Chemical Thermodynamics

Chemical Thermodynamics
Chapter I
Learning objectives
Reading this chapter would enable you to understand:
l Laws of Thermodynamics.
l Thermo Chemistry.
l Chemical equilibrium and its relation to free energy.
l Clasious clay peron equation and its application to vapour pressure of flammable
liquids.
Contents
1.1 Introduction
1.2 Terminology of thermodynamics
1.3 The first law of thermodynamics
1.4 The Joule-Thomson effect
1.5 Enthalpy
1.5.1 Relation between pressure-volume and work
1.6 Thermochemical definitions
1.7 Bond Energy
1.8 Hess's law of constant heat summation
1.9 Heat Capacity
1.10 Kirchoff's Equation
1.11 Entropy
1.12 Entropy change for an ideal gas
1.13 Free energy
1.14 The second law of thermodynamics
1.15 Gibbs -Helmholtz equation
1.16 Free energy change of an ideal gas in isothermal reversible change
1.17 The Clapeyron-Clausius equation
1.18 The third law of thermodynamics
1.19 Van't Hoff isotherm
Summing up
Self-assessment
1.1 Introduction
Thermodynamics literally means flow of heat. It is a branch of physical science

dealing with the quantitative relation between heat and mechanical energy.
Thus, in a broad sense, it deals with the relationship of heat to all other forms of
energy, light, kinetic energy, etc. The science of thermodynamics aims to
determine the efficiency of these engines i.e. the percentage of heat supplied
which is converted to mechanical energy. So for the engineer this information is
of utmost importance, because if the laws governing the transformation of heat
to energy are known, more efficient engines can be designed. Although,
originally the science of thermodynamics was meant to ascertain the efficiency
of heat engines, now it has found wider use in diverse branches of all physical
and chemical sciences.
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Fire Dynamics Book I - Fundamentals
1.2 Terminology of Thermodynamics
The thermodynamic system is defined as any portion of matter under

consideration, which is separated from the surroundings by real or imaginary
boundaries. The thermodynamic system may be homogeneous or
heterogeneous, but has to be macroscopic. A system is called homogeneous, if it
consists of one phase. i.e., its physical and chemical properties are identical
throughout the system.
On the other hand, a system is called heterogeneous, if it consists of parts (or

phases), each of which has different physical and possibly different chemical
properties.
The surrounding is the rest of the universe around the system. A system and its
surroundings are always separated by real (fixed or movable) or imaginary
boundaries, through which matter and energy may be exchanged between the
two.
Ordinarily, surroundings mean water or air or both.
The open system is a system, capable of exchanging both matter and energy (as
heat) with the surroundings. For example, plants and living-beings are all open
systems.
The closed system is a system, which is capable of exchanging only energy (as
heat or work) with the surroundings. For example, a sealed flask containing gas
(or matter) is a closed system.
The isolated system is a system, which can exchange neither matter nor energy
with the surroundings. For such a system, matter and energy remain constant.
There is no perfectly isolated system, but our universe can be considered as an
isolated system, since by definition it does not have any surroundings.
Extensive property is the property, which depends upon the amount of

substance present in the system. For example, total mass, volume, energy, etc of
a system are included in extensive property, since they cannot be determined
without considering the system as a whole.
Intensive property is the property, which is independent of the amount of

substance present in the system. For example, viscosity, surface tension,
refractive index, temperature, pressure, dielectric constant, density, specific
gravity, specific heat, vapour pressure of a liquid, etc are some of the important
intensive properties.
State of the system is a set of variables such as pressure, volume, temperature,

composition, etc, which describe the system. Thus, when one or more variables
undergo change, then the system is said to have undergone a change of state.
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The isothermal process is a process carried out at constant temperature. When

a system undergoes an isothermal process, the system is usually kept in contact
with a constant temperature bath (called a thermostat) and the system
maintains its temperature constant by the exchange of heat with the thermostat.
The adiabatic process is one in which no heat can leave or enter the system (i.e.,
thermally insulated). Thus, for carrying out the adiabatic process, the system is
carefully insulated from the surroundings. It may be pointed out that in an
adiabatic process, the temperature of the system may increase or decrease.
The isobaric process is carried out at constant pressure. For example, a reaction
taking place in an open vessel is always at atmospheric pressure and hence, such
a reaction is isobaric. In the isobaric process, change in volume takes place.
The isochoric process is one in which the volume of the system is kept constant.
The reversible process is one, when energy change in each step of the process
can be reversed in direction by merely a small change in a variable (like
temperature, pressure, etc.) acting on the system. A system that has undergone
a reversible process can be restored back to its original/initial state with an
infinitesimal change in the external system. To approach reversibility, two most
important requirements are: (a) the change must be performed slowly, and (b)
there must be no friction and no finite temperature differences. Reaction in the
Daniels cell is an example of a reversible process.
The Irreversible process is one in which the system or surroundings are not
restored to their initial state at the conclusion of the reverse process. All
naturally occurring processes are irreversible. They always tend to proceed in a
definite direction and if left to themselves, they will never proceed in the
opposite direction.
For example, a clock always runs down and cannot rewind itself. Other common
examples of irreversible process are: (1) flow of heat from a hotter to a colder
body; (2) expansion of gases from high-pressure regions to low-pressure
regions through orifices; (3) mixing of two gases.
Irreversible processes are also called "spontaneous processes", which means

that the process takes place in one direction.
State function is a thermodynamic property, which depends only on the state of

the system and is independent of the path followed (or chosen) to bring about
the change. For example, internal energy change (DE), enthalpy change (DH),
free energy change (DG), entropy change (DS), etc.
Internal energy: Every chemical system has some internal energy (E), which is
a function of the temperature, the chemical nature of the substance, and at times
the pressure and volume of the system. The magnitude of internal energy in a
given system of molecules is determined by the kinetic, rotational and
vibrational movement of molecules, and their component atoms, as well as by
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the way in which the molecules are put together, and the nature of individual
atoms. It is impossible to determine the absolute value of the internal energy of a
system. Fortunately, we are concerned only with the change in internal energy,
accompanying a chemical or physical change. This change in internal energy is
represented by DE. If E2 is the internal energy of the system in the final state and
E1 is the initial internal energy of the system (i.e., before change), then:
E  E2  E1
Internal energy is a state function as it depends only on the initial and final states
and not on the path followed between the states, i.e., no route is specified.
1.3 The First Law of Thermodynamics
As a result of a number of experimental observations, Helmhotlz, Clausius, and

Kelvin enunciated a generated law of nature, commonly known as the Principle
of the conservation of energy or the First law of thermodynamics, which may be
stated in different ways as follows:
i. "Energy can neither be created nor destroyed, though it may be converted

from one form to another.”
ii. "The total energy of an isolated system remains constant, although it may
change from one form to another.”
Convention of signs regarding heat (q) and work (w): The following sign
conventions are generally accepted in thermodynamics
i. Heat gained by the system is given a positive sign (+ q); while heat lost by the
system is given a negative sign (- q).
ii. The work done (w) by the system on the surroundings is given a positive
sign (+w); while work done on the system a negative sign (-w).
iii. A system containing a definite mass at a definite temperature possesses
definite internal energy E. Actual absorbed amount of internal energy is not
known, but the change in internal energy is indicated as DE =E2 - E1 , where E1
and E2 are the initial and final internal energies of the system respectively. If
E2 >E1, then DE is positive, and if E2 < E1, then DE is negative.
Mathematical formulation of the first law: Suppose heat supplied to the system
is q. A part of this heat may be used up by the system itself in increasing its
internal energy by DE, and the rest is used for performing external work, w.
Then, according to the first law:
q =DE +w
or DE= q - w ...(i)
For an infinitesimally small change, the equation (i) may be written as:
dE = dq - dw ...(ii)
where dE is the increase in energy; dq and dw represent small quantities of heat

absorbed and external work done by the system respectively.
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Equation (i) and (ii) are the mathematical forms of the first law.
In a cyclic process i.e., in which the system is subjected to a series of operations

such that it ultimately comes back to its initial state, so that the initial and the
final states becomes identical,
E1 < E2 or DE=0
DE = q - w = 0
or q - w = 0
or q = w
i.e., the work done is equal to the heat absorbed in a cyclic process.
Limitation of the first law of thermodynamics: This law merely states the exact
equivalence of various forms of energy involved, but provides no information
regarding the feasibility of the process. Moreover, this law does not say whether
a gas can diffuse from low pressure to high pressure or whether water itself can
flow uphill, etc.
1.4 The Joule-Thomson effect
The Joule-Thomson effect states "when a gas under high pressure is permitted
to expand to a region of low pressure, it suffers a fall in temperature".
M t t’ M’
P1 P2
T1P1V1 T2P2V2
Figure 1.1 Joule-Thomson effect
Suppose a volume V1 of a gas enclosed between the piston and the porous plug at
pressure P1 is forced through the plug by moving the piston inwards and allowed
to expand to a volume V2 at a lower pressure, P2 Then:
Word done on the system = - P1 V1

and work done by the system = P2 V2
Net work done by the system, w = (P2 V2 - P1 V1)
But for an ideal gas, P1 V1 = P2 V2
w=0
Hence, DE = q - w = q - 0 = q [From the 1 law of thermodynamics]

