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UNIT VI- THERMODYNAMICS

The branch of science which deals with the study of different forms of energy and the quantitative
relationships between them is known as thermodynamics.
The name “thermodynamics was given by mechanical engineers is the beginning who were interested only
in the conversion of heat into mechanical works (thermo means heat and dynamics means motion resulting
into mechanical work.
The importance of thermodynamic lies in the following two facts:-
i) It helps us to predict whether any given chemical reaction can occur under the given set of
conditions.
ii) It helps in predicting the extent of reaction before the equilibrium is attained.

Some Basic Terms and concepts: Some basic terms and concepts commonly used in thermodynamics are
briefly explained below:

1. System and Surroundings: The part of the universe chosen for thermodynamic consideration and
to study the effect of temperature, pressure etc.) is called a system
The remaining portion of the universe, excluding the system, is called surroundings.
A system usually consists of a definite amount of one or more substance and is separated from the
surroundings by a real or imaginary boundary through which matter and energy can flow from he system
to the surrounding or vice versa.

2. Open Closed and Isolated systems:

(a) Open system: A system is said to be an open system if it

can exchange both matter and energy with the surroundings.
For example if some water is kept in an open vessel of if some
reaction is allowed to take place in an open vessel (e.g. between
a piece of marble and HCI, exchange of both matter and energy
takes place between the system and the surroundings. Animals
and plants are open systems from the thermodynamic point of
view.
Fig (a) open system

(b) Closed system: If a system can exchange only energy with

the surrounding but not matter, it is called a closed system.
For example if some water is placed in a closed metallic vessel
or if some reaction is allowed to take place in a cylinder enclosed
by a piston then as the vessel is closed no exchange of matter
between the system and the surroundings can take place However
as the vessel has conducting walls exchange of energy can take
place between the system and the surroundings thus became an
example of closed system.
If the reaction is exothermic, heat is given by the system to the
surroundings. If the reaction is endothermic, heat is given by
surroundings to the system.

Fig(b)closed system
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(c) Isolated system: If a system can neither exchange

matter nor energy with the surroundings it is called
an isolated system. For example, if water is placed in
a vessel which is closed as well as insulated no exchange
of matter or energy can take place between the system
and the surroundings. This constitutes an isolated
system. Tea placed in thermos flask is an example of
an isolated system whereas tea placed in a closed
Steel tea- pot is an example of a closed system and
tea placed in an open cup is an example of an open system.

3. State of a system and state variables: The state of a system

means the condition of the system which is described in
terms of certain observable (measurable) properties such
as temperature (T) pressure (P) volume (V) etc of the system.
If any of these properties of the system changes the system
is said to be in different state i.e. the state of the system
changes. That is why these properties of system are called
state variables.

Fig (c) Isolated system

A process is said to occur when the state of the system changes. The first and the last state of a system are
called the initial state and the final state respectively.

4. State function: A physical quantity is said to be state function if its value depends only upon the state of
the system and does not depend upon the path by which this state has been attained. For example a person
standing on the roof of a five storied building ( i.e at a particular height) has a fixed value of potential energy
, irrespective of the fact whether the reached there by stairs or by a lift. Thus the potential energy of the
person is a state function. On the other hand the work done by the legs of the person to reach the same
height is not same in the two cases i.e. whether he went by lift or by stairs. Hence work is not a state
function. Instead it is sometimes called a ‘path function’.
Alternatively a physical quantity is said to be a state function if the change in its value during the process
depends only upon initial state and the final state of the system and does not depend upon the path by which
this change has been brought about.

5. Macroscopic properties (Expensive and Intensive properties): If a system contains a large number of
chemical species i.e. atoms ion or molecules, it is called a macroscopic system.
(i) Extensive properties: These are those properties which depend upon the quantity of the matter
contained in the system. The common examples of these properties are mass, volume and heat capacity.
Besides these, some other properties discussed later in this unit include internal energy enthalpy, entropy,
Gibbs free energy etc. The total value of an extensive property is equal to the sum of the values for the
separate parts into which the system may be divided for the sake of convenience.

