Unit-6

THERMODYNAMICS
their interconversion.
Thermodynamics deals with energy in its various forms and
conversion of heat into work and vice versa.
Thermodynamics literally, means

three fundamental generalisations. These

Thermodynamics is primarily based up
on

and Third laws of thermodynamics.

generalisations are called First, Second

Some basic concepts in thermodynamics

System and surroundings:
the part of the universe in which observations are made.
System may be defined as

of the universe other than the system. System and the

Surroundings may be defined as the part of space in the
universe. But usually for practical purposes the region
surroundings together constitute the
neighbourhood of the system constitutes the surroundings

The universe = The system + The surroundings

some sort of wall which is real or imaginary. The

The system and surroundings are separated by
is called boundary.
wall that separates the system from the surrounding
the
reaction in a beaker, then the beaker containing
For example, if we carry out a chemical The
reaction mixture is the system while the room
where the beaker is kept represents the surroundings.
between the system and the surrounding.
glass walls of the beaker represent the boundary
classified into 3 types.
Types of systems: Systems can be
a) Opensystem: matter as well as energy with the surroundings is called an open
A system which can exchange
system.
E.g. The reaction taking place in an an open beaker is an example of open system.

(b)AClosed svstem:
that can exchange energy with the surroundings
but no matter is called a closed system.
system
of conducting material is an example of open
E.g. The reaction taking place in a closed vessel made
system.

c)AIsolatedsystem:
system, which can neither exchange matter nor energy with the surroundings is called isolated

system.
E.g A reaction carried out in a closed and well insulated vessel like thermos flask.

State of the system:

particular system when its macroscopic
State of the system implies the conditions of existence of a
properties have definite values.
Here all the
For example consider liquid water as the system at 25'C and one atmosphere pressure.
25 C
Then water at is a state of the water system. Now
macroscopic properties will have definite values. will change automatically and attain
the temperature is increased to 50°C. Then the macroscopic properties
new definite values. So water at 50°C will constitute another state of the water system.
 The state of a thermodynamic system is described by its measurable or macroscopic properties.
The state of a system is usually described by quoting its pressure (P), volume (V), temperature (T),
amount(n) etc. These variables like P, V, T etc are called state variables or state functions.

But the two important thermodynamics parameters namely heat (q) and work (W) are not

the state functions becausethese are path dependent.

Extensive and intensive properties:
(a) Extensiveproperties: The properties of the system, which depend upon the quantity or size of matter
present in the system, are called extensive properties.
E.g. Mass, volume, internal energy, enthalpy, heat capacity etc.

(b)Intensive properties: The properties of the system which are independent of the quantity or size of
matter present in it are called intensive properties.
E.g Temperature, pressure, refractive index, viscosity, density, specific heat etc.

Usually molar properties like molar volume, molar heat capacity etc are intensive properties. A
molar property is the value of an extensive property () for 1 mole of the substance
Km

Therefore itis independent of matter.

Thermodynamic processes:
The operation, which brings about the changes in the state of the system, is called thermodynamic
process. The various types of processes are,

(1) Isothermal process: It is a process, which is carried out at constant temperature. For an isothermal
process, AT = 0.

(2) Adiabatic process: It is a process in which no heat exchange occurs between the system and the
surroundings (8q o). Here the system is completely isolated from the surroundings. Here the
temperature of the system does not remain constant.

(3) sobaric process: It is a process, which is carried out at constant pressure. (AP = 0).

(4) Isochoric process: It is a process, which is carried out at constant volume. (AV -0).

(5) Cyclic process: It is a process in which the system returns to the original state after a series of
changes.
The internal energy change (AU) and enthalpy change (AH) for a cyclic process is zero.

(6) Reversible_and irreversible process: Reversible process is a process, which is carried out
infinitesimally slowly so that all changes can be exactly reversed. Here the system and the
surroundings remain in a state of equilibrium. The process is conducted in infinite number of steps
and the opposing force is infinitesimally smaller than the driving force.

Ireversible process is a process, which is carried out rapidly, and it cannot be reverted
without the help of extemal agency. Here the system does not have chance to achieve equilibrium.
Here the driving force is greater than the opposing force. All natural processes are irreversible in
nature.

