MODULE-II: FREE ENERGY IN CHEMICAL EQUILIBRIA

Thermodynamics
It is the branch of physical Science dealing with the quantitative relation between heat and
mechanical energy.

It is the study of Energy changes associated with physical or chemical transformation.

It is main mainly concerned with transformation of heat into mechanical work and vice versa.

Another important aspect of thermodynamics is to establish the criteria of Spontaneity for a

particular chemical or physical transformation.

Terms Associated with Thermodynamics

System:- Any specific portion of matter under consideration or study, which is separated from the
rest of the universe. With a bounding surface (Real or imaginary boundary)

Classification of system:- On the basis of homogeneity, System is of two types.

〈𝒊〉 Homogeneous System: - The system which is uniform throughout and consists of only one
phase

Example-mixture of gases

〈𝒊𝒊〉 Heterogeneous System:-The System which is not uniform throughout and consists of more
than one phase, Example-mixture of Solids,

On the basis of the nature of boundary, System is of three types.

〈𝒊〉 Open system (Boundary allows the exchange of both matter & energy)

A system which can exchange mass as well as energy with the surroundings is called as open
system. ((𝜕𝐸 ≠ 0 , 𝜕𝑚 ≠ 0)

Example- Evaporation of water from a conical flask

〈𝒊𝒊〉 Closed System (Boundary allows only the exchange of energy)

A system which can exchange energy with the surroundings across the wall but not the mass is
called as closed system

Example-Boiling of water in a closed or sealed vessel 𝜕𝑚 = 0 , 𝜕𝐸 ≠ 0

〈𝒊𝒊𝒊〉 Isolated system (Insulated system)

A system which can neither exchange energy nor (or matter) mass with the surrounding is called as
isolated system. 𝜕𝐸 = 0 , 𝜕𝑚 = 0

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Example: - Reaction of sodium with water in an insulated vessel.

Sig:-

Surroundings: - Rest of the universe, other than system is known as surroundings.

Macroscopic system & Macroscopic Variables

A system which consists of a large number of atoms, ions or molecules is called a macroscopic
System. The variables associated with a macroscopic system are called macroscopic variables.

Example: - Temperature, pressure, concentration, mass, density composition etc. are macroscopic
variable.

Boundary or wall

The system generally is separated from the surroundings by a boundary or wall or partition

This wall can be of two types.

〈𝑖 〉 Diathermal wall:- The wall or boundary which allows heat but not matter to pass across it.

Diathermal wall conduct heat.

Two system can reach thermal Equilibrium. Example:- wall made up of copper or tin.

〈𝑖𝑖 〉 Adiabatic wall:- The wall or boundary which allows neither heat nor matter to pass across it.

Two system in contact by adiabatic wall do not communicate with each other and never reach
thermal equilibrium.

Two system in contact by adiabatic wall do not conduct heat

Ex. Wall made up of concrete, asbestos, polystyrene.

Properties: - The physically measurable parameters that enable to define the system.

Thermodynamic properties: - These properties are generally associated with the bulk of matter.

The properties of system are of two types

1) Extensive properties (Mass dependent properties)→ The property which depends upon the
amount of substance (quantity of matter) present in the system i.e size of the system is
called Extensive properties.

𝑚𝑎𝑠𝑠 𝑣𝑜𝑙𝑢𝑚𝑒 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑒𝑛𝑡𝑟𝑜𝑝𝑦

Example:- (𝑚) , ( ) , , , ( ) , ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
𝑉 (𝑈) (𝐻) 𝑠

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 2) Intensive properties :- The property which does not depend upon the amount of the
substance (quantity of matter) present in the system is called as Intensive property . i.e the
property is independent of size of the system, EX. Temperature (T) Pressure ,density
,concentration ,viscosity, surface tension etc. specific heat ,molar heat capacity.

State variable:- The measurable properties of a system which completely define the state of a
system are state variable or thermodynamic variable.

Example: - Pressure ,Volume, Temperature ,Concentration.

State function The property of a system which is uniquely determined by the present state of the
system and not at all by the previous history of the system is known as state function.

Example:- Internal Energy, Enthalpy, Entropy ,free Energy, pressure ,volume ,Temperature ,
Composition.

Path function :- A path function is that which does depend on the previous history of the system.i.e
path adopted as the system is generated ,i.e heat , work ,etc.

A quantity that depends on the path of the system i.e on the process which take the system to
achieve the current state .but not on the initial or final state of the system.

Example:- Heat , Work

Thermodynamic process:- The operation by which a thermodynamic system changes from one
state to another is called thermodynamic process.

Different thermodynamic process

(1) Isothermal process

Temperature remains constant during the process in spite of heat entering or leaving the
system . (𝜕𝑇 = 0)
Example: - Change of state like freezing ,melting ,evaporation and condensation is an
isothermal process.
(2) Adiabatic process
A process during which no heat enters or leaves the system during any step of the process.
Heat is neither absorbed or released,i.e change in heat dq =0
Ex:-Reaction carried out in an isolated system.
(3) Isobaric process
A process during which pressure of the system remains constant throughout the process.
The change in pressure 𝜕𝑝 = 0 and is always accompanied by the change in volume.
Example:-heating of water to its boiling point and its vaporisation takes place at same
atmospheric pressure.
(4) Isochoric process
A process during which volume of the system remains constant throughout the process
* Change in volume (𝜕𝑣 = 0)

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 (5) This is always accompanied by change in pressure. (Ex-heating of substance in a non-
expanding chamber)

(6) Cyclic process :- A process during which a system comes to its initial state through a
number of different process is called cyclic process.
 After a series of transformation the system comes back to its initial state.
(7) Reversible process :- A process is said to be reversible ,when the 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.
(8) Irreversible process:- Irreversible process is one which system or surroundings are not
restored to their initial state.
EX:- All natural process are Irreversible and hence spontaneous once undergone the
process cannot be reverted without changing the properties of the surrounding .

THERMOCHEMISTRY

Internal Energy (U)

The total Energy contained in a system due to potential Energy, Kinetic Energy, translational
Energy, rotational Energy, vibrational energy is called Internal Energy or Intrinsic Energy.

U =𝑈𝑡 + 𝑈𝑣 + 𝑈𝑟 + 𝑈𝑛 + 𝑈𝑖 𝑒𝑡𝑐

Absolute internal Energy of a system cannot be determined due to involvement of large number of
different types of energy .

However the change in internal energy during chemical reaction can be determined

If 𝑈1 &𝑈2 are internal energy of reactant and product respectively then change in internal energy is

∆u = (U2 – U1)
𝑖. 𝑒 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙

𝑑𝑢𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝜕𝑢𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑢𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔

Significance: - If a system is isochoric (volume is constant) then

∆v = 0, ∆u = q.

Thus ∆u signifies that the heat change taking place at const volume.

* Internal Energy of a system is an extensive property.

* Internal Energy is a state property.

*The change in Internal Energy does not depend upon the path followed.

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*In a cyclic process there is no change in Internal Energy .i.e ∆u =0

ENTHALPY:- Enthalpy or heat content of a system is the total amount of energy stored in the
system or substances at constant Pressure .It is denoted by ‘ H ‘

H = U + PV

∆H = ∆U + P∆V
In case of solid and liquid reactants & products ∆v = 0 ⟹ ∆H = ∆U

CHARACTERISTICS OF ENTHALPY ⟹

*It is a state function

*It is an extensive property

Change in enthalpy does not depends upon the path followed.

When ∆v = 0, ∆u = q

When ∆p = 0, ∆H = q

Relation Between ∆H & ∆U

∆𝐻 = ∆𝑈 + 𝑃∆𝑉

For Ideal gas, PV = ɳRT

⇒ 𝑷∆𝑽 = ∆ɳ𝑹𝑻

Now,∆𝑯 = ∆𝑼 + ∆ɳ𝑹𝑻

When ∆ɳ = 0, ∆H = ∆U

∆ɳ > 0, ∆H > ∆U

∆ɳ < 0, ∆H < ∆V

∆ɳ = no of gaseous products – no of gaseous reactants.

First law of thermodynamic

It is the law of conservation of energy, can be defined as

The heat transferred to a closed system is the net heat change of system & the useful work done
by the system. or the total Energy of the universe is constant or the energy can neither be created
nor destroyed but one form of energy can be converted into other form of energy.

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So, If dq is the amount of heat supplied, du is the change in internal energy, dw is the work done by
the system.

Then

dq = du + dw
If dw is the work done on the system,

dq = du - dw But we know, dw = pdv If dv =0, dq = du

In cyclic process du = 0, dq = dw

Disadvantages:- The first law of thermodynamics states that energy is inter- convertible. If one
form of energy disappears an equivalent amount of another form of energy will be generated. But
it doesn’t predict the following:-

i) It doesn’t indicate the direction of heat transfer.

ii) It can’t predict the reason for expansion of gas in vaccume
iii) It can’t predict why the whole heat energy can never be converted into work.
iv) It doesn’t predict about the spontaneity of the process.

Thus the second law of Thermodynamics can be defined in several ways

Second law of Thermodynamics

The second law of thermodynamics is a combination of several statements. The first statement
among these is-----

1. All spontaneous processes are thermodynamically irreversible.

This implies that a spontaneous process can only be reversed by the external agency, just
like water can be sent upwards for storage in a tank situated at the roof of a building by
means of a pump and electric motor. The second statement is stated as—
2. The complete conversion of heat into work is impossible without leaving a permanent
change elsewhere.
3. The second law of thermodynamics is stated in terms of entropy as ---
All spontaneous processes are accompanied by net increase in entropy and the total
entropy change is always positive. In other words , the entropy of the universe is increasing
continuously.
4. The second law of thermodynamics mainly deals with the concepts and applications
involving a heat engine which is a device that operates in a cycle and converts heat
continuously into work. In that regard, the Kelvin-Planck statement and the Clausius
statement are both discussed below.

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  Kelvin-Planck statement: The construction of an engine that operates in a cycle and
produces no effect other than the extraction of heat from a hot reservoir and
performance of an equivalent amount of work is not possible.
 Clausius statement: The construction of a device that operates in a cycle and
produces no effect other than the transfer of heat from a body having lower
temperature (colder body) to a body having higher temperature (hotter body) is not
possible.