(ii) Intensive properties: These are those properties which depend only upon the nature of the substance
and are independent of the amount of the substance present in the system. The common examples of these
properties are temperature, pressure later in this unit index, viscosity, density surface tension, specific heat
freezing point boiling point etc.
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Thermodynamics process: When a thermodynamic system changes from one state to the other the
operation or process is called thermodynamic process. The various types of the processes are as follows:
a) Isothermal process: A process is said to be isothermal in case the temperature of the system remains
fixed or constant (Iso: same, them: temperature) i.e. operation is carried at constant temperature. The system
is in thermal contact with the surroundings and heat energy can be exchanged between the two. It can flow
from system to the surroundings in case of exothermic process and vice versa in case of endothermic
process. For a isothermal process, dT= 0
(Where dT is the change in temperature) thus dE=0.

(b) Adiabatic process: In an adiabatic process, no exchange of heat between the system and the
surroundings is possible i.e., the system is completely isolated or insulated from the surroundings. In case,
the change carried in the system is exothermic, its temperature rises and if it is endothermic there is a fall
in temperature. In other words the temperature rises and does not remain constant in an adiabatic process.
In case, a change or reaction is carried in a thermos flask or some insulated contain, it will represent an
adiabatic process.

(c) Isobaric process:- A processes is said to be isobaric in which the pressure remains constant throughout
i.e., dP= 0. The volume may or may not change. For example, when water at 298 K and under atmosphere
pressure is heated to 373 K by keeping the pressure constant, it will be converted into steam. This is an
example of isobaric process.

(d) Isochoric process:- A process carried at constant volume is isochoric in nature. The pressure may or
may not change in the process. Thus for an isochoric process, dv=0. For example, in a gaseous reaction, if
there is no change in the number of gaseous reactants or product moles, it represents an isochoric process.
For example H2(g)+ Cl2 (g) → 2HCl (g)

(e) Cyclic process: When a system undergoes a series of changes and finally returns to its initial state it is
an example of cyclic process. There is no change in energy in a cyclic process. dE=0.

(f) Reversible process: A process is said to be reversible in case it is carried out infinitesimally slowly so
that all changes occurring in the direct process can be exactly reversed and the system and surroundings
remain in a state of equilibrium at any stage in the process.

(g) Irreversible process: It is a process in which the change is brought about rapidly and the system does
not have chance to achieve equilibrium. Actually, in an irreversible process, the force which drives the
reactants towards the products (called driving force) is greater than the opposing force which is to carry the
reverse process.

Zeroth Law of thermodynamics

Definition of Zeroth law.

This law was put forward much after the enunciation of the first and second law thermodynamics. However,
it is of primary importance as it gives the basis of the measurement of temperatures. Hence it is called as
zeroth law of thermodynamics or it is also called the law of thermal equilibrium.
To understand the origin of the law consider two bodies A and B separately in thermal equilibrium with the
third body C (i.e. bodies A and C have equality of temperature and bodies B and C also have equality of
temperature), then if the bodies A and B are brought in contact with each other the will also be
in thermal equilibrium.

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This leads to the following definition for the zeroth law

of thermodynamics.
When two bodies A and B are separately in thermal
equilibrium with a third body C, they in turn are
in thermal equilibrium with each other When
two bodies A and B have equality of temperature
with a third body C, they in turn have equality of
temperature with each other.

Internal energy: Whenever some process (physical or chemical) occurs, it is usually accompanied by
some energy change. The energy may appear in different forms such as heat, light, work etc.
The evolution or absorption of energy in different processes clearly shows that every substance must be
associated with some definite amount of energy, which is commonly known as Internal Energy. It is the
sum of different types of energies associates with atoms and molecules of the system such as electronic
energy (Ee), nuclear energy (En). Chemical bond energy (Ec), potential energy (Ep) and kinetic energy (Ek)
which is further the sum of translational energy (Et), vibrational energy (Ev) and rotational energy (Et).

Thus E= Eo+En+Ec+Ep+Ek

The energy thus stored within a substance (or system) is called its internal energy and is usually denoted by
the symbol ‘E’ or ‘U’.

It is not possible to fine the absolute value Internal Energy because it involves certain quantities which
cannot be measure. It is generally measured as Internal Energy Change, when the system passes from stage
I to stage II represented by E.

Further, internal energy is a state function i.e depends only upon the state of the system conditions of
temperature, pressure etc.) and is independent of the method by which this state has been attained. Thus if
the internal energy of a system in the initial state E1 and in the final state, it is E2 then the change of internal
energy (E) may be given by E= E2-E1

Sign of E: If E1> E2 (or ER>Ep) energy will be absorbed in the process and E will be positive. Hence E
is negative if energy is evolved and E is positive if energy is absorbed.

