Thermodynamics and Thermochemistry 403

60
Chapter

10

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Thermodynamics and Thermochemistry

Thermodynamics (iii) Open system : This type of system can

Thermodynamics (Greek word thermo means heat
and dynamics means motion) is the branch of science
ID
which deals with the study of different forms of energy
and the quantitative relationships between them.
exchange matter as well as energy with its surroundings.
The boundary is neither sealed nor insulated. Sodium
reacting with water in an open beaker is an example of
open system.
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(iv) Homogeneous system : A system is said to be
The complete study of thermodynamics is based
homogeneous when it is completely uniform
upon three generalizations called first, second and third
throughout. A homogeneous system is made of one
law of thermodynamics. These laws have been arrived
phase only. Examples: a pure single solid, liquid or gas,
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purely on the basis of human experience and there is no

mixture of gases and a true solution.
theoretical proof for any of these laws.
(v) Heterogeneous system : A system is said to be
Basic concepts heterogeneous when it is not uniform throughout, i.e.,
(1) System, surroundings and Boundary : A it consist of two or more phases. Examples : ice in
specified part of the universe which is under contact with water, two or more immiscible liquids,
observation is called the system and the remaining insoluble solid in contact with a liquid, a liquid in
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portion of the universe which is not a part of the contact with vapour, etc.
system is called the surroundings. (vi) Macroscopic system : A macroscopic system
The system and the surroundings are separated by is one in which there are a large number of particles
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real or imaginary boundaries. The boundary also defines (may be molecules, atoms, ions etc. )
the limits of the system. The system and the (3) Macroscopic properties of the system
surroundings can interact across the boundary. Thermodynamics deals with matter in terms of
(2) Types of systems bulk (large number of chemical species) behaviour. The
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(i) Isolated system : This type of system has no properties of the system which arise from the bulk
interaction with its surroundings. The boundary is behaviour of matter are called macroscopic properties.
sealed and insulated. Neither matter nor energy can be The common examples of macroscopic properties are
exchanged with surrounding. A substance contained in pressure, volume, temperature, surface tension,
an ideal thermos flask is an example of an isolated viscosity, density, refractive index, etc.
system. The macroscopic properties can be subdivided
(ii) Closed system : This type of system can into two types,
exchange energy in the form of heat, work or radiations (i) Intensive properties : The properties which do
but not matter with its surroundings. The boundary not depend upon the quantity of matter present in the
between system and surroundings is sealed but not system or size of the system are called intensive
insulated. For example, liquid in contact with vapour in properties. Its examples are pressure, temperature,
a sealed tube and pressure cooker. density, specific heat, surface tension, refractive index,
 404 Thermodynamics and Thermochemistry
viscosity, melting point, boiling point, volume per initial state, it is termed cyclic process. For a cyclic
mole, concentration etc. process dE = 0 and dH = 0.
(ii) Extensive properties : The properties whose (vi) Reversible process : A process which occurs
magnitude depends upon the quantity of matter present infinitesimally slowly, i.e. opposing force is
in the system are called extensive properties. Its infinitesimally smaller than driving force and when
examples are total mass, volume, internal energy, infinitesimal increase in the opposing force can reverse
enthalpy, entropy etc. These properties are additive in the process, it is said to be reversible process.
nature. (vii) Irreversible process : When the process
Any extensive property if expressed as per mole or occurs from initial to final state in single step in finite
per gram becomes an intensive property. time and cannot be reversed, it is termed an

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(4) State of a system and State Variables irreversible process. Amount of entropy increases in
Macroscopic properties which determine the state irreversible process.
of a system are referred to as state variables or state Irreversible processes are spontaneous in nature.
functions or thermodynamic parameters. The change in All natural processes are irreversible in nature
the state properties depends only upon the initial and
Internal energy, heat and Work

E3
final states of the system, but it is independent of the
manner in which the change has been brought about. In (1) Internal energy (E) : “Every system having
other words, the state properties do not depend upon a some quantity of matter is associated with a definite
path followed. amount of energy. This energy is known as internal
(5) Thermodynamic equilibrium : “A system is energy.”
said to have attained a state of thermodynamic E  E translatio nal  Erotational  E vibrationa l  E bonding  Eelectronic  ......
equilibrium when it shows no further tendency to change
its property with time”.
The criterion for thermodynamic equilibrium
requires that the following three types of equilibrium
ID (i) Characteristics of internal energy
(a) Internal energy of a system is an extensive
property.
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exist simultaneously in a system, (b) Internal energy is a state property.
(i) Chemical Equilibrium : A system in which the (c) The change in the internal energy does not
composition of the system remains fixed and definite. depend on the path by which the final state is reached.
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(ii) Mechanical Equilibrium : No chemical work

(d) There is no change in internal energy in a
is done between different parts of the system or
cyclic process.
between the system and surrounding. It can be
achieved by keeping pressure constant. (e) The internal energy of an ideal gas is a
function of temperature only.
(iii) Thermal Equilibrium : Temperature remains
constant i.e. no flow of heat between system and (f) Internal energy of a system depends upon the
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surrounding. quantity of substance, its chemical nature,

(6) Thermodynamic process : When the temperature, pressure and volume.
thermodynamic system changes from one state to (g) The unit of E is ergs in CGS or joules in SI
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another, the operation is called a process. The various

1 Joule = 10 7 ergs.
types of the processes are
(ii) Change in internal energy ( E ) : It is neither
(i) Isothermal process : In this process operation
possible nor necessary to calculate the absolute value
is done at constant temperature. dT = 0 thus E  0 .
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of internal energy of a system then, E  E f  Ein ; E

