Thermodynamics NARAYAN TUTORIALS IITian Sushil Kumar

The branch of science which deals with study of different forms of energy and their interconversion is called
thermodynamics.
A system in thermodynamics refers to that part of universe in which observations are made.
The remaining portion of universe which is not part of system constitutes the surroundings. The surroundings
include everything other than the system.
The wall (real or imaginary) that separates the system from the surroundings is called boundary.
Types of system Exchange of energy Exchange of matter
Open Yes Yes
Closed Yes No
Isolated No No
The state of a thermodynamic system is described by its measurable or macroscopic (bulk) properties. The
state of the surroundings can never be completely specified.
State variables are the measurable properties of system required to describe the state of the system.
Examples are temperature, pressure, volume etc.
Various types of processes:-
Type of process Definition
Isothermal (ΔT = 0) Process in which temperature of
system
remains constant
Adiabatic (ΔQ= 0) Process in which there is no transfer of
heat between the system and
surroundings
Isobaric (ΔP= 0) Process in which pressure of system
remains
constant
Isochoric(ΔV= 0) Process in which volume of system remains
constant
Sign Convention:
Work done by the system ΔW = positive
Work done on the system ΔW = negative
Heat transferred From surroundings to the system ΔQ = positive
Heat transferred From system to the surroundings ΔQ = negative
First law of Thermodynamics:-
First law of thermodynamics is also called as law of conservation of energy i.e. energy can neither be created
nor destroyed. It also states that the energy of an isolated system is constant.
ΔQ = ΔU+ ΔW
Expression of Work:
Isochoric ΔW = 0
Isobaric ΔW= P(V2–V1) = nR(T2–T1)
Isothermal ΔW = nRT ln(V2/V1) = 2.303nRT log(V2/V1)
Adiabatic ΔW = (P1V1-P2V2)/(γ – 1) = (nRT1-nRT2)/(γ – 1)
Reversible and Irreversible process:- A process or change is said to be reversible, if a change is brought out
in such a way that the process could, at any moment, be reversed by an infinitesimal change. A reversible
process proceeds infinitely slowly by a series of equilibrium states such that system and the surroundings are
always in near equilibrium with each other. Processes other than reversible processes are known as irreversible
processes.
Free Expansion:- Expansion of a gas in vacuum (Pex= 0) is called free expansion. No work is done during
free expansion of an ideal gas whether the process is reversible or irreversible.

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Thermodynamics NARAYAN TUTORIALS IITian Sushil Kumar

Enthalpy:- The enthalpy of a system may be defined as the sum of the internal energy and the product of its
pressure and volume. It is denoted by the symbol H and is given by H = U + PV.
ΔH = ΔU + PΔV
Types of reaction:-
Type of reaction Definition ΔH
Exothermic reactions Reactions in which heat is evolved during the reaction Negative
Endothermic reactions Reactions in which heat is absorbed during the reaction positive
Extensive and Intensive property:
An extensive property is a property whose value depends on the quantity or size of matter present in the
system. Examples are mass, volume, internal energy, enthalpy, heat capacity, etc.
An intensive property is a property whose value does not depend on the quantity or size of matter present in
the system. Examples are temperature, density, pressure etc.
Specific heat capacity:
Specific heat, also called specific heat capacity is the quantity of heat required to raise the temperature of one
unit mass of a substance by one degree Celsius (or one Kelvin).
Q = m x S x ΔT;
At constant pressure, QP = nCPΔT = ΔH;
At constant volume QV = nCVΔT =ΔU
For ideal gas: CP – CV = R
Calorimetry: -Calorimetry is an experimental technique that helps determining energy changes associated
with chemical or physical processes.
Reaction enthalpy: - The enthalpy change accompanying a reaction is called the reaction enthalpy (Δ rH).
ΔrH = (sum of enthalpies of products) - (sum of enthalpies of reactants)
The standard enthalpy of reaction is the enthalpy change for a reaction when all the participating substances
are in their standard states. The standard state of a substance at a specified temperature is its pure form at
pressure of 1 bar. It is denoted by (ΔrHΘ).
Thermochemical equation: - A balanced chemical equation together with the value of its Δ rHΘ is called a
thermochemical equation.
Hess’s Law of Constant Heat Summation: If a reaction takes place in several steps then its standard reaction
enthalpy is the sum of the standard enthalpies of the intermediate reactions into which the overall reaction may
be divided at the same temperature.