Spontaneity:- A spontaneous process is a process that occurs in a system by itself under a given
set of conditions. Once such processes are started, no action from outside the system, i.e, external
agency, is necessary to make the process continue. For example,

A. Processes that requires no initiation

1. An ice cube melts to water at room temperature.
2. Water always flows downhill.
3. Gases flow from higher pressure to lower pressure.
4. Heat is always transferred from a hotter body to a colder body.
5. Diffusion of solute particles in a solution always occurs from higher concentration to
lower concentration.
B. Processes that require only initiation.
1. A mixture of hydrogen and oxygen burns if ignited by a spark.
2. Burning of coal
3. Decomposition of calcium carbonate.

The spontaneous processes are generally irreversible in nature. All spontaneous processes have a
tendency to attain equilibrium.

A non-spontaneous process is one which cannot take place unless some external action is
continuously applied. They neither take place by their own nor have any tendency to occur. For
example,

1. Transfer of heat from colder body to hotter body.

2. Decomposition of H2O into H2 and O2
3. Movement of water uphill.
4. Flow of gases from low pressure to high pressure.

In general, both spontaneous and non-spontaneous processes are possible. If a process is

spontaneous, the reverse process will be non- spontaneous. The spontaneous processes occur
naturally whereas non-spontaneous processes require the help of an outside agency to occur. But
the obvious question that arises is why most of the reactions tend to be spontaneous. The answer
to this question lies in the fact that systems tend to be stable. For stability, the most important
factor is that the systems should have minimum energy. Thus, processes of transformation are
feasible if overall energy of the system lowers due to that process or transformation. Thus, water
flows downhill in order to acquire less potential energy. Tendency to attain maximum randomness

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is another criterion for spontaneity. If two gases are mixed, the randomness of the system
increases. Thus, ice melts to from water, due to which randomness increases.
Entropy: - The measure of degree of randomness of a system is called as entropy.

Greater the degree of disorderness of a system higher is the entropy.

It is denoted by the symbol S.

Absolute entropy of a system cannot be measured. It is measured as change in entropy.

𝑞𝑟𝑒𝑣
∆𝑠 = 𝑆𝑓 − 𝑆𝑖 and is given by ∆𝑠 = 𝑇

A system at absolute zero temperature may have very less entropy and a 100% crystalline solid at
o0k has zero entropy.

The unit of entropy is J mol-1 k-1 or Cal mol-1k -1

Characteristics of entropy

1) Entropy is a state function. Therefore, dS depends only upon the initial and final state of the
system and does not depend upon the path by which the system moves from the initial
state to the final state.
2) Entropy is an extensive property.
3) When heat is absorbed by a system, the entropy of the system increases and when heat is
rejected by a system, the entropy of the system decreases.
4) In a reversible adiabatic process dqrev =0, so dS =0.Therefore,if a system undergoes a
reversible adiabatic process then dS will be zero.
5) For an irreversible process, d S ≠ (𝑑𝑞𝑖𝑟𝑟 )/T; Where d S = entropy change of the irreversible
process, dqirr = heat absorbed in this process at temperature T.

Physical significance of entropy

Entropy is related to the disorderliness of system. If we add energy as heat to the system, then the
entropy of the system in increased due to the increase in thermal disorderliness. So the increase in
entropy is a measure of the increase in disorderliness or randomness of the system. Disorderliness
is the portion of energy that cannot be converted into useful work.

The type of energy is called unavailable energy. Since increase in entropy is a measure of the
increase in disorderliness or randomness, so we can say that entropy of the system is also a
measure of unavailable energy. Thus the property of a substance which measures the
disorderliness or randomness in a system is also called as entropy.

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Some common factors that affect the entropy of the system.

Since the increase in disorderliness or randomness is a measure of the increase in entropy of the
system ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 , we can often predict the entropy change of the system due to following change.

Temperature change:- If any sample is warmed then the particles within the sample will move
more randomly. Hence entropy of the system increases with rise in temperature

Volume change: - With increasing volume, the particles get more space to move randomly. Hence,
expansion is accompanied by an increase in entropy of the system. Conversely, when a sample is
compressed, molecules are more restricted in the locations. Hence, a compression is accompanied
by a decrease in entropy of the system.

Mixing of substances (even without chemical reaction) : we have already mentioned that mixed
gases are more disordered than unmixed gases. Also mixing process is spontaneous. So, entropy of
the system increases due to mixing of substances.

Phase change: - we know that in solid, the molecules are more orderly arranged than liquid or
gases. During melting, vaporization and sublimation, the molecules shift from their more ordered
arrangement to a more disordered one. Thus, the melting, vaporization and sublimation processes
are always accompanied by an increase in entropy of the system.

Change in the number of particles: With increase in the number of particles, the entropy of the
system increases and vice versa.
−1
For example 𝐶𝐿2 (𝑔) ⇢ 2𝐶𝑙(𝑔 ) ∆𝑆 0 = 107.2𝐽𝑚𝑜𝑙𝑒 −1𝑘

One molecule of chlorine dissociates to give two atoms of chlorine. Due to net increase in the
number of particles, the entropy of the system increases. Thus the ∆𝑆 0 for the above reaction is
positive.

Changes in the number of moles of gaseous substances: with increase in the no. of moles of
gaseous substances, the entropy of the system increases and vice versa.
−1
For example: 2𝐻2 (𝑔) + 𝑂2 (𝑔) ⇢ 2𝐻2 0(𝑔) ∆𝑆 0 = −163𝐽𝑚𝑜𝑙𝑒 −1𝑘

Hence 2 moles of H2 react with one mole of O2 (total number of mole of reactant =3) to from 2
moles of H2O (total number of mole of product =2) .Due to net decrease in the number of moles in
the gas phase, the entropy of the system decreases. This ∆𝑆 0 for the above reaction is negative.

Molecular interpretation of entropy: All spontaneous processes such as flow of electricity from a
point of higher potential to a point of lower potential, diffusion of a solute from a concentrated to
a dilute solution. Expansion of gas in vaccum and flow of heat from a hot end to a cold end of a
conductor are accompanied by increase of energy. It can also be known that these spontaneous
processes lead to increase in the disorder of the system. To understand this let us consider the
transfer of molecules of a solute from a more concentrated to a less concentrated solution. As
soon as the two solutions are brought into contact, spontaneous process of diffusion starts and
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disorderness increases till the equilibrium is attained. Thus spontaneous processes are
accompanied by increase in entropy as well as increase in disorder of the system.

Let us consider more examples .Melting of a solid or evaporation of a liquid is accompanied by

increase of entropy. In a solid, the atoms, ion or molecules are arranged in a definite order. The
order is less in liquid and least in gas. Thus, increase of entropy results in increasing disorder.
Therefore, entropy is regarded as a measure of the disorder of a system.

Entropy changes in phase transformation

The change of a substance from one state to the other is known as phase transformation. Such
changes taking place at definite temperatures are accompanied by change in entropy. This is
known as entropy of transformation.

Entropy of Phase Change

A process of change of state i.e melting of solid, vapourisation of liquid may be carried out at
constant temperature reversibly as the two phases are in equilibrium for all times during the
change.

For the process of change of state of one mole of substance is carried out reversibly.

i.e The amount of heat absorbed will be equal to the molar heat of fusion or vapourisation & the
temperature will be melting point & boiling point.

Entropy of fusion: - It is defined as the change in entropy when one mole of a solid substance
transforms in to the liquid state at its melting point. The molar entropy change accompanied by
fusion process is given by

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛
∆𝑆𝑓𝑢𝑠𝑖𝑜𝑛 =
𝑇𝑓𝑢𝑠𝑖𝑜𝑛

Where,∆𝑆𝑓 = molar entropy change (for one mole of solid) accompanied by fusion process

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 = 𝑚𝑜𝑙𝑎𝑟 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑢𝑠𝑖𝑜𝑛.

𝑇𝑓 = 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑟 𝑚𝑒𝑙𝑡𝑖𝑛𝑔 Point

Entropy of vaporisation:-It is defined as the change in entropy when one mole of a liquid changes
to the vapour state at its boiling point.

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛
𝑀𝑎𝑡ℎ𝑒𝑚𝑎𝑡𝑖𝑐𝑎𝑙𝑙𝑦, ∆𝑆𝑓𝑢𝑠𝑖𝑜𝑛 =
𝑇𝑏𝑜𝑖𝑙𝑖𝑛𝑔

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In the change of state from vapour to liquid & from liquid to solid ∆𝐻𝑉 & ∆𝐻𝑓 will be negative &
during the process of condensation of vapour or freezing of a liquid, decrease in entropy takes
place.

Entropy sublimation: - It is defined as the change in entropy which takes place when one mole of a
solid change to the vapour state at a temperature below its melting point.

∆𝐻𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛
𝑀𝑎𝑡ℎ𝑒𝑚𝑎𝑡𝑖𝑐𝑎𝑙𝑙𝑦, ∆𝑆𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 =
𝑇𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛

Entropy of Decomposition:-

Generally, heating a chemical compound produces more no. of the products and also gaseous
products where entropy increases. The entropy of the system increases, where no. of moles
increases, temperature increases and states changes from solid to liquid, and liquid to gas.

 Predict in which of the following,where entropy increases or decreases

(i) 𝐻2 (𝑔) → 2𝐻(𝑔)

Ans:-Entropy increases because H2 is a molecule of hydrogen and 2H is two moles of hydrogen.

The randomness of 2H is higher than H2,

(ii) 𝑁𝑎𝐻𝐶𝑂3 (𝑔) → 𝑁𝑎2 𝐶𝑂3 (𝑆) + 𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑔)

Ans:-Entropy increases because one moles of NaHCO3 is converted into 3 different moles with
different entropy.

(iii) Temperature of crystalline solid at ok to 220k

Ans:-Temperature of absolute ok is O at 220k entropy will increases.

(iv) Graphite → Diamond.

Ans:-Entropy decreases because diamond is purest. And changes to pure crystalline solid.

(v) L→S

Ans:- Entropy will increases due to the change of state.