(ii) Adiabatic process : In this a process there is
no exchange of heat takes place between the system is positive if E f  Ein and negative if E f  Ein .
and surroundings. The system is thermally isolated, (2) Heat (q) and work (w) : The energy of a
i.e., dQ = 0 and its boundaries are insulated. system may increase or decrease in several ways but
(iii) Isobaric process : In this process the two common ways are heat and work.
pressure remains constant throughout the change i.e.,
Heat is a form of energy. It flows from one system
dP = 0.
to another because of the difference in temperature
(iv) Isochoric process : In this process volume between them. Heat flows from higher temperature to
remains constant throughout the change, i.e., dV = 0. lower temperature. Therefore, it is regarded as energy
(v) Cyclic process : When a system undergoes a on the move.
number of different processes and finally return to its
 Thermodynamics and Thermochemistry 405
Work is said to be performed if the point of If a system does work (w) on the surroundings, its
application of force is displaced in the direction of the internal energy decreases. In this case,
force. It is equal to the force multiplied by the E  q  (w)  q  w
displacement (distance through which the force acts).
i.e.(Change in internal energy)=(Heat added to
There are three main types of work which we the system) – (work done by the system)
generally come across. These are, Gravitational work,
The relationship between internal energy, work
electrical work and mechanical work.
and heat is a mathematical statement of first law of
Mechanical work = Force  displacement = F.d thermodynamics.
Electrical work = potential difference  charge = Enthalpy and Enthalpy change
V.q

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Heat content of a system at constant pressure is
Gravitational work = mgh called enthalpy denoted by ‘H’.
(i) Units of heat and work : The heat changes are From first law of thermodynamics, q  E  PV
measured in calories (cal), Kilo calories (kcal), joules
……….(i)
(J) or kilo joules (kJ). These are related as, 1 cal = 4.184

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J; 1kcal = 4.184kJ Heat change at constant pressure can be given as

The S.I. unit of heat is joule (J) or kilojoule. The q  E  PV

Joule (J) is equal to Newton – metre (1 J= 1 Nm). ……….(ii)
Work is measured in terms of ergs or joules. The At constant pressure heat can be replaced at
S.I. unit of work is Joule. enthalpy.
1 Joule = 10 7 ergs = 0.2390 cal.
1 cal > 1 joule > 1 erg
(ii) Sign conventions for heat and work
ID H  E  PV
………(iii)
H  Heat change or heat of reaction (in
chemical process) at constant pressure
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Heat absorbed by the system = q positive
E  Heat change or heat of reaction at constant
Heat evolved by the system = q negative
volume.
Work done on the system = w positive
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In case of solids and liquids participating in a

Work done by the system = w negative. reaction,
Zeroth law of thermodynamics H  E (PV  0)
This law forms the basis of concept of temperature.
Difference between H and E is significant
This law can be stated as follows,
when gases are involved in chemical reaction.
“If a system A is in thermal equilibrium with a
H  E  PV
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system C and if B is also in thermal equilibrium with

system C, then A and B are in thermal equilibrium with H  E  nRT
each other whatever the composition of the system.” PV  nRT
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A ⇌ C B ⇌ C Here, n  nP – nR
Specific and Molar heat capacity
A ⇌ B
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(1) Specific heat (or specific heat capacity) of a

substance is the quantity of heat (in calories, joules,
First law of thermodynamics
kcal, or kilo joules) required to raise the temperature of
Helmholtz and Robert Mayer proposed first law of 1g of that substance through 1 o C . It can be measured at
thermodynamics. This law is also known as law of constant pressure (c p ) and at constant volume (cv ) .
conservation of energy. It states that,
(2) Molar heat capacity of a substance is the
“Energy can neither be created nor destroyed
quantity of heat required to raise the temperature of 1
although it can be converted from one form into
mole of the substance by 1 o C .
another.”
 Molar heat capacity = Specific heat capacity 
E2  E1  E  q  w
Molecular weight, i.e., Cv  cv  M and C p  c p  M .
i.e. (Change in internal energy) = (Heat added to
the system) +(Work done on the system)
 406 Thermodynamics and Thermochemistry
(3) Since gases on heating show considerable If the external pressure is decreased by an
tendency towards expansion if heated under constant infinitesimal amount dP, the gas will expand by an
pressure conditions, an additional energy has to be infinitesimal volume, dV. As a result of expansion, the
supplied for raising its temperature by 1o C relative to pressure of the gas within the cylinder falls to Pgas  dP ,
that required under constant volume conditions, i.e., i.e., it becomes again equal to the external pressure
C p  Cv or C p  Cv  Work done in expansion, PV ( R) and, thus, the piston comes to rest. Such a process is
repeated for a numberPext Pext –step
of times, i.e., in each dP the
where, C p  molar heat capacity at constant
gas expands by a volume dV.
pressure
Cv  molar heat capacity at constant dV

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volume.
(4) Some useful relations of Cp and Cv Pgas
Pgas
(i) C p  Cv  R  2 calories  8.314 J

3 3 Fig. 10.1
(ii) Cv  R (for monoatomic gas) and Cv   x

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2 2
(for di and polyatomic gas), where x varies from gas to Since the system is in thermal equilibrium with
gas. the surroundings, the infinitesimally small cooling
Cp produced due to expansion is balanced by the
(iii)   (Ratio of molar capacities) absorption of heat from the surroundings and the
Cv
(iv) For monoatomic gas, Cv  3 calories whereas,
C p  Cv  R  5 calories
5
RCp
ID
temperature
expansion.
remains constant

