THERMODYNAMICS

The branch of science which deals with

the quantitative relationship between
heat and other forms of energies is
called thermodynamics
System It refers to the part of universe in
which observations are carried out.
(ii) Surroundings The part of universe other
than the system is known as surroundings.
(ill) Boundary The wall that separates the
system from the surroundings is called
boundary.
Types of Systems

(i) Open system The system in which energy

and matter both can be exchanged with the
surroundings.

(ii) Closed system The system in which only

energy can be exchanged with the
surroundings.

(iii) Isolated system The system in which

neither energy nor matter can be exchanged
with the surroundings.
State of System
When microscopic properties have
definite value, the conditions of existence
of the system is known as state of system.
State functions When values of a
system is independent of path followed
and depend only on initial and final state,
it is known as state function,e.g., Δ U, Δ
H, Δ G etc.
Path functions These depend upon the
path followed, e.g., work, heat, etc.
Thermodynamic Process

It is the operation which brings change in the

state of the system.
Thermodynamic processes are
(i) Isothermal process In which
temperature remains constant, i.e., (dT = 0, Δ
U = 0).
(ii) Isochoric process In which volume
remains constant, i.e., (Δ V = 0).
(iii) Isobaric process In which pressure
remains constant, i.e., (Δp = 0).
Thermodynamic Process
 Adiabatic process In which heat is not exchanged by
system with the surroundings, i.e., (Δq = 0).
Cyclic process It is a process in which system returns to
its original state after undergoing a series of change, i.e.,
Δ U cyclic = 0; Δ H cyclic = 0
Reversible process A process that follows the reversible
path, i.e., the process which occurs in infinite number of
steps in this Way that the equilibrium conditions are
maintained at each step, and the process can be reversed
by infinitesimal change in the state of functions.
Irreversible process The process which cannot be
reversed and amount of energy increases. All natural
processes are Irreversible.
Thermodynamics Properties
1. Intensive Properties
Properties of the system which depend only
on the nature of matter but not on the
quantity of matter are called Intensive
properties, e.g., pressure, temperature,
specific heat, etc
2. Extensive Properties
Properties of the system which are dependent
on the quantity of matter are called extensive
properties, e.g., internal energy, volume,
enthalpy, etc.
Thermodynamic equilibrium A system in
which the macroscopic properties do not
undergo any change with time is called
thermodynamic equilibrium.
Thermal equilibrium If there is no flow of
heat from one portion of the system to
another, the system is said to be in thermal
equilibrium.
Mechanical equilibrium If no mechanical
work is done by one part of the system on
another part of the system. it is said to be in
mechanical equilibrium. Such a condition
exists when pressure remains constant.
Internal Energy (E or U)
It is the total energy within the substance. It is
the sum of many types of energies like
vibrational energy, translational energy. etc. It is
a extensive property and state function.
Its absolute value cannot be determined but
experimentally change in internal energy (Δ) can
be determined by
ΔU = U2 – U1 or ΣUp – ΣUR
For exothermic process, ΔU = -ve, whereas for
endothermic process ΔU = +ve
U depends on temperature, pressure, volume
and quantity of matter.
First Law of Thermodynamics

Energy can neither be created nor destroyed

although it can be converted from one form
to the other.
Mathematically, ΔU = q + W
Work (Pressure-volume Work)

Let us consider a cylinder which contains one

mole of an ideal gas in which a frictionless piston
is fitted.
WORK DONE IN ISOTHERMAL AND REVERSIBLE EXPANSION OF IDEAL GAS
Isothermal and Free Expansion of an Ideal Gas
For isothermal expansion of an ideal gas
into vacuum W = 0
Enthalpy (H)
It is defined as total heat content of the system.
It is equal to the sum of internal energy and pressure-volume work.
Mathematically,
H = U + PV

Change in enthalpy:
Change in enthalpy is the heat absorbed or evolved by the system at
constant pressure.

ΔH = qp

For exothermic reaction (System loses energy to Surroundings),

ΔH and qp both are -Ve.
For endothermic reaction (System absorbs energy from the Surroundings).
ΔH and qp both are +Ve.
Relation between ΔH and ΔU.
HEAT CAPACITY
Heat Capacity (c) of a system is defined as the
amount of heat required to raise the temperature
of a system by 1° C.