ΔrH ΔrH = ΔrH1 + ΔrH2 + ΔrH3

A B
ΔrH1
ΔrH3

C ΔrH2
D

Different types of Enthalpy:

Type of enthalpy Definition Symbol
Standard Enthalpy of fusion The enthalpy change that accompanies melting of one ΔfusHΘ
or Molar enthalpy of fusion mole of a solid substance in standard state
Standard Enthalpy of vaporization or The enthalpy change that accompanies vaporizing of ΔVapHΘ
Molar enthalpy one mole of a liquid at constant temperature and under
of vaporization standard pressure (1bar)
Standard Enthalpy of sublimation The enthalpy change when one mole of a solid ΔsubHΘ

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Thermodynamics NARAYAN TUTORIALS IITian Sushil Kumar

substance sublimes at a constant temperature and under

standard pressure (1bar).
Enthalpy of formation or Standard The enthalpy change for the formation of one mole of a ΔfHΘ
molar enthalpy of formation compound from its elements in their most stable states
of aggregation.
Enthalpy of combustion Enthalpy change when 1 mole of substance is ΔcHΘ
completely burnt in excess of oxygen or air.
Enthalpy of atomisation Enthalpy change in breaking one mole of bonds of a ΔaHΘ
substance completely into atoms in gaseous state.
Bond dissociation enthalpy Amount of energy required to break one mole of bond ΔbondHΘ
of a particular type between atoms in gaseous state
Enthalpy of solution Enthalpy of solution of a substance is ΔsolHΘ
the enthalpy change when one mole of substance
dissolves in a specified amount of solvent. ΔsolHΘ =
ΔlatticeHΘ + ΔhydHΘ
Lattice enthalpy Enthalpy change which occurs when one mole of an ΔlatticeHΘ
ionic compound dissociates into its ions in gaseous
state.
Enthalpy of Neutralisation Enthalpy change when one gram equivalent of an acid ΔneuHΘ
is completely neutralized by one gram equivalent of a
base.
H+(aq)+OH-(aq) H2O(l) ; ΔH=-13.7kcal

Born-Haber Cycle is used to determine lattice enthalpy of ionic compounds since they cannot be determined
by experiment directly.
Spontaneous and non-spontaneous process: A process that has natural tendency of occurrence in a
particular direction and is reversible only by application of some external agency is known as spontaneous
process.
The processes which are forbidden and are made to take place only by supplying energy continuously from
outside the system are called non-spontaneous process.
Entropy: - Entropy (S) is the measure of randomness of a system. It is a state function. Entropy increases from
solid to gas. Entropy is maximum for gases as they have maximum disorder.
According to Second law of thermodynamics, entropy of the universe always increases during a spontaneous
change.
For reversible process entropy change is given by:
ΔS = (ΔQrev)/ T ;
ΔQrev = is heat absorbed or released during the reaction
and T is the temperature of the reaction
At constant pressure ΔQrev = ΔH; ΔS = (ΔH)/T
For spontaneous process ΔStotal =ΔS system + ΔSsurr > 0

Gibbs energy: - Gibbs function or Gibbs energy is denoted by G.

G=H-TS ; ΔG = ΔH - TΔS
The criteria for spontaneous reaction in relation to ΔG at constant pressure and constant temperature is
If ΔG < 0, process is spontaneous
If Δ G = 0, process is in equilibrium
If ΔG > 0, process is non-spontaneous.
Relation between Gibbs energy change ΔG0and equilibrium constant (K):-
ΔG0 = -2.303RT logK

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Thermodynamics NARAYAN TUTORIALS IITian Sushil Kumar

Effect of temperature on Spontaneity of Reactions:

ΔH0 ΔS0 ΔG0 Description
- + - Reaction spontaneous at all temperature
- - - (at low T) Reaction spontaneous at low temperature
- - + (at high T) Reaction nonspontaneous at high temperature
+ + + (at low T) Reaction nonspontaneous at low temperature
+ + - (at high T) Reaction spontaneous at high temperature
+ - + (at all T) Reaction nonspontaneous at all temperatures

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