Q.1. Calculate the enthalpy of fusion at naphthalene, given that its melting point is 1280c and the
enthalpy of fusion is 47.7 JK -1mol-1.
∆𝐻
Solution:-Relation between ∆H and ∆S at constant pressure is, ∆S = 𝑇
Here ∆S = 47.7JK-1 mole -1 and T = (273 + 128) K =401K
∴ ∆𝑯 = 𝑻∆𝑺 = 𝟒𝟕. 𝟕 × 𝟒𝟎𝟏 𝑱𝒎𝒐𝒍−𝟏
= 𝟏𝟗. 𝟏𝟐𝟕 𝒌𝑱 𝒎𝒐𝒍𝒆−𝟏

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Q.2.The enthalpy change for transition of liquid into steam at 373 k is 40.8KJ mol-1.Calculate the
entropy of vaporisation?
∆𝐻𝑣
Ans:-∆𝑆𝑣 = 𝑇𝑣

Tv = 373k

∆𝐻𝑣
∆𝑆𝑣 =
𝑇𝑣
40800
⇒ = 109𝐽𝐾 −1 𝑚𝑜𝑙 −1
373

∆𝑆𝑣 = 109𝐽𝐾 −1 𝑚𝑜𝑙 −1

Estimation of Entropy change:-

Entropy of the universe increases continuously .Hence the value of the entropy varies from process
to process .The entropy can be calculated as:-
𝑆2 𝐹𝑖𝑛𝑎𝑙
𝑑𝑞𝑟𝑒𝑣
∆𝑆 = ∫ 𝑑𝑠 = ∫
𝑇
𝑆1 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

Where ∆𝑆𝑖𝑠 𝑡ℎ𝑒 change in entropy of the system between initial to final state.

Entropy change for Reversible process:-

Let dqrev be the heat flow into the system from surroundings during a reversible process at
temperature T .So, the heat gained by the system is dqrev and heat lost by the surrounding is –dqrev ,
𝑑𝑞𝑟𝑒𝑣
Therefore, entropy change of system, 𝑑𝑆𝑠𝑦𝑠 = 𝑇

𝑑𝑞𝑟𝑒𝑣
And entropy change of the surrounding, 𝑑𝑆𝑠𝑢𝑟𝑟 = − 𝑇

Total entropy change i.e entropy change of the universe is:

𝑑𝑞𝑟𝑒𝑣 𝑑𝑞𝑟𝑒𝑣
𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑆𝑆𝑌𝑆 + 𝑑𝑆𝑠𝑢𝑟𝑟 = + (− )=0
𝑇 𝑇

For a finite change, 𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 0

That is entropy of the system and surroundings taken together remains constant during a
reversible process.

Entropy change for Irreversible process:-

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Let’s take an irreversible process in which the system, at Lower temperature T1,absorbs heat q
from the surroundings, at higher temperature T2.Then, the increase in entropy of the system is
𝑞
given by ∆𝑆𝑆𝑦𝑠𝑡𝑒𝑚 = + 𝑇
1

𝑞
Decrease in entropy of the surroundings, ∆𝑆𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = − 𝑇
2

Total change in entropy in the process

𝑞 𝑞 𝑇 −𝑇
∆𝑆𝑆𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 or ∆𝑆 = 𝑇 − = q[ 𝑇2 𝑇 1 ] As 𝑇2 > 𝑇1 , ∆𝑆 > 0,i.e, entropy increases in
1 𝑇2 1 2
an irreversible processes.

Conclusion:-

The entropy of the system and surroundings taken together remains constant during a reversible
process while the same tends to increase during an irreversible process. This conclusion is often
regarded as a statement for the second law of thermodynamics in terms of entropy.

Entropy change during reversible change of state of an ideal gas :- Let n mole of an ideal gas
undergoes a reversible process & its state change from (P1 , V1 , T1) to (P2 ,V2 , T2) .

We know d U = dq + dw and for reversible process, 𝑑𝑈 = 𝑑𝑞𝑟𝑒𝑣 + 𝑑𝑤𝑟𝑒𝑣 .... (1)

If the system performs only PV work, then dwrev = - pdv.......... (2)

Again, 𝑑𝑞𝑟𝑒𝑣 = 𝑇𝑑𝑆 ....... (3)

𝑑𝑈 𝑃
∴ 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑜𝑟 𝑑𝑆 = + 𝑇 𝑑𝑉 ....... (4)
𝑇

𝑛𝑅𝑇
For n mole of an ideal gas, 𝑑𝑈 = 𝑛𝐶𝑉 𝑑𝑇 𝑎𝑛𝑑 𝑝 = .......(5)
𝑉

𝑑𝑇 𝑑𝑉
∴ 𝑑𝑆 = 𝑛𝐶𝑉 + 𝑛𝑅 ......(6)
𝑇 𝑉

𝑇 𝑑𝑇 𝑉 𝑑𝑉
∴ ∆𝑆 = ∫𝑇 2 𝑛𝐶𝑉 + 𝑛𝑅 ∫𝑉 2 .......(7)
1 𝑇 1 𝑉

𝑇2 𝑉
If CV is independent of temperature then∆𝑆 = 𝑛𝐶𝑉 𝐼𝑛 + 𝑛𝑅 𝐼𝑛 𝑉2 .....(8)
𝑇1 1

𝑇 𝑉
∆𝑆 = 2.303𝑛𝐶𝑣 𝑙𝑜𝑔 (𝑇2 ) + 2.303 𝑛𝑅 𝑙𝑜𝑔 (𝑉2 )........(9)
1 1

Entropy change for ideal gas where Temperature and pressure are variable:-

Assumed that, CV is constant over temperature limit T1 &T2 again for an ideal gas P1V1 = RT1 &
P2V2=RT2. For the initial & final state respectively

13
 𝑉 𝑇𝑃
⇒ 𝑉2 = 𝑇2𝑃1 ...........(10)
1 1 2

Putting the values of eqn (10) in eqn (9)

𝑇 𝑃 𝑇
∆𝑆 = 2.303𝑛𝐶𝑣 𝑙𝑜𝑔 (𝑇2 ) + 2.303 𝑛𝑅 𝑙𝑜𝑔 𝑃1 𝑇2 ............(11)
1 2 1

𝑇 𝑃 𝑇
⇒ ∆𝑆 = 2.303𝑛𝐶𝑣 log (𝑇2 ) + 2.303𝑛𝑅 log (𝑃1 ) + 2.303𝑛𝑅 𝑙𝑜𝑔 (𝑇2 ) ......(12)
1 2 1

𝑇 𝑃 𝑇
⇒ ∆𝑆 = 2.303𝑛(𝐶𝑝 − 𝑅) log (𝑇2 ) + 2.303𝑛𝑅 log (𝑃1 ) + 2.303𝑛𝑅 𝑙𝑜𝑔 (𝑇2 ) .........(13)
1 2 1

𝑇 𝑃 𝑇
⇒ ∆𝑆 = 2.303𝑛(𝐶𝑝 − 𝑅) log (𝑇2 ) + 2.303𝑛𝑅 log (𝑃1 ) + 2.303𝑛𝑅 𝑙𝑜𝑔 (𝑇2 ) ................(14)
1 2 1

𝑇 𝑇 𝑃 𝑇
⇒ ∆𝑆 = 2.303𝑛 𝐶𝑝 𝑙𝑜𝑔 (𝑇2 ) − 2.303𝑛𝑅 𝑙𝑜𝑔 (𝑇2 ) + 2.303𝑛𝑅 log (𝑃1 ) + 2.303𝑛𝑅 𝑙𝑜𝑔 (𝑇2 )
1 1 2 1

.........(15)
𝑇 𝑃
⇒ ∆𝑆 = 2.303𝑛 𝐶𝑝 𝑙𝑜𝑔 (𝑇2 ) + 2.303𝑛𝑅 log (𝑃1 ).........(16)
1 2

Case (1) for isothermal process:-

If the reversible process occurs isothermally, then T 1 = T2 .

𝑉 𝑃
So,∆𝑆𝑇 = 𝑛𝑅 𝐼𝑛 𝑉2 = 𝑛𝑅 𝐼𝑛 𝑃1
1 2

𝑉2 𝑃1
∆𝑆 = 2.303 𝑛𝑅 log = 2.303 𝑛𝑅 log
𝑉1 𝑃2

Case (2) for Isobaric process:-

If the reversible process occurs at constant pressure, then P1 = P2 .

𝑇
So,∆𝑆𝑃 = 2.303 𝑛𝐶𝑝 log 𝑇2
1

Case (3) for isochoric process:-

If the reversible process occurs at const. volume, then V1 = V2 .

𝑇
So,∆𝑆𝑉 = 𝑛𝐶𝑣 𝐼𝑛 𝑇2
1

Q. If the ideal gasundergoes a reversible expansion from 1L to 4 L at a constant temperature of

400k, assuming that neon behaves as an ideal gas and the internal energy of the gas remains
constant .What is the entropy change in the gas due to this process?

14
Solution:-If in an isothermal reversible expansion of an ideal gas, the volume increases from V1 to
𝑉
V2 then the entropy change of the gas during the process will be,∆𝑆 = 𝑛𝑅𝐼𝑛 𝑉2
1

4
∴ ∆𝑆 = 1 × 8.314 𝐼𝑛 = 11.525𝐽𝐾 −1 [∵ 𝑛 = 1, 𝑉1 = 1𝐿, 𝑉2 = 4𝐿]
1

Example:- Calculate the change in entropy when the volume of 1 mole of an ideal gas is doubled at
a constant temperature.
𝑉
Solution:- During isothermal expansion of an ideal gas, ,∆𝑆 = 𝑛𝑅𝐼𝑛 𝑉2
1

2𝑉1
Hence n =1mole, R =8.314 JK-1 mole-1 ,V2 = 2V1 So , ∆𝑆 = 1 × 8.314 𝐼𝑛 = 5.76𝐽𝐾 −1
𝑉1

Entropy of mixing/ Entropy changes during mixing of ideal gas

Let us consider 1 mol of an ideal gas. The entropy change can be expressed as,

𝐶𝑉 𝑑𝑇 𝑑𝑉
𝑑𝑆 = +𝑅
𝑇 𝑉
(𝐶𝑃 − 𝑅)𝑑𝑇 𝑑𝑉
𝑑𝑆 = +𝑅
𝑇 𝑉

On integration,

𝑆 = 𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑇 + 𝑅 𝑙𝑛 𝑉 + 𝑆 0

= 𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑇 + 𝑅 𝑙𝑛 𝑅 + 𝑅 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑆 0

= 𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑅 𝑙𝑛 𝑅 + 𝑆 0

= 𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑆 0′

Let us consider a number of gases, i.e., n1 moles of gas 1,n2 moles of gas 2 and so on. Let their
partial pressures be p1, p2..., etc. respectively. Then