Units of E: The units of energy are ergs (in CGS units) or joules (in SI units) 1 joule = 107 ergs.

Work: If ‘F’ is the magnitude of the force and ‘d’ is the displacement then the mechanical work done is
given by w= Fd.
Two main types of work used in thermodynamics are briefly described below:

1. Electrical work: The generalized force is the E.M.F and the generalized displacement is the
quantity of electricity flowing through the circuit.
Then Electrical work done = E.M.F Quantity of electricity.

2. Work of expansion /compression or pressure- volume work: This types of work is involved in
system consisting of gases. This is the most important form of works used in the study of

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thermodynamics. It is the work done when the gas expands or contracts against the external pressure
(usually, the atmospheric pressure). It is a kind of mechanical work. The expression for such a
work may be derived as follows.

Consider an ideal gas enclosed in a cylinder fitted with a frictionless piston having area of cross- section
‘a’ sq. cm. let ‘V’ is the volume of the gas enclosed and ‘P’ be the pressure acting on the piston which is
slightly less than the internal pressure of the gas. So that the gas in a position to expand.
Then the pressure acting on the piston is the force per unit area will be f= Pa suppose that the piston move
to outward through a distance‘d’.
Therefore work done by the gas (i.e. the system) W= Force  Distance = fd= pad.

But ad= dv, a small increase in the volume of the gas.

Hence the small amount of work (dw) done by the gas
can be written as dw = Pdv.
If the gas expands from initial volume V1 to the final
volume V2 then the total work done (w) will be given by
V2
W =P  dV=P (V2-V1) =P.V
V
1
Where V= (V2-V1) is the total change in volume of the gas
(or the system).
If the external pressure (P) is slightly more than the pressure of the gas, the gas will contract i.e., the work
will be done by the surroundings on the system. However the same formula will apply for the work done.
Sign of w: According to the latest S.I. convention, w is taken as negative if work is done by the system
whereas it is taken as positive if work is done on the system. Thus for expansion, we write w= - PV and
for contraction, we have w= PV.
Unit of W: The units of work are the same as those of energy viz. ergs or joules
.
Work done in isothermal reversible expansion of ideal gas: The small amount of work done dw, when
the gas expands through a small volume, dV, against the external pressure, P is given by dw= -PdV.
Total work done when the gas expands from initial volume V1 to final V2 will be
v2
w = - PdV
v
1
For an ideal gas, PV = n RT i.e. P = nRT
V
V2
Hence w = -  nRT dV For isothermal expansion, T = constant so that
V1 V

V2
w= nRT  1 dV = -nRT in V2 or w= - 2.303 nRT log V2 = 2.303 nRT, log P1
V
1 V V1 V1 P2

(At const. temp P1V1 = P2 V2 or V2 = P1) the – ve sign indicates work of expansion.
V1 P2

First Law of Thermodynamics:

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The first law of thermodynamics is simply the law of conservation of energy which states that
(i) Energy cannot be created or destroyed although one form of energy can be converted into the
other form and vice versa.
(ii) The sum total of the energy of the universe remains constant or is conserved during any physical
change or chemical reaction.
(iii) Whenever a certain quantity of energy in one form disappears, an equivalent amount of energy
in another form reappears.
(iv) It is impossible to construct a perpetual motion machine i.e. machine which could perform work
without consuming any energy.

Justification for First Law of thermodynamics:

This law is purely a result of experience. There is no theoretical proof for it. However, some of the following
observations support the validity of this law. Whenever a certain quantity of some form of energy
disappears, an exactly equivalent amount of some other form of energy must be produced. For example,

(a) In the operation of an electric fan, the electrical energy which is consumed is converted into
mechanical work which moves the blades of the fan.

(b) The electrical energy supplied to a heater is converted into heat whereas electrical energy passing
through the filament of a bulb is converted into light

.
Thus energy is conserved in one form or the other though one form of energy may changes into the other
form.
Mathematical formulation of the first law of thermodynamics: The internal energy of a system can be
increased in two ways: i) By supplying heat to the system
ii) By doing work on the system.
Suppose the initial internal energy of the system= E1 If it absorbs heat q, its internal energy will become =
E1+ q. If further work w is done on the system, the internal energy will further increase and become =
E1+q+w. Let us call this final internal energy as E2.

