1

INDEX

S.N Title Pg.N

o o
01. Abstract

02. Introduction

03. General Terms

04. Types of Reactions

05. Principles of Thermochemistry

06. Bond Enthalpy

07. Heat Capacity

08. Calorimeter And Its Uses

09. Heat of Reactions

10. Applications of Thermochemistry

11. Determination of Thermochemical

Process
12. Conclusion

13. Bibliography

2
ABSTRACT

Thermochemistry, a branch of physical chemistry, explores the

interplay between chemical reactions and heat energy. It
focuses on understanding how energy is absorbed, released, or
transformed during chemical processes, providing insights into
reaction spontaneity, energy efficiency, and system dynamics.
Central to thermochemistry are concepts such as enthalpy,
entropy, Gibbs free energy, and the laws of thermodynamics.

Key principles of thermochemistry include calorimetry, Hess’s

law, and the relationships between heat capacity and state
functions. These principles enable precise calculations of
energy changes, guiding research in reaction optimization,
material synthesis, and energy storage. Additionally,
thermochemical processes underpin combustion, phase
transitions, and bond dissociation, which are essential in
industrial and environmental applications.

Advances in thermochemical research continue to drive

innovation in green chemistry and energy storage solutions,
highlighting its significance in addressing global challenges.
3
INTRODUCTION

Thermochemistry is a vital branch of physical chemistry that

investigates the relationship between chemical reactions and
energy changes, primarily in the form of heat. It focuses on
understanding how energy is absorbed, released, or
transformed during chemical and physical processes. By
analyzing these energy dynamics, thermochemistry provides a
deeper understanding of reaction behavior, equilibrium, and
energy efficiency.

Central to thermochemistry are concepts like enthalpy ,

entropy , and Gibbs free energy , which together determine the
spontaneity and feasibility of chemical reactions.

Thermochemistry has applications in various scientific and

industrial fields. It plays a key role in energy production, such
as in combustion processes, fuel cell development, and
renewable energy technologies. It also contributes to
environmental studies by analyzing the thermal effects of
chemical reactions, including those involved in pollution and
climate change.

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This field not only enhances our theoretical understanding of
chemical reactions but also drives practical advancements in
green chemistry, sustainable energy, and material science.

ENTHALPY

Enthalpy is the measurement of energy in a thermodynamic

system. The quantity of enthalpy equals to the total content of
heat of a system, equivalent to the system’s internal energy
plus the product of volume and pressure.

When a process begins at constant pressure, the evolved heat

(either absorbed or released) equals the change in enthalpy.

H=U+PV

Enthalpy is also described as a state function completely based

on state functions P, T and U. It is normally shown by the
change in enthalpy (ΔH) of a process between the beginning
and final states.

ΔH=ΔU+ΔPV

If the pressure and temperature don’t change throughout the

process and the task is limited to pressure and volume, the
change in enthalpy is given by,

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ΔH=ΔU+PΔV

The flow of heat (q) at constant pressure in a process equals

the change in enthalpy based on the following equation,

ΔH=q

Enthalpy is used to describe the energy changes during

processes that occur at constant pressure, such as in heat
exchange. The change in enthalpy (ΔH) can help determine
whether a process is exothermic (releases heat) or endothermic
(absorbs heat). It is particularly useful in the study of phase
changes, chemical reactions, and other processes involving
heat flow

ENTROPY

Entropy is a measure of a system’s disorder and how much

energy is not available to do work.

During entropy change, a process is defined as the amount of

heat emitted or absorbed isothermally and reversibly divided
by the absolute temperature. The entropy formula is given as
follows:

∆S = qrev,iso/T

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Temperature is inversely proportional to entropy in the sense
that adding heat at a lower temperature leads to a greater
increase in entropy compared to adding the same amount of
heat at a higher temperature. This happens because the heat
transfer spreads out more effectively when the temperature is
lower, causing a greater increase in randomness.

Total entropy change, ∆Stotal =∆Ssurroundings+∆Ssystem

Total entropy change is equal to the sum of the entropy change

of the system and surroundings.

If the system loses an amount of heat q at a temperature T1,

which is received by surroundings at a temperature T2.