𝑆1 = [𝐶𝑃 𝐼𝑛 𝑇 − 𝑅 𝐼𝑛 𝑝1 + 𝑆 0′ ]

𝑆2 = [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑝2 + 𝑆 0′ ]

Now, total entropy

𝑆𝑇 = ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑝𝑖 + 𝑆 0′ ]

Now if each gas is taken under pressure P, then total entropy

𝑆𝑇 = ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑆 0′ ]

15
Entropy of mixing is the difference between the entropy of mixing of gases and the sum of the
entropies of the separate gases, each at a pressure P. Thus

∆𝑆𝑚𝑖𝑥 = ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃𝑖 + 𝑆 0′ ] − ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑆 0′ ]

= ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑥𝑖 − 𝑅 𝑙𝑛𝑃 + 𝑆 0′ ] − ∑ 𝑛𝑖 [𝐶𝑃 𝑙𝑛 𝑇 − 𝑅 𝑙𝑛 𝑃 + 𝑆 0′ ]

𝑃𝑖 = 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
∆𝑆𝑚𝑖𝑥 ∑ [ ]
= − 𝑛𝑖 𝑅. ln 𝑥𝑖 = −𝑅 𝑛1 𝑙𝑛𝑥1 + 𝑥1 𝑙𝑛𝑥2 + … [𝑃𝑖 = 𝑚𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 × 𝑇𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 ]
𝑃𝑖 = 𝑥 × 𝑃

Now ∆𝑆𝑀𝑖𝑥 per mole of mixture = ∑ 𝑥𝑖 𝑅. ln 𝑥𝑖

𝑛1
𝑥1 = 𝑛
1 +𝑛2
𝑛2
𝑥2 =
𝑛1 + 𝑛2

1. 1 moles of Hydrogen and 9 moles of Nitrogen are mixed at 293k and at 1 atm assuming the ideal
behaviour of the gas. Calculate the entropy of mixing per mole of the mixture?

Ans:- n1 = 1mole ,n2 = 9 moles

1 9
𝑛1 + 𝑛2 = 1𝑜𝑚𝑜𝑙𝑒 𝑚𝑜𝑙𝑒 𝑓𝑟𝑐𝑡𝑖𝑜𝑛, 𝑥1 = 10.0 = 0.1; 𝑥2 = 10 = 0.9.
∆𝑆𝑚𝑖𝑥 = −𝑅 [𝑥1 𝑙𝑛𝑥1 + 𝑥2 𝑙𝑛𝑥2 ]
∆𝑆𝑚𝑖𝑥 = −8.314 × 2.303[0.1 𝑙𝑜𝑔0.1 + 0.9𝑙𝑜𝑔0.9]
∆𝑆𝑚𝑖𝑥 = 2.67𝐽𝑘 −1 𝑚𝑜𝑙𝑒 −1 .
2. Calculate the entropy change of mixing when 1 mole of nitrogen & 2 moles of the oxygen
are as assuming the gas to be ideal and expressed the result in S.I units?
Ans:- n1 = 1.
n2 = 2.
𝑛1 + 𝑛2 = 3
1 2
𝑥1 = = 0.34; 𝑥2 = = 0.67.
3 3
∆𝑆𝑚𝑖𝑥 = −𝑅 [𝑥1 𝑙𝑛𝑥1 + 𝑥2 𝑙𝑛𝑥2 ]
∆𝑆𝑚𝑖𝑥 = −8.314 × 2.303[0.33 𝑙𝑜𝑔0.33 + 0.66𝑙𝑜𝑔0.166]

1 1 2 2
⇒ −8.314 × 2.303 [ 𝑙𝑜𝑔 + 𝑙𝑜𝑔 ]
3 3 3 3
−1 −1
⇒ 5.35𝐽𝑘 𝑚𝑜𝑙𝑒 .

3. 2 grams of hydrogen, 16gm of Helium are mixed at 298k and 1 atmospheric pressure. Calculate the
entropy of mixing for mole of the mixture formed assuming ideal behaviour of the gas?
Ans:- n1 = 1 mole
n2 = 4 mole.
16
 1
𝑥1 == 0.2
5
4
𝑥2 = = 0.8.
5
∆𝑆𝑚𝑖𝑥 = −8.314 × 2.303[0.2 log(0.2) + 0.8log(0.8)]
⇒ −19.148[0.2(−0.069) + 0.8(−0.096)]

⇒ −19.148[−0.2148]
⇒ 4.112𝐽𝑘 −1
4. At ntp 2.8L of O2 we are mixed with 19.6litres of Hydrogen calculate the increases in
entropy assuming ideal gas behaviour.
Ans:- 22.4L =1 mole
1
1L =22.4
1
2.8L= × 2.8
22.4

= 0.125 𝑚𝑜𝑙𝑒
1
19.6𝑙 = 22.4 × 19.6. = 0.875𝑚𝑜𝑙𝑒𝑠.

𝑛1 = 0.125 𝑚𝑜𝑙𝑒

𝑛2 = 0.875 𝑚𝑜𝑙𝑒

𝑛1 + 𝑛2 = 1 𝑚𝑜𝑙𝑒𝑠

𝑥1 = 0.125𝑥2 = 0.875

∆𝑆𝑚𝑖𝑥 = −8.314 × 2.303[0.125 log(0.125) + 0.875𝑙𝑜𝑔(0.875)]

= −19.148[0.125(−.903) + 0.875(−0.058)]
= −19.148[−0.112875 − 0.05075]
= −19.148(−0.163625)
= 3.134𝐽𝐾 −1
5. Calculate the change in entropy accompanying the isothermal expansions of 5 moles of an
ideal gas at 330k until its volume has increased six times?
Ans:- n = 5 moles ,R = 8.314.
𝑉
We known ∆𝑆 = 2.303𝑅 𝑙𝑜𝑔 𝑉2
1
6𝑉1
∆𝑆 = 2.303 × 5 × 8.314 × 𝑙𝑜𝑔
𝑉1
∆𝑆 = 2.303 × 5 × 8.314 × 𝑙𝑜𝑔6.
∆𝑆 = 74.49𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1
6. Calculate the entropy change when 5 moles of an ideals gas undergo isothermal expansions at 200c
at a pressure of 10 atm to a pressure to 2 atm.
Ans:- n = moles ,R = 8.314 ,P1=10 ,P2 = 2.
𝑃1
∆𝑆 = 2.303 × 𝑛𝑅 × 𝑙𝑜𝑔
𝑃2

17
 𝑃1
∆𝑆 = 2.303 × 𝑛𝑅 × 𝑙𝑜𝑔
𝑃2
10
∆𝑆 = 2.303 × 5 × 8.314 × 𝑙𝑜𝑔
2

∆𝑆 = 2.303 × 5 × 8.314 × log 5.

∆𝑆 = 66.91𝐽𝑘 −1 𝑚𝑜𝑙−1
7. 10moles of an ideal gas expands reversibly from a volume of 1 Dm 3 and temperature 250c to a
3
volume of 2 Dm3 and temperature 500c . At CV = 2 𝑟 (𝑎𝑠𝑠𝑢𝑚𝑒)
Ans:- n = 10moles ,
T1=250c = 298k ,
T2 = 500c = 273k.
𝑇2 𝑉2
∆𝑆 = 2.303𝑛𝐶𝑣 𝑙𝑜𝑔 ( ) + 2.303𝑛𝑅 𝑙𝑜𝑔 ( )
𝑇1 𝑉1
3 323 2
→ 10 × 2.303 × 8.314 [ 𝑙𝑜𝑔 ( ) + 𝑙𝑜𝑔 ]
2 298 1
→ 10 × 2.303 × 8.314[0.35]
→ 67.01𝐽𝑘 −1 𝑚𝑜𝑙−1

Standard entropy change:- Entropy change during transformation measured at 250c and 1
atm pressure is called as standard Entropy change.

ENTROPY OF CHEMICAL CHANGE:-

The entropy change of a chemical reaction is given by the difference between the sum of the
entropies of all the products and sum of the entropies of all the reactants.

Consider a chemical reaction of the type

𝑎𝐴 + 𝑏𝐵 + ⋯ → 𝑐𝐶 + 𝑑𝐷 + ⋯

The entropy change of the reaction, is given by

∆𝑆 = (𝑐𝑆𝐶 + 𝑑𝑆𝐷…… ) − (𝑎𝑆𝐴 + 𝑏𝑆𝐵 + ⋯ )

Where 𝑆𝐴 , 𝑆𝐵 , 𝑆𝐶 𝑎𝑛𝑑 𝑆𝐷 are the entropies of pure substances A,B,C, and D..... , taking part in the
reaction.

So, in general,∆𝑆 = ∑ 𝑆𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ 𝑆𝑟𝑒𝑐𝑡𝑎𝑛𝑡𝑠

Entropy of one mole of a substance in pure state at one atmospheric pressure and at 250c,is called
as standard entropy of that substance and is denoted as S0 .When a reaction involves each
reactant and each product in its standard state, the entropy change is said to be standard entropy
change. This is denoted by ∆𝑆 0

Thus,

18
 0
∆𝑆 0 = ∑ 𝑆 − ∑ 𝑆𝑟𝑒𝑐𝑡𝑎𝑛𝑡𝑠
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Concept of free energy: - Usually, the internal energy and entropy are used to describe the
feasibility of a physical or chemical process. In most of the chemical processes neither the energy
nor the entropy is held constant. So it is required to introduce new functions involving energy and
entropy. These new functions are-

(i) The Helmholtz free energy or work function (A) .

(ii) The thermodynamic potential or Gibb,s free energy(G)

WORK FUNCTION (HELMHOLTZ FREE ENERGY)

→ A part of the potential energy can be utilized at constant temperature to do useful work.

→ This fraction of internal Energy which is available to do work at constant temperature is called as
work function.

→ It is denoted as A and given by

A =U - TS
or

A = E - TS
Where A =work function is a state function.

U/E = Internal Energy

T= Absolute temperature

S= Entropy.

→ A (work function) is called as Helmholtz free energy.

→ Work function is a state function.

→ For a cyclic process, ∆A = 0

→ It is an extensive property of the system.