The increase or decrease in temperature is

proportional to the heat transferred.
q = coeff. x ΔT
where q= heat transferred
ΔT= change in temperature
q = CΔT
Where, coefficient C is called the heat capacity.
Thus, Heat Capacity = Heat absorbed/Rise in
temperature
Molar Heat Capacity

The amount of heat required to raise the

temperature of 1 mole of substance by 1 0 is
called molar heat capacity
Molar heat capacity = heat absorbed / Rise in
temperature x Molar mass
Units: JK-1mol-1
Specific Heat Capacity
The amount of heat required to raise the
temperature of 1 gram of substance by 1 0 is
called specific heat capacity or simply specific
heat.
Specific heat capacity = heat absorbed / Rise
in temperature x Mass of sample (gm)
Units: JK-1g-1
Enthalpy or Heat of Reaction (ΔrH)

It is the change in enthalpy that accompanies

a chemical reaction represented by a
balanced chemical equation.
ΔrH = ΣH(p) – ΣH(R)
Enthalpy of reaction expressed at the
standard state conditions is called standard
enthalpy of reaction (ΔH).
Factors affecting enthalpy of reaction

(i) Physical state of reactants and products.

(ii) Allotropic forms of elements involved.
(iii) Chemical composition of reactants and
products.
(iv) Amount of reactants.
(v) Temperature.
Various Forms of Enthalpy of Reaction
 Enthalpy of Formation (ΔHf)
It is heat change when one mole of compound
is obtained from its constituent elements.
Enthalpy of formation at standard state is
known as standard enthalpy of formation
ΔfH° and is taken as zero by convention. It
also gives the idea of stability.
Enthalpy of Combustion
It is the Enthalpy change taking place when
one mole of a compound undergoes complete
combustion In the presence of oxygen (ΔH c.)
 Enthalpy of Solution
It is the Enthalpy change when one mole of a
substance is dissolved in large excess of
solvent, so that on further dilution no
appreciable heat change occur.

Enthalpy of Hydration
It is the enthalpy change when one mole of
anhydrous substances undergoes complete
combustion. It is an exothermic process.
Enthalpy of Fusion
It is the enthalpy change that accompanies
melting of one mole of solid substance.

Enthalpy of Vaporisation
It is the enthalpy change that accompanies
conversion of one mole of liquid substance
completely into vapours
Enthalpy of Neutralisation
It is the enthalpy change that takes place
when 1 g-equivalent of an acid (or base) is
neutralised by 1 g-equivalent of a base (or
acid) in dilute solution

Enthalpy of Transition
It is the enthalpy change when one mole
of the substance undergoes transition
from one allotropic form to another.
Enthalpy of Sublimation
It is the enthalpy change, when one mole
of a solid substance sublimes.

Lattice Enthalpy
It is the enthalpy change, when one mole
of an ionic compound dissociates into its
ions in gaseous state.
 Hess’s Law of Constant Heat Summation

The standard enthalpy of a reaction.

which takes place in several steps, is the
sum of the standard enthalpies of the
intermediate reactions into which the
overall reactions may be divided at the
same temperature.
According to Hess’s law
ΔH = ΔH1 + ΔH2 + ΔH3
Applications of Hess’s law

(a) In determination of beat of formation.

(b) In determination of heat of transition.
(c) In determination of heat of hydration.
(d) To calculate bond energies.
Bond Dissociation Enthalpy
The energy required to break the particular
bond in a gaseous molecule is called bond
dissociation enthalpy. It is definite in quantity
and expressed in kJ mol-1.
In diatomic molecule,
Bond dissociation enthalpy = Bond enthalpy
In polyatomic molecule,
Bond dissociation enthalpy ≠ Bond Enthalpy
ΔH = [sum of bond enthalpies of reactants] –
[sum of bond enthalpies of products]
Factors affecting bond enthalpy