So, ∆Stotal can be calculated

∆Ssystem=-q/T1

∆Ssurrounding =q/T2

∆Stotal=-q/T1+q/T2

● If ∆Stotal is positive, the process is spontaneous.

● If ∆Stotal is negative, the process is non-spontaneous.

● If ∆Stotal is zero, the process is at equilibrium.

7
Entropy change during the isothermal reversible expansion of
an ideal gas

∆S = qrev,iso/T

According to the first law of thermodynamics,

∆U=q+w

For the isothermal expansion of an ideal gas, ∆U = 0

Qrev = -wrev = nRTln(V2/V1)

Therefore,

∆S = nRln(V2/V1)

For an adiabatic process, heat exchange will be zero(q = 0);

therefore, reversible adiabatic expansion is taking place at a
constant entropy (isentropic),

Q=0

Therefore,

∆S = 0

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Even though the reversible adiabatic expansion is isentropic,
the irreversible adiabatic expansion is not isentropic.

∆S is not equal to zero

Gibbs Free Energy

Gibbs free energy, also known as the Gibbs function, Gibbs

energy, or free enthalpy, is a quantity that is used to measure
the maximum amount of work done in a thermodynamic
system when the temperature and pressure are kept constant.
Gibbs free energy is denoted by the symbol ‘G’. Its value is
usually expressed in Joules or Kilojoules. Gibbs free energy can
be defined as the maximum amount of work that can be
extracted from a closed system.

Gibbs free energy is equal to the enthalpy of the system minus

the product of the temperature and entropy. The equation is
given as:

G = H – TS

Where,

G = Gibbs free energy

H = enthalpy

T = temperature
9
S = entropy

OR

Or more completely as:

G = U + PV – TS

Where,

U = internal energy (SI unit: joule)

P = pressure (SI unit: pascal)

V = volume (SI unit: m3 )

T = temperature (SI unit: kelvin)

S = entropy (SI unit: joule/kelvin)

Gibbs free energy is a state function; hence it doesn’t depend

on the path. So, change in Gibbs free energy is equal to the
change in enthalpy minus the product of temperature and
entropy change of the system.

ΔG = ΔH – Δ(TS)

If the reaction is carried out under constant temperature

(ΔT=O)

ΔG = ΔH – TΔS

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This equation is called the Gibbs-Helmholtz equation.

ΔG > 0; the reaction is non-spontaneous and endergonic

ΔG < 0; the reaction is spontaneous and exergonic

ΔG = 0; the reaction is at equilibrium

Exothermic Reaction

An exothermic reaction is a reaction in which energy is released

in the form of light or heat. Thus in an exothermic reaction,
energy is transferred into the surroundings rather than taking
energy from the surroundings as in an endothermic reaction. In
an exothermic reaction, the change in enthalpy ( ΔH) will be
negative

Therefore, it can be understood that the net amount of energy

required to initiate an exothermic reaction is less than the net
amount of energy released by the reaction. When a
calorimeter, a device used to measure the heat released by a
chemical reaction, the net amount of heat energy that flows
through the device is equal to the negative of the total energy
change of the system.

However, it is extremely difficult to measure or even calculate

the absolute total of energy in a given chemical system.

11
Therefore, the energy change (or the enthalpy change, denoted
by ΔH) is measured instead. The relation between the value of
ΔH and the bond energies of the reaction can be given by the
following equation.

ΔH = (energy used in the bond formation that yields

products) – (energy released when the reactant bonds
are broken)

Therefore, it can be understood that an exothermic reaction will

always have a negative value for the change in enthalpy, i.e.
ΔH < 0.

ΔH value negative  energy released  exothermic reaction

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Endothermic Reaction

Endothermic reactions are chemical reactions in which the

reactants absorb heat energy from the surroundings to form
products. These reactions lower the temperature of their
surrounding area, thereby creating a cooling effect. Physical
processes can be endothermic as well – ice cubes absorb heat
energy from their surroundings and melt to form liquid water
(no chemical bonds are broken or formed).

When a chemical bond is broken, it is usually accompanied by a

release of energy. Similarly, the formation of chemical bonds
requires an input of energy. The energy supplied/released can
be of various forms (such as heat, light, and electricity).
Endothermic reactions generally involve the formation of
chemical bonds through the absorption of heat from the
surroundings. On the other hand, exothermic reactions involve
the release of heat energy generated from bond-breakage.

