process is carried out in a constant volume. Under these conditions, no
vessel called calorimeter, which is immersed work is done as the reaction is carried out
in a known volume of a liquid. Knowing at constant volume in the bomb calorimeter.
the heat capacity of the liquid in which Even for reactions involving gases, there is no
calorimeter is immersed and the heat capacity work done as ∆V = 0. Temperature change of
of calorimeter, it is possible to determine the the calorimeter produced by the completed
heat 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 5.11.

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(b) ∆H Measurements of the bomb calorimeter is 20.7kJ/K,

Measurement of heat change at constant what is the enthalpy change for the above
pressure (generally under atmospheric pressure) reaction at 298 K and 1 atm?
can be done in a calorimeter shown in Fig. 5.8.
We know that ∆Η = qp (at constant p) and, Solution
therefore, heat absorbed or evolved, qp at Suppose q is the quantity of heat from
constant pressure is also called the heat of the reaction mixture and C V is the
reaction or enthalpy of reaction, ∆rH. heat capacity of the calorimeter, then
the quantity of heat absorbed by the
In an exothermic reaction, heat is evolved, calorimeter.
and system loses heat to the surroundings.
Therefore, qp will be negative and ∆rH will q = CV × ∆T
also be negative. Similarly in an endothermic Quantity of heat from the reaction will
reaction, heat is absorbed, qp is positive and have the same magnitude but opposite
∆rH will be positive. sign because the heat lost by the system
(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

5.4 Enthalpy change, ∆ r H of a

reaction – Reaction Enthalpy
In a chemical reaction, reactants are converted
Fig. 5.8 Calorimeter for measuring heat changes into products and is represented by,
at constant pressure (atmospheric
Reactants → Products
pressure).
The enthalpy change accompanying a
reaction is called the reaction enthalpy. The
Problem 5.6 enthalpy change of a chemical reaction, is
1g of graphite is burnt in a bomb given by the symbol ∆rH
calorimeter in excess of oxygen at 298 K ∆rH = (sum of enthalpies of products) – (sum
and 1 atmospheric pressure according of enthalpies of reactants)
to the equation
C (graphite) + O (g) → CO (g)
 a H i products   bi H reactants (5.14)
2 2 i i

During the reaction, temperature rises

from 298 K to 299 K. If the heat capacity
Here symbol ∑ (sigma) is used for
summation and ai and bi are the stoichiometric

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 THERMODYNAMICS 147

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

Table 5.1 Standard Enthalpy Changes of Fusion and Vaporisation

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

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 148 chemIstry

requires heat for evaporation. At constant

temperature of its boiling point Tb and at Solution
constant pressure: We can represent the process of
H2O(l) → H2O(g); ∆vapH = + 40.79 kJ moI–1 evaporation as
∆vapH is the standard enthalpy of vaporisation. H2 O(1) 
vaporisation
→ H2 O(g)
1mol 1mol
Amount of heat required to vaporize one
mole of a liquid at constant temperature No. of moles in 18 g H2O(l) is
and under standard pressure (1bar) is called 18g
= =1 mol
its standard enthalpy of vaporization or 18g mol –1
molar enthalpy of vaporization, ∆vapH . Heat supplied to evaporate18g water at
Sublimation is direct conversion of a 298 K = n × ∆vap H 
solid into its vapour. Solid CO2 or ‘dry ice’ = (1 mol) × (44.01 kJ mol–1)
sublimes at 195K with ∆subH=25.2 kJ mol–1; = 44.01 kJ
naphthalene sublimes slowly and for this (assuming steam behaving as an ideal
∆sub H = 73.0 kJ mol–1 . gas).
Standard enthalpy of sublimation,
∆subH is the change in enthalpy when one ∆vapU = ∆vapH – p∆V = ∆vapH – ∆ngRT
mole of a solid substance sublimes at a
constant temperature and under standard ∆vapHV – ∆ngRT = 44.01 kJ
pressure (1bar). –(1)(8.314 JK–1mol–1)(298K)(10–3kJ J–1)
The magnitude of the enthalpy change ∆vapUV = 44.01 kJ – 2.48kJ
depends on the strength of the intermolecular
= 41.53 kJ
interactions in the substance undergoing
the phase transfomations. For example,
Problem 5.8
the strong hydrogen bonds between water
molecules hold them tightly in liquid phase. Assuming the water vapour to be a perfect
gas, calculate the internal energy change
For an organic liquid, such as acetone, the
when 1 mol of water at 100°C and 1 bar
intermolecular dipole-dipole interactions are pressure is converted to ice at 0°C. Given
significantly weaker. Thus, it requires less the enthalpy of fusion of ice is 6.00 kJ
heat to vaporise 1 mol of acetone than it does mol-1 heat capacity of water is 4.2 J/g°C
to vaporize 1 mol of water. Table 5.1 gives The change take place as follows:
values of standard enthalpy changes of fusion Step - 1 1 mol H2O (l, 100°C)  1
and vaporisation for some substances. mol (l, 0°C) Enthalpy
change ∆H1
Problem 5.7
Step - 2 1 mol H2O (l, 0°C)  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
298 K ? Calculate the internal energy ∆H = ∆H1 + ∆H2
of vaporisation at 298K. ∆H1 = - (18 x 4.2 x 100) J mol-1
∆vap H  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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Table 5.2 Standard Molar Enthalpies of Formation (∆f H ) at 298K of a Few