Significance of work function:

(I) As A = U - TS----------------------(1)
𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 ............. (2)
From 1st law of thermodynamics, 𝑑𝑞 = 𝑑𝑈 + 𝑤𝑟𝑒𝑣 ........ (3)
𝑑𝑞
From the definition of entropy,𝑑𝑆 = ........... (4)
𝑇
⇒ 𝑑𝑞 = 𝑇𝑑𝑆......... (5)
∴ 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑤𝑟𝑒𝑣 ⇒ 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑤𝑟𝑒𝑣 ...... (6)

Substituting the value of d E from Equation -6 in Equation- 2

19
 𝑑𝐴 = 𝑇𝑑𝑆 − 𝑤𝑟𝑒𝑣 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝑑𝐴 = −[𝑤𝑟𝑒𝑣 + 𝑆𝑑𝑇]

At const temperature, d T = O

∴ −(𝑑𝐴) 𝑇 = 𝑊𝑟𝑒𝑣

i.e A decrease in work function at const. Temperature gives the maximum reversible work done by
the system, which includes both mechanical and non mechanical work.

→ The spontaneous changes at const. volume have ∆A < O

→ The concept of ∆A is commonly used to discuss the solid state and condense phase process
where the change in volume can be negligibly small.

→ ∆A is commonly used in consideration of Geo chemical problem where huge pressure changes
can be involved but the volume of a system does not change significantly.

Gibbs free Energy Concept:- Isothermaly available energy of a system is called as free energy. It is
denoted by the symbol G.

It is also known as Gibbs thermodynamic potentential.

G = H –TS,

∆𝐺 = ∆𝐻 − 𝑇∆𝑆
Where G =Gibbs free energy, H = Enthalpy, T = Temperature, S = Entropy.

 Free Energy is a State function.

 At cyclic process ∆𝐺 = 0
 At equilibrium ∆𝐺 = 0
 In case of spontaneous process ∆𝐺 < 0 ,⇒ ∆𝐺 𝑖𝑠 − 𝑣𝑒 .
 The decrease in Gibbs free –energy is equal to the amount of maximum work done
which a system can do at constant temperature.
𝑤𝑚𝑎𝑥 = −(𝑑𝐺 ) 𝑇,𝑃

Significance of ∆𝑮

1. As It is used for prediction of spontaneity of a process under different conditions.

As 𝐺 = 𝐻 − 𝑇∆𝑆
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 i.e the reaction is spontaneous if ∆𝐺𝑇,𝑃 < 0

(2) G = H - TS.......................... (1)

⇒ 𝐺 = (𝑈 + 𝑃𝑉 ) − 𝑇𝑆 ........ (2)

⇒ 𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇........ (3)

[𝐴𝑠 𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑊𝑟𝑒𝑣 ]

20
𝑑𝐺 = 𝑇𝑑𝑆 − 𝑤𝑟𝑒𝑣 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇....... (4)

[𝑁𝑜𝑤, 𝑤𝑟𝑒𝑣 = 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑤𝑜𝑟𝑘 + 𝑛𝑜𝑛 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑤𝑜𝑟𝑘, 𝑤𝑟𝑒𝑣 = 𝑃𝑑𝑉 + 𝑤𝑛𝑒𝑡 … … (5)]

Substituting the value of 𝑤𝑟𝑒𝑣 from (5) in equation (4)

𝑑𝐺 = −𝑃𝑑𝑉 − 𝑤𝑛𝑒𝑡 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑆𝑑𝑇 .............. (6)

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 − 𝑤𝑛𝑒𝑡 .............. (7)

At const temperature,𝑑𝑇 = 0 , Const. pressure 𝑑𝑝 = 0

(𝑑𝐺 ) 𝑇,𝑃 , = −𝑊𝑛𝑒𝑡

For a finite change

−(∆𝐺 )𝑇,𝑃 = 𝑤𝑛𝑒𝑡

Hence the decrease in free energy is equal to the amount of maximum work done of the system at
const temperature.

Condition for Spontaneity In terms of ∆𝑮

i) If ∆𝐺 < 0 ,the process will be spontaneous.

ii) If ∆𝐺 > 0 ,the process will be non- spontaneous.
iii) If ∆𝐺 = 0 ,the process will be in equilibrium.

Condition for spontaneous process

A chemical reaction is spontaneous when ∆𝐺 < 0 .At difference values of temperature the
spontaneity can be determined as follows.

∆𝐻 ∆𝑆 ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 Remark

-Ve + Ve -Ve for all values of temperature Spontaneous for all values of
temperature
-Ve -Ve (a) –Ve for low temperature Spontaneous at low temperature.
(∆𝐻 > 𝑇∆𝑆)

(b) +Ve for high temperature Non Spontaneous at high

∆𝐻 < 𝑇∆𝑆 temperature.
+Ve +Ve (a) - Ve for high temperature Spontaneous at high temperature.
(∆𝐻 < 𝑇∆𝑆)

(b) +Ve for low temperature Non Spontaneous at low

∆𝐻 > 𝑇∆𝑆 temperature.
+Ve -Ve +Ve for all values of temperature. Non spontaneous for all
temperature
The system increases

21
*→ A matter has a spontaneous tendency to acquire a state of minimum energy(∆𝐻 is –ve) and
maximum disorder(∆𝑆 is +ve)

*→The relative strengths’ of the body holding the particles of the reactants and the products (i.e
the sign of ∆𝐻 ) and the relative freedom of motion of the particles of the reactants and the
products ( i.e the sign of ∆𝑆) are to be known in predicting the spontaneity of the reaction.

*→ when ∆𝐻 and ∆𝑆 have the same sign, the sign of ∆𝑆 depends on the magnitude of the terms
∆𝐻 and 𝑇∆𝑆 .

Ex:-In case of Ice → liquid water ∆𝐻 and ∆𝑆 are both +ve .

i) Below 273k, ∆𝐻 > 𝑇 ∆𝑆 ,or ∆𝐻 - T ∆𝑆 = ∆𝐺 𝑖𝑠 + 𝑣𝑒 .

Reverse reaction is spontaneous.
ii) At 273k , ∆𝐻 and 𝑇∆𝑆 or ∆𝐻 -T ∆𝑆 ⇒ ∆𝐺 = 0
Hence ice and liquid water are in equation.
iii) Above 273k , ∆𝐻 < T ∆𝑆 OR ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 = −𝑉𝑒
Hence, ice melts spontaneously.

Standard Gibbs Energy of reaction for the reaction.

For the chemical reaction

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

∆𝐺𝑟0 = [∑ 𝑟∆𝐺𝑓0 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − ∑ 𝑟∆𝐺𝐹0 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 )]

0 0 0 0
∆𝐺𝑟0 = {𝐶∆𝐺𝑓.𝐶 + 𝑑∆𝐺𝑓.𝐷 } − {𝑎∆𝐺𝑓,𝐴 + 𝑏∆𝐺𝑓,𝐵 }

Where,∆𝐺 0 is the standard Gibbs energy of formation and it is the standard reaction.

Gibbs energy for formation of a compound from its element in their reference .states.

VARIATION OF FREE –ENERGY WITH PRESSURE AT CONSTANT TEMPERATURE.

From Equation (7)

𝑑𝐺 = 𝑉𝑑𝑝 − 𝑆𝑑𝑇 − 𝑊𝑛𝑒𝑡.............. (1)

If the system performs only mechanical work then,𝑤𝑟𝑒𝑡 = 0

𝑑𝐺 = 𝑉𝑑𝑝 − 𝑆𝑑𝑇........... (2)

At const temperature,𝑑𝑇 = 0

(𝑑𝐺 ) 𝑇 = 𝑉𝑑𝑝............. (3)

22
The total change in free energy can be calculated by changing the state of the system.

From initial (i) to final (f)

𝑓 𝑓
∫𝑖 𝑑𝐺 = ∫𝑖 𝑉𝑑𝑝............. (4)
𝑛𝑅𝑇
For ideal gases 𝑃𝑉 = 𝑛𝑅𝑇 ⇒ 𝑉 = . ........ (5)
𝑃

𝑓 𝑑𝑝 𝑃
∆𝐺 = 𝑛𝑅𝑇 ∫𝑖 = 𝑛𝑅𝑇𝑙𝑛 ( 𝑓⁄𝑃 ) ............. (6)
𝑝 𝑖

𝑃
∆𝐺 = 2.303 𝑛𝑅𝑇 𝑙𝑜𝑔 ( 𝑓⁄𝑃 ) … . . (7)
𝑖
𝑉𝑖
∆𝐺 = 2.303 𝑛𝑅𝑇 𝑙𝑜𝑔 ( ⁄𝑉 )...........(8)
𝑓

Q. Derive Gibbs Helmholtz equation

G = H – TS ........... (1)

(H = U+PV)............ (2)

G = U + PV – TS............. (3)

𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 ... (4)

𝑑𝑞
(∵ 𝑑𝑈 + 𝑃𝑑𝑣 = 𝑑𝑞 1𝑠𝑡 𝑙𝑎𝑤 , = 𝑑𝑆)
𝑇

⇒ 𝑑𝐺 = 𝑑𝑞 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 ..................... (5)

⟹ 𝑑𝐺 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 .................... (6)

⇒ 𝑑𝐺 = 𝑉𝑑𝑝 − 𝑆𝑑𝑇 ---------------- (7)

⇒ 𝑑𝐺 = −𝑆𝑑𝑇(𝑎𝑡 𝑐𝑜𝑛𝑠𝑡 𝑝 , 𝑣𝑑𝑝 = 0) ---------- (8)

𝑑𝐺
⇒ (𝑑𝑇 ) = −𝑆 ------------------- (9)
𝑃

Again G = H – TS
𝑑𝐺
OR,𝐺 = 𝐻 + 𝑇 ( 𝑑𝑇 ) [𝐹𝑟𝑜𝑚 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (9)]
𝑃

For the change

𝑑 ∆𝐺
∆𝐺 = ∆𝐻 + 𝑇 [ (𝑑𝑇 )] ....... (10)
𝑃

23
Equation (10) is called as Gibbs Helmholtz equation in terms of the free energy change and
enthalpy change at constant pressure.
𝑑𝐺
Again from,Equation (9) 𝐺 = 𝐻 + 𝑇 ( )
𝑑𝑇 𝑃

𝑑𝐺
⇒ 𝐺 − 𝑇 (𝑑𝑇 ) = 𝐻................ (11)
𝑃

Dividing both the side of equation (11) by T2

𝑑𝐺
𝐺−𝑇( ) 𝐻
𝑑𝑇 𝑃
⇒ =𝑇 2 … … … … (12)
𝑇2

𝑑 𝑑 1 𝑑 1 1 𝑑𝐺
Now 𝑑𝑇 (𝐺⁄𝑇) = 𝑑𝑇 (𝐺 × 𝑇 ) = 𝐺 𝑑𝑇 (𝑇 ) + 𝑇 ( 𝑑𝑇 )........... (13)

1 1 𝑑𝐺
= 𝐺. (− 𝑇 2) + 𝑇 ( 𝑑𝑇 ).......... (14)

𝑑𝐺
−𝐺+𝑇( )
𝑑𝑇
= ................. (15)
𝑇2

𝑑𝐺
𝐺+𝑇( )
𝑑𝑇
= −{ 2 }
𝑇

From equation (11) & (15)

𝑑 𝐻
⇒ 𝑑𝑇 (𝐺⁄𝑇) = − 𝑇 2 .............. (16)
𝑃

𝑑 ∆𝐺 −∆𝐻
⇒ ( ⁄𝑇) = 2 … … … . (17)
𝑑𝑇 𝑃 𝑇

Equation (16) & (17) are other from Gibb,s Helmholtz equation.