(i) Size of atoms

(ii) Electronegativity
(iii) Bond length
(iv) Number of bonding electrons
 Entropy (S)
It is the measurement of randomness or disorder of the
molecules. It is a state function and extensive property.
Units : JK-1 mol-1
The change in entropy during a process is mathematically
given as
ΔS° = Σ S° (products) – Σ S° (reactants)
= qrev / T
= ΔH / T
Where, qrev heat absorbed by the system in reversible
manner
T = temperature
Δ S > 0, Increase in randomness, heat is absorbed
Δ S < 0, Decrease in randomness, heat is evolved.
Entropy of even elementary substances are not zero.
Entropy Change During Phase Transition
The change of matter from one state to
another state is called phase transition.
The entropy changes at the time of phase
transition:
 Entropy (S)

It is the measurement of randomness or

disorder of the molecules. It is a state function
and extensive property.
Units : JK-1
The change in entropy during a process is
mathematically given as
ΔrS° = Σ S° (products) – Σ S° (reactants)
= qrev / T = ΔH / T
Where, qrev heat absorbed by the system in
reversible manner
T = temperature
NB
Δ S > 0, Increase in randomness, heat is
absorbed
Δ S < 0, Decrease in randomness, heat is
evolved.
Entropy of even elementary substances are
not zero.
 Entropy Change During Phase Transition
The change of matter from one state to
another state is called phase transition.
The entropy changes at the time of phase
transition:
Spontaneous Process
The physical or chemical process which
proceeds by its own in a particular
direction under given set of conditions
without outside heir is called spontaneous
process. It cannot be reversed.

All natural processes are spontaneous

process.
Spontaneous process where no
initiation is needed
(i) Sugar dissolves in water.
(ii) Evaporation of water.
(iii) Nitric oxide (NO) reacts with
oxygen.

Spontaneous process where some

initiation is required
(i) Coal keeps on burning once initiated.
Enthalpy & Entropy Criterion of Spontaneous Process
Enthalpy Criterion of Spontaneous Process
All the processes which are accompanied by
decrease of energy (exothermic reactions, having
negative value of ΔH) occur spontaneously.
It fails when some endothermic reactions occur
spontaneously.
Entropy Criterion of Spontaneous Process
A process is a spontaneous if and only if the
entropy of the universe increases.
For a process to be Spontaneous
(ΔSuniverse > 0 or ΔSsyst + ΔSsurr > 0)
At equilibrium state, ΔS = 0,
Limitations of ΔS criterion and need for
another term
We cannot find entropy change of
surroundings during chemical changes. So
we need another parameter for spontaneity
viz Gibbs’ energy of system (G).
Second Law of Thermodynamics

The entropy of the universe is always

Increasing in the course of every spontaneous
or natural change.
OR
All spontaneous processes or natural change
are thermodynamically irreversible without
the help of an external work. i.e., heat cannot
flow itself from a colder to hotter body.
Gibbs Energy or Gibbs Free Energy

It is the energy available for a system at some

conditions and by which useful work can be done. It is
a state function and extensive property.
Mathematically,
G = H – TS
Change in Gibbs energy during the process 1S given by
Gibbs Helmholtz equation.
(ΔG = G2 – G1 = ΔH – TΔS)
where, ΔG = Gibbs free energy
H = enthalpy of system
TS = random energy
ΔGsystem = – TΔStotal
THE GIBBS ENERGY CRITERION OF SPONTANEITY

ΔG > 0, process is non-spontaneous

ΔG < 0, 0, process is spontaneous
ΔG = 0, process is in equilibrium state
EFFECT OF TEMPERATURE ON SPONTANEITY
Standard Free Energy Change (Δ Go)

It is the change in free energy which takes

places when the reactants are converted into
products at the standard states, i.e., (1 atm
and 298 K)
where, ΔG°f = standard energy of formation
Standard energy of formation of all free
elements is zero.
Gibbs Energy Change and Equilibrium
Criterion for equilibrium,
Relation between ΔG° and EMF of the Cell
Third Law of Thermodynamics

This law was formulated by Nernst in 1906.

According to this law,
“The entropy of a perfectly crystalline
substance at zero K or absolute zero is taken
to be zero”.
This law is only applicable for perfectly crystalline substances. If there
is imperfection at 0 K, the entropy will be larger than zero.