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Zeroth Law of Thermodynamics
When two objects at different temperature are brought in thermal contact they exchange heat with
each other until they reach a state of thermal equilibrium. At this point the temperature of the two objects
is the same. These ideas are known as law ofthermal equilibrium or Zeroth law of thermodynamics

The Zeroth law can be states as followss

G) Two objects at different temperatures in thermal contact with each other tend to move towards
the same temperature.
OR
i ) Two objects in thermal equilibrium with the third one are in thermal equilibrium with each
other.

Internal energy (U) and changein internal energy (AU:

Every substance is associated with a definite amount of energy. This energy is called internal
energy (U) or intrinsic energy. It depends upon its chemical nature and its state of existence.

Internal energy represents the total energy of the system. It may be chemical, electrical,
mechanical or any other type of energy associated with the system.

Internal energy depends upon the quantity of substance and hence it is an extensive property.
Internal energy isa state property.
The internal energy of a system can be changed by
1 Heat passes into or out of the system
2. Work is done on or by the system
3. Matter enters or leaves the system

The absolute value of internal energy of a substance cannot be determined. However it is possible
to determine the change in internal energy (AU). The change in internal energy is the difference between
the internal energies of the products (U) and that of the reactants (UR).
AU 2Uproducts ZUreactants.
For processes involving evolution of energy, Up <UR, the sign of AU is negative.
For processes involving absorption ofenergy Up >Ue, the sign of AU is positive.
For isothemal processes, AU = 0.

Modes ofexchange ofenergy |Heat and workl

Energy is mainly exchanged as heat and work between the system and the surroundings. Work and
heat are the important modes by which the internal energy of a system can be changed.

Work (W
The intermal energy of a system can be changed by doing work. The work can be mechanical
work, presure-volume work or electrical work. According to latest sign conventions (1UPAC

Work done by the system is negative (W<0)

Work done on the system is positive (W>0)
The positive value of 'W' indicates that work done on the system causes an increase in the internal
energy of the system. The negative value of W indicates that work done by the system causes a decrease in
the internal energy of the system.
The two common forms of work are;

(a) Pressure volume work and (b) electrical work

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 (a) Pressure volume work:
This type of work is significant for systems, which consist of gases and involve volume changes
against external pressure.
Consider a gas enclosed in a cylinder fitted with a frictionless piston having areas of cross-section
a'. Let the gas expand against the external pressure 'P through a small distance P.
Then
Work force x displacement
W =Fxl1
But the force, F is given by the product of pressure and area,
F= Pex XKa
W = Pex x al

Piston
Since 'al' refers to the change in volume (AV) ie (V,-V area Q
W Pex AV
During expansion the work is done by the system. As per
sign conventions, a negative sings is put in the expression
for work. Gas

W=- Pex AV
For compression process work is done on the system. Here AV is negative. Therefore the work as obtained
from the above equation becomes positive.
The general expression for PV work can be written as

W--Pex AV

Work donein reversibleexpansion of ideal gas

If the pressure is not constant during the process, and changes in a number of finite steps, work
done on the gas will be summed over all the steps.
W - PAV
If the external pressure at each stage is infinitesimally greater than the pressure of the gas, the
volume decreases by an infinitesimal amount dV at each step. Such a process is called reversible process.
Then the total work done on the gas is given by
N
Wrev Padv
Here Pex at each stage = Pin t dp for compression.
In an expansion process, Pex = Pm-dP

Therefore in general case Pex (Pin t dP)

Wrev PamdV
P dP)dv
Pin dV + dP dV Volum

The product dPdV can be neglected since it is the product of two extremely small quantities.

W Pndv

Now the pressure of the gas can be expressed in terms of its volume through gas equation.
PV nRT P =nRT/V

W
Wrev nRTdV
V
- nRTln V

Vi
-2.303 nRTlog V
Vi
Free expansion called free expansion. free expansion the work
Expansion of a gas in vacuum (Pex =0 ) is During
done by the gas is zero whether the process is reversible or irreversible.

