Formula sheet of

Thermodynamics and Thermochemistry

1. Basic terms used in thermodynamics
a. Thermodynamic systems and properties

SYSTEM AND SURROUNDING :

A system may consist of one or more substances. The rest of the universe which might be in a position to
exchange energy and matter in a system is called surrounding.
(1) Open system:
There is energy as well as mass exchange between the system and surroundings.
(2) Closed system:
It is defined in which only energy exchange between system and surrounding, not mass is caused as a
closed system.
(3) Isolated system:
Neither energy nor mass is exchanged between the system and surrounding.

PROPERTIES OF SYSTEM :
(1) Extensive Properties: The property which depends on mass is extensive properties.
(2) Intensive properties: The property which does not depend on mass is called intensive property.

b. Thermodynamic functions, process and state

Thermodynamic functions, process and state

(1) Isothermal process:

(2) Isobaric process:

(3) Isochoric process :

(4) Adiabatic process :

(5) Cyclic process:

2. Heat
a. Thermal equilibrium and Zeroth law of thermodynamics

Thermal equilibrium:
If there is no flow of heat from one portion of the system to another. This is possible if the temperature remains
constant throughout all parts of the system.

The zeroth law of thermodynamics

It states that if two thermodynamic systems are each in thermal equilibrium with a third one, then they are in
thermal equilibrium with each other.

b. Heat transfer, mode of heat transfer and sign convention

There are three modes of heat transfer: conduction, radiation, and convection. Conduction and radiation are
fundamental physical mechanisms, while convection is really conduction as affected by fluid flow.
Exothermic reactions are reactions or processes that release energy, usually in the form of heat or light. In an
exothermic reaction, energy is released because the total energy of the products is less than the total energy of
the reactants.

Endothermic reactions are reactions that require external energy, usually in the form of heat, for the reaction to
proceed. Since endothermic reactions draw in heat from their surroundings.

3. Work
a. Definition, sign convention and difference in mechanical and thermodynamic work

For irreversible process,

b. P-V work done in reversible and inrreversible process

Reversible process :
A process that can be reverted back from any intermediate state is called reversible process. Difference
between driving force and opposing force is infinitely small.
Irreversible process:
A process that can‘t be reverted from any intermediate state is called irreversible process. Difference between
driving and opposing force is finite.

4. Internal Energy
a. Definition and characteristics of Internal Energy

Definition and characteristics of Internal Energy

It is the sum of all kinds of energy possessed by molecules. It includes translational kinetic energy, rotational
energy, vibration energy, bond energy, electronic energy, etc.
i. It is a ‘state function’

ii. For isochoric process: dV = 0

b. Degree of freedom

Where
T® Translational energy R ® Rotational energy
V ® vibrational energy f ® Degree of freedom

c. Heat capacity of matter

Heat capacity of matter

It is defined as the quantity of heat required to raise the temperature of 1gm of a substance by one degree is
called specific heat.
d. Comparison between Cp and Cv

Molar heat capacity is defined in two ways:

(1) Molar heat capacity at constant volume (Cv)

(2) Molar heat capacity at constant pressure (Cp)

5. Calorimetry
a. Bomb calorimeter and Dulong-Petit law

CALORIMETRY :
It can measure energy changes associated with chemical or physical processes by an experimental technique
is called calorimetric. In calorimetric the process is carried out in a vessel called calorimeter, which is
immersed in a known volume of liquid. Knowing the heat capacity of the liquid in which calorimeter is immersed
and the heat capacity of the calorimeter, it is possible to determine the heat evolved in the process by measuring
the temperature change.
In the calorimeter, the experiment is done in two ways.
(1) At constant volume, the calorimeter will be known as ‘BOMB CAORIMETER’.

(2) At constant pressure, the calorimeter will be known as ‘COFFEE CUP CALORIMETER’.

b. Definition and basic derivation of Enthalpy

ENTHALPY
If a gas is expanded from the volume V1 to V2 then, the amount of heat absorbed by system will be knows as
Enthalpy. It is denoted by ‘H’
H = E +PV
® Enthalpy is sum of internal energy and pressure volume energy.
® This formula is applicable for reversible or irreversible process at only steady state.

6. First law of thermodynamics

a. Statement and its basic applications

FIRST LAW OF THERMODYNAMICS :

The First Law of Thermodynamics states that heat is a form of energy and thermodynamic processes are
therefore subject to the principle of conservation of energy. This means that heat energy cannot be created or
destroyed. It can, however, be transferred from one location to another and converted to and from other forms
of energy.
ΔU = q + W
Where,
ΔU = change in internal energy of the system.
q = algebraic sum of heat transfer between system and surroundings.
W = work interaction of the system with its surroundings.

