COURSE SYNOPSIS

GEE206: Fundamentals of Thermodynamics (3Units)

Definitions and basic concepts of thermodynamics:

Introduction to thermodynamics
Basic concepts of thermodynamics:
System, types of system: Base on permeability of matter: Open and close system, Base on heat or energy:
Adiabatic and isolated system, Base on properties of the system: Homogeneous and heterogeneous system.
Solution, types of solutions: true, false and suspension solution, differences between them, example of true,
false and suspension solution. Component of a system. Property of system, types of property of system:
extensive and intensive properties of a system. Energy. Processes. Work. Entropy. Heat. Power. phase
rule. internal energy. enthalpy. Use of thermodynamics tables to read the intensives and extensive
properties, interpolation of values from steam tables. Conversion of units metric to S.I units.

• The first law of thermodynamics: application of first law of thermodynamics to closed (non-flow
processes) and steady state process, path functions and state function, kind of driving forces, reversible and
irreversible processes and their properties, heat capacity and types of heat capacity (heat capacity at
constant pressure and heat capacity at constant volume).
• Thermodynamics relationship of ideal gas, constant volume process (isometric), constant pressure
process (Isobaric), constant temperature process(Isothermal), Adiabatic process, Polytrophic process.

• P-V-T relationship of fluid and pure substance, types of equation of state: Viral equation of state, ideal
gas equation of state, Van der waals equation of state, Redlick kwong equation of state.

• Second law of thermodynamics: mathematical statement for second law of thermodynamics, thermal
energy reservoirs, types , Kelvin Planck and Clausius statement of second law of thermodynamics, heat
engines Carnot heat engines and Carnot cycle, Carnot refrigeration and heat pump cycle, efficiency of heat
cycle, coefficient of performance of the cycle.

• Zeroth law of thermodynamics. Conversion of different unit of temperature.

• Third law of thermodynamics: application to entropy change, adiabatic mixing process, isothermal
mixing of ideal gases.

TEXT BOOKS:
 Fundamental principles of thermodynamics ( for Engineers and Scientists) by Linus
EnemmorAneke
 Chemical Thermodynamics: Principles and Applications by J. Bevan Bevan Ott, Juliana Boerio-
Goates.
 Introduction to Chemical Engineering thermodynamics 6th edition, by J.M. Smith, H.C. Van Ness,
M.M. Abbolt.
 A Textbook of Chemical Engineering Thermodynamics 2nd edition by K.V. NARAYANAN
 FUNDAMENTALS OF THERMODYNAMICS
DEFINITIONS AND BASIC CONCEPTS OF THERMODYNAMICS.

1.1 INTRODUCTION TO THERMODYNAMICS

Thermodynamics is the science that deals with the study and transformation of energy of all kinds from one
form to another and the relationships that exist between various macroscopic properties of matter, such as
temperature, pressure, volume, entropy, enthalpy etc. It provides a basis for understanding and analyzing
the behavior of any physical systems, particularly with regard to heat transfer, work, and energy exchange.
In engineering, thermodynamics involves physical and chemical changes with regards to a particular
system. Thermodynamics has many practical applications in engineering. It plays a crucial role in the
design and analysis of engines, refrigeration systems, chemical reactions and understanding of natural
processes that occurs in the universe.
There are four fundamental laws of thermodynamics, which serve as the foundation for this field of study:
 The Zeroth Law of Thermodynamics: state that if two bodies (systems) are in thermal equilibrium
with a third body, the three bodies must be in thermal equilibrium with one another. This law forms
the basis for temperature measurement; it allows us to compare the temperatures of different bodies,
whether they are in contact or not.

 The First Law of Thermodynamics (Conservation of Energy): It states that energy cannot be created
or destroyed; but can be transformed from one form to another. In other words, the total energy of
an isolated system remains constant. This law is often summarized as the principle of conservation
of energy and is expressed as ΔU = Q - W, where ΔU is the change in internal energy, Q is the heat
added to the system and W is the work done by the system.