st
Hence, for an ideal gas, there should be no rise or fall in temperature. However,
Joule-Thomson noticed a small, but definite fall in temperature in most of the
gases.
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As energy of the gaseous system falls, so DE = -ve. Also q = 0, since the expansion
is carried out adiabatically. Consequently, w =+ve, i.e. while expanding by
passing through a porous plug from a region of high pressure into a region of
low pressure, the gas must have done some work, and hence, temperature falls.
According to kinetic theory, work has to be done in order to overcome the

attractive forces existing between gas molecules. This work is done at the
expense of K.E. of molecules. In other words, K.E. decreases, thereby cooling
results.
1.5 Enthalpy
Suppose a change of a system from state A to B is brought about at constant

pressure (P), let the volume be increased from VA to VB. Suppose heat absorbed
by the system during the changes is q. Therefore, by the first law of
thermodynamics:
q = (E B - E A) + External work done (w)
where EB and E A are the initial and final internal energies of the system. But work
done (w) by the system, on the surroundings in increasing volume from VA to VB
= P (VB - VA)
q = (E B -E A) +P (VB -VA) = (EB +P VB) - (E A +P VA) =H B -H A = DH
where the quantity (E+PV) is known as enthalpy or heat content of the system
and is denoted by H. Thus, enthalpy change (DH) is equal to the heat
absorbed (g).
Since E is a state (or definite) property and P and V are definite properties of a
system, it follows H is also a definite property, depending upon the state of the
system. Since HB and HA are definite properties, obviously DH, like DE, is a
definite or state property, depending only on the initial and final states of the
system. Thus the heat content or enthalpy change,
DH= (EB +P VB) - (EA +P VA) = (E B -E A) +P (VB - VA)

or DH=DE+PDV.
i. At constant pressure, DH > DE.
ii. If volume is constant, i.e., DV= 0, then
DH = DE
Thus, at constant volume, enthalpy change or heat absorbed,
(DH) = Change in internal energy (DE).
1.5.1 Relation between Pressure-volume and Work
Consider a certain amount of a gas enclosed in a cylinder of cross-sectional area

‘A' and fitted with a hypothetical, weightless and frictionless piston. Allow the
gas to expand against the opposing pressure, P (see Figure 1. 2). If the pressure
is reduced by a very small amount dP, the piston will be forced to move upward,
due to the expansion of the gas by a small distance dl.
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The corresponding work associated with the change, dw, is given by:
P
Piston
Area A
Vinitial
Vfinal
Figure 1.2 Work in P-V form
dw = Force x Distance
But pressure = Force / Area
dw = Pressure x Area x Distance
= P x A x dl
But the product A x dl is the volume swept by the piston, dV.,
dw = P.dV
This is nothing but the work done when the volume changes by a very small
amount dV against pressure P.
If the volume changes from V initial to V final, then the total work done by the gas is
obtained by integration.
Final V Final
Total w ork done   dw  w   P .dv
Initial V initial
If the external pressure (P) is constant, then:

V2
w  P dv  P(V final  Vinitial )  PV
V1
Relation between DH and DE in case of gaseous reaction:

Consider a reaction involving gases. Let:
V initial = total volume of the gaseous reactants;
V final = total volume of gaseous products;
n initial = number of moles of gaseous reactants;
n final = number of moles of gaseous products;
T = constant temperature;
and
P = constant pressure.
Then, from ideal gas laws, we have:

PV initial = n initial RT
and PV final = n final RT
P (V final - V initial) = (n final - n initial) RT
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or PV  ng .RT
but H  E  PV (From 1st law)
H  E  ng .RT ..(i)
where R = gas constant

= 0.08206 L - atm K-l mol -1 = 8.343 J K-l mol -l
Equation (i)can be utilised in converting DH value into DE value, and vice versa
in reactions involving gaseous reactants and/or products.
i. In case of expansion, Dng is positive, so DH > DE.
ii. In case of contraction, Dng is negative, so DH < DE.
iii. For no change in volume, Dng = 0, so DH = DE.
1.6 Thermochemical definitions
(1) Heat of reaction (DH) is the difference between the heat contents (or
enthalpies) of the products and the reactants, when molar quantities of the
reactants, indicated by the balanced chemical equation, react completely or
mathematically, heat of reaction,
DH = Enthalpy of product - Enthalpy of reactant.
Example: The thermochemical equation:

2 H 2 ( g )  O2 ( g )  2 H 2O(l ); H  285.9kJ
indicates that when 2 moles of gaseous hydrogen combine with 1 mole of
gaseous oxygen to produce 2 moles of liquid water, the heat content of the
system decreases by 285.9 kJ or the reacting system loses 285.9 kJ. Hence, the
heat of the above reaction is -285.9 kJ.
(2) Enthalpy (or heat) of combustion (DH) of a compound or an element is the

change in heat content, when 1 mole of the substance is completely burnt in
excess of oxygen. Since combustion reactions are always exothermic, heat of
combustion is always negative.
Example: Heat of combustion of methane (CH4) is - 890.2 kJ mol-1.

CH 4 ( g )  2O2 ( g )  CO2 ( g )  2 H 2O(l ); H  890.2kJ
(3) Enthalpy (or heat) of neutralisation of an acid (or base) is the change in heat
content (DH) when one gram equivalent of the acid (or base) in dilute aqueous
solution is neutralised by one gram equivalent of a dilute aqueous solution of a
base (or acid).
HNO3 (aq )  NaOH (aq )  NaNO3 (aq )  H 2O; H  57 kJ
HCl (aq )  KOH (aq )  KCl (aq )  H 2O; H  57 kJ
These thermochemical equations imply that heat of neutralisation (DH) of a
strong acid (HNO3 or HCI, etc.) by a strong base (NaOH, KOH, etc.) and vice
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versa is - 57kJ, no matter what acid or base is employed. This is because the heat
of neutralisation is in fact the heat of formation of 1 mole of water from 1 g
equivalent H ions (of acid) and 1 g equivalent OH ions (of base), while the other
+ -
ions of the strong acid and base remain unaltered. Thus:
A  H   B   OH   A  B   H 2O; H  57 kJ
Strong acid Strong base Salt
or H   OH   H O H  57 kJ
2
H   Cl   Na   OH   Na   Cl   H 2O; H  57 kJ
Strong acid Strong base Salt
or H   OH  H 2O H  57 kJ
( Ofacid ) ( Ofbase )
(4) Enthalpy (or heat) of formation (DHf) of a compound is the change in heat
content or enthalpy (DH), when one mole of the compound is formed from its
elements in their commonly occurring (or standard) states.
Example: The equation:

C ( graphite)  2 H 2 ( g )  CH 2 ( g ); H f  74.8kJ
indicates that when one mole of methane gas is formed from its elements,
carbon and hydrogen, 74.8 kJ of heat is given out. Thus, enthalpy (or heat) of
formation of methane is- 74.8kJ mol-1.
Enthalpy of formation and its stability: The enthalpy of formation is an important

property of a compound and is related to its stability. The stability of a compound
is inversely proportional to its heat content (or intrinsic energy). In other words,
lower the enthalpy of formation of a compound, more is its stability.
A compound with enthalpy of formation (DHf) is positive means that the energy
content of the compound is more than the energy contents of its constituent
elements. Hence, such a compound is unstable. On the other hand, a compound
with enthalpy of formation (DHf) is negative means that the energy content of
the compound is less than that of its constituent elements. Consequently, such a
compound is stable. Consequently, a compound with positive enthalpy of
formation is unstable and one with negative enthalpy of formation is stable.
Thus, it is quite clear that the relative stability of various compounds is inversely
proportional to their enthalpies of formation.
Example : The enthalpies of formation (DHf) of HI, HBr, HCI and HF are
+ 26.9, -36.1- 92.4 and - 161.7 kJ mol respectively. Consequently, HI is least
-1
stable, while HF is most stable. In other words, the stability of these halides is in
the order.
HF > HCI > HBr > HI.
(5) Enthalpy (or heat) of fusion of a substance is "the heat change in converting I
mole of it from the solid to the liquid phase at its melting point." Heat of fusion is
always positive, because heat is needed to overcome the intermolecular forces
between the constituent particles of a solid.
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Example: Heat of fusion of water,

H 2O( s )  H 2O(l ); H fu s io n  6 .0 k J
is +6.0kJ mol .
-1
(6) Enthalpy (or heat) of vaporisation of a liquid is the heat change in converting
1 mole of the substance from liquid to the gaseous state at its boiling point.
Example: Heat of vaporisation of water,

H 2O( s )  H 2O( g ); H vap  42.00kJ
is +42.4kJmol .
-1
(7) Enthalpy (or heat) of sublimation of a solid is the heat change in converting 1
mole of a solid directly into its vapour at a given temperature, below its melting
point.
Example: Heat of sublimation of iodine,

I 2 ( s )  I 2 ( g ); H sub  62.00kJ
is + 62.4 kJ mol I
-1
1.7 Bond Energy
Bond energy can be defined as the average amount of energy required (or
enthalpy change involved) during the breaking of one mole (or Avogadro's
number) of bonds of the same type, present in the molecules of a gaseous
compound, into gaseous fragments, atoms, radicals, etc. Bond energy is
sometimes also called the enthalpy or heat formation of the bond.
The strength of the bond joining the two atoms together depends upon the
environment. For example, the energy needed to break the O - H bond in water
(H-O-H) to give the H atom and OH groups is 118 kcal mol -1 ; while the energy
needed to break the O - H bond in the hydroxy radical (-O-H) to give O and H
atoms is 102 kcal mol . The difference in the two values can be related to the fact
-1
that OH radicals are much more reactive than oxygen atoms in combining with
H atoms to form more stable molecules. These bond-breaking reactions can be
written as:
H2O(g) ®OH(g)+H(g) ; DH = 118 kcal mol
-1
OH(g) ®O(g) + H (g) ; D H - = 102 kcal mol