The work done by the gas in each step of

expansion can be
dw  (Pext  dP)dV  Pext .dV  dP . dV
throughout

given
the

as,

 2  1 . 66
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(v) For monoatomic gas, ( ) 
Cv 3 dP .dV , the product of two infinitesimal quantities,
R
2 is negligible.
7 The total amount of work done by the isothermal
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Cp R
(vi) For diatomic gas ( )   2  1 . 40 reversible expansion of the ideal gas from volume V1 to
Cv 5
R V2
2 volume V2 is, given as, w  nRT log e or
V1
Cp 8R
(vii) For triatomic gas ( )    1 . 33 V2
Cv 6R w  2 .303 nRT log 10
V1
Expansion of an ideal gas At constant temperature, according to Boyle’s law,
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V P P
(1) Isothermal Expansion : For an isothermal P1 V1  P2 V2 or 2  1 So, w  2 .303 nRT log 10 1
V1 P2 P2
expansion, T  0 ; E  0.
Isothermal compression work of an ideal gas may
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According to first law of thermodynamics,

be derived similarly and it has exactly the same value
E  q  w q  w
with positive sign.
This shows that in isothermal expansion, the V P
w compressio n  2 .303 nRT log 1  2 .303 nRT log 2
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work is done by the system at the expense of heat V2 P1

absorbed. (ii) Work done in irreversible isothermal
Since for isothermal process, E and T are zero expansion : Two types of irreversible isothermal
respectively, hence, H  0 expansions are observed, i.e., (a) Free expansion and
(i) Work done in reversible isothermal (b) Intermediate expansion. In free expansion, the
expansion : Consider an ideal gas enclosed in a external pressure is zero, i.e., work done is zero when
cylinder fitted with a weightless and frictionless gas expands in vacuum. In intermediate expansion, the
piston. The cylinder is not insulated. The external external pressure is less than gas pressure. So, the
pressure, Pext is equal to pressure of the gas, Pgas . work done when volume changes from V1 to V2 is given
Pext  Pgas  P by


V2
w   Pext  dV   Pext (V2  V1 )
V1
 Thermodynamics and Thermochemistry 407
Since Pext is less than the pressure of the gas, the  T P  T1 P2 
or w  Cv (T2  T1 )   RPext  2 1 

work done during intermediate expansion is  P1 P2 
numerically less than the work done during reversible
isothermal expansion in which Pext is almost equal to Spontaneous and Non-spontaneous processes
Pgas . A process which can take place by itself under the
given set of conditions once it has been initiated if
(2) Adiabatic Expansion : In adiabatic expansion, necessary, is said to be a spontaneous process. In other
no heat is allowed to enter or leave the system, hence, words, a spontaneous process is a process that can
q 0. occur without work being done on it. The spontaneous
According to first law of thermodynamics, processes are also called feasible or probable processes.

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E  q  w  E  w On the other hand, the processes which are
forbidden and are made to take place only by supplying
work is done by the gas during expansion at the
energy continuously from outside the system are called
expense of internal energy. In expansion, E decreases
non-spontaneous processes. In other words, non
while in compression E increases.
spontaneous processes can be brought about by doing
The molar specific heat capacity at constant

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work.
volume of an ideal gas is given by
Examples of Spontaneous and Non-spontaneous
 dE  processes
Cv    or dE  Cv .dT
 dT v (1) The diffusion of the solute from a
and for finite change E  Cv T So, w  E  Cv T concentrated solution to a dilute solution occurs when
these are brought into contact is spontaneous process.
The value of T depends upon the process
whether it is reversible or irreversible.
(i) Reversible adiabatic expansion : The
following relationships are followed by an ideal gas
under reversible adiabatic expansion.
ID (2) Mixing of different gases is spontaneous
process.
(3) Heat flows from a hot reservoir to a cold
reservoir is spontaneous process.
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(4) Electricity flows from high potential to low
PV   constant
potential is spontaneous process.
where, P = External pressure, V = Volume
(5) Expansion of an ideal gas into vacuum through
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Cp a pinhole is spontaneous process.

 
Cv All the above spontaneous processes becomes
where, Cp  molar specific heat capacity at non-spontaneous when we reverse them by doing work.
constant pressure, Cv  molar specific heat capacity at Spontaneous process and Enthalpy change : A
spontaneous process is accompanied by decrease in
constant volume.
internal energy or enthalpy, i.e., work can be obtained
  1 1 
 T1  P  P  by the spontaneous process. It indicates that only
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   1    2 
T  P   exothermic reactions are spontaneous. But the melting
 2   2   P1 
of ice and evaporation of water are endothermic
knowing  , P1 , P2 and initial temperature T1 , the
processes which also proceeds spontaneously. It means,
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final temperature T2 can be evaluated. there is some other factor in addition to enthalpy
(ii) Irreversible adiabatic expansion : In free change (H ) which explains the spontaneous nature of
expansion, the external pressure is zero, i.e, work done the system. This factor is entropy.
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is zero. Accordingly, E which is equal to w is also Second law of thermodynamics

zero. If E is zero, T should be zero. Thus, in free
All the limitations of the first law of
expansion (adiabatically), T  0 , E  0 , w  0 and
thermodynamics can be remove by the second law of
H  0 .
thermodynamics. This law is generalisation of certain
In intermediate expansion, the volume changes experiences about heat engines and refrigerators. It has
from V1 to V2 against external pressure, Pext . been stated in a number of ways, but all the statements
 RT RT  are logically equivalent to one another.
w  Pext (V2  V1 )   Pext  2  1 
 2
P P1  (1) Statements of the law
(i) Kelvin statement : “It is impossible to derive a
 T P  T1 P2 
  Pext  2 1  R
 continuous supply of work by cooling a body to a
 P1 P2 
 408 Thermodynamics and Thermochemistry
temperature lower than that of the coldest of its (1) Definition : Entropy is a thermodynamic state
surroundings.” quantity which is a measure of randomness or disorder
(ii) Clausius statement : “It is impossible for a of the molecules of the system.
self acting machine, unaided by any external agency, to Entropy is represented by the symbol “S”. It is
transfer heat from one body to another at a higher difficult to define the actual entropy of a system. It is
temperature or Heat cannot itself pass from a colder more convenient to define the change of entropy during
body to a hotter body, but tends invariably towards a a change of state.
lower thermal level.” The entropy change of a system may be defined as
(iii) Ostwald statement : “It is impossible to the integral of all the terms involving heat exchanged
construct a machine functioning in cycle which can (q) divided by the absolute temperature (T) during each