(b)Electricalwork: Non-expansion work]

If 'Q' is the charge following through a conductor and 'E' is the potential difference, then electrical work,

WeleEQ

2) HeatHeat
( is another mode of changing the internal energy of the system. If heat is absorbed by the
system, its internal energy increases. If heat is given out by the system, its internal energy decreases.
According to sign convention (TUPAC)

Heat absorbed by the system is positive (q>-0)

Heat given out by the system is negative (q<0)

Units ofThe
heatSI
andunit
worki
of both heat and work is Joule (). The CGS unit of work is 'erg' and that of heat is
calorie. The different units are related as
1 J 10 ergs = 1Nm= 1Kgm's
1cal 4.184J
First law ofthermodynamics:
The law was first stated by Mayer and Halmholtz. This law is also called law of conservation of
energy. The law can be stated in a number of ways.
Energy can neither be created nor be destroyed although one form of energy can be converted
into the other form.
Or
In any physical or chemical process the energy of system and surroundings taken together
remains constant.
Or
Energy of an isolated system is constant.

Mathematical expression offirstlaw:

Consider a system having internal energy U. Let the system be supplied with 'q' amount of heat,
then the internal energy of the system will be U +9. If 'W amount of work is done on the system, then the
final internal energy U2 will be given by,
U,=Ui +q+ W
Ua-U, q + W Internal
interqal + Internal
energy
AU=q+W neroy energy
.cU+q U,+9+W
For a system which involve only pressure Final state
volume work, W = -PAV Initial state

Then
AU--PAV
This is the mathematical statement of first 1law of
thermodynamics.
9 and Ware path functions but (q+W)isstate function.
For isothermal irreversible or reversibleexpansion of ideal gas, AU =0. Thereforethe equation
AU=q+Wcan be expressed as follows
1. Forisothermal irreversible change: q = -W =+ PeaV

2. For isothermal reversible change : q

=
-W =+2.303 nRT logV
V
3. For adiabatic change: q = 0

Therefore in such a case AU =+ W

Significance of AU:
According to fist law of thermodynamics
AU =q+ W
For pressure -volume work, W = -PAV

AU = q - PAV

If the process is carried out at constant volume, AV = 0

Then AU =9

Thus AU represents the heat change-taking place when the process occurs at constant volume and constant
temperature.

Enthalpy and enthalpy change:

[Heat absorbed at constant volume is equal to the change in internal energy ie 4U = q» But most of
chemical reactions are carried out not at constant volume, but in flasks or test tubes under constant atmospheric
pressure. Therefore we need another state function which is suitable for these conditions]

Enthalpy may be defined as the sum of the internal energy and the pressure volume energy of the
system under a particular set of conditions. It is denoted by H.
Mathematically,
H=U+Pv Where H is enthalpy, U is internal energy, P is pressure andV is volume.

Enthalpy is an extensive property. It is also a state function.

The absolute value of enthalpy cannot be determined. However the change is enthalpy (AH) can
be experimentally determined.
For a chemical process

AH Hp HR
Where Hp is enthalpy of the products and HR is enthalpy of the reactants.

Significanceof AH
According to the first law of thermodynamics.
AU = q + W

Or g AU-W
Where "AU' is the internal energy change, 'q' is the net heat absorbed and 'W° is the work done.
Ifthe work done is only pressure-volume work, then W =-P AV
9 AU-(-PAV)
AU+PAV ( 1 )
The enthalpy 'H' is given by

H U+PV
The change in enthalpy AH is given by
AH AU +A(PV)

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 = AU + P AV+ V AP
When pressure 'P' is kept constant, AP = 0

AH AU +PAV - - - (2)

From(1) and (2)

AH p)
process occurring at
Therefore the enthalpy change represents the heat change-taking_place during the
constant temperature and constant pressure.
Relationship between AH and AU:
carried out at constant temperature and constant
Consider a reaction involving gases, which is
total volume of the gaseous
total volume of the gaseous reactants and Ve be the
pressure (P). Let VA be the the number of moles of gaseous
of moles of gaseous reactants and ng
products. Also na be the number
products.
Then PVA na RT
PVB np RT
PVB-PVA = ng RT- naRT

PCVB-V =
(ng-na) RT
PAV = AnRT

The change in enthalpy during the process is given by

AH-AU+PAV
Substituting the value of PAV
Or p) ) +AnRT
AH AU +(An) RT

Here An represents the change in the number of moles of gaseous species during the process.