 The Second Law of Thermodynamics: This law introduces the concept of entropy, which is a
measure of the disorderliness or randomness in a system. It states that in any energy transfer or
transformation, the total entropy of an isolated system always increases over time. This law gives
rise to the concept of heat transfer from hot to cold objects, the irreversibility of natural processes,
and the definition of thermodynamic processes that are either reversible or irreversible.

 The Third Law of Thermodynamics: This law states that as the temperature of a system approaches
absolute zero (0K), the entropy of the system approaches a minimum value. It implies that it is
impossible to reach absolute zero temperature through any finite sequence of thermodynamic
processes. This law is often used in the context of understanding the behavior of materials at very
low temperatures.
1.2 BASIC CONCEPTS OF THERMODYNAMICS

The following concepts are applicable in thermodynamics:

1.2.1 SYSTEM
In thermodynamics, a "system" refers to a specific portion or part of the physical universe that is under
analysis, observation, investigation or study. It is a well-defined region or part of the system (i.e. collection
of matter and energy) that is completely separated from its surroundings by an imaginary boundary. The
purpose of defining a system is to simplify the analysis of energy and matter exchanges that occurs within
that region without considering the complexities of the entire universe. While the surrounding is anything
outside the system, that serve as an imaginary envelope that encloses the system and it is immediately
adjacent to the system.
 [Link] TYPES OF SYSTEM

(a) BASE ON PERMEABILITY OF MATTER:

i. OPEN SYSTEM (Control Volume): An open system, also known as a control volume, allows
both energy and matter to be exchanged with its surroundings. This means that not only can heat
and work be transferred, but there can also be inflow or outflow of mass. Open systems are
commonly used in the analysis of engineering devices like pumps, turbines, heat exchangers
and others.

ii. CLOSE SYSTEM (Fixed Mass): A closed system is one that allows energy to be exchanged
with its surroundings (in the form of heat and work), but it does not permit the transfer of matter
across its boundaries. The total mass of a closed system remains constant over time, but its
energy content can change due to heat transfer and work done.

iii. AN ISOLATED SYSTEM: An isolated system is completely sealed off from its surroundings,
with no exchange of matter or energy. That is there is no reaction or interaction between the
system and the surroundings. A system surrounded by an insulating boundary is called a
thermally insulated system. This idealized concept is often used for theoretical purposes, as it
represents a closed system in its strictest sense, where there is no heat, work, or mass transfer
with the surroundings. In practice, truly isolated systems are rare, but they are useful for
simplifying certain thermodynamic calculations.

(b) BASE ON HEAT OR ENERGY:

i. AN ADIABATIC SYSTEM: is a type of system that does not allow exchange of heat between
the system and the surroundings. Changes in such system are referred to as adiabatic changes.
Similarly, a system in which there is no temperature change, no volume change or pressure
change are described as Isothermal, Isometric or Isobaric systems respectively. Subsequently,
they will be looked at in details.
(c) BASE ON PROPERTIES OF THE SYSTEM
i. HOMOGENEOUS SYSTEM: is a type of system that has the same macroscopic properties from
one point of the system to another point of the same system. It is also called a phase system or a
system that is made of one phase.

ii. HETEROGENEOUS SYSTEM: is a system that is made up of more than one phase and at the
phase boundary of this system the properties of the system will undergo discontinuities or sudden
changes. It is also a system that has non-uniform properties from one point to another within the
system.

1.2.2 SOLUTION
A solution is a homogeneous system consisting of more than one component. It can be seen as a uniform or
homogeneous mixture of two or more substances. A solution is made up of a solute and a solvent.

A solute is a dissolved substance which may be solid, liquid or gas and a solvent is a substance usually a
liquid, although it may be a solid or a gas which dissolved a solute.
Table 1: Examples of solutions.