Similarly A = U-TS ...................(18)

⇒ 𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 … … … … … (19)

⇒ 𝑑𝐴 = 𝑑𝑞 − 𝑝𝑑𝑣 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (𝑑𝑞 = 𝑑𝑈 + 𝑝𝑑𝑣)1𝑠𝑡 𝑙𝑎𝑤

𝑑𝑞⁄ ]
⇒ 𝑑𝐴 = 𝑇𝑑𝑆 − 𝑃𝑑𝑣 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 … … … … … … (20) [𝑑𝑆 = 𝑇

⇒ 𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 … … … … … . (21)

At const volume, dv = 0

𝑑𝐴 = −𝑆𝑑𝑇

24
 𝜕𝐴
( ) = −𝑆 … … … … … . . (22)
𝜕𝑇 𝑉

Substituting the value of S in Equation (5)

𝐴 = 𝑈 − 𝑇𝑆

𝜕𝐴
𝐴 = 𝑈+𝑇( ) … … … … . . (23)
𝜕𝑇 𝑉

OR,

𝜕(∆𝐴)
∆𝐴 = ∆𝑈 + 𝑇 [ ] ..............(24)
𝜕𝑇 𝑉
(Considering the finite change)
This is the equation in terms of work function at const volume.

Other form of G.H equation.

From equation (10)

𝜕𝐴
𝐴 = 𝑈 + 𝑇 (𝜕𝑇 ) ...........(25)
𝑉

Dividing this equation (25) by T2

𝐴⁄ 2 = 𝑈⁄ 2 + 1 (𝜕𝐴) … … … … … … … … … … … … … … (26)
𝑇 𝑇 𝑇 𝜕𝑇 𝑉

OR, − 𝐴⁄𝑇 2 + 1⁄𝑇 (𝜕𝐴⁄𝜕𝑇) = − 𝑈⁄𝑇 2 .................................... (27)

𝑉

𝑑⁄ (𝐴⁄ ) = − 𝑈⁄ 2
𝑑𝑇 𝑇 𝑉 𝑇
Relation between ∆𝑮 & ∆𝑨 :-

We have ,∆𝐴 = ∆𝑈 − 𝑇∆𝑆 … … … (1)

& ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 … … (2)

Subtracting equation (1) from equation (2)

∆𝐺 − ∆𝐴 = (∆𝐻 − 𝑇∆𝑆) − (∆𝑈 − 𝑇∆𝑆).

⇒ ∆𝐺 − ∆𝐴 = ∆𝐻 − ∆𝑈 .

⇒ ∆𝐺 = ∆𝐻 − ∆𝑈 + ∆𝐴 .

⇒ ∆𝐺 = ∆𝑈 + 𝑃∆𝑉 − ∆𝑈 + ∆𝐴 (∵ 𝐹𝑟𝑜𝑚 𝑑𝑒𝑓𝑖𝑛𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 △ 𝐻 =△ 𝑈 + 𝑃 △ 𝑉)

⇒ ∆𝐺 = ∆𝐴 + 𝑃∆𝑉 .

25
 At constant volume, V= Constant
⇒ ∆𝑉 = 0 ⇒ 𝑃∆𝑉 = 0.

⇒ (∆𝐺 )𝑉 = ∆𝐴 ( 𝑃𝑟𝑜𝑣𝑒𝑑)

VANTHOFF ISOTHERM

𝑑𝐺 = 𝑉𝑑𝑝 − 𝑆𝑑𝑇 ........... (1)

As we know (𝑑𝐺 ) 𝑇 = 𝑉𝑑𝑃 ...... (2)

𝑅𝑇
For 1 mole of ideal gas, PV = RT ⇒ 𝑉 = ....... (3)
𝑃

𝑑𝑃
Hence, at const temperature free energy change is given by 𝑑𝐺 = 𝑅𝑇 .....(4)
𝑃

On integration, we get
𝑑𝑝
∫ 𝑑𝐺 = 𝑅𝑇 ∫ 𝑝
......... (5)

𝐺 = 𝐺 0 + 𝑅𝑇𝑙𝑛𝑝 ..................... (6) Where as G is standard free energy.

i.e 𝐺 = 𝐺 0 𝑎𝑡 𝑝 = 1𝑎𝑡𝑚, 𝐼𝑛 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (6) 𝐺 0 𝑖𝑠 𝐼𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡.

for the reaction 𝑎𝐴 + 𝑏𝐵 ⟶ 𝑐𝐶 + 𝑑𝐷 ......(7)

Let 𝐺𝐴 , 𝐺𝐵 , 𝐺𝐶 &𝐺𝐷 are free energy of reactants (A and B) and products (C and D) at their respective
pressures 𝑃𝐴 , 𝑃𝐵 , 𝑃𝐶 &𝑃𝐷

Now, free energy change for the general reaction (7) is given by

∆𝐺 = Σ𝐺 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − Σ𝐺 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

=(𝑐𝐺𝐶 + 𝑑𝐺𝐷 ) − (𝑎𝐺𝐴 + 𝑏𝐺𝐵 )

From Equation (6)

Δ𝐺 = [(𝑐𝐺𝐶0 + 𝑐𝑅𝑇𝐿𝑛𝑃𝐶 ) + (𝑑𝐺𝐷0 + 𝑑𝑅𝑇𝑙𝑛𝑃𝐷 )] − [(𝑎 𝐺𝐴0 + 𝑎𝑅𝑇𝑙𝑛𝑃𝐴 ) + (𝑏𝐺𝐵0 + 𝑏𝑅𝑇𝑙𝑛𝑃𝐵 )]

[𝑃𝑐 ]𝑐 [𝑃𝐷 ]𝑑
⇒ ∆𝐺 = [(𝑐𝐺𝐶0 + 𝑑𝐺𝐷0 ) − (𝑎𝐺𝐴0 + 𝑏𝐺𝐵0 )] + 𝑅𝑇 𝑙𝑛 [ ]
[𝑃𝐴 ]𝑎 [𝑃𝐵 ]𝑏

[𝑃𝑐 ]𝑐 [𝑃𝐷 ]𝑑
⇒ ∆𝐺 = ∆𝐺 0 + 𝑅𝑇𝑙𝑛 [ ] − − − − − (8)
[𝑃𝐴 ]𝑎 [𝑃𝐵 ]𝑏

At equilibrium,∆𝐺 = 0

[𝑃𝑐 ]𝑐 [𝑃𝐷 ]𝑑
0 = ∆𝐺 0 + 𝑅𝑇 𝑙𝑛 [ ].
[𝑃𝐴 ]𝑎 [𝑃𝐵 ]𝑏

= ∆𝐺 0 + 𝑅𝑇𝑙𝑛 𝐾𝑒𝑞.

26
 ⇒ ∆𝐺 0 = −𝑅𝑇 ln 𝑘𝑒𝑞 … … … … . (9)

−∆𝐺 0
𝐾𝑒𝑞 = 𝑒𝑥𝑝 ( ) … … … … … . . (10)
𝑅𝑇

Substituting these value of ∆𝐺 0 in Equation (8)

[𝑃𝑐]𝑐 [𝑃𝐷 ]𝑑
∆𝐺 = −𝑅𝑇 ln 𝐾𝑒𝑞 + 𝑅𝑇 𝑙𝑛 [[𝑃 𝑎 𝑏
] ........... (11)
𝐴 ] [𝑃𝐵 ]

This equation (11) is known as vant-Hoff’s isotherm equation.

Vant-Hoff’s Isochore Equation:-

∆𝐺 0 = −𝑅𝑇 ln 𝑘𝑒𝑞 … … … … . (9)

−∆𝐺 0
⇒ ln(𝑘𝑒𝑞𝑚 ) = .......... (12)
𝑅𝑇

∆𝐻 0 − 𝑇∆𝑆 0
⇒ ln(𝑘𝑒𝑞𝑚 ) = − ( 𝑅𝑇
).......... (13)

−∆𝐻 0 ∆𝑆 0
⇒ ln(𝑘𝑒𝑞𝑚 ) = + ............. (14)
𝑅𝑇 𝑅

−∆𝑆 0 ∆𝐻 0
⇒ ln(𝑘𝑒𝑞𝑚 ) = + ............... (15)
𝑅 𝑅𝑇

∆𝑆 0 ∆𝐻 0
⇒ ln(𝑘𝑒𝑞𝑚 ) = − 𝑅𝑇 .................. (16)
𝑅 1

∆𝑆 0 ∆𝐻 0
ln(𝑘2 ) = − ........................ (17)
𝑅 𝑅𝑇2

Substracting equation (16) from equation (17)

∆𝑆 0 ∆𝐻 0 ∆𝑆 0 ∆𝐻 0
𝑙𝑛𝑘2 − 𝑙𝑛𝐾1 = [( − )− ( − )] ........... (18)
𝑅 𝑅𝑇2 𝑅 𝑅𝑇1

𝑘 ∆𝐻 0 ∆𝐻 0 ∆𝐻 0 1 1
⇒ 𝑙𝑛 (𝑘2 ) = − 𝑅𝑇 = [ − ] ............. (19)
1 𝑅𝑇1 2 𝑅 𝑇
1 𝑇 2

𝑘 ∆𝐻 0 𝑇2 −𝑇1
⇒ 𝑙𝑛 (𝑘2 ) = [ ] ............. (20)
1 𝑅 𝑇1 𝑇2

𝑘 ∆𝐻 0 𝑇 −𝑇
⇒ 𝑙𝑜𝑔 (𝑘2 ) = 2.303𝑅 [ 𝑇2 𝑇 1 ]............. (21)
1 1 2

CLAPEYRON-CLAUSIUS EQUATION

Let us consider the change of a pure substance from phase 1 to another phase II in equilibrium
with it at a given temperature and pressure.