If An is 0 AH AUU
IfAn is-ve AH < AU

If An is +ve AH> AUJ

reactants and
volume or those having same number of moles of
For reaction involving no change in
reactants or products.
products or those involving no gaseous
AH AU =

m 4 or
Heat Capacity and specificheat capacity
quantity of heat needed to raise its temperature by one
The heat capacity ofa substance is the
degree Celsius (or one Kelvin)

Heat capacity (C) =

T AT

temp from T2 to Ti
Where q is the quantity of heat given to the system to raise the
to the amount of a substance. Hence the terms
Heat capacity is directly proportional
used.
specific heat capacity and molar heat capacity
are

one mole
quantity of heat needed to raise the temperature of
The molar heat capacity is the
of a substance by one degree celsius.

raise the temperature of unit

The specific heat capacity is the quantity of heat required
to

mass of a substance by one degree Celsius ( or one Kelvin).

For finding the heat, q required to raise the temperature of a sample,

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 9 c x mxAT
where 'c is the specific heat capacity, 'm' mass and AT is the temperature change.

Therelationship between Cp and Cy

At constant volume, the heat capacity, C is denoted by Cv and at constant pressure, this is
denoted by Cp. For solids and liquids there is no much difference between the values of Cv and Cp.

The equation for heat, q can be written as

At constant volume, q , = CvAT= AU

At constant pressure, q CpAT- AH

The difference between Cp and Cv can be derived for an ideal gas
For one mole of an ideal gas, AH AU +A(PV)
= AU +A(RT)

- AU+ RAT
Therefore AH AU+RAT
On putting values of AH and AU
Thermometer
CpAT -CvAT + RATr Firing leads
Cp= Cv + R
Stirer
C p - Cv = R Oxygen
Inlet

Measurement of AU and AH
Heat changes in reactions can be measured with the help of
calorimeters. Reactions taking place at constant volume and Sample
involving gases are carried out in a bomb colorimeter. It is made of
heavy steel. The steel vessel is coated inside with gold or platinum
Bomb
to avoid oxidation of steel during chemical reactions. The vessel is
fitted with as tight screw cap. The steel vessel (the bomb) is Oxygen
under
immersed in a large volume of water. A combustible sample is pressureB
burned in pure oxygen supplied in the steel bomb. This raises the
temperature of water which is recorded from the thermometer. By
knowing the heat capacity of calorimeter and also the raise in Water
temperature, the heat of combustion at constant volume can be
calculated using the equation. Bomb calortmeter

AE -ZxAT xM
Z Heat capacity f calorimeter system
=

AT= Rise in temperature.

M =molecular mass of substance.
W mass of substance taken.
Thermometer
At constant volume heat absorbed
gives the increase in internal energy
AE qv

Measurement of AH
Measurement of heat
Foamed polystyrene
change of constant pressure can be done in cup
a calorimeter
kept open to the atmosphere. The calorimeter is immersed
in an insulated water bath fitted with stirer and
thermometer. The initial
temperature is noted. At the end of the reaction the change in temperature
is calculated. Knowing the heat
capacity, heat absorbed or evolved in the Reaction mixture
reaction çan be calculated. At constant
pressure, heat absorbed is equal to
increases in enthalpy.

8
 AH 9 p
9p at constant pressure is also called the heat of reaction.

In exothermic reaction heat is evolved. Therefore qp will be neagative. In an endothermic reaction heat is
absorbed. Then qp is positive and AH will be positive.

Exothermic and Endothermic reactions

Reactions which are accompanied by the liberation of heat energy are called exothermic reactions.
The reactions which are accompanied by absorption of heat energy are called endothermic reactions.

AH is negative and AU is also negative.

For exothermic reactions
For endothermic reactions AH is positive and AU is also positive.
Eg
AH -393.SKJ The reaction is exothermic
C) +O2)- COg)
2 NOg AH =
+ 180.5 KJ The reaction is endothermic.
N2g)+Oa.