Selected Substances

of aggregation (also known as reference

Therefore,
states) is called Standard Molar Enthalpy
∆H = - 7.56 kJ mol-1 + (-6.00 kJ mol-1)
of Formation. Its symbol is ∆f H , where the
   = -13.56 kJ mol-1
subscript ‘ f ’ indicates that one mole of the
There is negligible change in the volume
compound in question has been formed in its
during the change form liquid to solid
state. standard state from its elements in their most
stable states of aggregation. The reference
Therefore, p∆v = ∆ng RT = 0
state of an element is its most stable state
∆H = ∆U = - 13.56kJ mol-1
of aggregation at 25°C and 1 bar pressure.
For example, the reference state of dihydrogen
(c) Standard Enthalpy of Formation is H 2 gas and those of dioxygen, carbon
The standard enthalpy change for the and sulphur are O2 gas, Cgraphite and Srhombic
formation of one mole of a compound from respectively. Some reactions with standard
its elements in their most stable states 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
of formation and calculate the enthalpy
∆f H = –285.8 kJ mol–1
change for the reaction. The following general
C (graphite, s) + 2H2(g) → Ch4 (g); equation can be used for the enthalpy change
∆f H = –74.81 kJ mol–1 calculation.
2C (graphite, s)+3H2 (g)+ ½O2(g) → C2H5OH(1); ∆rH = ∑ ai ∆f H (products) – ∑ bi ∆f H (reactants)
i
∆f H  = – 277.7kJ mol–1
i
(5.15)
It is important to understand that a where a and b represent the coefficients of
standard molar enthalpy of formation, ∆f H  , the products and reactants in the balanced
is just a special case of ∆rH , where one mole equation. Let us apply the above equation for
of a compound is formed from its constituent decomposition of calcium carbonate. Here,
elements, as in the above three equations, coefficients ‘a’ and ‘b’ are 1 each. Therefore,
where 1 mol of each, water, methane and ∆rH = ∆f H  = [CaO(s)]+ ∆f H  [CO2(g)]
ethanol is formed. In contrast, the enthalpy – ∆f H  = [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)
∆rH  = – 178.3kJ mol–1
= 178.3 kJ mol –1
is not an enthalpy of formation of calcium
carbonate, since calcium carbonate has been Thus, the decomposition of CaCO3 (s) is
formed from other compounds, and not from an endothermic process and you have to heat
its constituent elements. Also, for the reaction it for getting the desired products.
given below, enthalpy change is not standard (d) Thermochemical Equations
enthalpy of formation, ∆fH  for HBr(g).
A balanced chemical equation together with
H2(g) + Br2(l) → 2HBr(g); the value of its ∆rH is called a thermochemical
∆r H  = – 178.3kJ mol–1 equation. We specify the physical state
Here two moles, instead of one mole of the (alongwith allotropic state) of the substance
product is formed from the elements, i.e., in an equation. For example:
∆r H  = 2∆f H C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l);
Therefore, by dividing all coefficients in ∆rH = – 1367 kJ mol–1
the balanced equation by 2, expression for The above equation describes the
enthalpy of formation of HBr (g) is written as combustion of liquid ethanol at constant
½H2(g) + ½Br2(1) → HBr(g); temperature and pressure. The negative sign
∆f H = – 36.4 kJ mol–1 of enthalpy change indicates that this is an
exothermic reaction.
Standard enthalpies of formation of some
common substances are given in Table 5.2. It would be necessary to remember the
By convention, standard enthalpy for following conventions regarding thermo-
formation, ∆f H , 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
moles (never molecules) of reactants and
Suppose, you are a chemical engineer and
want to know how much heat is required to products involved in the reaction.
decompose calcium carbonate to lime and 2. The numerical value of ∆rH  refers to the
carbon dioxide, with all the substances in number of moles of substances specified
their standard state. by an equation. Standard enthalpy change
CaCO3(s) → CaO(s) + CO2(g); ∆r H = ? ∆rH will have units as kJ mol–1.