-1
or H2 O(g)® O(g) + 2H(g); D H = 220 kcal mol

-1
Thus, the total dissociation energy of water into 2 H and O is 220 kcal mol.
Hence, the average bond energy of O - H bond in water is 110 kcal mol .
-1
In a polyatomic molecule (i.e., containing more than one covalent bonds) such
as ABn the average bond energy is calculated by dividing the heat of formation of
the compound ABn by n. For example, in case of the methane (CH4) molecule,
having four C - H bonds, the mean bond energy is one-fourth of the heat of
formation of methane. Thus, average bond energy of C - H bonds in methane
Heat of formation of methane 396kcalmol 1

   99.0kcalmol 1
4 4
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Alternatively, the C - H bond energy in methane may be calculated as the

average of the total dissociation energy of the C - H bonds in the series of
different dissocation species.
Thus, in methane,
CH4(g) ® CH3(g) + H(g); DH = 104 kcal mol -1
CH3 (g) ® CH2(g) + H(g); DH = 106 kcal mol
-1
CH2(g) ® CH(g) + H(g); DH = 106 kcal mol

-1
CH(g) ® C(g)+H(g) ; DH = 82 kcalmol-1

1
So the bond dissociation energy value is equal to [104 +106 + 106 + 82]
4
= 99.5 kcal mol-1
Calculation of bond energies: In a reaction between gaseous species, certain

bonds in reactants are broken and some new bonds are formed in products. So
the sum of enthalpy changes for bonds broken and bonds formed gives the
enthalpy change for the reaction, i.e.,
H rxn  H (bonds broken)  H (bonds formed)
The enthalpy of reaction in gas phase is also given by:
H rxn  BE (reactants)  BE (products)

= Total energy input - Total energy released
where BE stands for average bond energy and is the summation sign. Variation
of bond energy: (i) With the size of the atoms: Bond energy decrease with the
increase in the size of atoms. For example, bond energies of H-F and H-CI bonds
are 56.5 kJ mol and 43.1 kJ mol respectively.
-1 -1
(ii) With electronegativity bond energy increases with increase in difference in

electronegativities of the atoms involved in the bond. For example, bond energy
of H-CI = 43.1 kJ mol-1 with electronegativity difference of 0.9 units; while bond
energy of H-F = 56.5 kJ mol with electronegativity difference of 1.9 units.
-1
Applications of bond energies: (1) Calculation of heat reaction:

Suppose we want to calculate the heat of reaction:
C2H4(g) + H2(g) ® C2H6 (g)
given that bond dissociation energy of C=C is 146 kcal mol ; C-C is 83 kcal mol ;
-1 -1
H-H = 102 kcal mol and C -H = 99 kcal mol

-1 -1
Now heat of reaction
= - [Bond energies of (products - reactants)]
But in the given reaction:

H H H H H
H
C = C + (g) + (g) H C C H (g)
H
H H H H H
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(i) the four C - H bonds (i.e., 2 on each carbon atom) remain unaffected ; (ii) the
double bond (C = C) in C2H4 break up ; (iii) the bond (H-H) in Hg breaks up; (iv)
the product has one C - C bond plus two C - H bonds extra.
H reaction  [(H C C  2 H C  H )  (H C C  H H  H )]
= -(83+2 x 99)+(146+102)kcal=-281+248kcal=-33kcal.
Calculation of heat of formation:
Heat of formation can be calculated by taking the sum of the average bond
energies involved in the molecule. For example, the heat of formation of n-
pentane,
H H H H H
5C(g)  12 H(g)  H C C C C C H (g)
H H H H H
Can be calculated as follows. Since there are four C-C and twelve C-H bonds
H f forC5 H12  [4  B.E. for C  C  12  B.E. for C  H ]

 [4  79.5  12  98.5kcalmol 1  1,499.2kalmol 1
1.8 Hess's Law of Constant Heat Summation
According to Hess’s low “the heat change in a particular reaction is always

constant and is independent of the manner in which the reaction takes place." In
other words, the overall heat change in a chemical reaction carried out either at
constant pressure (or at constant volume) is the same, irrespective of the fact
whether the reaction proceeds in one or several stages. This law is a direct
consequence of the first law of thermodynamics, according to which heat
change, DH (enthalply change) or DE (internal energy change) of a reaction is
state function, i.e., dependent only on the initial and final states of the system.
Example: Let us consider the formation of CO2. Carbon might be burned

directly to CO2. On the other hand, carbon might be burned to carbon monoxide
and then the latter burnt to carbon dioxide. The two procedures can be
represented as follows:
First procedure (in one-step only):

C(s) + O2(g) ® CO2(g) , DH = - 393.5 kJ
Second procedure (in two-steps):
1
C(s)  O 2 (g)  O 2 (g) DH1 = -110.5 kJ
2
1 DH2 = -283.0 kJ
CO(g)  O 2 (g)  O 2 (g)
2
Adding: C(s)+ O2(g)® CO2(g); DH=- 393.5 kJ
Applications: Hess's law has made it clear that thermochemical equations are
simple algebraic equations, which can be added, subtracted, multiplied and
divided by any number. This has led us to compute indirectly heat of formation,
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heat of transition, etc., which cannot be measured experimentally.
(i) Calculation of heat of reaction: Heat of certain reactions is extremely difficult

to measure. However, Hess's law makes it possible. For example, it is extremely
difficult to measure the heat evolved when carbon burns in oxygen to form
carbon monoxide.
1
C(s)  O 2 (g)  CO(g); DH= ?
2
But heats of combustion of C to CO2 and CO and CO2 are known:
C(s) + O2(g) ® CO2(g); DH= -393.5 kJ ...(i)
1
CO(g)  O 2 (g)  CO 2 (g) DH= -283.0 kJ ...(ii)
2
C(s) + O2(g) ® CO2(g); DH= -393.5 kJ
1
- CO(g)  O 2 (g)  CO 2 (g) DH= 283.0 kJ
2
1
C(s)  O 2 (g)  CO(g); DH= -393.5+283.0 kJ
2
= -110.5kJ
Thus, DH for the combustion of carbon to carbon monoxide is -110.5 kJmol -1
(ii) Calculation of heat of formation: The heats of formation of compounds,

which either cannot be prepared directly from their elements or which
synthesis reaction proceeds too slow to allow direct measurement, can be
computed indirectly with the help of Hess's law by using their heat of
combustion values, which can be measured easily.
Suppose we want to calculate the heat of formation of hydrocarbon, CxHy. Let its
heat of combustion (DH) be ‘a' kJ mol i.e.,
-1
 y y DH = a kJ ...(i)
C x H y   x  O2(g)  CO 2 (g)  H 2O(l );
 4 2
Suppose heats of formation of CO2 and H2 O are ‘b' and ‘c' kJmol respectively,
then:
C(s) + O2(g) ® CO2(g); DH= b kJ...(ii)
1
H 2 (g)  O 2 (g) H 2 O(g); DH= c kJ.....(iii)
2
y
Multiplying (ii) by x, (iii) by and writing (i) in the reverse direction, we get:
2
y  y
xCO2 ( g )  H 2O(l )  C x H y   x  O2 ( g ); DH= -a kJ
2  4
xC ( s )  xO2 ( g )  xCO2 ( g ); DH= bx kJ
y y y y
H 2 (g)  O 2 (g)  H 2 O(l) ;  c kJ
2 4 2 2
13/MITSDE
y  1 
Adding: xC ( s )  H 2 ( g )  Cx H y ; H   bx  cy  a kJ
2  2 
Hence, the heat of formation (DHf) of CxHy is :
 1 
 bx  cy  a kJ
 2  mol -1
(iii) Calculation of heat of transition: The following example will illustrate the
heat of transition of C (graphite) to C (diamond). Suppose heats of combustion
(H) of graphite and diamond are x and y kJ mol -1 respectively, i.e.,
C ( graphite)  O2 ( g )  CO2 ( g ); H  xkJ .....(i )
C (diamond )  O2 ( g )  CO2 ( g ); H  ykJ .....(ii )
Subtracting (ii) from (i), we get:

C ( graphite)  C (diamond ) ; DH= (x-y) kJ
Hence, the heat of transition (DHf) of graphite into diamond is (x-y) kJmol
-1
1.9 Heat Capacity
Heat capacity (c) of a substance is "the amount of heat needed to raise the
temperature of 1g of it through 1 C"; whereas molar heat capacity (C) is the
0
amount of heat required to raise the temperature of 1 mole of it through 10C.