Enthalpy of a reaction (Heat of a reaction)

In a chemical reaction reactants are converted into products.
Reactants Products
The enthalpy change accompanying a reaction is called the enthalpy ofa reaction. It is denoted by the
symbol, A,H
A,H [sum of enthalpies of products] - [ sum of enthalpies of reactants]

Za Hproducts b Hreactans
Here 'a' and 'b' are stoichiometric coefficients in the balanced chemical equation
For example
Eg: CHa + 202g COz) +2H,O

A,H a Hproducts 2 b Hreactonis

-

[H(COa)+ 2
H (HO)) -
[H. (CH4)+ 2 Ha (O»)
where Hm is the molar enthalpy

Standard enthalpy of areaction

The enthalpy of a reaction depends on the conditions under which the reaction is carried out. For
the sake of comparison, AH for different reactions are expressed at a particular temperature and pressure
Standard state is the most stable state (pure form) of the
called the standard state of the substance.
substance at 1 bar pressure and 298K.

The enthalpy of a reaction at the standard state is called the standard enthalpy of the reaction and
is represented by AH

Enthalpy ofa reaction is given different names depending upon the type ofthe reaction.

Thermochemical equations
A balanced chemical equation together with a designation of its value of AH is called a
thermochemical equation.
For example
CaHOH+ 30292CO +3H,O AH° = -1367kJ/mol

9
The important conventions of thermochemical equations
1. The coefficients in a balanced thermochemical equation refer to the number of moles of reactants
and products involved in the reaction.
The numerical value of AH refer to the number of moles of substances specified by an equation.
When a chemical equation is reversed, the value of AH is also reversed.

N2 +3H2 2NH AH = -91.8 kJ/mol

2NH N2 + 3H2 AH° =
+91.8 kJ/mol

4. When the coefticients in the chemical equation are multiplied or divided by some intiger, the AH
value must also be multiplied.
H21)+ Ozg) HO AH=-286kJ
2H26)+ Oxg) 2H,0 AH=-572kJ
5. The physical state ofall species must be specified in a thermochemical equation.
6. The value of AH shows small change with increase of temperature.

Standard Enthalpy of Formation 1AH°L(Standard Heatof formation)

The standardenthalpy of formation is the enthalpy change accompanying the formation of one
mole of a compound from its elements in their standard states. It is denoted by A H. The starndard state
refers to 298K and 1 bar pressure.

For example
H2)+ O2(g) H,O AH°=-285.8kJ
This means that when one mole of H,O is formed, 286 kJ of heat energy is liberated.

Eg: It may be noted that

1. The standard enthalpy of formation of substance is also called its standard enthalpy. (H)
2. Byconvention thestandard enthalpies offree elementsaretaken to be zero.
Standard state of element refer to the pure element in its most stable form at 298K and one
3.
atmosphere pressure. Eg The standard states of carbon, oxygen, sulphur, bromine and iodine are C
(graphite), O:(g), S«(rhombic), Br2(1) and I2(s) respectively.
Knowing the standard enthalpies of formation of the different reactants and products, the standard
enthalpy change of the particular reaction can be calculated.
AH A,H° (Products) 2AH° (Reactants)

(2)Standard Enthalpy of combustion A.H

Standard enthalpy of combustion is defined as the enthalpy per mole of a substance when it
undergoes combustion and all the reactants and products are in their standard states. (at 298K and 1 bar
pressure)
Eg: For example during the combustion of 1 mole of butane, 2658 KJ of heat is liberated
CH10(+ 13/2 O2g) 4CO2(g) + SH2O AH =2658 kJ/mol
Combustion reactions are generally accompanied by liberation of heat. Therefore the enthalpy of
combustion (AH) is always negative.