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 THERMODYNAMICS 151

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,
Fe2O3  s   3H2  g   2Fe  s   3H2O  l  , therefore the change in enthalpy is independent
of the path between initial state (reactants)
From the Table (5.2) of standard enthalpy of and final state (products). In other words,
formation (∆f H ), we find : enthalpy change for a reaction is the same
∆f H (H2O,l) = –285.83 kJ mol–1; whether it occurs in one step or in a series
∆f H (Fe2O3,s) = – 824.2 kJ mol–1; of steps. This may be stated as follows in the
form of Hess’s Law.
Also ∆f H (Fe, s) = 0 and
If a reaction takes place in several
∆f H (H2, g) = 0 as per convention
steps then its standard reaction enthalpy
Then, is the sum of the standard enthalpies of
∆f H1 = 3(–285.83 kJ mol–1) the intermediate reactions into which the
– 1(– 824.2 kJ mol–1) overall reaction may be divided at the same
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
reaction
are equal to the respective stoichiometric
c o e f f i c i e n t s . T h e u n i t f o r ∆ rH  i s C (graphite,s) +   O2 (g) → CO (g); ∆r H  = ?
kJ mol–1, which means per mole of reaction. Although CO(g) is the major product, some
Once we balance the chemical equation in a CO2 gas is always produced in this reaction.
particular way, as above, this defines the mole Therefore, we cannot measure enthalpy
of reaction. If we had balanced the equation change for the above reaction directly.
differently, for example, However, if we can find some other reactions
1 3 3 involving related species, it is possible to
Fe2O3  s   H2  g   Fe  s   H2O  l 
2 2 2 calculate the enthalpy change for the above
reaction.
then this amount of reaction would be one
mole of reaction and ∆rH  would be Let us consider the following reactions:
3 C (graphite,s) + O2 (g) → CO2 (g);
∆f H 2 = (–285.83 kJ mol–1)
2 ∆r H  = – 393.5 kJ mol–1 (i)
1
– (–824.2 kJ mol–1) 1
2 CO (g) + O (g) → CO2 (g)
= (– 428.7 + 412.1) kJ mol–1 2 2 ∆r H  = – 283.0 kJ mol–1 (ii)
= –16.6 kJ mol–1 = ½ ∆r H 1 We can combine the above two reactions
It shows that enthalpy is an extensive in such a way so as to obtain the desired
quantity. reaction. To get one mole of CO(g) on the
3. When a chemical equation is reversed, right, we reverse equation (ii). In this, heat
the value of ∆rH  is reversed in sign. For is absorbed instead of being released, so we
example change sign of ∆rH  value
N2(g) + 3H2 (g) → 2NH3 (g); CO2 (g) → CO (g) +  O2 (g);
∆r H  = – 91.8 kJ. mol–1 ∆r H  = + 283.0 kJ mol–1 (iii)
2NH3(g) → N2(g) + 3H2 (g);
∆r H  = + 91.8 kJ mol–1

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 152 chemIstry

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
1 equation is :
C  graphite, s   O2  g   CO  g  ;
2 C6 H12O6 ( g )  6O2 ( g )  6CO2 ( g )  6H2O(1);
for which ∆r H  = (– 393.5 + 283.0) ∆C H  = – 2802.0 kJ mol–1
= – 110.5 kJ mol–1 Our body also generates energy from food
by the same overall process as combustion,
In general, if enthalpy of an overall although the final products are produced after
reaction A→B along one route is ∆rH and a series of complex bio-chemical reactions
∆rH1, ∆rH2, ∆rH3..... representing enthalpies involving enzymes.
of reactions leading to same product, B along
another route, then we have
Problem 5.9
∆rH = ∆rH1 + ∆rH2 + ∆rH3 ... (5.16)
The combustion of one mole of benzene
It can be represented as:
takes place at 298 K and 1 atm. After
combustion, CO2(g) and H2O (1) are
∆rH produced and 3267.0 kJ of heat is
A B
liberated. Calculate the standard
∆H1 ∆rH3 enthalpy of formation, ∆f H  of benzene.
Standard enthalpies of formation of
C D CO2(g) and H2O(l) are –393.5 kJ mol–1
∆rH2 and – 285.83 kJ mol–1 respectively.

5.5 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  = ? ... (i)
(symbol : ∆cH )
The enthalpy of combustion of 1 mol
Combustion reactions are exothermic in of benzene is :
nature. These are important in industry, 15
rocketry, and other walks of life. Standard C6 H6  l   O2  6CO2  g   3H2O  l  ;
enthalpy of combustion is defined as the 2
enthalpy change per mole (or per unit amount) ∆C H  = – 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 CO2(g) :
in their standard states at the specified C  graphite   O2  g   CO2  g  ;
temperature.
∆f H  = – 393.5 kJ mol–1... (iii)
Cooking gas in cylinders contains mostly
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
H2  g   O2  g   H2 O  l  ;
reactions for this as: 2
13 ∆C H  = – 285.83 kJ mol–1... (iv)
C4 H10 ( g )  O2 ( g )  4CO2 ( g )  5H2O(1);
2 multiplying eqn. (iii) by 6 and eqn. (iv)
∆C H  = – 2658.0 kJ mol–1 by 3 we get:

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 THERMODYNAMICS 153

In this case, the enthalpy of atomization is

6C  graphite   6O2  g   6CO2  g  ; same as the enthalpy of sublimation.

∆f H  = – 2361 kJ mol–1 (c) Bond Enthalpy (symbol: ∆bondH )