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convert heat completely into equivalent amount of work infinitesimally small change of the process carried out
without producing changes elsewhere, i.e., perpetual reversibly at constant temperature.
motions are not allowed.” q rev
S  S final  S initial 
(iv) Carnot statement : “It is impossible to take T
heat from a hot reservoir and convert it completely into If heat is absorbed, then S  ve and if heat is

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work by a cyclic process without transferring a part of it evolved, then S  ve.
to a cold reservoir.” (2) Units of entropy : Since entropy change is
(2) Proof of the law : No rigorous proof is expressed by a heat term divided by temperature, it is
available for the second law. The formulation of the expressed in terms of calorie per degree, i.e.,cal deg-1 .
second law is based upon the observations and has yet In SI units, the entropy is expressed in terms of joule
to be disproved. No deviations of this law have so far
been reported. However, the law is applicable to cyclic
processes only.
The Carnot cycle
ID per degree Kelvin, i.e., JK 1 .
(3) Characteristics of entropy : The important
characteristics of entropy are summed up below
(i) Entropy is an extensive property. Its value
Carnot, a French engineer, in 1824 employed
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depends upon the amount of the substance present in
merely theoretical and an imaginary reversible cycle the system.
known as carnot cycle to demonstrate the maximum (ii) Entropy of a system is a state function. It
convertibility of heat into work. depends upon the state variables (T , p, V , n) .
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The system consists of one mole of an ideal gas

(iii) The change in entropy in going from one
enclosed in a cylinder fitted with a piston, which is
state to another is independent of the path.
subjected to a series of four successive operations.
(iv) The change in entropy for a cyclic process is
For cyclic process, the essential condition is that
always zero.
net work done is equal to heat absorbed. This condition
is satisfied in a carnot cycle. (v) The total entropy change of an isolated
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system is equal to the entropy change of system and

w T  T1
 2  Thermodynamic efficiency entropy change of the surroundings. The sum is called
q2 T2
entropy change of universe.
Thus, the larger the temperature difference S universe  S sys  S Surr
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between high and low temperature reservoirs, the more

the heat converted into work by the heat engine. (a) In a reversible process, S universe  0 and,
T2  T1 therefore
 1 , it follows that w  q 2 . This means
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Since
T2 S sys  S Surr
that only a part of heat absorbed by the system at the
(b) In an irreversible process, S universe  0 . This
higher temperature is transformed into work. The rest
of the heat is given out to surroundings. The efficiency means that there is increase in entropy of universe is
of the heat engine is always less then 1. This has led to spontaneous changes.
the following enunciation of the second law of (vi) Entropy is a measure of unavailable energy
thermodynamics. for useful work.
It is impossible to convert heat into work without Unavailable energy = Entropy × Temperature
compensation. (vii) Entropy, S is related to thermodynamic
Entropy and Entropy change probability (W) by the relation,
S  k log e W and S  2.303 k log10W
 Thermodynamics and Thermochemistry 409
where, k is Boltzmann's constant T2 p
S  nC P ln  nR ln 2 . Assuming C p , is
(4) Entropy changes in system & surroundings T1 p1
and total entropy change for Exothermic and constant
Endothermic reactions : Heat increases the thermal (a) Thus, for an isothermal process (T constant),
motion of the atoms or molecules and increases their V p
disorder and hence their entropy. In case of an S  nR ln 2 or  nR ln 2
V1 p1
exothermic process, the heat escapes into the
(b) For isobaric process (p constant),
surroundings and therefore, entropy of the
T2
surroundings increases on the other hand in case of S  n C p ln
endothermic process, the heat enters the system from T1

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the surroundings and therefore. The entropy of the (c) For isochoric process (V constant),
surroundings decreases. T2
S  n Cv ln
In general, there will be an overall increase of the T1
total entropy (or disorder) whenever the disorder of (d) Entropy change during adiabatic expansion : In
the surroundings is greater than the decrease in such process q=0 at all stages. Hence S  0 . Thus,

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disorder of the system. The process will be spontaneous reversible adiabatic processes are called isoentropic
only when the total entropy increases. process.
(5) Entropy change during phase transition : Free energy and Free energy change
The change of matter from one state (solid, liquid or
gas) to another is called phase transition. Such changes Gibb's free energy (G) is a state function and is a
occur at definite temperature such as melting point measure of maximum work done or useful work done
(solid to liquid). boiling point (liquid to vapours) etc,
and are accompanied by absorption or evolution of
heat.
When a solid changes into a liquid at its fusion
ID from a reversible reaction at constant temperature and
pressure.

(1) Characteristics of free energy

(i) The free energy of a system is the enthalpy of
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temperature, there is absorption of heat (latent heat). the system minus the product of absolute temperature
Let H f be the molar heat of fusion. The entropy and entropy i.e., G  H  TS
change will be (ii) Like other state functions E, H and S, it is also
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H f expressed as G . Also G  H  TS system where S is

S f 
Tf entropy change for system only. This is Gibb's
Similarly, if the latent heat of vaporisation and Helmholtz equation.
sublimation are denoted by H vap and (iii) At equilibrium G  0
H sub , respectively, the entropy of vaporisation and (iv) For a spontaneous process decrease in free
energy is noticed i.e., G  ve .
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sublimation are given by

(v) At absolute zero, TS is zero. Therefore if
H vap H sub
S vap  and S sub  G is – ve, H should be – ve or only exothermic
Tb Ts reactions proceed spontaneously at absolute zero.
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Since H f , H vap and H Sub are all positive, these (vi) Gsystem  TS universe , where H  0
processes are accompanied by increase of entropy and (vii) The standard free energy change,
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the reverse processes are accompanied by decrease in

G o  2 . 303 RT log 10 K , where K is equilibrium
entropy.
constant.
(6) Entropy change for an ideal gas : In going
from initial to final state, the entropy change, S for an (a) Thus if K  1, then G o  ve thus reactions
ideal gas is given by the following relations, with equilibrium constant K>1 are thermodynamically
(i) When T and V are two variables, spontaneous.