CalorifieThe
value of foods
energy and fuels,
released by the combustion of food or fuel is usually compared in terms of their
calorific values. The calorific value of food or fuel is defined as the amount of heat energy produced when
one gram of the substance (food or fuel) is completely burnt or oxidised.
Eg. When methane burns 890.3 kJ/mol of energy is released.
CH4g)+202 CO2g)2H,O AH ="890.3kJ

10
 The calorific value of methane 890 55.64 kJ/g
16

3)Enthalpy of atomization:A,H
It is the enthalpy change accompanying the breaking of one mole of a substance into its atoms in
the gaseous state.
H-Hg) 2Hg AH° 435 kJ/mol
=

For diatomic molecules it is same bond dissociation energy. But in the case of metals the enthalpy
of atomization is same as the sublimation energy
A,H = 108.4 kJ/mol
Nag) Nat)

Enthalpy of Neutralisation
It is defined as the enthalpy change accompanying the neutralisation of one gram equivalent of an
acid by one gram equivalent of a base in dilute solutions.
Eg
HCI +NaOH NaCl (ag) HO AH =57 kJ.
HNO (0g) +KOH(aa) KNOs(ag) +H,O AH =57 kJ
Experiments reveal that the heat of neutralization of all strong acids and bases is almost a constant
and is equal to "57 KJ. Heat of neutralization is the heat of formation of one mole of water from H' and
OH ions.

However, if the acid or base is weak, then the heat liberated is less than 57 kJ. This is because aa
part of the energy liberated during the combination of H and OH ions is utilized for the ionization of the
weak electrolyte.
Eg:
CH-COOHa) +
NaOHo) CH-COONa (aq) +H,O» AH=-5.5 kJ

5Enthalpy of solution (Heat ofsolution)AH

Enthalpy of solution is defined as the change in enthalpy when I mol of a substance is dissolved in
a specified amount of solvent.
Eg: HCle) +50 HO)> HCI (50H,0) AH ="72 kJ.
This means that when 1 mol of HCI is dissolved in 50 moles of water, 72 kJ of heat energy is liberated.

If the final solution is very dilute the equation is represented as

H C k +( a q ) - HCl( AH = QkJ.

Where 'aq' represents large excess of water. The corresponding AH is called the heat of solution
at infinite dilution.

Bondenthalpy_Asanh
With reference to the enthalpy changes associated with chemical bonds, two different terms are
used in thermodynamics
1. Bond dissociation enthalpy
2. Mean bond enthalpy

Bond dissociation enthalpy is defined as the change in enthalpy when one mole of covalent bonds
of a gaseous covalent compound is broken to form products in the gas phase. It is expressed in k/mol.

H-H) 2Hg) AH-HH=435 kJ/mol

11
 However in polyatomic molecules, the bond dissociation enthalpy is not the same for successive
bonds although they may be of the same type.
For example: the bond dissociation energy of the two O-H bonds of water are different.
AH 498 kJ/mol
H-O-HH +O-H
AH = 430 kJ/mol.
0-H O+Ho
Thus when a molecule contains more than one bond of the same kind, the mean value of the bond
dissociation enthalpy is calculated. The average amount of bond dissociation enthalpy required to break 1
mol of a particular bond i called the mean bond enthalpy
Thus the mean bond enthalpy of O-H bond in water =498 + 430 464 KJ/mol
2
Bondenthalpy can beused to calculate the enthalpies of chemical reactions
a,H-Sum ofthe bond enthalpies of the reactants -Sum of the bond enthalpies of the products

A,H= 2Bond enthalpiesReactants - 2Bond enthalpies Products

Enthalpy changes during Phase transformations,

Enthalpy of Fusion (Heat offusion)or Molar enthalpy of fusion
It is the enthalpy change accompanying the conversion of 1 mol of a substance from
the solid to the liquid state at its melting point.

=6 kJ.
HO HO AH s

le when one mole ofice changes into water at its m.p. 6 kJ of heat energy is absorbed.

2) Enthalpy ofvapourisation(Heat ofvapourisation)

It is defined as the change in enthalpy when 1 mol of a substance is converted from liquid to the
gaseous state at its boiling point.
H,O HOg) AH,ap40.6 KJ
(3)Enthalpy ofsublimation
It is the change in enthalpy when 1 mol of a solid substance is converted directly to the vapour
state at a temperature below its melting point.
xample, when I mol of solid Ih sublimes, the enthalpy change is +62.39 kJ.
h ho AHsub62.39 KJ.
Enthalpy of sublimation is equal to the sum of the enthalpy of fusion and enthalpy of vapourisation.
AHsub AH fus + AH vap
Hess's law
One of the important applications of first law of thermodynamics is Hess's law. The law states
that "the enthalpy change in a chemical or physical process is same whether the process is carried out in
one step or in several steps."