ΔH value positive  energy absorbed  endothermic reaction

13
Principles

Lavoisier And Laplace’s Law

Lavoisier was a French chemist who influenced the history of

chemistry. He is known as the father of modern chemistry. He
identified the element oxygen and also identified the
stoichiometry of hydrogen.

Lavoisier and Laplace law states that the energy change

accompanying any transformation is equal and opposite to
energy change accompanying the reverse process.

The law illustrates the law of conservation of energy states that

energy can neither be created nor be destroyed it can only be
changed from one form to another. It also illustrates the law of
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conservation of mass which states that the mass in an isolated
system can neither be created nor be destroyed; it can only be
changed from one form to another.

The law of conservation was given by Lavoisier and Laplace in

the year 1789.

Hess’s Law

Hess’s law, also called Hess law of constant heat summation, is

one of the important outcomes of the first law of
thermodynamics. The enthalpy change in a chemical or
physical process is similar whether it is carried out in one step
or in several steps.

Hess’s law of constant heat summation was derived in 1840,

from a Swiss-born Russian chemist and physician, where,
Germain Hess, derived a thermochemistry relationship for
calculating the standard reaction enthalpy for the multi-step
reactions. In general, it exploits the state functions’ properties,
where the state functions’ value does not depend on the path
taken for dissociation or formation. Rather, it depends only on
the state at the moment (pressure, formation volume, and
more related).

Hess’s law, also known as the law of constant heat summation,

is a principle in thermochemistry that states that the total

15
enthalpy change of a reaction is the same, regardless of the
number of steps the reaction is carried out in.

Bond Enthalpy

Bond enthalpy (which is also known as bond-dissociation

enthalpy, average bond energy, or bond strength) describes
the amount of energy stored in a bond between atoms in a
molecule. Specifically, it’s the energy that needs to be added
for the homolytic or symmetrical cleavage of a bond in the gas
phase. A homolytic or symmetrical bond breaking event means
that when the bond is broken, each atom that originally
participated in the bond gets one electron and becomes a
radical, as opposed to forming an ion.

Chemical bonds form because they’re thermodynamically

favorable, and breaking them inevitably requires adding
energy. For this reason, bond enthalpy values are always
positive, and they usually have units of The higher the bond
enthalpy, the more energy is needed to break the bond and the
stronger the bond. To determine how much energy will be
released when we form a new bond rather than break it, we
simply make the bond enthalpy value negative.

Because bond enthalpy values are so useful, average bond

enthalpies for common bond types are readily available in
reference tables. While in reality the actual energy change
when forming and breaking bonds depends on neighboring
16
atoms in a specific molecule, the average values available in
the tables can still be used as an approximation.

Bond Breaking And Forming

Whether a reaction is endothermic or exothermic depends on

the difference between the energy needed to break existing
bonds and the energy released when the new bonds are formed

Bond breaking is always an endothermic process as energy

needs to be taken in from the surroundings to break the
chemical bonds

Bond making is always an exothermic process as energy is

transferred to the surroundings as the new bond is formed

Activation Energy

Activation energy (Ea) is the minimum amount of energy

required for a chemical reaction to occur. It represents the
energy barrier that reactants must overcome to be converted
into products. In thermochemistry, activation energy is a key
concept in understanding how energy changes influence the
rate and feasibility of chemical reactions.

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Activation energy is the threshold that determines whether a
reaction can proceed. It ensures that only molecules with
sufficient kinetic energy will react, which is crucial for studying
reaction rates.

In exothermic reactions, the energy released during product

formation is greater than the activation energy. Despite the
reaction being thermodynamically favorable (negative enthalpy
change, ΔH), a certain energy input (Ea) is still required to start
the reaction.

In endothermic reactions, activation energy is even higher, as

additional energy is needed to overcome both the initial energy
barrier and the positive enthalpy change (ΔH).

Heat Capacity

Heat energy is the measure of the total internal energy of a

system. This includes the total kinetic energy of the system and
the potential energy of the molecules.

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It has been seen that the internal energy of a system can be
changed by either supplying heat energy to it, or doing work on
it.

The internal energy of a system is a fundamental concept in

thermodynamics, representing the total energy stored within a
system. This includes the kinetic energy of particles (due to
their motion) and potential energy (due to intermolecular
forces).