E1 q w E1+q
w
E1+q+w

Then E2= E1+q+w or E2-E1= q +w or E = q + w ------------------- (i)

This equation is the mathematical formulation of the first law of thermodynamics.

If the work done is the work of expansion. Then w= - PV.Where V is the change in volume and p is the
external pressure. Equation (i) can then written as
E = q-PV or q = E + PV _________ (ii)
Two interesting results follow from the mathematical formulation of the first thermodynamics as under:-
(i) Neither q nor w is a state function, yet the quantity q+ w (= E) is a state function
(ii) For an ideal gas undergoing as isothermal change,E= 0. Hence q = - w i.e. the heat absorbed
by the system is equal to work done by the system.

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Enthalpy

The energy stored within the system or substance that is available in the form of heat is called enthalpy of
the system or substance. It is also called heat content. It is denoted by ‘H’.
The enthalpy may be defined mathematically be the following equations

H= E+PV

If H2 is the enthalpy of system at final state. And H1 is the enthalpy of system at initial state, them
H1= E1 + PV1 _______ (i)
H2 =E2 +PV2 ________ (ii)
Change in enthalpy can be calculated by subtracting equation (ii) from (i)

H2-H1 =E2-E1 +P(V2-V1)

H = E + PV

Hence the change in enthalpy is the sum of increase in internal energy of the system and the pressure volume
work done.

(i) Enthalpy of reaction: Enthalpy of reaction is defined as the mount of heat evolved or absorbed when
the numbers of moles of the reactants as represented by the balanced equation have completely reacted.

((s) +O2(g) → CO2 (g) H = -393.5Kj mol-1

H2(g) +1/2 O2 (g) → H2O (i)  H =- 286.5 Kj mol-1

(ii) Enthalpy of formation:- The standard enthalpy of formation ( usually represented by H. It is defined
as the enthalpy change that takes place when one mole of the substance under standard conditions is formed
from its constituent elements in their stable form and in their standard state. It is usually represented by Ht.

Example
C(s) +O2 (g) → CO2(g) H =- 393.5 KJ mol-1
H2(g) +1/2O2 (g) → H2O (I) H = - 286.5 KJ mol-1

Thus the enthalpy of formation of carbon dioxide and water is 393.5 and 286.5 KJ mol-1 respectively.

(iii) Enthalpy of combustion: The enthalpy of combustion of a substance is defined as the amount of heat
evolved when 1 mole of the substance is completely burnt or oxidized in oxygen.
C(s)+O2(g)→CO2 (g)H=-393.5 KJ mol-1

CH4(g)+ 2O2(g) → CO2(g) +2H2O(i) H=- 890.4 KJ mol-1

Standard Enthalpy of Combustion. The standard enthalpy of combustion of a substance is defined as the
amount of heat evolved when 1 mole of the substance under standard condition (298K, 1Atm. Pressure) is
completely burnt or oxidized in oxygen.
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Calorific values of foods and fuels. Just as the fuels like coal kerosene oil, gasoline (petrol). Diesel oil etc
are burnt to produce energy for the running of machines, similarly the carbohydrates are first decomposed
in our body by the enzymes to form glucose which then undergoes oxidation by the oxygen that we inhale
to produce energy.
Different fuel and foods produce different amounts of heat on combustion. These are usually expressed in
terms of their calorific value which is defined as follows:-

The calorific value of fuel or food is the amount of heat in calories or joules produced from the complete
combustion of one gram of the fuel or the food.

(IV) Enthalpy of Neutralization

The enthalpy of neutralization of an acids by a base is defined the heat change (usually the heat evolved)
When one gm. Equivalent of the acid is neutralized by a base the reaction being carried out in dilute aqueous
solution.
The enthalpy of neutralization of a base by an acid is a similar manner.
For example, when one gram equivalent of HCI is neutralized by NaOH or one gram equivalent of NaOH
is neutralized by HCI both solution being dilute and aqueous, 57.1 KJ of heat is produced. Thus we may
write