3 Chemical reactions involve the breaking and
3H 2  g   O2  g   3H2O 1 ; making of chemical bonds. Energy is required
2
to break a bond and energy is released when a
∆f H  = – 857.49 kJ mol–1
bond is formed. It is possible to relate heat of
Summing up the above two equations : reaction to changes in energy associated with
15 breaking and making of chemical bonds. With
6C  graphite   3H2  g   O2  g   6CO2  g 
2 reference to the enthalpy changes associated
 3H 2 O  l  ; with chemical bonds, two different terms are
used in thermodynamics.
∆f H  = – 3218.49 kJ mol–1... (v)
(i) Bond dissociation enthalpy
Reversing equation (ii);
(ii) Mean bond enthalpy
15
6CO2  g   3H2O  l   C6 H6  l   O2 ; Let us discuss these terms with reference
2
to diatomic and polyatomic molecules.
∆f H  = – 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
6C  graphite   3H2  g   C6 H6  l  ; dihydrogen gas (H2) are broken:
H2(g) → 2H(g); ∆H–HH  = 435.0 kJ mol–1
∆f H  = – 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
(b) Enthalpy of Atomization change in enthalpy when one mole of covalent
(symbol: ∆aH ) bonds of a gaseous covalent compound is
Consider the following example of atomization broken to form products in the gas phase.
of dihydrogen Note that it is the same as the enthalpy of
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 Cl2(g) → 2Cl(g); ∆Cl–ClH  = 242 kJ mol–1
enthalpy change in this process is known
as enthalpy of atomization, ∆aH . It is the O2(g) → 2O(g); ∆O=OH = 428 kJ mol–1
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.
atomization is also the bond dissociation The 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);
CH4(g) → C(g) + 4H(g); ∆aH = 1665 kJ mol
 –1
∆a H  = 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
Na(s) → Na(g); ∆aH = 108.4 kJ mol–1 C – H bonds in each successive step differ :

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 154 chemIstry

CH4(g) → CH3(g)+H(g);∆bond H = +427 kJ mol–1 given in Table 5.3. The reaction enthalpies are
CH3(g) → CH2(g)+H(g);∆bond H = +439 kJ mol–1 very important quantities as these arise from
the changes that accompany the breaking of
CH2(g) → CH(g)+H(g);∆bond H = +452 kJ mol–1 old bonds and formation of the new bonds.
CH(g) → C(g)+H(g);∆bond H = +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, ∆rH is
CH4(g) → C(g)+4H(g);∆a H = 1665 kJ mol–1 related to bond enthalpies of the reactants
In such cases we use mean bond enthalpy and products in gas phase reactions as:
of C – H bond.
For example in CH4, ∆C–HH  is calculated as: ∆r H  
bond enthalpiesreactants
∆C–HH = ¼ (∆a H) = ¼ (1665 kJ mol–1)   bond enthalpies products
(5.17)**
= 416 kJ mol–1 This relationship is particularly more
We find that mean C–H bond enthalpy useful when the required values of ∆f H are
in methane is 416 kJ/mol. It has been not available. The net enthalpy change of a
found that mean C–H bond enthalpies differ reaction is the amount of energy required
slightly from compound to compound, as to break all the bonds in the reactant
in CH3CH2Cl, CH3NO2, etc., but it does not molecules minus the amount of energy
differ in a great deal*. Using Hess’s law, bond required to break all the bonds in the product
enthalpies can be calculated. Bond enthalpy molecules. Remember that this relationship is
values of some single and multiple bonds are approximate and is valid when all substances

Table 5.3(a) Some Mean Single Bond Enthalpies in kJ mol–1 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 CI
192 180 Br
151 I

Table 5.3(b) Some Mean Multiple Bond Enthalpies in kJ mol–1 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), which is the enthalpy change when one mole of a particular type of
bond is formed from gaseous atom, then ∆f H  = ∑ ∆f Hbonds of products – ∑ ∆f H bonds of reactants

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 THERMODYNAMICS 155

(reactants and products) in the reaction are  1

2. Na( g )  Na ( g )  e ( g ) , the ionization of
in gaseous state.
sodium atoms, ionization enthalpy
(d) Lattice Enthalpy ∆iH = 496 kJ mol–1

The lattice enthalpy of an ionic compound is 3. 1 Cl 2 ( g ) → Cl( g ), t h e d i s s o c i a t i o n o f

the enthalpy change which occurs when one 2
mole of an ionic compound dissociates into chlorine, the reaction enthalpy is half the
its ions in gaseous state. bond dissociation enthalpy.
Na  Cl   s   Na  ( g )  Cl   g  ;
1 ∆ H = 121 kJ mol–1
bond
2
∆latticeH = +788 kJ mol
 –1

Since it is impossible to determine lattice 4. Cl( g )  e 1 ( g )  Cl( g ) e l e c t r o n g a i n e d

enthalpies directly by experiment, we use by chlorine atoms. The electron gain
enthalpy, ∆egH  = – 348.6 kJ mol–1.
an indirect method where we construct an
You have learnt about ionization enthalpy
enthalpy diagram called a Born-Haber Cycle
and electron gain enthalpy in Unit 3.
(Fig. 5.9).
In fact, these terms have been taken
Let us now calculate the lattice enthalpy from thermodynamics. Earlier terms,
of Na+Cl–(s) by following steps given below : ionization energy and electron affinity
1. Na( s ) → Na( g ) , sublimation of sodium were in practice in place of the above
metal, ∆subH  = 108.4 kJ mol–1 terms (see 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
∆rH (T ) = ∆rH(0) + ∫
0
∆rCPdT

The value of Cp for each species in the above

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

5. Na + (g) + Cl − (g) → Na + Cl − (s)

Fig. 5.9 Enthalpy diagram for lattice enthalpy of The sequence of steps is shown in
NaCl Fig. 5.9, and is known as a Born-Haber