7. Application of First law of thermodynamics

a. Isothermal Process

Work done in reversible expansion

Work done in irreversible expansion

Key Points
• For an ideal gas, the product of pressure and volume (PV) is a constant if the gas is kept at isothermal
conditions.
• For an ideal gas, the work involved when a gas changes from state A to state B through an isothermal
process is given as

• For many systems, if the temperature is held constant, the internal energy of the system also is constant. It
follows that Q = - W in this case.
Key Terms
• reversible: Capable of returning to the original state without consumption of free energy and increase of
entropy.
• ideal gas: A hypothetical gas whose molecules exhibit no interaction and undergo elastic collision with each
other and with the walls of the container.
• Boyle's law: The observation that the pressure of an ideal gas is inversely proportional to its volume at
constant temperature.
b. Isobaric Process

Reversible expansion:

Irreversible:

c. Cyclic Process

Cyclic process :
When a system undergoes a number of different states by different processes and finally returns to its initial
state , it is said to have completed a cycle and process is called a cyclic process.

d. Adiabatic Reversible Process

Reversible process:

e. Adiabatic Irreversible Process

Adiabatic Irreversible Process

f. Polytropic Process and its Application

Polytrophic Process :
CProcess of a polytrophic process which follows equation PVm = constant.
PVm = constant
For every step PVm = k …… (Reversible)

g. Area under the curve and Graph

Area under the curve and Graph

The work done during a thermodynamic process is equal to the area under the curve as seen in the diagram
below.

Enclosed area in cyclic process gives work.

h. Isochoric Procses

Reversible:

Irreversible

8. Basic law of thermochemistry

a. Exothermic, Endothermic process and Laplace and Lavoisier law
Endothermic Reactions
The endothermic process is a term that describes a reaction where the system absorbs the energy from its
surrounding in the form of heat. A few examples of the endothermic process are photosynthesis, evaporating
liquids, melting ice, dry ice, alkanes cracking, thermal decomposition, ammonium chloride in water and much
more.

Exothermic Reactions
The exothermic reaction is the opposite of an endothermic reaction. It releases energy by light or heat to its
surrounding. A few examples are neutralization, burning a substance, reactions of fuels, deposition of dry ice,
respiration, solution of sulfuric acid into water and much more.

Laplace and Lavoisier law

“The enthalpy of a reaction is accurately equal but contradictory in the sign for the reverse reaction.” It states
that the heat change (or enthalpy change) of a chemical reaction is accurately equivalent but reverses in the
sign for the reverse reaction.

b. Relationship between Enthalpy and Internal Energy

ENTHALPY
If a gas is expanded from the volume V1 to V2 then the amount of heat absorbed by system will be knows as
Enthalpy. It is denoted by ‘H’

9. Measurement of Enthalpy change

a. Enthaply of Chemical Reaction Or Heat of Reaction

Enthaply of Chemical Reaction Or Heat of Reaction

→ To calculate enthalpy change of any chemical reaction we need molar enthalpy of all the involved reactant
and product.
→ But enthalpy is referential quantity and its absolute value cannot be calculated.
→ All elements in their elementary state or in their more stable allotropic state at 25oC temperature and 1 atm
pressure are assigned zero enthalpy.

b. Enthalpy of Combustion

Enthalpy of Combustion
It is defined as enthalpy change when 1 mole of substance is burned in sufficient amount of O2 to produce
stable product which cannot be burned further.
RESONANCE ENERGY:

c. Enthalpy of fusion, vapourization and sublimation

Enthalpy of fusion

Enthalpy of vaporization
The heat of vaporization (∆Hvap) is defined by the amount of enthalpy (heat energy) that is required to transform a liquid substance into a gas or vapor.
It is measured in Joules per mole (J/mol), or sometimes in Calories (C).
Enthalpy of Sublimation

ΔHsub is the change in heat of sublimation

ΔHfus is the change in heat of fusion
ΔHvap is the change in heat of vaporization

d. Enthalpy of atomisation,Bond Energy and Bond Dissociation Energy

Bond Energy: (B .E)

It is defined as average heat energy required to break all kinds of same nature of bond.