NaOH + HCI → NaCI +H2O H = - 57.1 KJ mol-1

The neutralization is simply a reaction between the H+ ions given by the acid with the OH- ions given by
the base to form one mole of H2O.
Since strong acids and strong bases ionize completely in dilute aqueous solution, the number of H+ ions and
OH-1 ions produces by one gram equivalent of the strong acid and the strong base is always the same. Hence
the enthalpy of neutralization between a strong acid and a strong base is always constant.
In case either the acid or the base or both are weak, the enthalpy of neutralization is usually less than 57.1KJ.
In the neutralization of NH4OH with HCI, 5.6KJ of heat is used up for the dissociation of weak base i.e.
NH4OH. Hence the enthalpy of neutralization in this case is only 57.1-5.6= 51.5 KJ.
(V) Enthalpy of atomization.
When one mole of a given substance dissociates into gaseous atoms, the enthalpy change accompanying
the process is called Enthalpy of atomization.
It is represented by symbol ∆a Ho

o -1
H2 (g) + 2H (g), a H = 435.0kj mol

(VI) Enthalpy of sublimation of a substance is the enthalpy change accompanying the conversion of 1
mole of a solid directly into vapour phase at a given temperature below its melting point.
For example,

I2 (s) + I2 (g), H= +62.39 kj mol-1

sub

(VII) Enthalpy of ionization.

When a covalent compound on dissolution in water splits to produce ions in the solution, the enthalpy
change accompanying the process is called Enthalpy of ionization.
For example,

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HCl (g) + aq H+ (aq) + Cl- (aq), o -1
ion H = -75.2 kj mol

(VIII) Bond energies or Bond Enthalpy: We now that energy is evolved when a bond is formed and
energy is required for the dissociation of a bond. Hence bond energy is defined as follows:-
Bond energy is the amount of energy released when one mole of bonds are formed from the isolated atoms
in the gaseous state or the amount of energy required to dissociate one mole of bonds present between the
atoms in the gaseous molecules.

Heat Capacity
The heat capacity of a system is defined as the amount of heat required to raise the temperature of the
system through IC.
Thus if q is the amount of heat supplied to a system and as a result, if the temperature of the system rises
from T1 and T2 then heat capacity (C) of the system is given by
C= q = q or C = sq
T2-T1 T dT

Specific Heat Capacity

The specific heat capacity of a substance is defined as the amount of heat required to raise the temperature
of 1 gram of the substance through IC.
If instead of 1g, 1 mole of the substance is taken, the term used is called ‘molar heat capacity’.

Thus Molar heat capacity of a substance is defined as the amount of heat required to raise the temperature
of one mole of the substance through 1C.

Example. To understand the difference between heat capacity, specific heat capacity and molar heat
capacity, let us take the following example.

A piece of Al metal weighing 3g requires 5.4 J of heat to raise the temperature from 298 K to 300K. Then
Heat capacity of the piece of Al = 5.4J = 2.7JK-1
2K
Specific heat capacity of Al = 5.4J = 0.9Jg-1 K-1
3g 2K
Molar Heat Capacity of Al = 5.4J  27= 24.3J mol-1 K-1
3g 2K
Types of heat capacities.
Since ‘q’ is not a state function and depends upon the path followed therefore C is also not a state function.
Hence to know the value of C, the conditions, such as constant volume or constant pressure have to be
specified which define the path. Thus there are two types of heat capacities, which are
i) Heat capacity at constant volume Cv
ii) Heat capacity at constant pressure Cp
The supplied to a system to raise its temperature through IC keeping the volume of the system constant is
called heat capacity at constant volume Similarly, the heat supplied to a system to raise its temperature
through lC keeping the external pressure constant called heat capacity at constant pressure.
According to the 1st law of thermodynamic we know that dQ= dE +P dV
or dQ= dE +PdV
dT dT

or C= dE + PdV
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dT dT ………………………….1

When the volume of the system is constant. dv =0

Then PdV=0  Cv= dE  Heat capacity Cv = dE

dT dT

Thus heat capacity at constant volume may be defined as the rate of change of internal energy with temp.
at constant volume.
When the pressure is kept constant during the absorption of heat, equation (1) becomes

Cp = dE + P dV …………………………2
dT dT
Also, we know that the heat content or enthalpy of a system is given by

H = E + PV
Differentiating w.r.t T at constant P , we get

dH = dE + P dV …………………………3
dT dT dT

Combining equation 2 and 3 . we get

Cp = dH
dT

Thus heat capacity at constant pressure may be defined as the rate of change of enthalpy with at constant
pressure.

Relationship between Cp & CV.

