• Important Terms and Definitions

System: Refers to the portion of universe which is under observation.

Surroundings: Everything else in the universe except system is
called surroundings. The Universe = The System + The Surroundings.

Open System: In a system, when there is exchange of energy and

matter taking place with
the surroundings, then it is called an open system.
For Example: Presence of reactants in an open beaker is an example
of an open system. Closed System: A system is said to be a closed
system when there is no exchange of matter ‘ but exchange of energy
is possible.
For example: The presence of reactants in a closed vessel made of
conducting material.
Isolated System: In a system, when no exchange of energy or matter
takes place with the surroundings, is called isolated system.
For example: The presence of reactants in a thermoflask, or substance
in an insulated closed vessel is an example of isolated system.
Homogeneous System: A system is said to be homogeneous when all
the constituents present is in the same phase and is uniform
throughout the system.
For example: A- mixture of two miscible liquids.
Heterogeneous system: A mixture is said to be heterogeneous when
it consists of two or more phases and the composition is not uniform.
For example: A mixture of insoluble solid in water. ’
The state of the system: The state of a thermodynamic system means
its macroscopic or bulk properties which can be described by state
variables:
Pressure (P), volume (V), temperature (T) and amount (n) etc.
They are also known as state functions.
Isothermal process: When the operation is carried out at constant
temperature, the process is said to be isothermal. For isothermal
process, dT = 0 Where dT is the change in temperature.
Adiabatic process: It is a process in which no transfer of heat
between system and surroundings, takes place.
Isobaric process: When the process is carried out at constant
pressure, it is said to be isobaric. i.e. dP = 0
Isochoric process: A process when carried out at constant volume, it
is known as isochoric in nature.
Cyclic process: If a system undergoes a series of changes and finally
returns to its initial state, it is said to be cyclic process.
Reversible Process: When in a process, a change is brought in such a
way that the process could, at any moment, be reversed by an
infinitesimal change. The change r is called reversible.
• Internal Energy
It is the sum of all the forms of energies that a system can possess.
In thermodynamics, it is denoted by AM which may change, when
— Heat passes into or out of the system
— Work is done on or by the system
— Matter enters or leaves the system.
Change in Internal Energy by Doing Work
Let us bring the change in the internal energy by doing work.
Let the initial state of the system is state A and Temp. TA Internal
energy = uA
On doing’some mechanical work the new state is called state B and
the temp. TB. It is found to be
TB > TA
uB is the internal energy after change.
∴ Δu = uB – uA
Change in Internal Energy by Transfer of Heat
Internal energy of a system can be changed by the transfer of heat
from the surroundings to the system without doing work.
Δu = q
Where q is the heat absorbed by the system. It can be measured in
terms of temperature difference.
q is +ve when heat is transferred from the surroundings to the system.
q is -ve when heat is transferred from system to surroundings.
When change of state is done both by doing work and transfer of heat.
Δu = q + w
First law of thermodynamics (Law of Conservation of Energy). It
states that, energy can neither be created nor be destroyed. The energy
of an isolated system is constant.
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.
• Extensive property
An extensive property is a property whose value depends on the
quantity or size of matter present in the system.
For example: Mass, volume, enthalpy etc. are known as extensive
property.
• Intensive property
Intensive properties do not depend upon the size of the matter or
quantity of the matter present in the system.
For example: temperature, density, pressure etc. are called intensive
properties.
• Heat capacity
The increase in temperature is proportional to the heat transferred.
q = coeff. x ΔT
q = CΔT
Where, coefficient C is called the heat capacity.
C is directly proportional to the amount of substance.
Cm = C/n
It is the heat capacity for 1 mole of the substance.
• Molar heat capacity
It is defined as the quantity of heat required to raise the temperature of
a substance by 1° (kelvin or Celsius).
• Specific Heat Capacity
It is defined as the heat required to raise the temperature of one unit
mass of a substance by 1° (kelvin or Celsius).
q = C x m x ΔT
where m = mass of the substance
ΔT = rise in temperature.
• Relation Between Cp and Cv for an Ideal Gas
At constant volume heat capacity = Cv
At constant pressure heat capacity = Cp
At constant volume qv= CvΔT = ΔU
At constant pressure qp = Cp ΔT = ΔH
For one mole of an ideal gas
ΔH = ΔU + Δ (PV) = ΔU + Δ (RT)
ΔH = ΔU + RΔT
On substituting the values of ΔH and Δu, the equation is modified as
Cp ΔT = CvΔT + RΔT
or Cp-Cv = R
• Measurement of ΔU and ΔH—Calorimetry
Determination of ΔU: ΔU is measured in a special type of calorimeter,
called bomb calorimeter.
Working with calorimeter. The calorimeter consists of a strong vessel
called (bomb) which can withstand very high pressure. It is
surrounded by a water bath to ensure that no heat is lost to the
surroundings.
Procedure: A known mass of the combustible substance is burnt in
the pressure of pure dioxygen in the steel bomb. Heat evolved during
the reaction is transferred to the water and its temperature is
monitored.
• Enthalpy Changes During Phase Transformation
Enthalpy of fusion: Enthalpy of fusion is the heat energy or change
in enthalpy when one mole of a solid at its melting point is converted
into liquid state.

Enthalpy of vaporisation: It is defined as the heat energy or change

in enthalpy when one mole of a liquid at its boiling point changes to
gaseous state.
Enthalpy of Sublimation: Enthalpy of sublimation is defined as the
change in heat energy or change in enthalpy when one mole of solid
directly changes into gaseous state at a temperature below its melting
point.

• Standard Enthalpy of Formation

Enthalpy of formation is defined as the change in enthalpy in the
formation of 1 mole of a substance from its constitutin elements under
standard conditions of temperature at 298K and 1 atm pressure.

Enthalpy of Combustion: It is defined as the heat energy or change

in enthalpy that accompanies the combustion of 1 mole of a substance
in excess of air or oxygen.
• Thermochemical Equation
A balanced chemical equation together with the value of ΔrH and the
physical state of reactants and products is known as thermochemical
equation.

Conventions regarding thermochemical equations

1. The coefficients in a balanced thermochemical equation refer to the
number of moles of reactants and products involved in the reaction.
• Hess’s Law of Constant Heat Summation
The total amount of heat evolved or absorbed in a reaction is same
whether the reaction takes place in one step or in number of steps.

• Born-Haber Cycle
It is not possible to determine the Lattice enthalpy of ionic compound
by direct experiment. Thus, it can be calculated by following steps.
The diagrams which show these steps is known as Born-Haber Cycle.
• Spontaneity
Spontaneous Process: A process which can take place by itself or has
a tendency to take place is called spontaneous process.
Spontaneous process need not be instantaneous. Its actual speed can
vary from very slow to quite fast.
A few examples of spontaneous process are:
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
• Entropy (S)
The entropy is a measure of degree of randomness or disorder of a
system. Entropy of a substance is minimum in solid state while it is
maximum in gaseous state.
The change in entropy in a spontaneous process is expressed as ΔS

• Gibbs Energy and Spontaneity

A new thermodynamic function, the Gibbs energy or Gibbs function
G, can be defined as G = H-TS
ΔG = ΔH – TΔS
Gibbs energy change = enthalpy change – temperature x entropy
change ΔG gives a criteria for spontaneity at constant pressure and
temperature, (i) If ΔG is negative (< 0) the process is spontaneous.
(ii) If ΔG is positive (> 0) the process is non-spontaneous.
• Free Energy Change in Reversible Reaction