S  nC v ln
T2 V
 nR ln 2 . Assuming Cv is (b) If K<1, then G o  ve and thus reactions
T1 V1 with equilibrium constant K<1 are thermodynamically
constant spontaneous in reverse direction.
(ii) When T and p are two variables, (2) Criteria for spontaneity of reaction : For a
spontaneous change G  ve and therefore use of
 410 Thermodynamics and Thermochemistry
G  H  T S , provides the following conditions for a change to be spontaneous.

Table :10.1 Criteria for spontaneity of reaction

ΔH ΔS ΔG Reaction characteristics Example
– + Always negative Reaction is spontaneous at all 2 O 3 ( g )  3 O 2( g )
temperatures
+ – Always positive Reaction is non spontaneous at all 3 O 2( g )  2 O 3 ( g )
temperatures
– – Negative at low Reaction is spontaneous at low CaO (s)  CO 2(g)  CaCO 3(s)
temperature but positive temperature but becomes non

60
at high temperature spontaneous at high temperature
+ + Positive at low Reaction is non spontaneous at low CaCO 3(s)  CaO (s)  CO 2(g)
temperature but negative temperature but becomes spontaneous at
at high temperature high temperature

E3
Third law of thermodynamics exothermic reactions may be represented as,
A  B  C  D  q (heat energy)
This law was first formulated by German chemist
Walther Nernst in 1906. According to this law, In the exothermic reactions the enthalpy of the
“The entropy of all perfectly crystalline solids is products will be less than the enthalpy of the reactants,
zero at the absolute zero temperature. Since entropy is a so that the enthalpy change is negative as shown below
H  H p  H r ; H p  H r ; H   ve
measure of disorder, it can be interpretated that at
ID
absolute zero, a perfectly crystalline solid has a perfect
order of its constituent particles.”
The most important application of the third law of
thermodynamics is that it helps in the calculation of
Examples : (i) C(s)  O2 (g)  CO 2 (g)  393 .5kJ
(at constant temperature and pressure)
or C(s)  O2 (g)  CO 2 (g); H  393 .5kJ
1
U
(ii) H 2 (g)  O 2 (g)  H 2 O(l); H  285 .8kJ
absolute entropies of the substance at any temperature 2
T. (iii) Fermentation is also an example of
S  2.303 C p log T exothermic reaction.
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Where CPis the heat capacity of the substance at (2) Endothermic reactions : The chemical
constant pressure and is supposed to remain constant reactions which proceed with the absorption of heat
in the range of 0 to T. energy are called endothermic reactions. Since the heat
Limitations of the law is added to the reactants in these reactions, the heat
(1) Glassy solids even at 0oK has entropy greater absorbed is indicated by either putting (–) or by writing
than zero. the actual numerical value of heat on the reactant side
A  B  C  D  q (heat energy)
D

(2) Solids having mixtures of isotopes do not have

zero entropy at 0oK. For example, entropy of solid The heat absorbed at constant temperature and
chlorine is not zero at 0oK. constant pressure measures enthalpy change. Because
of the absorption of heat, the enthalpy of products will
U

(3) Crystals of CO, N2O, NO, H2O, etc. do not have

perfect order even at 0oK thus their entropy is not be more than the enthalpy of the reactants.
equal to zero. Consequently, H will be positive (ve ) for the
Thermochemistry endothermic reactions.
ST

“Thermochemistry is a branch of physical chemistry H  H p  H r ; H p  H r ; H  ve

which is concerned with energy changes accompanying
Example : (i) N 2 (g)  O2 (g)  2 NO(g); H  180 .5 kJ
chemical transformation. It is also termed as chemical
energetics. It is based on the first law of (ii) C(s)  2S (s)  CS 2 (l) H  92 .0kJ
thermodynamics.” (iii) Preparation of ozone by passing silent
Exothermic and Endothermic reactions electric discharged through oxygen is the example of
endothermic reaction.
(1) Exothermic reactions : The chemical
reactions which proceed with the evolution of heat (iv) Evaporation of water is also the example
energy are called exothermic reactions. The heat of endothermic reaction.
energy produced during the reactions is indicated by For exothermic reaction : H or E  ve
writing +q or more precisely by giving the actual For endothermic reaction : H or E  ve
numerical value on the products side. In general
 Thermodynamics and Thermochemistry 411
Heat of reaction or Enthalpy of reaction Kirchhoff's equation at constant volume may be
given as,
Heat of reaction is defined as the amount of heat
evolved or absorbed when quantities of the substances ET2  ET1
 C
indicated by the chemical equation have completely T2  T1
reacted. The heat of reaction (or enthalpy of reaction)
(iv) Reaction carried out at constant pressure or
is actually the difference between the enthalpies of the
constant volume : When a chemical reaction occurs at
products and the reactants when the quantities of the
constant volume, the heat change is called the internal
reactants indicated by the chemical equation have
completely reacted. Mathematically, energy of reaction at constant volume. However, most
Enthalpy of reaction (heat of reaction) of the reactions are carried out at constant pressure;