The more matter (particles) present in a system, the greater

the total internal energy, as each particle contributes to the
overall kinetic and potential energy.

When the temperature of a system increases, its internal

energy also increases. This is because the particles within the
system move faster and their kinetic energy rises.

Heat capacity is defined as the amount of heat energy required

to raise the temperature of a given quantity of matter by one
degree Celsius.

Heat capacity for a given matter depends on its size or quantity

and hence it is an extensive property. The unit of heat capacity
is joule per Kelvin or joule per degree Celsius.

Mathematically,

Q=CΔT

19
Where Q is the heat energy required to bring about a
temperature change of ΔT and C is the heat capacity of the
system under study.

Specific Heat Capacity

Scientists needed a quantity that has no dependence on the

quantity or size of matter under consideration for
thermodynamic studies this made them define specific heat
capacity. It is an intensive property as it is independent of the
quantity or size of the matter. Specific heat capacity for any
substance or matter can be defined as the amount of heat
energy required to raise the temperature of a unit mass of that
substance by one degree Celsius. Mathematically it is given as:

Q= m s ΔT

Here Q is the amount of heat energy required to change the

temperature of m (kg) of a substance by ΔT, s is the specific
heat capacity of the system.

Phase Change

Phase changes are always accompanied by a change in the

energy of a system. For example, converting a liquid, in which

20
the molecules are close together, to a gas, in which the
molecules are, on average, far apart, requires an input of
energy (heat) to give the molecules enough kinetic energy to
allow them to overcome the intermolecular attractive forces.
The stronger the attractive forces, the more energy is needed
to overcome them. Solids, which are highly ordered, have the
strongest intermolecular interactions, whereas gases, which are
very disordered, have the weakest. Thus any transition from a
more ordered to a less ordered state (solid to liquid, liquid to
gas, or solid to gas) requires an input of energy; it is
endothermic. Conversely, any transition from a less ordered to
a more ordered state (liquid to solid, gas to liquid, or gas to
solid) releases energy; it is exothermic.

Calorimeter

A calorimeter is a device used for heat measurements

necessary for calorimetry.

1. Isolation:

The calorimeter is designed to thermally isolate the system

being studied from the external environment. This ensures that
any heat transfer occurs only between the substances inside
the calorimeter and the heat-absorbing medium (e.g., water).

2. Heat Exchange:

21
When a reaction or process occurs within the calorimeter, heat
is either absorbed (endothermic) or released (exothermic).

This heat is transferred to or from the medium (usually water)

in the calorimeter.

3. Temperature Measurement:

A thermometer or temperature sensor monitors the

temperature change () in the calorimeter’s medium (e.g.,
water).

The temperature change directly relates to the heat

exchanged.

4. Energy Calculation:

Using the principle of conservation of energy:

qsystem + qsurroundings = 0

The heat exchanged is calculated using:

Q= m s ΔT

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Such measurements can be made easily with this. Say in a
calorimeter a fixed amount of fuel is burned. The vessel is filled
with water, and the fuel is burned, leading to the heating of the
water. Heat loss by the fuel is equal to the heat gained by the
water. This is why it is important to insulate the calorimeter
from the environment; to improve the accuracy of the
experiment. This change in heat can be measured through the
thermometer. Through such a measurement, we can find out
both the heat capacity of water and also the energy stored
inside a fuel.

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Uses

Determines heat changes () during chemical reactions, such as

neutralization, combustion, or dissolution.

Example: Measuring the heat released when an acid reacts with

a base.

Used to measure the heat involved in melting, boiling, freezing,

or condensation.

Example: Determining the latent heat of fusion or vaporization

of water.

Helps calculate the energy required to break or form chemical

bonds.

Determines the specific heat capacity of solids, liquids, and

gases.

Example: Finding the specific heat of metals for material

design.

Determines the energy content of fuels (e.g., coal, petrol,

diesel).

Example: Bomb calorimeters measure the calorific value of

fuels to assess energy efficiency

The Heat of Reaction

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The heat of reaction, also known as the enthalpy of reaction, is
the amount of heat change that occurs after moles of reactants
involved in a thermochemical process have completely
interacted with one another.