Consider a process in which a substance 'A' is changed into B

in one step. Let the enthalpy change of the process is represented by
AH. Now let the process is carried out in two steps involving change
from A to C and then from C to B. Let AHi, and AH, be the enthalpy
changes. Then according to Hess's law AH
AH = AH +AH2
Aplications of Hess's law
Determination ofenthalpy of formation
There are a large number of compounds such as CsH6, CO, etc whose AH values cannot be
directly determined. But their AH values can be determined by Hess's law.

For example the AH° of CO) cannot be directly Ceplt) + Oa(s

determined. This is because when graphite is burned in
limited supply of oxygen some CO2 is always produced.
Therefore AH° of C0 can be calculated by using Hess's
law.
Cop)+ %O
Now accordingto Hess's law
AH2 AH, +AH
AH A H 2 - AH|

= -393.5 -(-283)= -110.5 KJ

i) Calculation of standard enthalpies of reactions

co
The practical application of Hess's law is that thermochemical equations can be added, subtracted,
multiplied or divided like algebraic equations. Thus it is possible to calculate heat of reaction which cannot
be determined by direct experiments.

i Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change occurs when one mole of an
ionic compound dissociates into its ions in gaseous state.
NaCl Na () + C ) Alatice +788 KJ/mol
It is impossible to determine the lattice enthalpy directly by experiment. It can be calculated
indirectly by using Born-Haber Cycle.

Born Haber Cycle

Born Haber developed a simplified method to correlate lattice energies of ionic crystals to other
thermodynamic data. This procedure is based on the Hess's law. This can be explained by considering the
formation of NaCl. The net energy change during the process is represented as AH

Na +
%Ck NaCl» + AH° Na'+Cl(g

The overall process takes place in following intermediate steps. 1/2 ApordH
aH
1. Sublimation of sodium metal Nalg+1/2C,8
Na) Nao
The energy required for this process is AsubH
2. Ionization of sodium atoms Na'lg+CIg_
Nag)Na"(+ e Nalg+1/2C,0
The energy required for this process is ionization enthalpy
AinH

3. Dissociations of chlorine molecule into chlorine atoms. Nals) +1/2C,(g

Clg) Cie)
The energy required for this process is half the
dissociation enthalpy %ApondH
NaCl(s)

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 4. Conversion of gaseous chlorine atom into gaseous anion.
Cl (+ e Cl s
This step involves the release of energy and is called electron gain enthalpy AgH
5. Combination of oppositely charged gaseous ions to form solid crystal.
Na e+ Cl NaCls)
This step involves the release of energy and is called lattice energy AlatticeH°

Applying Hess's law

AH AabH+ A,H+ % AponaH +AH+ AnieH

Thus by using Born Haber cycle we can calculate the lattice energy of an ionic solid by knowing
the values of other thermodynamic parameters.

Limitation of thefirst aw:

The major limitation of the first law of thermodynamics is that it provides no information about
the spontaneity or feasibility of a process. That is it provides no information about why a particular change
or reaction takes place while the other does not.

Spontaneous and non-spontaneous processes

A process which has a natural tendency to occur of its own or after proper initiation is known as
spontaneous process.
A spontaneous process is an irreversible process and may only be reversed by some external
agency.
Examples:
Spontaneous process that need no initiation:
(1) Evaporation of water HOH0
(2) Dissolution of sugar in water to form a solution
Ci2HO1(o *aq CH22011 ()
(3) Neutralization reaction between HCl and NaOH

HCI+NaOH-NaCl+HO
(4) Spreading of a drop of ink in water.
(5) Mixing of two gases.
Spontaneous process that need initiation:
(1) Coal burns to give cO2 when ignited
C+O2 CO2
(2) Hydrogen reacts with oxygen to produce water. This reaction is initiated by passing an electric
discharge.
2H2 (8)+O2 (g) 2H,O0)
All spontaneous changes proceed till equilibrium is achieved.