60
 H  H P  H R the enthalpy change is then termed as the enthalpy of
reaction at constant pressure. The difference in the
(1) Factors which influence the heat of reaction
: There are a number of factors which affect the values is negligible when solids and liquids are
magnitude of heat of reaction. involved in a chemical change. But, in reactions which
(i) Physical state of reactants and products : involve gases, the difference in two values is

E3
Heat energy is involved for changing the physical state considerable.
of a chemical substance. For example in the conversion E  nRT  H or qv  nRT  q p
of water into steam, heat is absorbed and heat is
evolved when steam is condensed. Considering the E = q v  heat change at constant volume;
following two reactions E H = q p  heat change at constant pressure,

H 2 (g ) 
1
H 2 (g)  O 2 (g)  H 2 O(g); H   57 .8 kcal
2
1
2
O 2 (g)  H 2 O(l); H   68 .32 kcal
ID n  total number of moles of gaseous product
- total number of moles of gaseous reactants.
(2) Types of heat of reaction
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It is observed that there is difference in the value (i) Heat of formation : It is the quantity of heat
of H if water is obtained in gaseous or liquid state. evolved or absorbed (i.e. the change in enthalpy) when
H value in second case is higher because heat is one mole of the substance is formed from its
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evolved when steam condenses. Hence, physical sate constituent elements under given conditions of
always affects the heat of reaction. temperature and pressure. It is represented by H f .
(ii) Allotropic forms of the element : Heat energy When the temperature and pressure are as 25°C and 1
is also involved when one allotropic form of an element atmospheric pressure. The heat of formation under
is converted into another. Thus, the value of H these conditions is called standard heat of formation. It
depends on the allotropic form used in the reaction. For is usually represented by H 0f .
example, the value of H is different when carbon in
D

the form of diamond or in amorphous form is used. The standard heat of formation of 1 mole of
NH 3 (g) and 1 mole of HCl (g) .
C (diamond) O2 (g)  CO 2 (g); H   94 .3 kcal
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C (amorphous) O2 (g)  CO 2 (g); H   97 .6 kcal 1 3

N 2 (g)  H 2 (g)  NH 3 (g); H (g)  11kcal
2 2
The difference between the two values is equal to
1 1
the heat absorbed when 12g of diamond is converted H 2 (g)  Cl 2 (g)  HCl ; H f  22 kcal
ST

2 2
into 12g of amorphous carbon. This is termed as heat of
transition. It may be calculated by
(iii) Temperature : Heat of reaction has been H 0  [H 0 (products) – H 0 (Reactants) ]
found to depend upon the temperature at which
(ii) Heat of combustion : It is the amount of heat
reaction is occurring. The variation of the heat of
evolved or absorbed (i.e. change in enthalpy) when one
reaction with temperature can be ascertained by using
mole of the substance is completely burnt in air or
Kirchhoff's equation.
oxygen. For example
H T2  H T1
 C P CH 4 (g)  2O2 (g)  CO 2 (g)  2 H 2 O(l); H   192 kcal
T2  T1
C2 H 6 (g)  3.5 O2 (g)  2CO 2 (g)  3 H 2 O(l); H   372 .8 kcal
 412 Thermodynamics and Thermochemistry
It may be calculated by In case of neutralisation of a weak acid or a weak
base against a strong base or acid respectively, since a part
H 0  [H 0f (Products) - H 0f (Reactants) ]
of the evolved heat is used up in ionising the weak acid or
The enthalpy or heat of combustion have a base, it is always less than 13 .7 kcal mole 1 (57 kJ mole 1 ) .
number of applications. Some of these are described
For example,
below,
HCN (aq.)  NaOH (aq.)  NaCN (aq.)  H 2 O
(a) Calorific value of foods and fuels : Energy is
H   2.9 kcal
needed for the working of all machines. Even human
body is no exception. Coal, petroleum, natural gas etc. HCN (aq.) ⇌ H+ + CN–; H = 10.8 Kcal

60
serve as the principal sources of energy for man-made 10 .8 KCal of heat is absorbed for ionisation of
machines, the food which we eat serves as a source of HCN it is heat of dissociation or ionisation
energy to our body. (iv) Heat of solution : It is the amount of heat
The energy released by the combustion of foods or evolved or absorbed (i.e., change in enthalpy) when one
fuels is usually compared in terms of their combustion mole of the solute is dissolved completely in excess of

E3
energies per gram. It is known as calorific value. The the solvent (usually water). For example,
amount of heat produced in calories or Joules when one NH 4 Cl(s)  H 2 O(l)  NH 4 Cl(aq.); H   3.90 kcal
gram of a substance (food or fuel) is completely burnt BaCl 2 (s)  H 2 O(l)  BaCl 2 (aq.); H   2.70 kcal
or oxidised.
(v) Heat of hydration : It is the amount of heat
When methane burns, 890.3 kJ mol–1 of energy is evolved or absorbed (i.e change in enthalpy) when 1 mole
released.
CH 4 (g)  2O 2 (g)  CO 2 (g)  2 H 2 O(l); H CH 4  890 .3 kJ
1 mole (16g)

So, the calorific value of methane =

ID of an anhydrous or a partially hydrated salt combines
with the required number of moles of water to form a
specific hydrate. For example,
CuSO 4 (s)  5 H 2 O(l)  CuSO 4 . 5 H 2 O(s); H   18 .69
U
890 .3 (vi) Heat of vapourisation : When a liquid is
  55 .6 kJ / g
16 allowed to evaporate, it absorbs heat from the
(b) Enthalpies of formation : Enthalpies of surroundings and evaporation is accompanied by
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formation of various compounds, which are not directly increase in enthalpy. For example: 10 .5 k cals is the
obtained, can be calculated from the data of enthalpies increase in enthalpy when one mole of water is allowed
of combustions easily by the application of Hess's law.
to evaporate at 25 o C . When the vapours are allowed to
Heat of reaction   Heat of combustion of reactants condense to liquid state, the heat is evolved and
–  Heat of combustion of product s. condensation of vapour is accompanied by decrease in
D