S/N SOLUTION SOLUTE(STATE) SOLVENT(STATE)

1 BRINE Nacl(s) H2O(l)
2 Anti-freeze Alkanol(l) H2O(l)
3 Soda- water CO2(g) H2O(l)
4 Brass Zinc(s) Copper(s)
5 Air Mainly oxygen(g) Nitrogen(g)

[Link] TYPES OF SOLUTIONS:

(a) TRUE SOLUTION: a true solution is a resultant homogeneous mixture that is form, when a solute
particle dissolves such that they are able to get in between the solvent particles. When the solute
particle are simple molecules or ions and are too small to be seen by the naked eyes they are called
CRYSTALLOIDS. The particle of a true solution are less than 10-9 m, in size. Examples of true
solution are aqueous solution of sodium chloride and copper tetraoxosulphate(VI).

(b) FALSE SOLUTION OR COLLOIDAL SOLUTION: in a colloidal solution, the individual

solute particles are large than the particles of the true solution but not large enough to be seen by the
naked eyes. The particle of a false solution is between 10-9 m and 10-6 m, in size Example are
starch and albumen.

[Link] TYPES OF COLLOIDS

In a colloidal or false solution, the liquid solvent is more appropriately known as the dispersion medium
while the solid solute particle constitutes the dispersion substance. As in the case of solution in colloids too,
the dispersion medium and dispersion substance may be a solid, liquid or gas.
(i) Sols and gels: the most common type of colloid is one where the solid particles are dispersed in
liquid medium, such solid-liquid colloidal systems are called sols. Most sols can solidify under
certain conditions to form gels. Examples of sols are starch, glue, agar, jelly, gelatin and clay
(ii) Aerosols: these are systems where liquid or solid particles are dispersed in a gas. Examples are
insecticide spray and deodorants from cans, fog and smoke.
(iii) Emulsion: in this colloidal system, a liquid is dispersed in another liquid. Examples of
emulsions are milk, hair cream and cod liver oil emulsion. Butter is a solid emulsion i.e. liquid
particles are dispersed in a solid medium.
Table 2: examples of colloids
Examples of colloids Solvent or dispersion medium Solute or dispersion substance
Fog Gas Liquid
Smoke Gas Solid
Foam or latter Liquid Gas
Emulsion Liquid Liquid
Sols Liquid Solid

[Link] COAGULATION OF COLLOIDS

The dispersed particles in colloids cannot be separated from the medium by filtration. However, they can
be precipitated or coagulated by the addition of solutions containing metals ions.

Table 3: difference between true solution and colloid (false solution)

S/N TRUE SOLUTION FALSE SOLUTION
1 The solutes can pass through a filter paper The solutes cannot pass through a filter paper
2 The solution can be dialyzed that is the The solution cannot be dialyzed
solution can diffuse through a semi permeable
membrane
3 The solutes don‟t scatter light rays The solutes can scatter light rays ie the solution
exhibits the Tyndall effect.

iii. SUSPENSIONS: is a heterogeneous mixture of undissolved particles in a given medium, the

particles are usually large enough to be seen without the aid of an instrument and they eventually
settle down if left standing. The particles of a suspension solution are large than 10-6 m.

1.2.3. COMPONENT OF A SYSTEM

The components of a thermodynamic system are the smallest part or the minimum number of independent
variable of chemical species from which the system in all its variation can be organized.
It can also be refers to a distinct substance or chemical species that makes up the system. Components are
the individual constituents within a system that can be identified and analyzed in terms of their properties,
concentration, and behavior during thermodynamic processes. The number and types of components in a
system depend on the nature and complexity of the system being studied.

1.2.4. PROPERTY

A property of a system is that quantity or variable that is fixed once the state or condition of the system is
fixed. A quantitative system attribute, such as pressure, energy, and entropy, evaluated at a given time by
means of a well-designed experiment or by a reliable prediction method is called property. It also refers to
as the characteristic or attribute of a system that can be measured or specified independently of the system's
history or previous states. Examples of properties of a system are temperature, pressure, volume; mass etc.
the number of independent variables whose values must be specified before the state of the system is
definitely fixed is called the degree of freedom of the system. The relationship between the number of the
components, the number of phases and the degree of freedom of a system in phase equilibrium is given by
the phase rule.