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 156 chemIstry

cycle. The importance of the cycle is that, The enthalpy of solution of AB(s), ∆solH ,
the sum of the enthalpy changes round a in water is, therefore, determined by the
cycle is zero. Applying Hess’s law, we get, selective values of the lattice enthalpy, ∆latticeH
∆latticeH = 411.2 + 108.4 + 121 + 496 – 348.6 and enthalpy of hydration of ions, ∆hydH as
∆sol H  = ∆latticeH  + ∆hydH 
∆latticeH = + 788kJ
for NaCl(s)  Na+(g) + Cl–(g) For most of the ionic compounds, ∆sol
Internal energy is smaller by 2RT (because ∆ng H is positive and the dissociation process
= 2) and is equal to + 783 kJ mol–1. is endothermic. Therefore the solubility of
most salts in water increases with rise of
Now we use the value of lattice enthalpy temperature. If the lattice enthalpy is very
to calculate enthalpy of solution from the high, the dissolution of the compound may
expression: not take place at all. Why do many fluorides
∆solH = ∆latticeH + ∆hydH tend to be less soluble than the corresponding
For one mole of NaCl(s), chlorides? Estimates of the magnitudes of
lattice enthalpy = + 788 kJ mol–1 enthalpy changes may be made by using
and ∆hydH  = – 784 kJ mol–1( from the tables of bond energies (enthalpies) and lattice
literature) energies (enthalpies).
∆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
(e) Enthalpy of Solution (symbol : ∆solH ) amount of solvent at a constant temperature
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.
in an infinite amount of solvent when the
interactions between the ions (or solute for water
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 Let us consider the following set of
on the crystal lattice. These are now more free in enthalpy 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
∆H = –72.03 kJ / mol
same 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 157

If we subtract the first equation (equation many years without observing any perceptible
S-1) from the second equation (equation S-2) change. Although the reaction is taking place
in the above set of equations, we obtain– between them, it is at an extremely slow
rate. It is still called spontaneous reaction.
HCl.25 aq. + 15 aq. → HCl.40 aq.
So spontaneity means ‘having the potential
∆H = [ –72.79 – (–72.03)] kJ / mol to proceed without the assistance of external
= – 0.76 kJ / mol agency’. However, it does not tell about the
This value (–0.76kJ/mol) of ∆H is enthalpy rate of the reaction or process. Another aspect
of dilution. It is the heat withdrawn from of spontaneous reaction or process, as we see
the surroundings when additional solvent is is that these cannot reverse their direction on
added to the solution. The enthalpy of dilution their own. We may summarise it as follows:
of a solution is dependent on the original A spontaneous process is an
concentration of the solution and the amount irreversible process and may only be
of solvent added. reversed by some external agency.
5.6 spontaneity (a) Is Decrease in Enthalpy a Criterion
The first law of thermodynamics tells us for Spontaneity ?
about the relationship between the heat If we examine the phenomenon like flow of
absorbed and the work performed on or water down hill or fall of a stone on to the
by a system. It puts no restrictions on ground, we find that there is a net decrease
the direction of heat flow. However, the in potential energy in the direction of change.
flow of heat is unidirectional from higher By analogy, we may be tempted to state that
temperature to lower temperature. In fact, a chemical reaction is spontaneous in a
all naturally occurring processes whether given direction, because decrease in energy
chemical or physical will tend to proceed has taken place, as in the case of exothermic
spontaneously in one direction only. For reactions. For example:
example, a gas expanding to fill the available 1
volume, burning carbon in dioxygen giving N (g) + H2(g) = NH3(g);
2 2
carbon dioxide. ∆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 H (g) + Cl2(g) = HCl (g);
2 2 2
will not spontaneously contract into one ∆r H  = – 92.32 kJ mol–1
corner or carbon dioxide will not form carbon 1
H2(g) + O2(g) → H2O(l) ;
and dioxygen spontaneously. These and many 2 ∆ H  = –285.8 kJ mol–1
other spontaneously occurring changes show r

unidirectional change. We may ask ‘what is The decrease in enthalpy in passing from
the driving force of spontaneously occurring reactants to products may be shown for any
changes ? What determines the direction of a exothermic reaction on an enthalpy diagram
spontaneous change ? In this section, we shall as shown in Fig. 5.10(a).
establish some criterion for these processes Thus, the postulate that driving force for
whether these will take place or not. a chemical reaction may be due to decrease
Let us first understand what do we mean in energy sounds ‘reasonable’ as the basis of
by spontaneous reaction or change ? You evidence so far !
may think by your common observation that Now let us examine the following reactions:
spontaneous reaction is one which occurs 1
N2(g) + O2(g) → NO2(g);
immediately when contact is made between 2
the reactants. Take the case of combination ∆r H = +33.2 kJ mol–1
of hydrogen and oxygen. These gases may C(graphite, s) + 2 S(l) → CS2(l);
be mixed at room temperature and left for ∆r H = +128.5 kJ mol–1

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 158 chemIstry

Fig. 5.10 (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. 5.10(b).

