THERMODYNAMICS

UNIT-6

Thermodynamics: The branch of science that deals with the quantitative relationship
between heat and other forms of energy.
System: A specified part of the universe that is under investigation.
Surroundings: The part of the universe other than the system.
Boundaries: The imaginary boundary that separates the system and the surroundings.
Types of system:
Open system: The system that can exchange matter as well as energy with the
surroundings.
Closed system: The system which cannot exchange matter, but can exchange energy,
with the surroundings.
Isolated system: The system that cannot exchange matter and energy with the
surroundings.
Macroscopic system: A system containing a large number of chemical species.
Macroscopic properties: The properties that arise from the bulk behavior of matter.
Macroscopic Properties. e.g. pressure, volume, temperature, viscosity, surface
tension, density, refraction, index etc. It is of two types:
a) Intensive Properties: The properties of the system whose value is independent of
the amount of substance present in the system are called Intensive Properties, e.g.
Temperature, Pressure, Viscosity, Surface tension.
b) Extensive Properties: Whose value depends on the amount of substance present in
system e.g. mass, volume, surface area, energy, enthalpy.
State of the system: The condition of existence of a system when the macroscopic
properties have definite values is called the state of the system.
State variables or state functions: A thermodynamic property whose value depends
on the initial and final states of the system and is independent of the manner by which
the change is brought about.
Thermodynamic processes: The process, which brings about the changes in the state
of the system.
Isothermal process: A process, which is carried out at constant temperature.
Adiabatic process: A process in which no heat exchange takes place between the
system and the surroundings.
Isobaric process: A process, which is carried out at constant pressure.
Isochoric process: A process, which is carried out at constant volume.
Reversible process: when a process is carried out slowly so that the system and the
surroundings are always at equilibrium the process is termed as reversible process.
Irreversible process: A process which takes place so rapidly that the system and the
surroundings are not at equilibrium is termed as an irreversible process.
Internal energy: Every substance possesses a definite amount of energy which
depends on the chemical nature of the substance and the state of existence.
Enthalpy: The sum of the internal energy and the sum of the pressure volume work
of a system is called enthalpy of the system.
First law of thermodynamics: Energy can neither can be created nor destroyed
although it may be changed from one form to another.
Change in Internal Energy U= q + w
Expression for pressure – Volume work
w = - PV
For isothermal (T = constant) expansion of an ideal gas into vacuum w = 0 since
pex= 0. Also, Joule determined experimentally that q = 0; therefore, ΔU = 0

Exothermic reactions: The reactions which proceed with the evolution of heat energy
are called exothermic reactions.
Endothermic reactions: The reactions which proceed with the absorption of heat
energy are called endothermic reactions.
Thermochemical equation: A balanced chemical equation together with enthalpy
change is called thermochemical equation.
Some important aspects of thermochemical equations:
The coefficients in a balanced chemical thermochemical equation refer to the number
of moles of the reactants and products involved in the reaction.
When the chemical equation is reversed the value of ∆H is reversed in sign.
Physical states of all the species should be specified in the equation.
Standard enthalpy change is expressed as enthalpy change per mole as shown in the
equation.
Standard enthalpy of reaction:
The enthalpy change for a reaction when all the reacting substances are in the standard
state. (Pure state of a substance at 298K and 1bar)
Standard enthalpy of the combustion[∆cHο]: The enthalpy change accompanying
the combustion of one mole of a substance. ∆cHο is always negative.
Enthalpy of formation: The enthalpy change for the formation of one mole of a
compound from the constituent elements in their standard state.
As a convention the ∆fHοof every element is assumed to be zero.
Enthalpy of fusion: The enthalpy change accompanying the conversion of 1mole of
a solid substance into its liquid state at its melting point.
Enthalpy of vaporization[ΔvapH0]: The enthalpy change accompanying the
conversion of 1mole of liquid into its vapours at the boiling point.
Enthalpy of sublimation[ΔsubH0]: The enthalpy change accompanying the conversion
of 1 mole of solid into a liquid.
Bond dissociation energy: the enthalpy change involved in the breaking the bond
between atoms in a gaseous homonuclear molecule.
Bond enthalpy[ΔbondH0]: The amount of energy required to break a bond in one mole
of a covalent substance in the gaseous state.
∆H = ∑∆Hf  (product) – ∑∆Hf  (reactants).
∆H = ∆U + ∆ng RT ∆ng =No. of gaseous moles of products- No. of gaseous
moles of reactants
∆H = ∆U + P∆ V R=8.314J/mol/K
∆H = Bond enthalpy of reactants– Bond enthalpy of products
Hesss Law of Constant Heat Summation: If the reaction occurs 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.
Enthalpy of Solution ( ΔsolH0)Enthalpy of solution of a substance is the enthalpy
change when one mole of it dissolves in a specified amount of solvent.
Lattice Enthalpy:The lattice enthalpy of an ionic compound is the enthalpy change
which occurs when one mole of an ionic compound dissociates into itsions in gaseous
state.
Since it is impossible to determine lattice enthalpies directly by experiment, we
use an indirect method where we construct an enthalpy diagram called a Born-
Haber Cycle

Entropy(S):Entropy may be defined as “The property of a system which measures the

degree of disorder or randomness in the system”. It is a state function.
S= S(final) –S(initial) {S-Entropy; S- Change in Entropy}
S= qrev/T {qrev represents the heat supplied at temperature T}
Second Law of Thermodynamics:
In an isolated system the change in entropy is positive i.e S>0. However, if the sytem
is not isolated we have to take into account the entropy change of the system and
surroundings.
Stotal= Ssytem + Ssurroundings
For a spontaneous process S total must be positive i.e
Stotal= Ssytem + Ssurroundings>0
The second law of thermodynamics states that:
“The entropy of the universe always increases in the course of every spontaneous
change.”

Free Energy or Gibb’s energy (G) And Free Energy Change or Gibb’s energy
change(∆G)
G = H – TS
∆G = ∆H -T∆S (Gibbs’s eqn.)
Gibbs energy change for predicting feasibility of a reaction:
We have seen that for a system which is not isolated from it’s surrounding, it is S total
which decide the spontaneity of a process.
S total = S system + S surrounding
S Total = S (system) + H (surrounding) / {S surrounding = H (surrounding) / T}
S Total = S (system) - H (system) / T { H (surrounding) = –H (system) }
Multiplied by T
TS (Total) = TS (system)−H (system)
H (system)− TS (system) = −TS (total)

G = −TS (total) {since G= H (system)− TS (system) }

Gibbs Free Energy: It is defined as maximum amount of energy available to a system

during the process that can be converted into useful work. It is the measure of capacity
to do useful work.
Standard Gibbs energy change G,
G = Standard Gibbs energy change (at 298 K and 1 bar)
G = {Sum of the standard Gibbs energies of product} − {sum of the
standard Gibbs energies of reactants)
 G = [G (Product)] − [G (Reactants)]
Sign of H Sign of S Value of T Spontaneity
- + Any Spontaneous
+ - Any Non-Spontaneous
- - Low Spontaneous
- - High Non-Spontaneous
+ + Low Non-Spontaneous
+ + High Spontaneous
At equilibrium S = 0 so that if G = 0 the system has attained
equilibrium
If G = +ve, the process is non-spontaneous
If G = -ve, the process is spontaneous
If G = zero, the process is at equilibrium