4.1 TYPES OF PROPERTIES

(a) EXTENSIVE PROPERTIES: Extensive properties are properties that depend on the size or extent
of the system. They are additive, meaning that the value of an extensive property for a system is the
sum of the individual components values. Examples of extensive properties include total mass (m),
total volume (V), total internal energy (U), and total entropy (S), amount of substance, Gibbs
energy, heat capacity etc. All extensive properties are homogeneous functions of the first order in
term of mass of the system. For example, doubling the mass of a system at constant composition
doubles the internal energy.

(b) INTENSIVE PROPERTIES: Intensive properties are properties that do not depend on the
quantity or size of the system. They are inherent to the system itself and are uniform throughout the
system. Common examples of intensive properties include temperature (T), pressure (P), density
(ρ), specific volume (v), and composition (e.g., mole fraction), solubility, hardness, refractive index
etc. Intensive properties are often used to describe the state of a system. They define the values at
each point in a system.

1.2.5. ENERGY

Thermodynamic energy refers to the total energy within a system that arises from both the motion of
particles that constitute the system and their interactions with the system. Energy is an extensive property,
meaning it depends on the amount of matter or size of the system. It is also additive, meaning if the size of
a system is double; the total energy in the system will also doubles. Its value depends only on the state and
independent of the measuring device, other systems within the environment, and history of system.

In thermodynamics, energy is typically divided into several forms:

1. Internal Energy (U): This is the sum of all microscopic forms of energy within a system, including
kinetic energy (due to the motion of particles) and potential energy (due to the interactions between
particles). It is the energy stored in the molecules of a substance, which can change through
processes like heating, cooling, or performing work. The total internal energy of a system depends
on the number of particles or the amount of substance present. For example, if you have two
identical systems, each with the same internal energy, the combined system will have twice the
internal energy.
2. Heat (Q): Heat is the transfer of energy due to a temperature difference between two systems or a
system and its surroundings. It flows from a hotter object to a cooler one.
3. Work (W): In thermodynamics, work refers to the transfer of energy that results from a force being
applied over a distance, like when a gas expands in a piston and pushes it. The amount of heat
transferred or work done also depends on the size of the system. Larger systems can transfer more
heat or do more work under the same conditions than smaller systems.
4. Potential Energy: and potential energy refers to the energy due to the system‟s position in a field,
such as gravity or molecular scale.
 Forms of kinetic energy:

 Macroscopic Potential Energy: this refers to potential energy associated with objects on a large,
observable scale, typically within gravitational, elastic, or electrical fields. Examples include:
 Gravitational Potential Energy: The energy an object possesses due to its height in a
gravitational field. The formula is: ,
Where, m is mass, g is the gravitational acceleration, and h is the height.

 Elastic Potential Energy: The energy stored in stretched or compressed elastic materials, such
as springs. The formula is: P.E
Where, k is the spring constant and x is the displacement from the equilibrium position.

 Microscopic Potential Energy: on the molecular or atomic scale, microscopic potential energy
arises from the interactions between particles that constitute the system. Examples include:
 Intermolecular Potential Energy: This includes forces such as van der Waals forces, dipole-dipole
interactions, or hydrogen bonding. These forces determine how molecules attract or repel each
other.
 Chemical Potential Energy: Stored within the chemical bonds between atoms in a molecule. This
energy is released or absorbed during chemical reactions (e.g., combustion or photosynthesis).
 Electric Potential Energy: The energy associated with the positions of charged particles in an
electric field.

At the microscopic level, potential energy plays a crucial role in determining how particles interact and
how energy is stored in matter. This microscopic potential energy is critical in thermodynamics and
statistical mechanics, where the total internal energy of a system includes both the microscopic kinetic
energy (due to particle motion) and microscopic potential energy (due to particle interactions).

Kinetic Energy: where kinetic energy refers to the energy due to the system‟s motion (e.g., a moving
object). Both microscopic and macroscopic kinetic energy can be evaluated using:

K.E

Where:
 m is the mass of the large object or the mass of the particle,
 u is velocity large body or velocity of the particle.