Let G1 = free energy per mole of the substance in the initial phase I, and

GII = free energy per mole of the substance in the final phase II.
27
 At equilibrium, there will be no change in free energy,∆𝐺 = 𝐺𝐼𝐼 − 𝐺𝐼 = 0

⟹ 𝐺𝐼 = 𝐺𝐼𝐼

If the temperature of such a system is raised, say, from T to T+ d T, the pressure will also have
to change, say from P to P + dP, in order to maintain the equilibrium.

The relationship between 𝑑𝑇 𝑎𝑛𝑑 𝑑𝑃 can be derived from thermodynamics

Let 𝐺1 + 𝑑𝐺1 = free energy per mole of the substance in phase I at the new temperature and
pressure.

And 𝐺𝐼𝐼 + 𝑑𝐺𝐼𝐼 = free energy per mole of the substance in phase II at the new temperature and
pressure.

As the two phase are still in equilibrium, hence,

𝐺1 + 𝑑𝐺1 = 𝐺𝐼𝐼 + 𝑑𝐺𝐼𝐼

But when a system undergoes reversibly a change of temperature (d T) and a change of pressure
(dP), the change of free energy is given by the expression

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇.

For the two phases, this equation can be written as

For phase I,𝑑𝐺𝐼 = 𝑉𝐼 𝑑𝑃 − 𝑆𝐼 𝑑𝑇 ......................... (ii)

And for phase II, 𝑑𝐺𝐼𝐼 = 𝑉𝐼𝐼 𝑑𝑃 − 𝑆𝐼𝐼 𝑑𝑇 .................. (iii)

As 𝐺𝐼 = 𝐺𝐼𝐼

∴ 𝑑𝐺𝐼 = 𝑑𝐺𝐼𝐼 ................................. (iv)

⇒ 𝑉𝐼 𝑑𝑃 − 𝑆𝐼 𝑑𝑇 = 𝑉𝐼𝐼 𝑑𝑃 − 𝑆𝐼𝐼 𝑑𝑇 ⇒ (𝑉𝐼𝐼 − 𝑉𝐼 ) = (𝑆𝐼𝐼 − 𝑆𝐼 )𝑑𝑇

𝑑𝑃 (𝑆𝐼𝐼 −𝑆𝐼 ) ∆𝑆
⇒ 𝑑𝑇 = = ∆𝑉 ..................... (v)
𝑉𝐼𝐼 −𝑉𝐼

Since V1 and VII are the molar volumes of the pure substance in phases I and II respectively,∆𝑉 =
𝑉𝐼𝐼 − 𝑉𝐼 represents the change in volume when one mole of the substance phases from the initial
phase I to the final phase II.

Similarly,∆𝑆 = 𝑆𝐼𝐼 − 𝑆𝐼 represents the change in entropy when one mole of the substance passes
from the initial phase I to the final phase II.

Let the heat exchanged reversibly per mole of the substance during phase transformation at
constant temperature T, be q, then, the change in entropy (∆𝑆) = 𝑞/𝑇

Putting this value of ∆𝑆 in equation (v), we get

28
 𝑑𝑃 𝑞 𝑞
= =
𝑑𝑇 𝑇∆𝑉 𝑇(𝑉𝐼𝐼 − 𝑉𝐼 )
This is the Clapeyron-Clausius equation.

Clapeyron-Clausius equation evidently gives change in pressure(dP) which must accompany the
change in temperature(d T) or vice versa in the case of a system of a pure substance containing
two phases in equilibrium with each other.

The Clapeyron-Clausius equation for liquid-Vapour equilibria

Let us consider water in liquid and vapour phases and the two phases in equilibrium at constant
temperature (T),

Water(liquid) ⇌ Water (vapour)

Here VI = volume of one mole of water in the liquid state = VI

VII= volume of one mole of water in the vapour state, = Vg

q = molar heat of vaporization, = ∆𝐻𝑉

In this case, equation(vi) becomes,

𝑑𝑃 ∆𝐻𝑉
=
𝑑𝑇 𝑇(𝑉𝑔 − 𝑉𝐼 )

Since Vg > > VI ∴ 𝑉𝑔 − 𝑉𝐼 = 𝑉𝑔

Thus,
𝑑𝑃 ∆𝐻𝑉
=
𝑑𝑇 𝑇𝑉𝑔

Assuming, vapours of water to behave ideally, Vg = RT/P

Hence,
𝑑𝑃 ∆𝐻𝑉 ∆𝐻𝑉
= =𝑃
𝑑𝑇 𝑇(𝑅𝑇/𝑃) 𝑅𝑇 2

𝑑𝑃 ∆𝐻𝑉 𝑑𝑇
⇒ =
𝑃 𝑅 𝑇2
𝑃 ∆𝐻𝑉 𝑇
On Integration ∫𝑃 2 𝑑𝑃⁄𝑃 = 2
∫𝑇1 𝑑𝑇⁄𝑇 2
1 𝑅

−∆𝐻𝑉 1 𝑇2
⇒ 𝐼𝑛 (𝑃2 ⁄𝑃1 ) = [ ]
𝑅 𝑇 𝑇1

29
 ∆𝐻𝑉 𝑇2 − 𝑇1
𝐼𝑛(𝑃2 ⁄𝑃1 ) =[ ]
𝑅 𝑇1 𝑇2
This is known as integrated from of Clapeyron-Clausis equation.

The Clapeyron-Clausis equation for Solid-vapour equilibria

Let ∆𝐻𝑠 = ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒

Differential:

𝑑𝑃 ∆𝐻𝑠𝑢𝑏
=
𝑑𝑇 𝑇(𝑉𝑔 − 𝑉𝑠 )

𝑑𝑃 ∆𝐻𝑠𝑢𝑏
=
𝑑𝑇 𝑇𝑉𝑔

Integral form:
∆𝐻𝑠𝑢𝑏 𝑇2−𝑇1
In𝑃2 ⁄𝑃1 = [ ]
𝑅 𝑇1𝑇2

The Clapeyron-Clausis equation for Solid-liquid equilibria.

Let ∆𝐻𝑓 = Molar heat of fusion of substance

𝑓 ∆𝐻 𝑑𝑇 𝑇(𝑉1 −𝑉𝑔 )
Differential form 𝑑𝑃⁄𝑑𝑇 = 𝑇(𝑉 −𝑉 or 𝑑𝑃 =
1 𝑔) ∆𝐻𝑓

Applications of Clapeyron-Clausis equation.

(i) Molar heat of vaporization of liquid (∆𝐻𝑉 ) can be calculated provided we know the
vapour pressures at two temperatures. It illustrates how a quantity like ∆𝐻𝑉 ( which
cannot otherwise be experimentally measured) can be precisely evaluated in terms of
the other measured properties.
(ii) Vapour pressure at a desired temperature can be calculated from the knowledge of a
single value of vapour pressure at a given temperature, provided ∆𝐻𝑉 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛.
(iii) Clapeyron-Clausius equation can also be used for calculating the effect of pressure on
boiling point of liquid.

Example:-01

The vapour pressure of water at 950C and 1000C are 634 and 760 mm of Hg, respectively.
Calculate the latent heat of vaporization per mole of water.

30
 Solution. Using the Clapeyron- Clausius relation

𝑝2 ∆𝐻𝑉 𝑇2 − 𝑇1
𝐼𝑛 = [ ]
𝑝1 𝑅 𝑇1 𝑇2

760 ∆𝐻𝑉 373 − 368

𝑜𝑟 𝐼𝑛 = [ ]
634 1.98 373 × 368

Or∆𝐻𝑉 = 9.89 𝑘𝑐𝑎𝑙 𝑚𝑜𝑙 −1

Example:-02

Water boils at 1000C at 1atm pressure. At what temperature will water boil at a pressure of 2
atm? Given that latent heat of vaporization of water is 536 cal g -1.

Solution

∆𝐻𝑉 = 536 × 18 𝑐𝑎𝑙 𝑚𝑜𝑙𝑒 −1

Using the Clapeyron –Clausius relation

2 536×18 𝑇2−373
𝐼𝑛 = [ ] or 𝑇2 = 277.66𝐾
1 1.98 373𝑇2

Example: -03 - The vapour pressure of water at 950C is 634 mm of Hg. What will be the vapour
pressure 1500c? Given ∆𝐻 = 41.27𝐾𝐽 𝑚𝑜𝑙 −1 .

Solution

Using the Clapeyron –Clausius relation

𝑝
2 41270 423−368 𝑝
𝐼𝑛 634 = [ ] 𝑜𝑟 𝐼𝑛 2 = 1.754 or 𝑝2 = 3663𝑚𝑚 𝑜𝑓 𝐻𝑔
8.314 423×368 634

Example 04 :- Chloroform,CHCl3 has a vapour pressure of 197mmHg and at 23.o 0c and

448mmHg at 45.0 0c .Estimate the heat of vaporizations and normal boiling point.

Ans:- P1 =197mmHg.

P2 =448mmHg.

T1 =230C =273 +230 =296 k.

T2 = 450C = 2730+450 =318k.

∆𝐻𝑣 =?
𝑃 𝑇 −𝑇1
We know 𝑙𝑛 (𝑃2 ) = ∆𝐻𝑉 [ 𝑇2 ]
1 2. 𝑇1

31
 448 ∆𝐻𝑉 318 − 296
⇒ 𝑙𝑛 ( )= [ ]
197 1.98 318.296
∆𝐻
⇒ 0.82 = 1.98𝑉 × 0.00023372

⇒ 0.82 × 1.98 = ∆𝐻𝑉 × 0.00023372

⇒ 1.625 = ∆𝐻𝑉 0.00023372

1.625
⇒ ∆𝐻𝑉 =
0.00023372

∆𝐻𝑉 = 6952.7 𝑐𝑎𝑙.

∆𝐻𝑉 = 6.9𝑘 𝑐𝑎𝑙 (𝐴𝑛𝑠)

MAXWELL’S RELATION
Maxwell’s relations are the important relations that equate the rate of change of particular
quantities which can’t be determined experimentally with the experimentally determined

quantities such as pressure, volume, temperature etc.