By the definition of enthalpy we have the elation H = E +PV and PV = RT for one mole of an ideal gas

 H= E+RT – (i)

Differentiating this eq. w.r.t. T, we get

dH = dE +R
dT dT

or Cp= Cv + R

or Cp- Cv= R

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R= 2colouries
= 8.314J.

Hess’s Law of Constant Heat Summation

G.H. Hess, a Russian chemist, in 1844, gave a law about the heats of reactions on the basic of experimental
observations. This law is known after his name as Hess’s law. It states as follows:
The total amount of heat evolved or absorbed in a reaction is the same whether the reaction takes place in
one step or in a number of steps. In other words, the total amount of heat change in a reaction depends only
upon the nature of the initial reactants and the nature of the final products and is independent of the path or
the manner by which this change is brought about.
Example when carbon (graphite) burns to form carbon dioxide directly in one step 393.5 KJ mol-1 of heat
is produced i.e
C(s) + O2 (g) → CO2 (g) H = - 393.5 KJ mol-1
If carbon burns to from carbon monoxide first which the burns
to from carbon dioxide, the heats evolved in the two steps are as follow

C(s)+ ½ O2 → CO(g) H =- 110.5 KJmol-1

CO(g) +½ O2 → CO2 (g)  H = - 283.0 KJ mol-1

Thus the total heat evolved in the two steps will be H= (-110.5)+(-283)Kj mol-1 Which is the same when
the reaction takes place directly in one step.
Theoretical Proof of Hess’s Law.
Consider the general reaction A→ D
Suppose the heat evolved in this reaction directly is Q joules.
Now Suppose the same reaction takes place in three steps as follows
A →B→ C →D
Suppose the heats evolved in these three steps are q1 , q2, q3 joules reapectively
Thus the total heat evolved = q1+q2+q3 = Q’ joules
According to Hess’s law, we must have Q = Q’
If Hess’s law were not correct, then either Q’ < Q or Q’>Q

Suppose Q’ >Q. This means that if we go from A to D in a number of steps, the heat evolved is more than
the heat absorbed when we return from D to A directly in one step. (Remember that for the direct process
A →D. Q’ joules of heat is evolved. So for the reverse process viz. D → A, Q joules of heat will be
absorbed). Thus when the cyclic process is completed, Q – Q’ joules of heat is produced. Thus by repeating
the cyclic process a number of times, a large amount of heat can be created. This is however against the law
of conservation of energy. Hence Q must be equal to Q i.e Hess’s law must be correct.
Applications of Hess’s law, The most important application of Hess’s law is in the calculation of heat
changes for those reactions for which experimental determination is not possible.

Spontaneous Process: A process which has a natural tendency to occur with or even without initiation
under a given set of conditions (i.e temp. Pressure, concentration etc.) is called a spontaneous Process. A
spontaneous process is also known as a feasible or Probable Process. The tendency of a process to take

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place at its own is called spontaniety or feasibility of the process. Some examples of spontaneous processes
are given below:-
(a) Spontaneous Process that need no initiation:
(i) Flow of heat from a hot body to a cold body.
(ii) Evaporation of water in an open container.
(iii) Flow of water down the hill.
(b) Spontaneous Process that need initiation:
(i) Burning of methane in air to form CO2 and H2O.
CH4 + 2O2 Ignition CO2 + 2H2O.
(ii) Burning of coal in air
C + O2 Ignition CO2.
Driving force for a spontaneous Process: The force which is responsible for the spontaniety of a process
is called the driving force. There are two factors which are responsible for the spontaniety of a process.
(1) Tendency of a system to acquire a state of minimum energy:
Most of the systems have tendency to acquire a state of minimum energy for maximum stability e.g. A
stone lying at a height has a tendency to fall down as to have minimum energy. In other words most of the
spontaneous processes are exothermic in nature i.e H is negative. But there are also some processes which
are endothermic in nature and are also spontaneous.
(2) Tendency of a Process to have a state of Maximum randomness.
Most of the spontaneous processes have a tendency to acquire the state of maximum randomness or
disorder. e.g. evaporation of water is a spontaneous process because when water changes to vapour phase,
the randomness increases. But there are also some spontaneous processes in which randomness decreases.
e.q. liquefaction of a gas, solidification of a liquid etc. Thus it may be concluded that the overall tendency
for a process to be spontaneous will depend upon both the factors i.e. (1) Tendency of minimum energy (2)
Tendency of maximum randomness.
The resultant of the above two tendencies which gives the overall tendency for a process to occur is called
the driving force of the spontaneous process.