Forms of kinetic energy:

 Macroscopic Kinetic Energy: This refers to the kinetic energy of an object as a whole,
moving through space. For example, a car moving down the road or a ball rolling across the
floor has macroscopic kinetic energy.
 Microscopic Kinetic Energy: on the molecular or atomic level, microscopic kinetic energy
refers to the motion of particles within a system, such as atoms, ions, or molecules. These
motions contribute to the thermal energy of a substance. The faster the particles move
(which can include translational, rotational, and vibrational motion), the higher the
substance‟s temperature. This is often discussed in the context of thermodynamics and
statistical mechanics.

Average Kinetic Energy of a Gas Particle: In a large collection of particles, such as a gas, the average
kinetic energy per particle is related to temperature. According to the kinetic theory of gases, the average
translational kinetic energy of a particle in a system is proportional to the absolute temperature T of the
gas:

where:
 KB is the Boltzmann constant (approximately 1.38×10−23 J/K)
 T is the absolute temperature in Kelvin (K).
This formula tells us that the average microscopic kinetic energy of particles in an ideal gas depends
directly on the temperature of the system.

Microscopic Kinetic Energy for Different Types of Motion:

 Translational Motion: The formula above applies to the translational motion of particles in
all three spatial dimensions (x, y, z).
 Rotational and Vibrational Motion: In more complex molecules, energy is also stored in
rotational and vibrational modes. These modes contribute additional terms to the total microscopic
kinetic energy, but the translational part is often the primary contributor in simpler gases like
monatomic gases (e.g., helium, neon).

Hence, the key home is that the average translational microscopic kinetic energy is given by , and
it is directly tied to the temperature of the system.

The first law of thermodynamics, which is a statement of the conservation of energy, says that the change
in the internal energy of a system (ΔU) is equal to the heat added to the system (Q) minus the work done by
the system (W):

( )

In essence, thermodynamic energy covers all forms of energy exchanges and transformations within a
system and between the system and its surroundings. In summary, energy is extensive because it scales
with the size or quantity of the system involved. Energy may be transferred in the forms of heat or work
through the boundary of a system. In a complete cycle of steady-state process, internal energy change is
zero and hence the work done on the system is converted to heat by the system. The mechanical work of
expansion or compression proceeds with the observable motion of the coordinates of the particles of
matter. Chemical work, on the other hand, proceeds with changes in internal energy due to changes in the
chemical composition (mass action).Potential and kinetic energies are external, while sensible heat and
latent heat are internal energies. The conservation of mass in an open system states that the change in the
total mass is equal to the mass exchanged with the surroundings. During a process, energy can be
transferred and converted from one form to another, while the total energy remains constant. This is known
as the law of conservation of energy. Available energy is the maximum amount of energy that is
transferable. Available energy is a property of any state of a system and with respect to a reservoir usually
is greater than the adiabatic availability of the same state. Adiabatic availability is the maximum energy
transferable without net changes in the values of amounts of constituents and parameter. Since the value of
adiabatic availability is positive, available energy is also always positive. The unit of energy is same as
work. The various forms of energy are interconvertible.

Derivative for Kinetic Energy

When a body of mass “m”, acted upon by a force F, is displaced a distance dl during a differential interval
of time dt, the work done is given below. In combination with Newton's second law this equation becomes:
Recall that acceleration is , where u is the velocity of the body.

Also:

Since the definition of velocity is , the expression for work becomes:

This equation can be integrated for a finite change in velocity, taking the limits from u1 to u2 with respect
to the state or conditions of the system or body.