Since U, H, G and A are thermodynamic function and the exact differentials of the type.

𝒅𝒛 = 𝑴𝒅𝒙 + 𝑵𝒅𝒚 𝒕𝒉𝒆𝒏

𝑑𝑀 𝑑𝑁
( ) =( )
𝑑𝑌 𝑥 𝑑𝑋 𝑦

Considering this relation the four Maxwell ’s relations are as follows.

Thermodynamic Independent Differential Expressions MAXWELL’S RELATION

Properties. variable
U S,V 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝑇 𝑑𝑃
( ) = −( )
𝑜𝑟 𝑑𝐸 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝑉 𝑆 𝑑𝑆 𝑉
H S,P 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 𝑑𝑇 𝑑𝑉
( ) =( )
𝑑𝑃 𝑆 𝑑𝑆 𝑃
G T,P 𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 𝑑𝑆 𝑑𝑉
( ) = −( )
𝑑𝑃 𝑇 𝑑𝑇 𝑃
A T,V 𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉. 𝑑𝑆 𝑑𝑃
( ) =( )
𝑑𝑉 𝑇 𝑑𝑇 𝑉

DEVIVATION OF MAXWELL’S REACTION

From the 1st law of thermodynamics,

𝑑𝑞 = 𝑑𝑈 + 𝑃𝑑𝑉 … … … … … … … … … … … … … … … . . (𝐴)
32
 𝑞 𝑑𝑞
& form entropy, 𝑆 = 𝑇 ⇒ 𝑑𝑆 = , ⇒ 𝑇𝑑𝑆 = 𝑑𝑞
𝑇

Substituting the value of dq in equation (A) .

Where 𝑑𝑞 → change in heat.

⇒ 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉.

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 … … … … … … … … … … … … … … … . (1)

From the definition of Enthalpy

H = U + PV................................... (B)

⇒ 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃.

Putting the value of𝑑𝑈 from Equation (1)

⇒ 𝑑𝐻 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃.

𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃............. (2)

From the definition of free energy, 𝐺 = 𝐻 − 𝑇𝑆 … … . (𝐶)

𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇.

Substituting the value of 𝑑𝐻 from equation (2).

𝑑𝐺 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 .......... (3)

From the definition of Heltmholtz free energy

𝐴 = 𝑈 − 𝑇𝑆..............(D)
⇒ 𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇.

Substituting the value of d U from equation (1)

𝑑𝐴 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆- SdT

⇒ 𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 … … … … … … . (4)

Proof of Maxwell’s Relation:-

𝑑𝑇 𝑑𝑃
𝐼𝑓 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 , 𝑡ℎ𝑒𝑛 𝑝𝑟𝑜𝑣𝑒 ( ) = −( )
𝑑𝑉 𝑆 𝑑𝑆 𝑉

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 … . . (1) 𝑊ℎ𝑒𝑛 𝑆 ′ 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑑𝑆 = 0.

⇒ (𝑑𝑈)𝑆 = −𝑃𝑑𝑉 … … . (2)

33
 𝑑𝑈
⇒( ) = −𝑃 … … … … … … … (3)
𝑑𝑉 𝑆

Differentiating Equation (3) with (S) at constant V Equation becomes,

𝑑2𝑈 −𝑑𝑃
( )=( ) … … … … … … … (4 )
𝑑𝑆𝑑𝑉 𝑑𝑆 𝑉

Again when V is constant PdV = 0

(𝑑𝑈)𝑉 = 𝑇𝑑𝑆 … … . (5)

𝑑𝑈
⇒( ) = 𝑇 … … … … … … … … … … … … . (6)
𝑑𝑆 𝑉

On differentiation Equation (6) with respect to V at constant S’

𝑑 𝑑𝑈 𝑑𝑇
( )( ) = ( )
𝑑𝑉 𝑑𝑆 𝑑𝑉 𝑆

𝑑2𝑈 𝑑𝑇
⇒ = ( ) … … … … … … … … . . (7)
𝑑𝑉 𝑑𝑆 𝑑𝑉 𝑆

Since 𝑑𝑈 is an exact differential

𝑑2𝑈 𝑑2𝑈
=
𝑑𝑆 𝑑𝑉 𝑑𝑉 𝑑𝑆

Since L.H.S of Equation (4) & (7) are same

−𝑑𝑃 𝑑𝑇
( ) =( ) 𝑃𝑟𝑜𝑣𝑒𝑑
𝑑𝑆 𝑉 𝑑𝑉 𝑆

Proof of (II)
𝑑𝑇 𝑑𝑉
𝐼𝑓 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 Then prove ( 𝑑𝑆 ) = ( 𝑑𝑆 )
𝑆 𝑃

Given 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 ......... (1)

When ‘S’ is const. 𝑑𝑆 = 0, 𝑇𝑑𝑆 = 0

⇒ (𝑑𝐻)𝑆 = 𝑉𝑑𝑃 ....... (2)

𝑑𝐻
⇒( ) = 𝑉 … … (3)
𝑑𝑃 𝑆

𝑑𝐻
⇒( ) =𝑉
𝑑𝑃 𝑆

34
Differentiation of (3) w .r .t ‘S’ at constant P

𝑑 𝑑𝐻 𝑑𝑉
( − )=( )
𝑑𝑠 𝑑𝑃 𝑑𝑆 𝑃

𝑑2𝐻 𝑑𝑉
( ) = ( ) … … … … . . (4)
𝑑𝑆 𝑑𝑃 𝑑𝑆 𝑃

Again from, equation (1)

When P is constant VdP=0 .

⇒ (𝑑𝐻)𝑃 = 𝑇𝑑𝑆 … … . (5)

𝑑𝐻
⇒( ) = 𝑇 … … … (6)
𝑑𝑆 𝑃

Differentiating equation (6) w . r. t p at const. ‘S’

𝑑 𝑑𝐻 𝑑𝑇
( ) =( )
𝑑𝑃 𝑑𝑆 𝑆 𝑑𝑃 𝑆

𝑑2𝐻 𝑑𝑇
⇒( ) = ( ) … … … … … … … … … … … … (7)
𝑑𝑃 𝑑𝑆 𝑠 𝑑𝑃 𝑠

Since 𝑑𝐻 is exact differential

𝑑2𝐻 𝑑2𝐻
=
𝑑𝑠 . 𝑑𝑝 𝑑𝑝 . 𝑑𝑠

As L.H.S of Equation (4) & (7) are same

𝑑𝑣 𝑑𝑇
(𝑑𝑠 ) = (𝑑𝑝) … … … … … … … … . . (8) (proved)
𝑝 𝑠

Proof of (III)
𝑑𝑆 𝑑𝑉
If 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇. 𝑡ℎ𝑒𝑛 𝑝𝑟𝑜𝑣𝑒 𝑡ℎ𝑎𝑡 (𝑑𝑃) = − ( 𝑑𝑇 ) .
𝑇 𝑃

Given 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 … . (1)

When P is constant VdP = 0.

⟹ (𝑑𝐺 )𝑃 = −𝑆𝑑𝑇 − − − (2)

𝑑𝐺
⟹( ) = −𝑆 − − − (3)
𝑑𝑇 𝑃
35
Differenting the equation (3) w.r.t p at constant T.

𝑑2𝐺 𝑑𝑆
⟹( ) = − ( ) − − − (4)
𝑑𝑃. 𝑑𝑇 𝑑𝑃 𝑇

Again from equation (1).

When, T is constant SdT = 0.

⟹ (𝑑𝐺 ) 𝑇 = 𝑉𝑑𝑃 − − − (5)

𝑑𝐺
⟹( ) = 𝑉 − − − (6)
𝑑𝑃 𝑇

Differenting equation (6) w.r.t T at constant P.

𝑑2𝐺 𝑑𝑉
⟹( ) = − ( ) − − − (7)
𝑑𝑇. 𝑑𝑃 𝑑𝑇 𝑃

𝑑2 𝐺 𝑑2 𝐺
Since 𝑑𝐺 is an exact differential 𝑑𝑇.𝑑𝑃 = 𝑑𝑇 .𝑑𝑃

Since the L.H.S of equation (4) & equation (7) are same .

𝑑𝑆 𝑑𝑣
⟹ −( ) =( )
𝑑𝑝 𝑇 𝑑𝑇 𝑃

𝑑𝑆 𝑑𝑉 ....... (8) proved

⇒( ) = −( )
𝑑𝑃 𝑇 𝑑𝑇 𝑝

𝑑𝑆 𝑑𝑃
iv) If 𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 . 𝑡ℎ𝑒𝑛 𝑝𝑟𝑜𝑣𝑒 (𝑑𝑉 ) = (𝑑𝑇 )
𝑇 𝑉
Given , 𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 . 𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 … . . (1)
When T is constant SdT=0
⟹ (𝑑𝐴) 𝑇 = −𝑃𝑑𝑉 … … … . (2)
𝑑𝐴
⟹ ( ) = −𝑃 … … (3)
𝑑𝑉 𝑇
Differentiating equation (3) w.r.t T at constant V .
𝑑2𝐴 𝑑𝑃
⇒( ) = − ( ) … … . . (4).
𝑑𝑇𝑑𝑉 𝑑𝑇 𝑉
Again from equation (1)
When V is constant PdV = 0,
⇒ (𝑑𝐴)𝑉 = −𝑆𝑑𝑇 … … . (5)
𝑑𝐴
⟹ ( ) = −𝑆 … … … . (6)
𝑑𝑇 𝑉
Differentiating equation (6) w.r.t V at constant T .
𝑑2𝐴 𝑑𝑆
⟹( ) = − ( ) … … … (7)
𝑑𝑉𝑑𝑇 𝑑𝑉 𝑇
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 𝑑2 𝐴 𝑑2 𝐴
Since d A is an exact differential 𝑑𝑇.𝑑𝑉 = 𝑑𝑉𝑑𝑇
Since the LHS of equation (4) & equation (7) are same
𝑑𝑝 𝑑𝑆
⟹ −( ) = −( )
𝑑𝑇 𝑉 𝑑𝑉 𝑇
𝑑𝑆 𝑑𝑃
⟹ (𝑑𝑉 ) = (𝑑𝑇 ) ........(8) Proved
𝑇 𝑉
.

..............................END...............

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