Fig. 5.11 Diffusion of two gases

respectively and separated by a movable

partition [Fig. 5.11 (a)]. When the partition is
withdrawn [Fig. 5.11(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. 5.10 (b) Enthalpy diagram for endothermic sure that these will be molecules of gas A
reactions and similarly if we were to pick up the gas
molecules from right container, we would
Therefore, it becomes obvious that while
be sure that these will be molecules of gas
decrease in enthalpy may be a contributory
B. But, if we were to pick up molecules from
factor for spontaneity, but it is not true for
container when partition is removed, we are
all cases.
not sure whether the molecules picked are of
(b) Entropy and Spontaneity gas A or gas B. We say that the system has
Then, what drives the spontaneous process become less predictable or more chaotic.
in a given direction ? Let us examine such a We may now formulate another postulate:
case 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 more disordered or chaotic and this could be
into each other in a closed container which a criterion for spontaneous change !
is isolated from the surroundings as shown At this point, we introduce another
in Fig. 5.11. thermodynamic function, entropy denoted
The two gases, say, gas A and gas B are as 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 159

picture, one can think of entropy as a measure qrev

of the degree of randomness or disorder in the ∆S = (5.18)
T
system. The greater the disorder in an isolated The total entropy change (∆Stotal) for the
system, the higher is the entropy. As far as a system and surroundings of a spontaneous
chemical reaction is concerned, this entropy process is given by
change can be attributed to rearrangement of
Stotal  Ssystem  Ssurr  0 (5.19)
atoms or ions from one pattern in the reactants
to another (in the products). If the structure When a system is in equilibrium, the
of the products is very much disordered than entropy is maximum, and the change in
that of the reactants, there will be a resultant entropy, ∆S = 0.
increase in entropy. The change in entropy
We can say that entropy for a spontaneous
accompanying a chemical reaction may be
process increases till it reaches maximum
estimated qualitatively by a consideration of
and at equilibrium the change in entropy is
the structures of the species taking part in the
zero. Since entropy is a state property, we can
reaction. Decrease of regularity in structure
calculate the change in entropy of a reversible
would mean increase in entropy. For a given
process by
substance, the crystalline solid state is the
state of lowest entropy (most ordered), The qsys ,rev
gaseous state is state of highest entropy. ∆Ssys =
T
Now let us try to quantify entropy. One way We find that both for reversible and
to calculate the degree of disorder or chaotic irreversible expansion for an ideal gas, under
distribution of energy among molecules isothermal conditions, ∆U = 0,  but ∆S total
would be through statistical method which
i.e., Ssys  Ssurr is not zero for irreversible
is beyond the scope of this treatment. Other
process. Thus,  ∆U does not discriminate
way would be to relate this process to the
between reversible and irreversible process,
heat involved in a process which would make
whereas ∆S does.
entropy a thermodynamic concept. Entropy,
like any other thermodynamic property such
as internal energy U and enthalpy H is a state Problem 5.10
function and ∆S is independent of path.
Predict in which of the following, entropy
Whenever heat is added to the system, increases/decreases :
it increases molecular motions causing (i) A liquid crystallizes into a solid.
increased randomness in the system. Thus
(ii) Temperature of a crystalline solid
heat (q) has randomising influence on the
is raised from 0 K to 115 K.
system. Can we then equate ∆S with q ? Wait !
Experience suggests us that the distribution  iii  2NaHCO3  s   Na 2 CO3  s  
of heat also depends on the temperature at CO2  g   H2O  g 
which heat is added to the system. A system at
higher temperature has greater randomness (iv) H2  g   2H  g 
in it  than one at lower temperature. Thus,
Solution
temperature is the measure of average
chaotic motion of particles in the system. (i) After freezing, the molecules attain
Heat added to a system at lower temperature an ordered state and therefore,
causes greater randomness than when the entropy decreases.
same quantity of heat is added to it at higher (ii) At 0 K, the contituent particles are
temperature. This suggests that the entropy static and entropy is minimum.
change is inversely proportional to the If temperature is raised to 115 K,
temperature. ∆S is related with q and T for a these begin to move and oscillate
reversible reaction as :

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 160 chemIstry

about their equilibrium positions = 4980.6 JK–1 mol–1

in the lattice and system becomes This shows that the above reaction is
more disordered, therefore entropy spontaneous.
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
there are one solid and two gases. total entropy change, ∆Stotal which decides
Therefore, the products represent a the spontaneity of the process. But most of
condition of higher entropy. the chemical reactions fall into the category
(iv) Here one molecule gives two atoms of 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 entropy. It is clear from the discussion in
higher entropy than one mole of previous sections that neither decrease in
dihydrogen molecule. enthalpy nor increase in entropy alone can
Problem 5.11 determine the direction of spontaneous
change for these systems.
For oxidation of iron,
For this purpose, we define a new
4Fe  s   3O2  g   2Fe2O3  s  thermodynamic function the Gibbs energy
entropy change is – 549.4 JK–1 mol–1 or Gibbs function, G, as
at 298 K. Inspite of negative entropy G = H – TS (5.20)
change of this reaction, why is the Gibbs function, G is an extensive property
reaction spontaneous? and a state function.
(∆rH  for this reaction is The change in Gibbs energy for the
–1648 × 103 J mol–1) system, ∆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,