Molar heat capacity is of two types:
i. Molar heat capacity at constant volume (Cv) is measured by keeping the
volume constant. It is given by:
 E 
Cv   
 T  v
ii. Molar heat capacity at constant pressure (Cp) is measured by keeping
pressure constant. It is given by:
 H  dq
Cp    
 T  p dT
Relation between Cp and Cv: H = E + PV
When the temperature is changed; then DH =DE + D(PV)
or
H E ( PV )
 
T T T
or C p  Cv 
( PV ) .......(i)
T
For 1 mole of any ideal gas P1 V2 = -RT2 and P1 V1 = RT1,
so that D(PV) = R (T 2-T2)=RT
For 1 mole of gas C p  Cv  R .........(ii)
For solids and liquids, DH = DE and D(PV) = 0, so that Cp = Cv.
14/MITSDE
1.10 Kirchoff's Equation
The variation of heat of reaction with temperature can be derived with the help of
the first law of thermodynamics. Consider a simple hypothetical reaction in
which the reactant in state A at the temperature T1 yields the product in state B at
the temperature T2 . We may proceed from state A at T1 to B at T2 by two paths as
shown in Figure 1.3.
D H2
At T2 B (Product)
Path 1
Cp (T2 - T1) Cp’ (T2 - T1)
Path 2
At T1 A
(Reactant) D H1
Figure 1.3 Alternative paths for changing reactants into products
Let DH1 be the heat of reaction at temperature T1 and DH2 be the heat of reaction
at temperature T2. Again let Cp and Cp’ represent respectively the mean molar
heat capacity of the reactants and product at constant pressure.
i. In the first path, the reactants are first heated from T1 to T2 and then
allowed to react at the higher temperature, T2. Therefore, the total heat
change involved is given by:
DH (path1) = Cp (T2 -T1) + DH2
ii. In the second path, the reactants are allowed to react at the lower
temperature, T1, and then the products are heated to T2. The value of total
heat change (DH) for this path is as follows:
DH (path2) = DH1 + C'p (T2 -T1)
According to the first law of thermodynamics,
DH (path1) = DH (path 2)
or Cp (T2 -T1) + DH2 = DH1 + C'p (T2 -T1)
. H 2  H1
..  C ' p C p  C p ........(iii)
(T2  T1 )
where DCp = difference in the heat capacities of the products and the
reactants at constant pressure.
This equation (iii), is called Kirchoff's equation.
The above equation may also be written as:
H 2  H1 ........... [where DT=T2-T1]

 C p
T
15/MITSDE
If DT is small, then it takes the form:
  (H ) 
   C p .......(iv)
 T  p
Similarly, we can obtain the equation for the variation of DE with temperature,
namely:
E2  E1
 Cv ........(v)
T
or if DT is small, then
  (E )  ......(vi)
   Cv
 T  v
1.11 Entropy
Entropy of a system is a measure of randomness or disorder of the system and is

denoted by the symbol S. It is a state function (i.e., the change in entropy is
independent of path). It can also be regarded as the measure of "unavailable
energy".
The change in entropy of a system (or a reaction) is given by:
DS = S final - S initial = S2 - S1
Entropy is expressed in Joule deg (JK ).

-1 -1
Physical significance of entropy: Entropy has been regarded as "a measure of

disorder or randomness of a system". Thus, when a system goes from a more
orderly to less orderly state, there is an increase in its randomness, and hence,
entropy of the system increases. Conversely, if the change is one in which there
is an increase in orderliness, there is a decrease in entropy. For example, when a
solid changes to a liquid, an increase in entropy takes place, because with the
breaking of the orderly arrangement of the molecules in the crystal to the less
orderly liquid state, the randomness increases. Conversely, the process of
solidification brings about a more orderly state and consequently, there is a
decrease in entropy. The process of vaporisation produces an increase in
randomness in the distribution of molecules, hence an increase in entropy. This
concept of entropy as a measure of orderliness or randomness, has led to the
conclusion that "all substances in their normal crystalline state at the absolute
zero temperature would be in the condition of maximum orderly arrangement,
because all motion has essentially ceased at OK". In other words, entropy of a
substance at OK is minimum.
It may be added here that in any system, only a part of the total energy is made
available for useful work, since some energy is always dissipated (or wasted)
isothermally. This "unavailable energy" of the system is considered equal to the
product of the intensity factor and a capacity factor. The intensity factor is
referred to as the temperature, while the capacity factor is entropy. Thus, we can
say that entropy signifies the unavailable form of energy of the system.
16/MITSDE
1.12 Entropy Change for an Ideal Gas
Consider the reversible expansion of an ideal gas enclosed in a container, fitted

with a frictionless weightless, and movable piston at constant pressure, P. Let
the volume change from V1 to V2. Since the process is reversible, the pressure of
the gas is approximately equal to the external pressure against which the gas is
expanding at all stages. Hence, under these conditions, the work done by the
gas is maximum; and is equal to P.dV.
We know from the first law of thermodynamics:

dq = dE + dw = dE + P.dV
dV  dE RT 
 Cv .dT  RT  Cv  ;P  
V  dT V 
Dividing by T, we get:
dq dT dV
 Cv . R
T T V
dT dV  dq 
dS  Cv . R   dS 
T V  T 
Thus, for a definite change from state 1 to 2, the total change in entropy is
given by:
S2 T2 V
2
dT dV
 dS  S  C .
S1
v
T1
T
 R
V1
V
T2 V
 Cv .In  RIn 2 ..........(i)
T1 V1
The corresponding expression for n moles would be:
T2 V
S  nCv .In  RIn 2
T1 V1
V2 P2
 .........(ii)
V1 P1
But for an ideal gas:
T2 P
S  nCv .In  nRIn 1
T1 P2
T2 P
 nCv .In  nRIn 2 .......(iii)
T1 P1
(1) At constant temperature, i.e., when T1 = T2 then for isothermal expansion of
the gas, the equations (ii) and (iii) take the form:
V2 P1 V ........(iv)
S T  nRIn   2.303nR log 2
V1 P2 V1
(2) At constant pressure, i.e., when P1 = P2 the equation (iii):
S p  nC p In T2  2.303nC p log

T2
........(v)
T1 T1
17/MITSDE
In this equation Cv has been changed to Cp, because the change in temperature
has taken place at constant pressure.
(3) At constant volume, i.e., for an isochoric process, V1 = V2, so the equation (ii)
takes the form
T2 T
S V  nCv In  2.303nCv log 2 ........(vi)
T1 T1
1.13 Free Energy
Free energy of system, (denoted by the symbol ‘G" is a thermodynamic state

function, which is related to enthalpy and entropy as:
G = H - TS .......(i)
Free energy change (DG) of a system (or reaction) a measure of energy

available for doing useful work. Thus:
Energy available  Total energy   Non - available 
as useful work   available   form of energy 
     
or G = H - TS
The change in free energy between two states of a system,
or DG = G 2 - G1= (H2 - T2 S2 ) - (H1 - T1 S1 )

= (H 2 H1) - (T2 S2 - T1 S1 )= DH -(T2 S2 - T1 S1 )
whence, at constant temperature (i.e., T1 = T2):
G  H  TS ….(ii)
Physical significance of free energy: From the law of conservation, of

energy, the total heat energy supplied to the system,
q  E  Wexp ansion  Wnon exp ansion
 E  PV  Wnon exp ansion
 H  Wnon exp ansion ….(iii)
Now in a reversible change at constant temperature T, we have:

S  q T
q  T .S ......(iv)
From (iii) and (iv), we get:
T .S  H  Wnon exp ansion
or
H  TS  Wnon exp ansion

 G P.T .
18/MITSDE
or
 G P.T .  Wnon exp ansion ......(v)
i.e., -DG is a measure of non-expansion or useful work obtainable in a reversible

reaction at constant temperature and pressure. In other words, decrease in free
energy, during a process, is equal to the "useful work" obtainable from the
process.
Standard state for a substance is defined as the pure material in its most stable
form (gas, liquid or solid) at the external pressure of 1 atm and at the specified
temperature (most usually = 298 K). The standard state conventions are:
For a solid: The pure substance at 1 atm external pressure.

For a liquid: The pure substance at 1 atm external pressure.
For a gas: An ideal gas at 1 atm partial pressure.
For a solution: An ideal solution at 1 M concentration.
Standard free energy change (DG ) is defined as "the free energy change for a
0
process at 298 K in which the reactants in their standard states are converted
into the products in their standard states". Thus:
o o o
G  G ( p ro d u c ts )  G (reactants )
The value of DG0 for a reaction can be derived from the standard free energies of
formation (DG f). The standard free energy of formation (DG f) of a compound is
o o
defined as "the change in free energy, when I mol of the compound is formed
from its constituent elements in their standard states". Thus:
G o  G o ( products )  G o ( reac tan ts )
Sum of the standard  Sum of the standard 
 free energies of   free energies of
 


formation of products  formation of reactants 
It may be pointed here that "the standard free energy of formation of an element
in its standard state is zero".
Relation between (DG0 and equilibrium constant (Keq); The standard free energy
change (DG ) of a reaction is related to the equilibrium constant (Keq) by the
0
relation:
G o  2.303RT log K eq
where R = gas constant (= 8.314 JK-1 mol 1), T = temperature in Kelvin.
Relation between standard free energy changes and cell potential: We know that
decrease in free energy is equal to maximum useful work that can be obtained
from a process, i.e.,
 G  wmax
If the useful work involved is electrical work (e.g., in Daniel cell), then:
 G  wmax  electricalwork  nFE
19/MITSDE
where n = number of electrons involved in the cell reaction; E = emf