Non-Spontaneous Process: A process which can neither take place by itself nor by initiation is called non-
spontaneous process e.g.
(i) Flow of water up a hill. (ii) Flow of heat from a cold body to a hot body.

Some important points

1. Both internal energy and enthalpy are state functions.
2. Both are extensive properties.
3. The absolute value of neither internal energy nor enthalpy can be determined.
4. Internal energy change is the heat evolved or absorbed at constant volume while enthalpy change is that
at constant pressure i.e E = qv, H = qp.
5. In a cyclic process i.e. when the system returns to original state after a number of changes, E or H =
0.

Entropy :
The spontaneous processes like melting of ice into water, evaporation of liquid into vapours etc. undergo
change to a state of higher energy or to a state of more disorder or randomness. Thus, the property of the
substance or a system which measures the randomness or disorder in it is known as entropy of the
system. It is denoted by S. More is the disorder or randomness more is the value of S i.e. entropy and vice
versa. A perfectly crystalline substance is considered to be in most ordered state at 0k (-273oC) and
Dr. SANDEEP VERMA
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therefore, its entropy at this temperature is taken to be zero. As the temperature is increased, the molecular
motion sets in leading to the increase in disorder due to which entropy of the system increases. For a given
substance, the solid state is the state of least entropy (most ordered) gaseous state is the state of highest
entropy while liquid state is intermediate between the two. Like internal energy & enthalpy, entropy of a
system is also a state function. It is not possible to determine the absolute value of entropy of a system,
however a change in entropy ( S) can be determined.
Entropy is a state function. The change in entropy is given by the entropy in the final state minus. the
entropy in the initial state.
 Change in entropy (S) = S final – S initial
Entropy change during a process is defined as the amount of heat (q) absorbed isothermally and reversibly
divided by the absolute temperature (T) at which the heat is absorbed.

 S = qrev.
T
Now according to first law of thermodynamics,
qrev = E + PV
E + PV
 S =
T
For a chemical reaction
S = Sproducts−Sreactants
Units: In C.G.S system the entropy change is expressed in Cal. K -1mol-1 and in S.I units it is expressed in
Joules k-1 mol-1.
Physical Significance of entropy: Entropy is a measure of disorder or randomness of a system. Thus when
a system undergoes a change from more ordered state to a less ordered state, there is an increase in
randomness and hence the entropy of the system increases e.g. When a solid changes to a liquid form, there
is increase in entropy because in a solid, there is ordered arrangement while in the liquid state, there is less
ordered arrangement. On the other hand, when a system undergoes a change from a less ordered state to a
more ordered state, the entropy of the system decreases. e.g. When a liquid changes into a solid there is an
increase in ordered arrangement and hence entropy decreases.
Spontaniety in terms of entropy: (i) For a spontaneous process in an isolated system, the randomness
increases and thus entropy change (S) is positive.
In case of non-isolated systems, the total entropy change of the system and the surrounding is taken into
consideration.
Stotal = Ssystem + Ssurrounding = O (For reversible process)
and Stotal = Ssystem + Ssurrounding > O (For irreversible process).
(i) For spontaneous process Stotal is +ve
(ii) For non-spontaneous process Stotal is -ve
(iii) For a process in equilibrium Stotal = 0.

FREE ENERGY: The free energy of a system may be defined as the net available energy of the system,
which can be converted into useful work. It is also known as Gibbs free energy. (After the name of Willard
Gibbs who gave the concept of free energy). It is denoted by G.
Mathematically,
G = H – TS Where H = Enthalpy of the System T = Absolute temperature
S = Entropy of the system
Change in free energy: It is denoted by G and is given by
G = G2 – G1 Where G1 is the free energy in the initial State and G2 is the free energy in the final State.
Dr. SANDEEP VERMA
 14
Let us consider a system that undergoes a change from one state to another at constant temperature
(Isothermal process).
Then in the initial state,
G1 = H1 – TS1 - - - - - - (1)
And in the final state,
G2 = H2 – TS2 - - - - - - - (2)
Subtracting (1) from (2) we have
G2–G1 = (H2 –TS2) – (H1–TS1)
or G = H2–TS2–H1 + TS1
or G = (H2–H1) – (TS2–TS1)
or G = H – T(S2 – S1)
or  G = H – T  S
G(T,P) = H – TS
G(T,P) is the free energy change at constant temp. and pressure
H = Enthalpy change and
S = Entropy change.
Since H = E + PV
 Above equation can be written as
GT,P = E + PV – TS
This equation is also known as Gibb’s Helmholtz equation.