The Different Types of Heat of Reaction

The Heat of Combustion or Enthalpy of Combustion

The Heat of Combustion (also known as the Enthalpy of

Combustion) is the amount of energy released during
combustion.

It is known as the heat of combustion when the quantity of heat

released by the full combustion of one mole of a substance is
measured.

CH4 (g) + 2O2(g) → CO2 (g) + 2H2O (g)

The Heat of Formation or Enthalpy of Formation

When one mole of a compound is produced from its constituent

elements that are in their standard or stable state, the quantity
of heat that is released or absorbed is referred to as the Heat of
Formation or Enthalpy of Formation.

It is assumed that the standard heat of creation of all stable

and free elements is zero for all of them.

C (s) + 2 H2 (g) → CH4 (g)

25
The Heat of Neutralization or Enthalpy of Neutralization

In chemistry, this is known as the Heat of Neutralization or the

Enthalpy of Neutralization.

In a dilute solution, the amount of heat released when one

gramme equivalent of acid is entirely neutralized by one
gramme equivalent of base is measured.

The heat of neutralization of strong acid and strong base is

always constant, and its value is -13.7 Kcal-1, because some
amount of heat is used in the dissociation of weak acid or base,
and this difference in amount of heat is known as the heat of
dissociation. The heat of neutralization of strong acid and
strong base is always constant, and its value is -13.7 Kcal-1. As
an exception, the heat of neutralization of HF (weak acid) is
greater than -13.7 Kcal-1 due to the high hydration energy of
the fluoride ions in the solution.

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

The Heat of Solution or Enthalpy of the Solution

Known as the heat of solution, the amount of heat evolved or

absorbed when one mole of a substance is dissolved in an
excess amount of solvent such that further dilution does not
result in any more heat change is equal to the amount of
solvent used.

NaCl+H2O⇄Na+(aq.) +Cl−(aq.)

26
The Heat of Hydration

When one mole of anhydrous or partially hydrated salt

combines with the requisite number of water molecules to
generate hydrated salt, the amount of heat emitted or
absorbed is measured.

CuSO4 (s) + 5 H2O (l) → CuSO4.5H2O (s)

The Heat of Transition or Enthalpy of Transition

The heat of transition is the amount of heat that changes when

one allotropic form of one mole of a substance turns into
another allotropic form. It is measured in degrees Celsius.

C(graphite) → C(diamond)

The Heat of Fusion or Enthalpy of Fusion

In the case of a solid substance, the amount of heat required to

turn one mole into a liquid at its melting point is known as the
enthalpy of fusion.

H2O(s) → H2O(l)

The Heat of Vaporization or Enthalpy of Vaporization

The amount of heat required to transform one mole of liquid

into vapour form is referred to as the enthalpy of vaporisation.

H2O(l) → H2O(g)

27
The Heat of Sublimation or Enthalpy of Sublimation

This is referred to as the enthalpy of sublimation, which is the

amount of heat necessary to transform one mole of solid into a
gaseous state.

I2(s) → I2(g)

The Energy of the Lattice

In ionic solids, lattice energy is defined as the amount of heat

generated when one mole of an ionic solid is performed from
the gaseous ion that formed it.

Na (s) + Cl2 (g) → NaCl (s)

The Heat of Hydrogenation

Also known as the enthalpy of hydrogenation, is a quantity that

describes the amount of heat that is produced by
hydrogenation.

In the reaction of 1 mole of unsaturated organic saturated

chemical with hydrogen to generate a saturated organic
compound, the quantity of heat released is known as the heat
of hydrogenation.

CH 2 = CH 2 ( g )+ H 2 ( g ) → CH 3 – CH 3

Heat of Atomisation

28
The heat of atomisation is the amount of energy necessary to
dissociate one mole of a stable molecule into a single gaseous
atom, and it is measured in joules

H2 ( g )→ 2H (atom )

Factors Affecting Thermochemical Process

Temperature

Effect: Higher temperatures generally increase the rate of

chemical reactions. This is due to the increased kinetic energy
of molecules, leading to more frequent and energetic collisions
between reactant molecules.

Reactant Concentration

Effect: Increasing the concentration of reactants increases the

rate of reaction because the number of reacting molecules or
ions is higher. This leads to more collisions between reactant
particles, which increases the likelihood of effective collisions
(collisions that result in a chemical reaction).

