First Law of Thermodynamics

First law of thermodynamics states the law of conservation of energy in a different

manner. According to this law, whenever a quantity of one kind of energy disappears an
equivalent amount of energy appears in some other form.

According to first law of thermodynamics,

ΔQ = ∆U + ∆W

Where, Q = Heat change

W = Work done
ΔU = Change in internal energy

Enthalpy (H)

The total heat content of a system at constant pressure is known as its enthalpy.
Mathematically it is the sum of internal energy and pressure-volume energy

ΔH = ΔU + PΔV

It is an extensive property and a state function. Increase in enthalpy H is equal to heat

absorbed at constant pressure.

Heat Capacity

Heat capacity is amount of heat require to raise the temperature of a system by unity. It
is represented as "C". It is an extensive property and temperature dependent.

Types of heat capacity

(i) Specific heat: For 1 gram system the heat loose or gained by system to bring one
unit change in temperature is called specific heat denoted by 's'. specific heat is the
intensive property.

S = C /m

(ii) Molar heat capacity: It is heat capacity for a system having 1 mole of material. It is
represented as Cm. It is an intensive property.

Cm=C/m
(iii) Heat capacity at constant volume: Heat capacity of a system in isochoric
condition is called heat capacity at constant volume, it is represented as C v means
molar heat capacity at constant volume.

Cv=dU/dT

(iv) Heat capacity at constant pressure: Heat capacity of a system in isobaric

condition. It is represented by Cp means molar heat capacity at constant pressure.

Cp=dH/dT

Relation between Cp and Cv

We know that,

ΔH = ΔU + PΔV .....(i)

As per ideal gas equation

PΔV = RΔT .....(ii)

From (i) and (ii)

ΔH = ΔU + RΔT

ΔH/ΔT=ΔU/ΔT+RΔ
Cp=Cv+R
Cp−Cv=R

Hess’s Law

According to Hess's law, 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.

Ist method

C(s) + O2(g) ⟶ CO2(g) = ΔH

IInd method

C(s) + 1/2O2(g) ⟶ CO(g) = ΔH1

CO(s) + 1/2O2(g) ⟶ CO2(g) = ΔH2

According to Hess's law,

ΔH = ΔH1 + ΔH2

Application of Hess's Law

1. Calculation of enthalpy of formation.
2. Determination of standard enthalpies of reactions.
3. In determination of heat of formation.
4. In determination of heat of transition.
5. In determination of heat of hydration.
6. To calculate bond energies.

What is Enthalpy?

In a thermodynamic system, enthalpy is the measurement of energy. It is a

thermodynamic property of a system.

The product of volume and pressure, plus the system’s internal energy, determines the
quantity of enthalpy; it is equal to the total heat content of a system. The SI unit
of enthalpy is kJ mol-1.

H = U + PV

Where H is enthalpy, U is the internal energy of a system, and PV is the product of the
pressure and volume of the system.

The change in enthalpy between initial and final states.

△H = △U + △PV

When a system is at constant pressure, the change in enthalpy is equal to the heat flow
(q) for the process. In equation form, we can define the above statement as:

△H = qp

H is positive if the heat flow is positive during an endothermic reaction. Similarly, during
an exothermic reaction, the △H is negative when the heat flow is negative.

Use of Enthalpy
 The concept of enthalpy is important to determine the temperature and pressure
required during a chemical reaction. It helps determine the total amount of heating and
cooling a substance may require during commercial production.

Types of Enthalpy
There are several different types of enthalpy of reaction, which are enthalpy of


o Bond Dissociation
o Combustion
o Formation
o Atomisation
 Sublimation
o Phase Transition
 Ionisation
 Solution And Dilution
This article will discuss these different types in detail.

Enthalpy of Bond Dissociation

Enthalpy of bond dissociation refers to the heat absorbed or heat evolved during the
complete dissociation of one mole of a substance into its ions. It is nothing but the
energy required to break the bond of one mole to give separated atoms.

The concept of enthalpy of bond dissociation is useful to determine the strength of a

chemical bond. The strongest enthalpy of bond dissociation is between silicone and
fluorine.

Enthalpy of Combustion

The heat change or absorbed when 1 mole of a substance is completely oxidised and
burnt in oxygen is known as the enthalpy of combustion (△Hc). The concept
of enthalpy of combustion is useful while elucidating the structure of various organic
compounds.

Standard enthalpy of combustion refers to the amount of heat absorbed when 1 mole
of a substance is completely burnt under normal conditions, i.e. under 298 K and 1 bar
pressure.