(or potential) of the cell, and F = Faraday (= 96,500 C).
O
If reactants as well products of the cell reaction are in their standard states
(i.e., 298 K and 1 atm), then:
 G o  nFE o
where DG = standard free energy change, and E = standard EMF (or potential)
0 0
of cell.
Feasibility of cell reaction: The cell reaction is feasible if- DG is positive (or
0
standard free energy change is negative). A positive value of DG0 shows that the
reaction may be feasible in the reverse direction.
1.14 The Second Law of Thermodynamics
Statements of the second law of thermodynamics: The law can be stated in the
following several ways:
i. It is impossible to convert heat completely into an equivalent amount of

work, without producing some other changes in some parts of the system.
ii. It is impossible for a self-acting machine, unaided by any external agency,
to convey heat from a body at a lower temperature to a body at a higher
temperature.
iii. Heat cannot pass by itself from a colder to a hotter body.
iv. Only a fraction of a given quantity of heat may be converted to work, when
it is allowed to flow from a body at a higher temperature to a body at a
lower temperature, and that its value depends on the temperature
difference and the higher temperature.
v. It is impossible to convert heat from a reservoir into work by a cyclic
process, without transferring it to a colder reservoir.
vi. All natural or spontaneous processes tend to take place in one direction,
and they cannot be reversed.
vii. The energy of the universe is constant, but the entropy approaches a
maximum or the universe is approaching a condition of maximum
randomness.
viii. All naturally occurring processes always tend to change spontaneously in
a direction, which will ultimately lead to equilibrium.
ix. There is a general tendency in nature for energy to pass from a more to a
less ordered form.
1.15 Gibbs -Helmholtz equation
We know: G=H-TS and H=E+PV

G=E+PV-TS
Upon differentiation we get:
dG=dE+PdV+VdP-TdS-SdT
But dq=dE+dw=dE+PdV......(1st law)
.
.. dG=dq+VdP-TdS-SdT
20/MITSDE
For reversible process:

dS=dq/T or T.dS=dq
.
. . dG=VdP-SdT
If pressure remains constant, i.e., dP = 0 then:

dG= - SdT ..........(i)
Let G1 = initial free energy of a system at T; and G 1 + dG 1 = initial free energy of

the system at T + dT, where dT is infinitesimally small and pressure is constant,
dG 1 = -S1 dT ….....(ii)
where S1 is the entropy of the system in the initial state.
Now suppose that the free energy of the system in the final state is G2 at T. Let G2 +
dG2 be the free energy of the system at T + dT in the final state, then:
dG 2 =-S 2 dT .........(iii)
where S2 is the entropy of the system in the final state.
Subtracting (ii) from (iii), we get:
dG 2 dG 1 =-(S 2 S1 )dT
or d (G )   SdT .…...(iv)
At constant pressure,
  (G )  .........(v)
 T   S
 
We know: G  H  TS
G  H
 S  ........(vi)
T
From (v) and (vi), we get:
G  H   (G ) 
 
T  T  P
or
  (G ) 
G  H  T  
 T  P
This equation is called the Gibbs-Helmholt equation in terms of free energy and
enthalpy changes at constant pressure.
Application of the Gibbs-Helmholtz Equations: Calculation of E.M.F. of a

reversible cell: Suppose the e.m.f. of a reversible cell, when operated at constant
pressure and constant temperature is E. Let n faraday, i.e., nF coulombs of
electricity is yielded by the cell, then:
Electrical work obtained = nFE

We know: Net electrical work = decrease in free energy
.
. . nF=- DG
21/MITSDE
Substituting in the Gibbs-Helmholtz equation, we have:

  (nFE ) 
 nFE  H  T  
 T  P
 E  ..
 H  nFT   . (n and Fare constant)
 T  P
 H  E 
E T 
nF  T  P
Thus, by knowing E (e.m.f. of the cell) and 
E  (i.e., Variation of e.m.f. with

 T 
temperature at constant pressure), the value of heat of reaction (DH) occurring
in the cell can be calculated.
Significance of the Gibbs-Helmholtz Equation: The Gibbs-Helmholtz

equation helps us in a better understanding of the force that causes the chemical
reaction to proceed forward. We know that if DG is negative, the reaction occurs
spontaneously, and if free energy of the reactants and the products are equal,
i.e., DG = 0, the reaction is in equilibrium. From the relation,
G  H  T .S
it is clear that DG is made up of two opposing parts, viz.,
i. DH: When the reaction is exothermic, DH is negative, so DG tends to be
negative and consequently, the reaction tends to the spontaneous. This is
supported by the fact that generally exothermic reactions at ordinary
temperature and pressure are spontaneous.
ii. TDS: If DS is positive, DG tends to be negative. Thus, physical and
chemical changes proceed spontaneously in a direction in which the
entropy increases. For example, a solid substance dissolves in the solvent,
because entropy (or randomness) of the system increases.
Criteria of the spontaneity of the process: For a reaction to be spontaneous, DG
must be negative. The DG is negative under the following condition:
i. If DH is negative, and DS is positive, since both factors make

DG negative.
ii. If both DH and DS are positive, and the magnitude of TDS > DH.
iii. If both DH and DS are negative, and the magnitude of DH > TDS.
DH DS -TDS DG Comment
- ve + ve -ve -ve at all T Spontaneous at all T

-ve -ve +ve -ve at low T Spontaneous at low T
+ ve at high T Non-spontaneous at high T
+ ve +ve -ve -ve at high T Spontaneous at high T
+ve -ve +ve +ve at all T Non-Spontaneous at all T
Table 1.1 Spontaneous and non-spontaneous reactions
22/MITSDE
1.16 Free Energy Change of an Ideal Gas in Isothermal Reversible

Change
We know: G=H-TS and H=E+PV
.
.. G= E+PV-TS
Upon differentiation, we get:
dG=dE+P . dV+V . dP -T.dS S.dT ......(i)
From 1 law, we have dq = dE + dw = dE + PdV .....(ii)

st
.
. . From (i) and (ii), we get :
dG=dq+V .dP-T.dS-S .dT ....(iii)
We know that for a reversible process,

dq
dS  orT .dS  dq
T
or
dq - T . dS = 0 ....(iv)
From (iii) and (iv), we get:

dG=V . dP S . dT .....(v)
If temperature is kept constant (isothermal change), i.e., dT=0, then the

equation (r) takes the form:
dG = V.dP ....(vi)
Free energy change from state 1 to 2 at constant temperature is given by:

P2 P2 dP ...(vii)
G  G2  G1   V .dP   PV
P1 P1 P
where P1 and P2 are the initial and final pressures respectively.
For n moles of an ideal gas: PV = nRT
. dP P2
. . G  nRT 
P P1
P
or G  nRTin 2
P1
. P V .....(viii)
. . G  2.303nRT log 2  2.303nRTkg 2
P1 V1
where V1 and V2 are the initial and final volumes respectively.
1.17 The Clapeyron-Clausius Equation
Consider a system consisting of only 1 mole of a substance, which exists in two

phases A and B. Let the temperature and pressure of the system be T and P
respectively. Suppose the free energy/mole of the substance in two phases is A
and B be GA and GB. The system being in equilibrium, so there is no free energy
change, i.e.,
23/MITSDE
GA =GB .....(i)
Let the temperature of the system be raised to T + dT, so that the pressure
becomes P+dP. Suppose the new free energies per mole of A and B phases be GA
+ dGA and GB + dGB respectively. As the two phases are still in equilibrium, so:
GA + dGA = GB + dGB .....(ii)
We know: G = H TS = E + PV TS ....(iii)
dG=dE+PdV+VdP-TdS-SdT ...(iv)
But dq=dE+dw =dE+PdV ....(v)
and dq/T=dS or TdS=dq ...(vi)
From (iv), (v) and (vi), we get :

dG = V.dP - S.dT ...(vii)
As the various equilibria considered here are such in which work done is only
due to volume change, so equation (vii) may be applied to phase A as well as B.
dGA=VA dP-SdT ...(viii)
and dGB=VB dP-SB dT ...(ix)
where VA and VB are the molar volumes of phase A and B respectively, and SA and
SB are their molar entropies.
From (vii), (viii), and (ix), we get:

VA.dP-SA-dT = VB.dP-SB.dT
or
dP S B  S A S ...(x)
 
dT VB  VA VB  VA
where DS = molar entropy change, and VB - VA is the change in volume when 1
mole of substance changes from A to B.
If molar heat of transition from phase A to B is q, then

DS=q/T ..(xi)
From (x) and (xi), we get:
dP q
 ...(xii)
dT T (VB  VA )
This is the Clapeyron-Clausius equation.
Applications:
i. Determination of latent heat from vapour pressure: If the vapour pressure at

two different temperatures of the two phases in equilibrium are known, then the
latent heat can be calculated by using the Clapeyron-Clausius equation,
In case of vaporisation. Vv >> Vt
or Vv -Vl=Vv
(The molar volume Vl is neglected in comparison with Vv)
24/MITSDE
The Clapeyron-Clausius equation takes the form:

dP L
 v
dT TVv
Assuming that the gas law (PV=RT) is applicable to vapour, we may substitute.
=RT/P, in above equation.
dP Lv P

dT RT 2
or
dP Lv .dT

P RT 2
Integrating, on the assumption than Lv is constant, over a small temperature
change, we get:
P2 Lv  1 1 
in    
P1 R  T1 T2 
P2 Lv T2  T1 
or in    ....(xiii)
P1 R  T1T2 
where P1 and P2 are the vapour pressure at T1 and T2 respectively. By substituting

these values, the molar heat of vaporisation, Lv can be computed with the help of
the Integrated Clapeyron-Clausius equation (xiii).
ii. To study the effect of pressure on boiling point: If the boiling point of a liquid at
one pressure and its latent heat of vaporisation are known, then boiling point of
liquid at another pressure can be computed with the help of the integrated
Clapeyron-Clausius equation (xiii).
iii. To study the effect of temperature on the vapour pressure of a liquid: If latent
heat (Lv) and vapour pressure of a liquid at one temperature are known, then
vapour pressure of liquid at another temperature can be calculated with the help
of the Interated claperyron-Clausius equation (xiii).
1.18 The Third Law of Thermodynamics
This law was stated by Nernst in 1906 and according to it: "at absolute zero, the
entropy of a perfectly crystalline substance is taken as zero".
At absolute zero, the kinetic energy is zero and the substances (element and
compounds) are in a rigid state, thereby providing them complete order. Due to
total lack of disorder, the entropy of all pure elements and compounds at
absolute zero is zero.
Calculation of absolute entropy values: Absolute value of entropy at room

temperature can be measured by determining heat capacities (Cp) of the
substance at different temperatures (T). Then, Cp values are plotted against T.
The area of the curve between T =0 and the required temperature gives the
value of absolute entropy of a substance (ST).
25/MITSDE
1.19 Van't Hoff Isotherm