Physical Significance of free energy :

The decrease in free energy of a system during any change is a measure of useful work derived from the
system.
According to first law of thermodynamics
q = E + w ----------- (1)
Where q = Heat absorbed by the system
w = Work done by the system on the surroundings
E = Increase in internal energy of the system
Since w = Wexp + Wnon-exp
q = E + Wexp. + Wnon-exp.
But Wexp. = PV (at constant pressure)
q = E + PV + W non-exp.
or q = H + Wnon-exp -------- (2)
Now for a reversible process taking place at constant temp.
S = qrev./T where q is the heat absorbed reversibly at temperature T.
qrev = TS
Substituting the value of q in equation (2)
We have
TS = H + Wnon-exp
Or −Wnon-exp. = H − TS --------- (3)
But at constant temp. and pressure
G = H - TS - - - - - -- - (4)
 From = ns (3) and (4) we have
Wnon-exp. = −G
For most of the cases, the expansion work cannot be converted into useful work whereas non-expansion
work is convertible to useful work.

Dr. SANDEEP VERMA

 15
Wuseful = − G
Hence decrease in free energy during any change is a measure of useful or net work derived from the system.
In other words free energy is a part of the energy of the system which is free for its conversion into
useful work..
Spontaniety in terms of free energy change (G)
The total entropy change for a system which is not isolated from the surrounding is given by
STotal = + Ssystem + Ssurroundings - - - - - (i) constant T and P. Suppose the heat is lost by the surroundings
and gained by the system.
qp − H
Then Ssurrounding = = - - - (ii)
T T
From (i) and (ii), we have

Stotal = Ssystem − H
T
or Simply, Stotal = S – H - - - - (iii)
T
or TStotal = TS – H - - - - - (iv)
Now G = H – TS
Or – G = TS – H - - - - - (v)
From eq(iv) and (v) we get.
TStotal = – G
or G = – TStotal - - - - - (vi)
But in terms of total entropy change, it is known that.
(i) If Stotal is positive, the process is spontaneous
(ii) If Stotal is zero, the process is in equilibrium and
(iii) If Stotal is negative, the direct process is non-spontaneous and the reverse process may be spontaneous.
It implies from eq(vi) that
(i) If G is negative, the process will be spontaneous
(ii) If G is zero, the process is in equilibrium.
(iii) If G is positive, the direct process is non-spontaneous; the reverse process may be spontaneous.
The value of G depends upon the value of H, S and T as given below :
H S G = H – TS Nature of the Process
(i) -ve +ve Always –ve Spontaneous at all temp.
(ii) -ve +ve +ve at low temp. Non-Spontaneous at low
temp if TS <H
(iii) -ve +ve -ve at high temp Spontaneous if TS>H
(iv) -ve -ve -ve at high temp Spontaneous if H>TS
(v) -ve -ve +ve at high temp Non-Spontaneous if
TS>H
(vi) +ve -ve Always +ve Non-Spontaneous or
Forbidden at all temp.

Dr. SANDEEP VERMA

 16

Criteria for the prediction of spontaniety of a process:

Depending upon the signs of ∆H and and their relation, the spontaneity of the process can be
predicted as follow:
1) When and are negative i.e. energy factor favours the process but randomness factors
apposes it .Then:
i) If , the process is in equilibrium and
ii) If the process is spontaneous and
iii) If the process is non-spontaneous and
2) When both ∆H and are i.e. energy factor opposes the process but randomness factor
favours it. Then:
i) If , the process is an equilibrium and
ii) If the process is non-spontaneous and
iii) If the process is spontaneous and
3) When ∆H is negative but is positive i.e. energy factor and randomness factors both favour the
process. The process will be highly spontaneous and ∆G will be highly
4) When H is but T S is e.g. energy factor as well as randomness factor opposes the
process. The process will be highly non-spontaneous and ∆G will be highly

Dr. SANDEEP VERMA