 
Stotal Ssys  Ssurr . For calculating  Gsys = H sys  T Ssys
∆Ssurr, we have to consider the heat Usually the subscript ‘system’ is dropped
absorbed by the surroundings which
and we simply write this equation as
is equal to – ∆rH . At temperature T,
entropy change of the surroundings is G  H  T S (5.21)
Thus, Gibbs energy change = enthalpy
change – temperature × entropy change, and
is referred to as the Gibbs equation, one of

 1648 10 3
J mol 1  the most important equations in chemistry.
298 K Here, we have considered both terms together
for spontaneity: energy (in terms of ∆H)
= 5530 JK–1mol–1 and entropy (∆S, a measure of disorder) as
Thus, total entropy change for this indicated earlier. Dimensionally if we analyse,
reaction we find that ∆G has units of energy because,
r Stotal  5530 JK –1mol –1  both ∆H and the T∆S are energy terms, since
 549.4 JK –1
mol –1  T∆S = (K) (J/K) = J.
Now let us consider how ∆G is related to
reaction spontaneity.

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 THERMODYNAMICS 161

We know, be small. The former is one of the reasons

∆Stotal = ∆Ssys + ∆Ssurr why reactions are often carried out at high
If the system is in thermal equilibrium with temperature. Table 5.4 summarises the effect
the surrounding, then the temperature of the of temperature on spontaneity of reactions.
surrounding is same as that of the system. (d) Entropy and Second Law of
Also, increase in enthalpy of the surrounding Thermodynamics
is equal to decrease in the enthalpy of the
We know that for an isolated system
system.
the change in energy remains constant.
Therefore, entropy change of surroundings, Therefore, increase in entropy in such
H surr H sys systems is the natural direction of a
Ssurr =  spontaneous change. This, in fact is the
T T
second law of thermodynamics. Like first
 H sys  law of thermodynamics, second law can also
Stotal  Ssys   
 T  be stated in several ways. The second law of
thermodynamics explains why spontaneous
Rearranging the above equation:
exothermic reactions are so common.
T∆Stotal = T∆Ssys – ∆Hsys In exothermic reactions heat released
For spontaneous process, Stotal  0 , so by the reaction increases the disorder
T∆Ssys – ∆Hsys > Ο of the surroundings and overall entropy
change is positive which makes the reaction
 
  H sys  T Ssys  0 spontaneous.

Using equation 5.21, 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 straight line in any direction, they may
(5.22) spin like a top and the bonds in the
∆Hsys is the enthalpy change of a reaction, molecules may stretch and compress.
T∆Ssys is the energy which is not available to do These motions of the molecule are called
useful work. So ∆G is the net energy available translational, rotational and vibrational
to do useful work and is thus a measure of the motion respectively. When temperature of
‘free energy’. For this reason, it is also known the system rises, these motions become
as the free energy of the reaction. more vigorous and entropy increases. On the
∆G gives a criteria for spontaneity at other hand when temperature is lowered, the
constant pressure and temperature. entropy decreases. The entropy of any pure
crystalline substance approaches zero as
(i) If ∆G is negative (< 0), the process is the temperature approaches absolute zero.
spontaneous. This is called third law of thermodynamics.
(ii) If ∆G is positive (> 0), the process is non This is so because there is perfect order in
spontaneous. a crystal at absolute zero. The statement is
confined to pure crystalline solids because
Note : If a reaction has a positive enthalpy
theoretical arguments and practical evidences
change and positive entropy change, it can
have shown that entropy of solutions and
be spontaneous when T∆S is large enough to
super cooled liquids is not zero at 0 K. The
outweigh ∆H. This can happen in two ways; importance of the third law lies in the fact that
(a) The positive entropy change of the system it permits the calculation of absolute values
can be ‘small’ in which case T must be of entropy of pure substance from thermal
large. (b) The positive entropy change of the data alone. For a pure substance, this can
system can be ‘large’, in which case T may

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 162 chemIstry

n
q is minimum. If it is not, the system would
be done by summing rev increments from 0
T spontaneously change to configuration of
K to 298 K. Standard entropies can be used lower free energy.
to calculate standard entropy changes by a So, the criterion for equilibrium
Hess’s law type of calculation. A + B  C + D; is
∆rG = 0
5.7 G i bb s e n e r g y c h a n g e a n d
Gibbs energy for a reaction in which all
equilibrium
reactants and products are in standard state,
We have seen how a knowledge of the sign ∆rG  is related to the equilibrium constant of
and magnitude of the free energy change of a the reaction as follows:
chemical reaction allows: 0 = ∆rG  + RT ln K
(i) Prediction of the spontaneity of the or ∆rG  = – RT ln K
chemical reaction. or ∆rG  = – 2.303 RT log K (5.23)
(ii) Prediction of the useful work that could We also know that
be extracted from it.
So far we have considered free energy (5.24)
changes in irreversible reactions. Let us now For strongly endothermic reactions, the
examine the free energy changes in reversible value of ∆rH may be large and positive. In
reactions. such a case, value of K will be much smaller
‘Reversible’ under strict thermodynamic than 1 and the reaction is unlikely to
sense is a special way of carrying out form much product. In case of exothermic
a process such that system is at all reactions, ∆rH is large and negative, and ∆rG
times in perfect equilibrium with its is likely to be large and negative too. In such
surroundings. When applied to a chemical cases, K will be much larger than 1. We may
reaction, the term ‘reversible’ indicates expect strongly exothermic reactions to have a
that a given reaction can proceed in either large K, and hence can go to near completion.
direction simultaneously, so that a dynamic ∆rG also depends upon ∆rS, if the changes
equilibrium is set up. This means that the in the entropy of reaction is also taken into
reactions in both the directions should account, the value of K or extent of chemical
proceed with a decrease in free energy, which reaction will also be affected, depending upon
seems impossible. It is possible only if at whether ∆rS is positive or negative.
equilibrium the free energy of the system Using equation (5.24),
Table 5.4 Effect of Temperature on Spontaneity of Reactions