Consider a general reaction:
aA  bB  cC  dD ....(i)
We know: G  H  TS  E  PV  TS
or dG  dE  PdV  VdP  TdS  SdT
But dq  dE  PdV and dS  dq / T
dG=V . dP - SdT
At constant temperature, (dG)T = V. dP
Free energy change for 1 mole of any gas at a constant temperature is given by:
dP
dG  V .dP  RT .  PV  RT 
P
dP
Integrating:  dG  RT  P
G  G o  RTInP ....(ii)
where G0 integration constant and is known as standard free energy, i.e.,

G0 =- G when P = 1 atm.
Let the energy/mole of A, B, C and D at their respective pressures PA, PB, PC and
PD are GA, GB, GC and GD respectively. Then, free energy change for the reaction
(i) is given by:
G  G product  Greac tan ts  cGC  dGD  aG A  bGB  ....(iii)
Substituting the value of GA, GB, GC and GD in (iii) from (ii), we get:
 
G  cG o C  cRTInPC  dG o D  dRTInPD  cG o A  aRTInPA  dG o B  bRTInPB 
c d
 cG o
C  dG o
D  aG o
A  bG o
B  RTIn ((PP )) ((PP ))
c
a
D
b
A B
or
( Pc ) c ( PD ) d
G  G o  RTIn ....(iv)
( PA ) a ( PB ) b
where DG = standard free energy of reaction (i).
0
We know at equilibrium, DG = 0
 ( Pc ) c ( PD ) d 
o
G  G  RTIn  a b
 ( PA ) ( PB )  eq
  ( P )c ( P )d  
o
 G  RTInK eq   c a D b   K eq 
  ( PA ) ( PB )  eq 
or
G o   RTInK eq ...(v)
26/MITSDE
From (iv) and (v), we get:

( Pc ) c ( PD ) d
G   RTInK eq  RTIn
( PA ) a ( PB ) b
( Pc ) c ( PD ) d
or  G   RTInK eq  RTIn ...(vi)
( PA ) a ( PB ) b
This expression, called Van't Hoff isotherm, is very important and gives a
quantitative relation for free energy change accompanying a chemical reaction.
Van't Hoff isotherm: G o   RTInK eq
 G o  (H o  TS o )  H o S o
or LnK eq    
RT RT RT R
o
  H o
 S o  H S o
 L nK 1   and L n K 2  
R T1 R R T1 R
H o 1 1   H o  T2  T1 
or LnK 2  InK 1   T T   RT  T T 

RT1  1 2  1  1 2 
K2  H o  T 2  T1 
or L n 
K1 R T1  T1T 2 
or
K2 H o  T2  T1 
log    ....(vii)
K1 2.303R  T1T2 
This expression, called the Van't Hoff isotherm, can be used to calculate the
equilibrium constant at T2, if its value at T1 is known.
Solved examples
Example 1. Calculate the heat of formation of benzene, given the heats of

combustion of benzene, carbon, and hydrogen are -780kcal, -94.0 kcal and
- 68.0 kcal, at 300 K. (Sri Venkateswara, I B.Tech., Nov. 1993)
Solution. Given data is:
(i) C6 H6 (l)  7.5O2 (g)  6CO2 (g)  3H2O(l); H  780kcal

(ii) C (s)  O2 ( g )  CO2 ( g ); H  94.0kcal
(iii ) H 2 ( g )  0.5O2 ( g )  H 2O(l ); H  68.0kcal
Our aim is 6C ( s )  3H 2 ( g )  C6 H 6 (l ); H f  ?
 6  Eq.(ii )  3  Eq.(iii )  Eq.(i ) gives : H  564kcal
6C ( s )  6O2 ( g )  6CO2 ( g ); H  204kcal
6CO2 ( g )  3H 2O2 ( g )  C6 H 6 (l )  7.5O2 ( g ); H  780kcal
Adding: 6C ( s )  3H 2 ( g )  C6 H 6 (l ); H f  12kcal
Hence, heat of formation (DHf) of C6H6(l) is + 12 kcal mol-1
27/MITSDE
Example 2. Determine the heat of formation of C6 H6, given the heat of

combustion of C6 H6, C and H2 as 3,345 kJ, 393.5 kJ and 284.6 kJ respectively.
(Anna I B.E. Dec. 1997)

(i) C6 H6 (l)  7.5O2 (g)  6CO2 (g)  3H2O(l); H  3,345kJ
(ii) C (s)  O2 ( g )  CO2 ( g ); H  3,93.5kJ
(iii ) H 2 ( g )  6.5O2 ( g )  H 2O(l ); H  284.6kJ
Our aim is 6C ( g )  3H 2 ( g )  C6 H 6 (l ); H  ?
 6  Eq.(ii )  3  Eq.(iii )  Eq.(i ) gives :
6C ( s )  6O2 ( g )  6CO2 ( g ); H  2,361kJ
3H 2 ( g )  1.5O2 ( g )  3H 2O(l ); H  853.8kJ
6CO2 ( g )  6 H 2O2 ( g )  C6 H 6 (l )  7.O2 ( g ); H  3,345kJ
Adding: 6C ( s )  3H 2 ( g )  C6 H 6 (l ); H f  130.2kJ
Hence, heat of formation (DHf) of C6H6 is + 130.2 kJ mol
-1
Example 3. Calculate the heat of formation of ethane, if the heats of combustion

of ethane, carbon, and hydrogen are -372.8, -94.5, and -68.4 kcals respectively.
(Alagappa. I B.E., April, 1991)

7 3
(i ) C 2 H 6  O 2  2C O 2  H 2O ; H  372.8kcal
2 2
(ii ) C  O 2  CO 2 ; H  94.5kcal
1
(iii ) H 2  O2  H 2O; H  68.4kcal
2
Our aim is to get:
2C  3H 2  C2 H 6 ; H  ?
 2  Eq.(ii )  3  Eq.(iii )  Eq.(i ) gives :
2C  2O2  2CO2 ; H  189.0kcal
3
3H 2  O2  3H 2O; H  205.2kcal
2
7
2CO2  3H 2O  C2 H 6  O2 ; H  372.8kcal
2
Adding: 2C  3H 2  C2 H 6 ; H f  21.4kcal
Hence, heat of combustion of ethane (DHf) is -21.4kcal mol -1
Example 4. Combustion of diborane (B2 Hg) proceeds according to the

equation: B2H6(g) + 3O2(g) B2 O3(g) + 3 H2 C(g) ; and 464 kcal is liberated per
mole of B2H6. Combustion of the element boron also produces B2 O3(g) and gives
out 283 kcal g atom-1. The standard heat of formation of H2 O(g) is -57.79 kcal
mole-1. Calculate the heat of formation of diborane. (Madras B.E., Nov. 1982)
28/MITSDE
Solution. Expressing given data in thermochemical equation form:

(i ) B2 H 6 ( g )  3O2 ( g )  B2 H 3 ( g )  3H 2O( g ); H  464kcal
3
(ii )2 B( s )  O2 ( g )  B2O3 ( g ); H  566kcal
2
1
(iii ) H 2 ( g )  O2 ( g )  H 2O(l ); H  57.79kcal
2
Our aim is to obtain:
2 B( s )  3H 2 ( g )  B2 H 6 ( g ); H f  ?
To obtain the result, rearrange Eq. (i) in reverse order, add Eq. (ii), and 3 times
Eq.(iii).
(i ) B2 H 3 ( g )  3H 2O( g )  B2 H 6 ( g )  3O2 ( g ); H  464kcal
3
(ii )2 B( s )  O2 ( g )  B2O3 ( g ); H  566kcal
2
3
(iii )3H 2 ( g )  O2 ( g )  3H 2O( g ); H  173.37 kcal
2
Adding: 2 B ( s )  3H 2 ( g )  B2 H 6 ( g ); H  275.37 kcal
Hence, heat of formation (DHf) of diborane gas is -275.37 kcal mol .
-1
Example 5. Given that the bond enthalpies for C-H, Cl-Cl, C-Cl, and H-Cl are
respectively, 99, 58, 78, and 103 kcal per mole, determine DH for the reaction:
CH4(g)+Cl2(g) CH3Cl(g)+HCl(g). (Madras B.E., Nov. 1982)
Solution. The reaction may be better represented as:

H Cl H H
H C H ( g )  ... (g)  H C Cl ( g )  Cl ( g )
H Cl H
During this reaction: (i) one C-H bond is broken; (ii) one Cl-Cl bond is broken;
(iii) one C-Cl bond is formed, and (iv) one H-Cl bond is formed.
Now heat of reaction (DHrxn)
= Bond energy of [bond broken in reactants - bonds formed in products]
= Bond energy of [(C-H + Cl-Cl) - (C-Cl + H-Cl)]
= [(99 +58)-(78+103)] kcal = - 24 kcal.
Example 6. From the following bond enthalpies, calculate the DH for the
reaction:
H2 + Br2 2 HBr. B.E. H-H = 435.24 kJ/mol , B.E. Br-Br = 192.5 kJ/mol ;
B.E. H-Br = 368.3 kJ/mol. (Anna I B.E., Dec. 199)
Solution. During the reaction:
H -H (g) + Br - Br (g) 2 HBr (g)
(i) one H-H bond is broken, (ii) one Br-Br bonds broken, and (iii) two H-Br
bonds are formed.
DH = Bond energy of bond (broken in reactants - formed in product)
= BE of [(H-H + Br-Br) - 2 (H-Br)]
= [(435.24 + 192.5) - 2 x 368.3] kJ = - 108.86 kJ.
29/MITSDE
Example 7. Calculate q, w, DE and DH for isothermal reversible expansion of

an ideal gas at 27°C from a volume of 10 dm to 20 dm against a constant external
3 3
pressure of atmosphere? (Maharishi Dayanand I B.E., May 1996)
Solution
i. Since operation is isothermal and the gas is ideal, so DE = 0.
ii. Now DE=0=q+w or q=-w
But for a reversible process, work done by system,
w=-P(V2-Vi)
=-1atm(20-10)dm =-10atmdm =-10atmL
3 3
 8.314 J 
 10 Latm     1,012.7 J
 0.021Latm 
iii. q = - w = 1,012.7 J
iv. DH=DE+PDV=0+1,012.7J=1,012.7J
Example 8. Calculate the heat of formation of CO at constant pressure, if the

heat of formation of CO at constant volume and at 30 C is 28.6 kcals.
0
(Algappa I B.E., April, 1991)

Solution. For reaction:
1
C ( s )  O2 ( g )  CO ( g )
2
1 1
H  28.6kcalmol 1 , T  273  30  303K , ng  1   ,
2 2
and R  0.001987 kcalK 1mol 1.
\ On substituting of these values in:

DH=DE+Dng RT
1
we get : 28.6kcal=DE+  0.001987 x 303kcal
2
=DE+0.30kcals
or heat of formation of CO at constant volume,
DE = (28.6-0.3) kcal = 28.3 kcal mol
-1
Example 9. Calculate the change in free energy at 25°C for the reaction:
1
CO ( g )  O2 ( g )  CO ( g ) H  67.37 kcal
2
and the change in entropy accompanying the process is - 20.7 col deg mol .
-1 -1
(Andhra I B.E., Oct. 1997)
Solution.
G  H  TS
=-67.37kcalmol-1 298K(-20.7caldeg-1 mol-1)
=-67.37kcalmol + 6,169cal mol
-1 -1
=-67.37kcalmol-1 + 6.169kcal mol-1

= 6.169kcal mol-1
30/MITSDE
Example 10. When 1 g of liquid naphthalene (C10 H8) solidifies, 149 joules of
heat is evolved. Calculate the enthalpy of fusion of naphthalene.
(Maharishi Dayanand I B.E., May 1997)
Solution. Enthalpy of fusion of naphthalene
=149 J/g x (10 + 12 + 8 x 1) g mol
-1
= 149 J/g x 129 g mol =19,072 J mol -1

-1
= 19.072 kJ mol
1
Example 11. Calculate DH, DS, DG, and DE when 1 mole of water is vaporised at
1000C and 1 atm pressure. The latent heat of vaporisation of water is 540 cal g-1
(Madras B.E., April 1981)
Solution,
i. 1 mole of water (H2 O) is 18 g, so enthalpy change,
H  18  540cal  9,720cal.
ii. But T = 100 C = 373 K.
0
\ Entropy change,
H 9,720cal
S    26.6cal deg 1 (ore.u.)
T 373K
iii. Now free energy change is given by the expression:
G  H  TS
= 9,720 cal - 373 x 26.06 cal
= 9.720-9,720 cal = 0.
i.e., free energy change is zero.
iv. Now E  H  PV  H  P V2  V1 

where V= Volume of 1 mole of liquid water = 18 cm ;
3
and Vg = Volume of 1 mole of steam at 373 K (100°C).

Applying ideal gas equation to calculate,
P1V1T1  P1  P2  1atm 
V2   
P2T1 V1  22,400cm 
3
1 22,400  373 T1  273K 

  
1 273 T2  373K 
whence,
DV=V2 -V1 =(30,600-18)cm3 =30,600 cm3 (nearly)
PDV=(1atm)(30,600cm )=(1 atm) (30.6L)=30.6L-atm
3
= 30.6 x 24.2cal = 740.5 cal (L-atm = 24.2cal)

Hence, DE=DH-PDV=9,720cal 740.5 cal = 8,979.5cal.
Example 12. DG and DH values for a reaction at 300 K are -16.0 kcal and-10 kcal
respectively. Calculate the free energy at 330 K. (Allahabad B.Sc., 1996)
Solution. We know that entropy change,
H  G  10,000cal  16,000cal
S  
T 300
31/MITSDE
= 20 cal deg -1
\At 330K, DG= DH-TDS=-10,000 cal 330 x 20 cal
= -16,600 cal = -16.6kcal.
Example 13. Gibbs free energy of a reaction at 27°C and 37°C are -29.0 kcal and
- 30.0 kcal respectively. Determine its DH and DS in this temperature range.
(Madurai Kamraj I B.E., April, 1991)
Solution. Here T1 = 300 K ; T2 = 310 K ; DG300 = -29.0 kcal = -29,000 cal ;

DG310 = -30.0kcal = -30,000cal.
 (G ) G310  G300  30,000  29,000
 S     100cal deg 1
T (T2  T1 ) 310  300
or DS=100 cal deg -1
But G  H  TS
\ At 300K (27o C):
-29,000 cal = DH-300 x 100cal
or
DH = -30,000 + 29,000 cal = -1,000 cal = -1.0 kcal.
Example 14. The mean molar heat capacities, at constant pressure, of

hydrogen, oxygen and water vapour in the temperature range from 25 C to
0
1000C are as follows:

H2(g) = 6.92; O2(g) = 7.04; H2O (g) = 8.03 cal deg mol .
1 1
The heat of reaction at 25°C is-57.8 kcal mol-1 . Calculate the standard heat of
formation of water vapour at 100°C. (Sri Venkateswara I B.E., Sept. 1997)
Solution. Here DH1 at 100 C = -57.8 kcal mol , (T2-T1) = 100 C

0 -1 0
- 250C = 75 deg.
DCp = Cp of (products - reactants) = Cp of [H2 O(g) - (H2 (g) + 0.5 O2 (g)]
= [(8.03 - (6.92 + 0.5 x 7.04)] cal deg· mol =- 2.41 cal deg mol
-1 -1 -1 -1
DH2=DH1+(T2-T1) DCp
=-57.8 kcal mol -1 deg (-2.41 cal deg- 1 mol-1)
= - 57,800 cal mol-1 181cal mol-1 =-57,981 cal mol - 1
Example 15. At what temperature will water boil when the atmospheric
pressure is 528 mm Hg? The late heat of vaporisation of water is 545.5 cal/g.
(Andhra I B.E., July 1997)
Solution. From the integrated Clapeyron equation, we have:
P2 H v  1 1 
log    
P1 2.303R  T1 T2 
Here P1 = 528 mm Hg; P2=1atm= 760mm Hg; T1 = ?;

T2 = 100 C = 373K; DHv= 545.5 cal/g= 545.5 x 18 cal/mol = 9,819 cal/mol,
0
R= 1.987 calK-l mol-l
32/MITSDE
760 9,819calmol 1 1 1 
log  0.1582  1 1 
 
528 2.303 1.987calK mol  T1 373K 
or
1 1 0.158  2.303 1.987 K 1
   0.0000737
T1 373K 9,819
1
or  0.0026810 K 1  0.0000737 K 1
T1
or T1= (1/0.0027547) K= 363 K.
Example 16. Calculate the free energy change when one mole of sodium
chloride is dissolved in water at 298 K (Given: lattice energy of NaCl = - 777.8
kJmol ; hydration energy of NaCl = -774.1 kJmol and DS = 0.043 kJK mol
-1 -1 -1 -1)
Solution. Na+ (g) + Cl- (g) NaCl (s) ; DH = - 777.8 kJ

NaCl (s) Na (g) + Cl (g) ; DH = + 777.8 kJ
+ -
Na (g) + Cl (g)-aq Na+ (aq) + Cl- (aq) ;

+ -
DH=- 774.1 kJ
Add NaCl (s) +aq Na (aq) + Cl (aq), DH = 3.7 kJ mol
+ - -1
DG= DH - TDS
= 3.7 kJ mol-1 - 298 K x 0.043 kJ K-1 mol-1
= 3.7kJmol -12.14kJmol
-1 -l
= - 9.114 kJ mol-1
Example 17. Calculate the free energy and entropy change per mole when
liquid water boils at 1 atomosphere. [For water, DHvap = 2.0723 kJ/g]
Solution. DHvap = 2.0723 kJ/g x 18 g mol -1 [\ Mol. wt. of H2 O = 18 amu]

= 2.0723 x 18 kJ mol =37.30 kJ mol
-1 -1
Entropy change, S 
H vap 37.30kJmol 1

Tb 373K
=0.1kJ mol K = 100 Jmol K
-1 -1 -1 -1
Free energy change,

G  H  TS
= 37.30 kJ mol - 373 K x 0.1 kJ mol K
-1 -1 -1
= 37.30 kJ mol 1- 37.30 kJ mol -1= 0
Example 18. The standard molar enthalpies of formation of cyclohexane (1)

and benzene (l) at 25 C are -156 and + 49 kJmol respectively. The standard
0 -1
enthalpy of hydrogenation of cydohexene (1) at 25 C is - 119 kJmol . Use these

0 -1
data to estimate the magnitude of the resonance energy of benzene.
Solution. Cydohexene (l) + H2 (g) Cydohexane (1),

DH=-119kJmol-1
. . Bond energy of 1 double bond = 119 kJ mol
.
33/MITSDE
\ For the introduction of 3 double bonds (present in benzene), the decrease in

energy
3 x ll9 kJ = 357 kJmol
-1
But DHf for cydohexane = 156 kJ mol-1.