Enthalpy of Formation

Under given conditions and pressures, 1 mole of a substance is formed due to the heat
evolved, absorbed, or changed. Enthalpy of formation is defined as △Hf.

Standard heat of formation refers to the value of heat formation at 298 K and 1
atmospheric pressure. When elements are in a free state, the standard heat of
formation is zero.

Enthalpy of Atomisation
The change in enthalpy accompanying the total separation of all atoms in a chemical
compound is known as the enthalpy of atomisation.

Enthalpy of atomisation can be defined as the energy or heat absorbed or evolved to

break 1 mole of a bond into atoms.

It can symbolise as: △Ha

Enthalpy of Sublimation

Sublimation refers to the chemical process in which a solid transforms into a gas
without passing through the liquid phase.

At a constant temperature, the energy required for converting one mole of a solid into
vapour is called the enthalpy of sublimation. The symbol
for enthalpy of sublimation is:

△Hsub

Enthalpy of Phase Transition

The transformation of a substance/element from one state to another under specific

circumstances is known as a phase transition.

There are three major types of enthalpy changes during phase transitions. These
are enthalpy of fusion, enthalpy of vaporisation, and enthalpy of sublimation.

Enthalpy of fusion refers to the transformation of 1 mole of a solid substance into a

liquid state at its melting point. Enthalpy of vaporisation refers to the amount of heat
absorbed or evolved to convert 1 mole of a liquid into its vapour state at its boiling
point.

Enthalpy of Ionisation

You can measure the tendency of an element to lose its electrons by

its ionisation enthalpy. It refers to the removal of an electron, in its ground state, from
an isolated gaseous atom. The SI unit of ionisation enthalpy is kJ mol-1.

Enthalpy of ionisation is always positive because energy is required to remove

electrons from an atom. It is harder to remove an electron from a positively charged
ion than a neutral atom; therefore, the second ionisation enthalpy will be higher than
the first ionisation enthalpy.

Enthalpy of Solution and Dilution

Enthalpy of solution (△Hsol) refers to the quantity of heat evolved or absorbed when
one mole of a substance is dissolved in a solvent so that no further dilution of solution
produces any heat. Enthalpy of solution at infinite dilution refers to a scenario where
the addition of a solvent doesn’t produce any more change in heat.
Enthalpy of dilution (△Hdil) refers to the heat evolved or absorbed to dilute one mole of
a solution from one concentration to another.

Entropy

The entropy is a state function because it depends on the final and initial state of the
process. It does not depend on the path by which the process is completed.

The reason for entropy to be a state function:

1. The entropy is a state function because it depends on the final and initial state of
the process.
2. It does not depend on the path by which the process is completed.
3. For example, entropy change for a reversible process is the same when the
same process undergoes an irreversible manner but for work and heat, it is not
the same because entropy is a state function and work and heat are path
functions.

Second law of thermodynamics

The total entropy of an isolated system always increases over time, or remains constant
in ideal cases where the system is in a steady-state or undergoing a reversible process,
according to the second law of thermodynamics. The irreversibility of natural processes
is explained by the increase in entropy.

Second law of thermodynamics equation

The second law of thermodynamics is represented mathematically as;

∆Suniv >0

where ∆Suniv is the change in the universe’s entropy.

Entropy is a measure of a system’s randomness, or it is a measure of energy or chaos

within an isolated system. It can be thought of as a quantitative index describing the
quality of energy. Meanwhile, there are only a few factors that increase the entropy of a
closed system. To begin, while the mass remains constant in a closed system, there is
an exchange of heat with the surroundings. This change in heat content causes a
disturbance in the system, increasing the system’s entropy. Second, internal changes in
the system’s molecule movements may occur. This causes disturbances, which in turn
cause irreversibilities within the system, increasing its entropy.

There are two statements about the second law of thermodynamics:

Kelvin-Planck Statement:

A heat engine cannot produce a network in a complete cycle if it only exchanges heat
with bodies at a single fixed temperature.

Clausius’s Statement:

It is impossible to build a device that can transfer heat from a colder body to a warmer
one without consuming any work. Furthermore, energy will not spontaneously flow from
a low-temperature object to a higher-temperature object. It is critical to understand that
we are discussing the net transfer of energy. Energy can be transferred from a cold
object to a hot object through the transfer of energetic particles or electromagnetic
radiation. In any spontaneous process, however, the net transfer will occur from the hot
object to the cold object. And work is required to transfer the net energy to the hot
object.