Bond dissociation Energy :

It is defined as energy required to break a particular bond. In above example a1, a2, a3 and a4 are bond
dissociation energy. C – H bond.
Example:

Enthalpy of Atomization :
For an element, it is defined as enthalpy change to produce 1mole of isolated gaseous atom from the most
stable allotropic form element.
Example

e. Hess Law and Born Haber Cycle and its application

HESS LAW :
It states that enthalpy change of the reaction remains same whether it is done in single step or multiple steps.
If the reactants and product of a required chemical reaction can be obtained by the summation of many other
chemical reactions, the enthalphy of the required reaction of reactants to the product also can be obtained by
the sum of the enthalpy changes of all those chemical reactions.
a) Hess law and multi-step reaction:

Reactant can form product B by following three different steps. C, D and E are intermediates in the other
stepwise reactions. Hess' law states that the enthalphy of the reaction ( ∆ H1) is the same irrespective of the
path.
So, the enthalphy of direct single-step reaction and other paths given intermediates C, D and E should be the
same.
DH1 = DH2 + DH3 = DH4 + DH5 + DH6

f. Enthaply of Formation

Enthaply of Formation
It is defined as the enthalpy change when 1 mole of compound is formed by reaction of its constituents in their
most stable allotropic form at 250C temp. and 1 atm pressure.
ENTHALPY OF HYDROGENATION :

10. Enthalpy change involving solutions

a. Enthalpy of neutralization

HEAT OF NEUTRALIZATION
It is defined as when 1g equivalent acid is neutralized by 1g equivalent of base. Heat of neutralization is -13.68k
cal /eq. or – 57.32 kJ /mole.
1 equivalent: That many moles of acid or base which contain 1mole of H+ or 1mole of OH- ions.

If any acid or base is weak then heat of neutralization will be lesser than 13.68 K cal./ eq. or 57.32 kJ /eq. in
magnitude and the difference will account ionization energy of weak species. For 100% dissociation of weak
acid or weak base, we provide external energy (I.E) for complete neutralization of 1 g eq. of H+ + 1 g eq. of OH-

b. Enthalpy of Solvation and Enthalpy of Hydration

Enthalpy change of solvation:

It is define as enthalpy change when 1 mole of solute is dissolved in a solvent to get a solution of infinite
dilution.
Hydration energy -
(also hydration enthalpy) is the amount of energy released when one mole of ions undergoes hydration.
Hydration energy is one component in the quantitative analysis of solvation. It is a particular special case of
water.

11. Second law of Thermodynamics

a. Limitations of First law of thermodynamics and statement of second law of thermodynamics

Limitations of First law of thermodynamics and statement of second law of thermodynamics

The limitation of the first law of thermodynamics is that it does not say anything about the direction of the flow
of heat. The reverse process is not possible. In actual practice, the heat doesn't convert completely into work.

Statement of the second law of thermodynamics

In simple words, the law explains that an isolated system’s entropy will never decrease over time.
Mathematically, the second law of thermodynamics is represented as;
DSuniv > 0
Where, DSuniv > 0 is the change in the entropy of the universe.

b. Heat Engine and Carnot Cycle

HEAT ENGINE:
It is a device to convert heat energy to work in cyclic process.

RESULT:

c. Entropy and basic calculation of entropy

ENTROPY:
Entropy is measurement unit of randomness or disorderness. It is state function. So, small change in entropy of
system is;

According to first law of thermodynamics, energy of universe remains constant. But according to second law of
thermodynamics :
Entropy Statement
Only those process occur spontaneously in universe in which entropy of universe increases.

d. Change in Entropy in physical process

Entropy Change: for chemical Reaction

e. Entropy calculation in different thermodynamic process

Case – (1)

Case – (2)

Case – (3)

Case – (4)

Case – (5)

Case – (6)

f. Change in Entropy calculation during Mixing of Gases and Phase Change

Entropy change: Isothermally mixing of gases

g. Gibbs Free Energy and Helmholtz Equation

GIBB'S FREE ENERGY :

Amount of energy released for useful work.
G = - Wuseful

For a chemical reaction,

12. Kirchhoff equation

a. Temperature dependence of ΔH

KIRCHHOFF’S EQUATION :
It is defined as the enthalpy of chemical reactions at different temperatures.

b. Temperature dependence of ΔS

For chemical reaction,

To calculate DS at different temperature:

c. Temperature dependence of ΔG
Temperature dependence of ΔG

13. Gibbs Free Energy

a. Relationship between free energy and equilibrium constant

ΔG° indicates that all reactants and products are in their standard states. For a system at equilibrium (K=Q,),
and as you’ve learned in this chapter ΔG = 0 for a system at equilibrium. Therefore, we can describe the
relationship between ΔG° and K as follows:

b. Temperature Derivative Of Gibbs Free Energy

Other factor to change temperature then change of Gibb's Free Energy

14. Third Law Of Thermodynamics

a. Statement and its basic applications

According to the third law of thermodynamics, S0 = 0 at 0 K,

The value of this integral can be obtained by plotting the graph of CP/T versus T and finding the area of this
curve from 0 to T. The simplified expression for the absolute entropy of a solid at temperature T is as follows:

Here CPis the heat capacity of the substance at constant pressure and this value is assumed to be constant in
the range of 0 to T K