∆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 163

(i) It is possible to obtain an estimate of ∆G

from the measurement of ∆H and ∆S,
 –13.6  10 3
J mol –1 
=
and then calculate K at any temperature 2.303 8.314 JK –1
mol –1
 298 K 
for economic yields of the products. = 2.38
(ii) If K is measured directly in the laboratory, Hence K = antilog 2.38 = 2.4 × 102.
value of ∆G at any other temperature Problem 5.14
can be calculated.
At 60°C, dinitrogen tetroxide is 50
Using equation (5.24), per cent dissociated. Calculate the
standard free energy change at this
temperature and at one atmosphere.
Problem 5.12
Calculate ∆rG for conversion of oxygen Solution
to ozone, 3/2 O2(g) → O3(g) at 298 K. if Kp N2O4(g) 2NO2(g)
for this conversion is 2.47 × 10–29.
If N 2O 4 is 50% dissociated, the mole
Solution fraction of both the substances is given
We know ∆rG = – 2.303 RT log Kp and by
R = 8.314 JK–1 mol–1 1 0.5 2  0.5
xN O  : x NO2 
Therefore, ∆rG = 2 4
1 0.5 1  0.5
– 2.303 (8.314 J K–1 mol–1) 0.5
× (298 K) (log 2.47 × 10 )
–29 pN   1 atm, p NO 
2 O4 1.5 2

= 163000 J mol–1
1
= 163 kJ mol–1.  1 atm.
1.5
Problem 5.13
Find out the value of equilibrium constant The equilibrium constant Kp is given by
p 
2
for the following reaction at 298 K. NO2 1.5
Kp = 
p N 2 O4 (1.5)2 (0.5)
= 1.33 atm.
Standard Gibbs energy change, ∆rG at 
Since
the given temperature is –13.6 kJ mol–1.
∆rG = –RT ln Kp
Solution
∆rG = (– 8.314 JK–1 mol–1) × (333 K)
We know, log K =
× (2.303) × (0.1239)
= – 763.8 kJ mol –1

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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 
f
i f  i

H products   bi  f H reactions 
and in gaseous state by
∆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
∆rG = – RT ln K.
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 165

Exercises

5.1 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.
5.2 For the process to occur under adiabatic conditions, the correct condition is:
(i) ∆T = 0
∆p = 0
(ii)
q=0
(iii)
(iv) w = 0
5.3 The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) < 0
(iv) different for each element
5.4 ∆U  of combustion of methane is – X kJ mol–1. The value of ∆H is
(i) = ∆U 
(ii) > ∆U 
(iii) < ∆U 
(iv) = 0
5.5 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.
5.6 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
5.7 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?
5.8 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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 166 chemIstry

5.9 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.
5.10 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
5.11 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.
5.12 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)
5.13 Given
N2(g) + 3H2(g) → 2NH3(g); ∆rH = –92.4 kJ mol–1
What is the standard enthalpy of formation of NH3 gas?
5.14 Calculate the standard enthalpy of formation of CH3OH(l) from the following data:
3
CH3OH (l) + O (g) → CO2(g) + 2H2O(l) ; ∆rH = –726 kJ mol–1
2 2
C(graphite) + O2(g) → CO2(g) ; ∆cH = –393 kJ mol–1
1
H2(g) + O (g) → H2O(l); ∆f H = –286 kJ mol–1.
2 2
5.15 Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
∆vapH(CCl4) = 30.5 kJ mol–1.
∆fH (CCl4) = –135.5 kJ mol–1.
∆aH (C) = 715.0 kJ mol–1, where ∆aH is enthalpy of atomisation
∆aH (Cl2) = 242 kJ mol–1
5.16 For an isolated system, ∆U = 0, what will be ∆S ?
5.17 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.
5.18 For the reaction,
2 Cl(g) → Cl2(g), what are the signs of ∆H and ∆S ?
5.19 For the reaction
2 A(g) + B(g) → 2D(g)
∆U 
= –10.5 kJ and ∆S = –44.1 JK–1.
Calculate ∆G for the reaction, and predict whether the reaction may occur
spontaneously.

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 THERMODYNAMICS 167

5.20 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.
5.21 Comment on the thermodynamic stability of NO(g), given
1 1
N2(g) + O (g) → NO(g);  ∆rH = 90 kJ mol–1
2 2 2
1
NO(g) + O2(g) → NO2(g):  ∆rH= –74 kJ mol–1
2
5.22 Calculate the entropy change in surroundings when 1.00 mol of H2O(l) is formed
under standard conditions. ∆f H = –286 kJ mol–1.

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