29
Pressure

Effect: Increasing the pressure generally accelerates the

reaction rate, especially for reactions involving gases. By
increasing the pressure, the reactant molecules are forced
closer together, which increases the frequency of collisions and
thus speeds up the reaction.

Catalyst

Effect: A catalyst accelerates a chemical reaction without

being consumed in the process. It works by providing an
alternative reaction pathway with a lower activation energy,
which allows the reaction to proceed faster and at lower
temperatures.

Residence Time

Effect: Residence time refers to the amount of time that

reactants stay in the reaction zone or reactor. A longer
residence time allows the reaction more time to proceed to
completion, which can increase the yield of the desired
product.

Carrier Gas Flow

Effect: The flow rate of carrier gas (usually inert gases like
nitrogen or steam) in thermochemical processes can influence
the rate of reaction by helping to transport reactants through
the system or remove products. It also affects temperature
control and the residence time of reactants.

30
Applications Of Thermochemistry

Energy content

Thermochemistry is used to determine the energy content of

fuels and foods.

Weather

Thermochemistry can help explain how water’s heat capacity

and temperature insensitivity moderates local weather.

Drug development

Thermochemistry is used to optimize reaction conditions for

drug synthesis, and to determine the dosage, effectiveness,
and side effects of drugs.

Food science

Understanding heat changes during cooking helps achieve

desired flavors and textures. Thermochemistry is also used to
determine the energy content of foods.

Pharmaceutical industry

Thermochemistry helps optimize reaction conditions for drug

synthesis. It’s also used to determine the enthalpy change of a
drug reaction, which is important for determining dosage,
effectiveness, and potential side effects.
31
Environmental science

Thermochemical principles are used to study combustion

processes and their impact on air quality.

Engineering

Thermochemistry is used to improve energy efficiency, find

better ways to heat and cool homes, and refrigerate food and
drinks.

Biology

Thermochemistry is used to study the energetics of living

organisms, such as the metabolic combustion of sugar into
carbon dioxide and water.

Challenges And Innovations

Thermochemical water splitting cycles

These cycles can turn waste heat and sunlight into green
hydrogen. However, they face challenges such as high energy
requirements, low loading of active material, and high
temperatures that can negatively affect the long-term
performance of materials.

Thermochemical heat storage

This method can store heat in small containers with high

energy density. However, it faces challenges such as the need
32
for additional energy to start discharging, and the
corrosiveness of tetrachloromethane with metal containers.

High temperature thermochemical processes

These processes can convert atmospheric carbon dioxide and

water into liquid aviation fuels using solar energy. However,
challenges include low solar to fuel conversion efficiency and
the long-term stability of the reactant materials.

Thermochemical cycles

These cycles can be powered by solar or nuclear power.

However, they face challenges such as corrosion associated
with the chemicals involved in the cycle, and different reaction
temperatures for various steps.

33
Conclusion

Thermochemistry is a fundamental branch of science that

bridges chemistry and energy, providing insight into how heat
and energy changes occur in chemical reactions and physical
processes. By understanding concepts such as enthalpy,
calorimetry, and the laws of thermodynamics, we can predict
and manipulate energy transfers in various systems.

The principles of thermochemistry are vital to numerous real-

world applications, including energy production, environmental
sustainability, and industrial processes. It helps us design
efficient energy systems, understand the environmental impact
of reactions, and develop new technologies like renewable
energy sources and biofuels.

Ultimately, thermochemistry not only enhances our

understanding of the natural world but also empowers us to
address global challenges, from energy demands to climate
change, making it an essential field of study in both scientific
and practical contexts.

34
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Enthalpy. Retrieved from https://chem.libretexts.org

2. Khan Academy. (2023). Thermochemistry Overview. Retrieved from

https://www.khanacademy.org

3. NIST Chemistry WebBook. (2023). Thermochemical Data for Selected

Substances. Retrieved from https://webbook.nist.gov

Book

NCERT Chemistry Textbook for Class 11 – Part 1

Atkins, P., & De Paula, J. (2010). Physical Chemistry. Oxford University

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Brown, T. L., LeMay, H. E., Bursten, B. E., Murphy, C., & Woodward, P.
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