DHf (theoretical) for benzene = 357-156 = 201 kJ mol
-1
However, actual value of DHf for benzene is 49 kJ mol .

-1
Hence, resonance stabilisation energy of benzene

= (201 - 49) kJ mol = 152 kJ mol
-1 -1
Example 19. Calculate the standard entropy change for the reaction X = Y, if
the value of DH = 28.40 kJ mol and equilibrium constant is 1.8 x 10 at 298K.
0 -1 -7
Solution. DG0 = - 2.303 RT log Keq.

=-2.303 x 8.31JK mol x 298 Klog 1.8 x 10
-1 -1 -7
=-2.303 x 8.31 x 298 J mol (-7+ 0.2553)

1
= - 2.303 x 8.31 x 298 J mol (-6.7447)

-1
= 38,466 J mol
-1
H o  G o 28,400 Jmol 1  38,466 Jmol 1

S o  
T 298 K
 10,466 Jmol 1
  - 35,12 J K-1 mol 1 .
298 K
Example 20. DH and DS for the reaction:

Ag 2O( s )  2 Ag ( s )  1 / 2O2 ( g )
are 30.56 kJ mol and 60 JK mol respectively. Calculate the temperature at
-1 -1 -1
which the free energy change for the reaction will be zero. Predict whether the
forward reaction will be favoured above or below this temperature.
Solution. Here DH = 30.56 kJ mol =30,650 J mol , DS = 60 JK mol

-1 -1 -1 -l
Now DG=DH - TDS

At equilibrium: DG=0=DH - TDS
H 30,560 Jmol 1
or T  = 509.3K
S 60 JK 1mol 1
i. If T> 509.3 K, then DGo is negative and reaction is spontaneous in forward
direction.
ii. If T < 509.3 K, then DG is positive and reaction is non-spontaneous or the
reaction will proceed in the reverse direction.
Example 21. Calculate the equilibrium constant for the following reaction at
278 K and 1 atmosphere pressure:
CO (g) +3H2(g) CH4 (g) + H2O(l)
Given DHof at 278 K for CO(g) = -110.5 kJ mol 1; CH4 (g) = -74.8 kJ mol 1;
H2 O(l) = -286.0kJmol ; S for the reaction at 298K=-333.3kJ K mol , and
-1 o -1 -1
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R = 8.31J K-1 mol 1.
Solution. DH = DH f [CH4 (g) + H2 O (l) CO (g) 3H2 (g)]

o o
= [-74.8-286.0+110.5+3 x 0] kJ mol 1
= - 250.3 kJ mol
-1
Now DG = DH - TDS
o o o
= - 250.3 kJ mol -1 -298 K x (- 333.3) J K-1 mol-1

= - 250,300 J mol - 1+ 99,323.4 Jmol-1
= - 150,976.6 J mol
-1
Also
  G o    G o 
K eq  Anti log   log K eq   
 2.303RT   2.303RT 
 (150,976.6 Jmol 1 )
 Anti log
2.303  8.31JK 1mol 1  298 K
= Antilog 26.4727 = 2.970 x 1026.
Summing Up
The most important driving force for fire is heat release rate. The science of
thermodynamics studies the flow of energy from system to the surrounding and
vice versa. Thermochemistry Clasius Clayperon equation concepts of
equilibrium constant and its relation to free energy change are important to
study of fire dynamics.
Self-assessment
i. Photosynthesis in plants is an example of:

a) open system b) a closed system
c) an isolated system d) an adiabatic system.
ii. Identify the state function among the following:

a) q b) q-w
c) q/w d) q+w
iii. An isolated system is that in which:

a)there is no exchange of energy with its surroundings
b)there is exchange of mass and energy with its surroundings
c) there is no exchange of mass and energy with its surroundings
d)there is exchange of mass with its surroundings
iv. In thermodynamics, which one of the following is not an intensive

property?
a) pressure b) volume
c) temperature d) time
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v. A well-stoppered thermos-flask contains some ice cubes. This is an

example of a:
a) closed system b) open system
c) isolated system d) non-thermodynamic system
vi. Which among the following state functions is an extensive property of the
system?
a) temperature b) volume c) refractive index d) viscosity
vii. Evaporation of water is:

a) an exothermic process b) an endothermic process
c) a process where no heat change occurs
d) a process accompanied by chemical reaction
viii. Which of the following expressions expresses the first law of

thermodynamics?
a) q = DH-w b) DE=q-w
C) DH=q+w d) DE=DH+PDV
ix. Which one of the following is contrary to the first law of thermodynamics?
a) Energy can neither be created nor destroyed
b) Total energy of the system is constant
c) One kind of energy can be converted into an exactly equivalent amount
of other kind of energy
d) Continuous production of mechanical work is possible without the
supply of equivalent quantity of heat.
x. A system changes its position from state A to state B. The change is

internal energy is given by DE= EB - EA. This relationship is valid if:
a) the change is brought about in a reversible manner
b) the change is brought about in an irreversible manner
c) the change is brought about at constant pressure
d) the change is brought about in a manner irrespective of the above.
xi. During the isothermal expansion of an ideal gas, its:

a) internal energy increases b) enthalpy decreases
c) enthalpy remains constant d) enthalphy reduces to zero.
Reference
1. Atkins, P.W. (1994). Physical Chemistry (5th edn.) Oxford University

Press. Oxford. U.K.
36/MITSDE

Chemical Thermodynamics

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Chemical Thermodynamics

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Chemical Thermodynamics

Thermodynamics literally means flow of heat. It is a branch of physical science

1.2 Terminology of Thermodynamics

The thermodynamic system is defined as any portion of matter under

On the other hand, a system is called heterogeneous, if it consists of parts (or

Extensive property is the property, which depends upon the amount of

Intensive property is the property, which is independent of the amount of

State of the system is a set of variables such as pressure, volume, temperature,

The isothermal process is a process carried out at constant temperature. When

Irreversible processes are also called "spontaneous processes", which means

State function is a thermodynamic property, which depends only on the state of

1.3 The First Law of Thermodynamics

As a result of a number of experimental observations, Helmhotlz, Clausius, and

i. "Energy can neither be created nor destroyed, though it may be converted

where dE is the increase in energy; dq and dw represent small quantities of heat

In a cyclic process i.e., in which the system is subjected to a series of operations

1.4 The Joule-Thomson effect

Figure 1.1 Joule-Thomson effect

Word done on the system = - P1 V1

Hence, DE = q - w = q - 0 = q [From the 1 law of thermodynamics]

According to kinetic theory, work has to be done in order to overcome the

Suppose a change of a system from state A to B is brought about at constant

q = (E B - E A) + External work done (w)

DH= (EB +P VB) - (EA +P VA) = (E B -E A) +P (VB - VA)

1.5.1 Relation between Pressure-volume and Work

Consider a certain amount of a gas enclosed in a cylinder of cross-sectional area

Figure 1.2 Work in P-V form

If the external pressure (P) is constant, then:

Relation between DH and DE in case of gaseous reaction:

Then, from ideal gas laws, we have:

or PV  ng .RT

but H  E  PV (From 1st law)

H  E  ng .RT ..(i)

where R = gas constant

1.6 Thermochemical definitions

DH = Enthalpy of product - Enthalpy of reactant.

Example: The thermochemical equation:

(2) Enthalpy (or heat) of combustion (DH) of a compound or an element is the

Example: Heat of combustion of methane (CH4) is - 890.2 kJ mol-1.

ions of the strong acid and base remain unaltered. Thus:

Example: The equation:

Enthalpy of formation and its stability: The enthalpy of formation is an important

Example: Heat of fusion of water,

Example: Heat of vaporisation of water,

Example: Heat of sublimation of iodine,

1.7 Bond Energy

OH(g) ®O(g) + H (g) ; D H - = 102 kcal mol

or H2 O(g)® O(g) + 2H(g); D H = 220 kcal mol

Heat of formation of methane 396kcalmol 1

Alternatively, the C - H bond energy in methane may be calculated as the

CH2(g) ® CH(g) + H(g); DH = 106 kcal mol

CH(g) ® C(g)+H(g) ; DH = 82 kcalmol-1

Calculation of bond energies: In a reaction between gaseous species, certain

H rxn  BE (reactants)  BE (products)

(ii) With electronegativity bond energy increases with increase in difference in

Applications of bond energies: (1) Calculation of heat reaction:

H-H = 102 kcal mol and C -H = 99 kcal mol

Now heat of reaction

= - [Bond energies of (products - reactants)]

But in the given reaction:

Calculation of heat of formation:

H f forC5 H12  [4  B.E. for C  C  12  B.E. for C  H ]

1.8 Hess's Law of Constant Heat Summation

According to Hess’s low “the heat change in a particular reaction is always