(iii) Heat of neutralisation : It is the amount of enthalpy.

heat evolved (i.e., change in enthalpy) when one The evaporation and condensation can be
equivalent of an acid is neutralised by one equivalent of represented as,
U

a base in fairly dilute solution, e.g., Neutralisation H 2 O(l)  H 2 O(g); H   10 .5 kcals (43 .93 kJ )
reactions are always exothermic reaction and the value H 2 O(g)  H 2 O(l); H   10 .5 kcals (43 .93 kJ )
of H is (ve ) .
Thus the change in enthalpy when a liquid
ST

HCl(aq.)  NaOH (aq.)  NaCl (aq.)  H 2 O changes into vapour state or when vapour changes into
liquid state is called heat of vapourisation.
H   13 .7 kcal
(vii) Heat of fusion : When a solid is allowed to
The heat of neutralisation of a strong acid against melt, it changes into liquid state with the absorption of
a strong base is always constant (13 .7 kcal or heat (increase in enthalpy) and when a liquid is
1
57 kJ mole ) . It is because in dilute solutions all strong allowed to freeze, it changes into solid with the
acids and bases ionise completely and thus the heat of evolution of heat (decrease in enthalpy). The change in
neutralisation in such cases is actually the heat of enthalpy of such type of transformations is called
enthalpy of fusion. For example,
formation of water from H  and OH  ions, i.e.,
H 2 O(ice)  H 2 O(liquid ); H   1.44 kcals ( 6.02 kJ )
H   OH   H 2 O; H   13 .7 kcal
H 2 O (liquid )  H 2 O (ice); H   1.44 kcals ( 6.02 kJ )
 Thermodynamics and Thermochemistry 413
(viii) Heat of precipitation : It is defined as the (1) Levoisier and Laplace law : According to this
amount of heat liberated in the precipitation of one law enthalpy of decomposition of a compound is
mole of a sparingly soluble substance when solutions of numerically equal to the enthalpy of formation of that
suitable electrolytes are mixed, for example compound with opposite sign, For example,

Ba 2   SO 42  (aq)  BaSO 4 (s): H   4 . 66 kcal C(s)  O2  CO 2 (g); H  94 .3 kcal

(ix) Heat of sublimation : Sublimation is a CO 2 (g)  C(s)  O2 (g); H  94 .3kcal

process in which a solid on heating changes directly
into gaseous state below its melting point. (2) Hess's law (the law of constant heat
summation) : This law was presented by Hess in 1840.
Heat of sublimation of a substance is the amount

60
According to this law “If a chemical reaction can be
of heat absorbed in the conversion of 1 mole of a solid
made to take place in a number of ways in one or in
directly into vapour phase at a given temperature
several steps, the total enthalpy change (total heat
below its melting point.
change) is always the same, i.e. the total enthalpy
I2 (s)  I2 (g) ; H   62 .39 kJ change is independent of intermediate steps involved in

E3
Most solids that sublime are molecular in nature the change.” The enthalpy change of a chemical reaction
e.g. iodine and naphthalene etc. depends on the initial and final stages only. Let a
substance A be changed in three steps to D with
H sub .  H fusion  H vaporisation
enthalpy change from A to B, H 1 calorie, from B to
(3) Experimental determination of the heat of C, H 2 calorie and from C to D, H 3 calorie. Total
reaction : The heat evolved or absorbed in a chemical
reaction is measured by carrying out the reaction in an
apparatus called calorimeter. The principle of
measurement is that heat given out is equal to heat
ID enthalpy change from A to D will be equal to the sum of
enthalpies involved in various steps, Total enthalpy
change H steps  H1  H 2  H 3
U
taken, i.e., Q  (W  m)  s  (T2  T1 ), Now if D is directly converted into A, let the
enthalpy change be H direct . According to Hess's law
Where Q is the heat of the reaction (given out), W
H steps  H direct  0, i.e. H steps must be equal to H direct
is the water equivalent of the calorimeter and m is the
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mass of liquid in the calorimeter and s its specific heat, numerically but with opposite sign. In case it is not so,
T2 is the final temperature and T1 the initial say H steps (which is negative) is more that

temperature of the system. Different types of H direct (which is positive), then in one cycle, some
calorimeters are used but two of the common types are, energy will be created which is not possible on the
(i) Water calorimeter and (ii) Bomb calorimeter basis of first law of thermodynamics. Thus, H steps
D

Bomb calorimeter : This is commonly used to find must be equal to H direct numerically.
the heat of combustion of organic substances. (i) Experimental verification of Hess's law
Since the reaction in a bomb calorimeter proceeds
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(a) Formation of carbon dioxide from carbon

at constant volume, the heat of combustion measured is First method : carbon is directly converted into
E CO 2 (g).
(W  m )(t 2  t1 )  s
ST

E   M kcal C(s)  O2 (g)  CO 2 (g); H  94 .0 kcal

w1
Second method : Carbon is first converted into
Where M is the molecular mass of the substance,
CO (g) and then CO (g) into CO 2 (g) , i.e. conversion has
w 1 is the weight of substance taken, W is the water
been carried in two steps,
equivalent of calorimeter, m is the mass of liquid in the
1
calorimeter and s is the specific heat of liquid. C(s)  O 2  CO (g) ; H  26 .0 kcal
2
H can be calculated from the relation, 1
CO (g)  O 2  CO 2 (g); H   68 .0 kcal
H  E  nRT 2
Laws of thermochemistry Total enthalpy change C(s) to CO 2 (g);
H  94 .0 kcal
 414 Thermodynamics and Thermochemistry
(b) Formation of ammonium chloride from dissociation energy depends upon the nature of bond
ammonia and hydrochloric acid: and also the molecule in which the bond is present.
First method When a molecule of a compound contains more than
NH 3 (g)  HCl  NH 4 Cl(g); H   42 .2 kcal one bond of the same kind, the average value of the
dissociation energies of a given bond is taken. This
NH4Cl(g)+aq= NH4Cl(aq); H = + 4.0 kcal
average bond dissociation energy required to break each
NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38 .2 kcal bond in a compound is called bond energy.