A process which has no natural tendency to occur is called a non-spontaneous process. Many
non-spontaneous processes may be made to occur when energy from some external source is supplied.
E.g Electrolysis of water. Electrolysis takes place only when electrical energy is supplied to water. When
electric current is stopped, the electrolysis also stops.
H2O0) H2 (s) +% O, (s) (non spontaneous)

Energy andspontaneity:
Some kind of driving force is responsible for a spontaneous process. Common experience shows
that spontaneous processes proceed towards the state of lower energy. Therefore processes which are

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exothermnic in nature must be spontaneous. This leads to the conclusion that negative value of AH may be
the criterion of spontaneity.

E.g H2t+% O2-H,O AH -286KJ (spontaneous)

C +O2 CO AH -394 KJ (spontaneous)
But many reactions in which AH is tve or even zero are spontaneous.
E -g
(1) Evaporation of water
H,O() H,O(g) AH =+40.6KJ

(2) Dissolution of NH,CI in water

AH=+15KJ
NH,CI(s)+water NH" (aq) +Cl(aq)
(3) Decomposition of N,Os
4NO; (8) +0 (g) AH=+219 KJ/mol
2N,Os(g)
(4) Intermixing of non reacting gases AH =0

A careful study of the above processes reveals that all those processes proceed towards a more
disordered or more random state. Therefore another criterion of spontaneity is disorder or randomness of
the system.

Entropy is denoted by the

Entropy is a measure of the degree of randomness or disorder of a system. It
symbol 'S'. It is a statefunction and depends upon the state of a system. It is also an extensiveproperty

The change in entropy during a process is represented by AS

Changein entropy (4S) SfinalSinitial
S.
products Dreactants

When heat is added to a system, it increases molecular motions causing increased randomness in
the system. Entropy also depends on the temperature at which heat is absorbed. Heat added to a system at
lower temperature causes greater randomness than when same quantity of heat is added to it at higher
temperature. Thus AS is related with 'q' and T for a reversible process as

AS (rev/T
Thus change in entropy 'AS' is defined as the ratio of heat absorbed by the system isothermally
and reversibly to the temperature at which it is absorbed.

Ifq is expressed in joule (J) and temperature in Kelvin (K), then entropy change is given by J/K or
JK
The total entropy change [AS total j for the system and surroundings is given by
AStotal = AS system+ AS surroundings.

For the process to be spontaneous, AS total must be positive.

AStotal =
AS system +AS surroundings >0

When an isolated system is in equilibrium, the entropy is maximum and the change in entropPy
(AS) is zero.

AS =0 (at equilibrium).

AStotal>0: process is spontaneous.

AStotal0 : equilibrium state.
AS total <0: process is non-spontaneous.

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Physical meaning of entropy:
of degree of disorder randomness of the system. The greater the
Entropy provides a measure or

randomness, the higher will be its entropy.

For a given substance solid state has the state of lowest entropy and the gaseous state has the
highest entropy. The liquid state has intermediate entropy.

If a system changes from less random state to more random state, the value of entropy change
(AS)will be positive
Gibbs energy (G)and spontaneity
Free energy is defined as the amount of energy available from a system at particular set of
conditions that can be put into useful work. That is free energy refers to the capacities of the system to do
the useful work.
Mathematically,
G = H- TS
H Enthalpy of the system, S = Entropy of system, T =Temperature.

It is a state function. It is an extensive property. Its units are J/mol or kJ/mol

But H=U+PV

G U+PV-TS
The change in free energy AG is given by
AG AU+A(PV) - A(TS)
I fthe process is carried out at constant pressure and constant temperature, A(PV) = PAV and A(TS)= TAS

AGTP) =
AU + PAV -
TAS

AGT =
AH- TAS (since AU+PAV =AH

This equation is known as Gibb's Helmholiz equation.

Free energy change and spontaneity

For a non-isolated system, the total entropy change (AS total) decides the spontaneity of the
process.
AStotal AS system +AS surrounding

AS surrounding can be calculated from the knowledge of AH surroundings and T.

AS surrounding =
AHsurrounding = -

AH system
T T
Therefore
AS total= AS system -

AH system
Multiplying throughout by T
TAStotal =
TASsystem AHsystem -

TAStotal =
AHsystem -

T ASsystem
TAStotal = AGsystem.

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