Second method Bond energy is also called, the heat of formation

of the bond from gaseous atoms constituting the bond
NH 3 (g)  aq  NH 3 (aq); H  8.4 kcal

60
with reverse sign.
HCl(g)  aq  HCl(aq); H  17 .3 kcal
H(g)  Cl(g)  H  Cl (g); H   431 kJ mol 1
NH 3 (aq)  HCl(aq)  NH 4 Cl(aq); H  12 .3 kcal
Bond energy of H  Cl   (enthalpy of formation)
NH 3 (g)  HCl(g)  aq  NH 4 Cl(aq); H  38 .0 kcal  (431 )   431 kJ mol 1

E3
(ii) Applications of Hess's law
Consider the dissociation of water molecule which
(a) For the determination of enthalpies of consists of two O  H bonds. The dissociation occurs in
formation of those compounds which cannot be two stages.
prepared directly from the elements easily using
H 2 O(g)  H(g)  OH (g); H  497 .89 kJ mol 1
enthalpies of combustion of compounds.
(b) For the determination
extremely slow reactions.
(c) For the determination
of

of
enthalpies of

enthalpies
ID
of
OH (g)  H (g)  O(g); H  428 .5 kJ mol 1

The average of these two bond dissociation

energies gives the value of bond energy of O  H.
U
transformation of one allotropic form into another.
Bond energy of O  H bond
(d) For the determination of bond energies.
497 .8  428 .5
  463 .15 kJ mol 1
H reaction   Bond energies of reactants – 2
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 Bond energies of products. Similarly, the bond energy of N  H bond in NH 3

(e) For the determination of resonance energy. is equal to one – third of the energy of dissociation of
(f) For the determination of lattice energy. NH 3 and those of C  H bond in CH 4 is equal to one –

Bond energy or Bond enthalpies fourth of the energy of dissociation of CH 4 .

D

When a bond is formed between atoms, energy is 1664

Bond energy of C  H   416 kJ mol 1
released. Obviously same amount of energy will be 4
required to break the bond. The energy required to
[CH 4 (g)  C(g)  4 H(g); H  1664 kJ mol 1 ]
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break the bond is termed bond dissociation energy. The

more precise definition is, Applications of bond energy

“The amount of energy required to break one mole (1) Heat of a reaction   Bond energy of
ST

of bond of a particular type between the atoms in the reactants –  Bond energy of products.
gaseous state, i.e., to separate the atoms in the gaseous (2) Determination of resonance energy : When a
state under 1 atmospheric pressure and the specified compound shows resonance, there is considerable
temperature is called bond dissociation energy.” difference between the heat of formation as calculated
For example, H  H (g)  2 H (g); H   433 kJ mol 1 from bond energies and that determined
experimentally.
Cl  Cl(g)  2Cl (g); H   242 . 5 kJ mol 1
Resonance energy = Experimental or actual
1 heat of formation – Calculated heat of formation.
H  Cl(g) H(g)  Cl(g); H   431 kJ mol

The bond dissociation energy of a diatomic

molecule is also called bond energy. However, the bond
 Thermodynamics and Thermochemistry 415
(c) 0
(d) Always positive
5. A well stoppered thermos flask contains some ice
 T  cubes. This is an example of a [AIIMS 1992]
 Joule thomson coeffient    
 p  H (a) Closed system
For cooling   ve (b) Open system

For Heating   ve (c) Isolated system

Neither cooling nor heating   0 (d) Non-thermodynamic system

60
6. Identify the intensive quantity from the following
 The temperature at which a real gas shows neither
cooling nor heating effect on adiabatic expansion [IIT JEE 1993]
(i.e.,   0 ) is called inversion temperature. (a) Enthalpy and temperature
 Hydrogen has highest calorific value. (b) Volume and temperature

E3
 13 .7 Kcal / mol  57 KJ / mol (be cause of 1 cal =4.2 (c) Enthalpy and volume
Joule) (d) Temperature and refractive index
 Enthalpy of fusion of ice per mole is 6 KJ . 7. Which of the following units represents the
 Order of bond energy in halogen largest amount of energy[CPMT 1989; MP PET 2000]
Cl2  Br2  F2  I2 .

 Heat of vapourisation of water per mole is 10.5

KCal.
 The heat of reaction is independent of the time
ID 8.
(a) Electron volt
(c) Joule
(b) Erg
(d) Calorie
Energy equivalent to one erg, one joule and one
calorie is in the order [NCERT 1980; CPMT 1997]
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consumed in the process.
(a) 1 erg 1 joule 1 calorie (b) 1 erg 1 calorie 1 joule

(c) 1 calorie 1 joule 1 erg (d) 1 joule 1 calorie 1 erg

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Basic concepts
D

1. Internal energy of an ideal gas depends on

(a) Volume (b) Temperature
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(c) Pressure (d) None of these

2. Any series of operations so carried out that at the
end, the system is back to its initial state is called
ST

(a) Boyle's cycle (b) Reversible process

(c) Adiabatic process (d) Cyclic process
3. One calorie is equal to [CPMT 1988]

(a) 0.4184 Joule (b) 4.184 Joule

(c) 41.84 Joule (d) 418.4 Joule
4. The total internal energy change for a reversible
isothermal cycles is
(a) Always 100 calories per degree
(b) Always negative