∫ ( )

( ) ( )

Energy may be transferred in the forms of heat or work through the boundary of a system, in this case, “W”
will be same with “K.E”, thus

K.E

Derivative for Potential energy

If a body or particle of mass m is raised from an initial elevation z1 to a final elevation z2, an upward force
at least equal to the weight of the body must be exerted on it, and this force must move through the distance
z2 – z1. Since the weight of the body is the force of gravity on it, the minimum force required is given by
Newton's law:

Where, g is the local acceleration of gravity. The minimum work required to raise the body or particle is
the product of this force and the change in elevation:
( ) ( )
( ) ( )
The work done on a body in elevating it is said to produce a change in its potential energy:
( )

Otherwise potential energy will be given as:

In general, energy is measured in joules (J) in the International System of Units (SI).
1.2.6. PROCESSES

A process is any kind of change either chemical or physical change a thermodynamic system undergoes.
Examples of such changes are adiabatic, isothermal, isometric and isobaric changes. During energy
conversion and degradation physical and chemical processes to occur. A change of state and the modes of
interaction taking place specify a system and carry it from one state to another. Any process that
experiences work interactions only (no heat exchange) is known as an adiabatic process. A process that
takes place with only an infinitesimal change in the macroscopic properties of a system is called an
infinitesimal process. However, a spontaneous change of state creates a spontaneous process.

The classification of processes according to Planck considers three independent infinitesimal processes.
They are natural processes, unnatural processes, and reversible processes.

 Natural processes actually occur and always proceed in a direction toward equilibrium.
 Unnatural processes are those that proceed in a direction away from equilibrium and never occur.
 A reversible process is a case between natural and unnatural processes and proceeds in either
direction through a continuous series of equilibrium states.

In a steady-state process the variables in a system remain constant with time, while in an unsteady state
process or in a transient process the variables change with time. At steady state, a system exchanges
energy or matter at a constant rate.
1.2.7. WORK

Thermodynamic work refers to the transfer of energy that occurs when a system exerts a force over a
distance on its surroundings, or when its surroundings exert a force on it. In thermodynamics, work is one
of the main means energy can be exchanged between a system and its surroundings, together with heat.
Work is an Extensive property.
Why Work is Extensive:

 The amount of work done by or on a system scales with the size or extent of the system. For
example, if you have a gas in a container and you double the volume of the gas while keeping
all other conditions the same, the amount of work involved in compressing or expanding the gas
will also double.
 Work is associated with energy transfer, and like energy, it is additive. If you perform work on
two separate systems, the total work will be the sum of the work done on each system.

Formula for thermodynamic Work:

For systems where the work is done by expanding or compressing a gas, the most common expression for
work is related to changes in the system's volume.

In engineering thermodynamics, work is done in a given systems by expanding or compressing a gas or a

fluid due to change in volume. Considering the pressure acting on the gas or the fluid in the system as a
result of expansion or compression acting on a surface, “A”. Assume that the gas or fluid exerts a force “F”
which acts through a certain distance “dl”. The following relationship hold for work done(W) and
volume(V):

Recall that Also

For a section area of the system:

 The pressure-volume (PV) work and the formula is:

Equation () is an expression for the work done as a result of a finite compression or expansion process.
Where:
W is the work done by the system,
P is the pressure exerted by the system (or the external pressure if considering the work done on the
system),
dV is the change in volume,
V1 and V2 are the initial and final volumes of the system.

Key Concepts in thermodynamic Work:

1. Sign Convention:

 Work done by the system (on the surroundings) is typically considered positive. For
example, when a gas expands and pushes a piston, the system does work on the
surroundings.
 Work done on the system (by the surroundings) is typically considered negative. For
example, when a piston compresses a gas, work is done on the system.

2. Isobaric Process (Constant Pressure): If the process occurs at constant pressure (isobaric), the
work done is simplified to:

( )

Where:
W is the work done by the system,
P is the pressure exerted by the system (or the external pressure if considering the work done on the
system), P is constant.
V1 and V2 are the initial and final volumes of the system.

3. Adiabatic Process: In an adiabatic process, where no heat is exchanged with the surroundings, the
work done results entirely from the internal energy change of the system, as there is no heat
transfer.
4. Cyclic Processes: For a cyclic process (where the system returns to its initial state), the total work
done over one complete cycle is equal to the area enclosed by the process curve on a PV diagram.
5. In an isochoric process (also called an isometric or iso-volumetric process), the volume of the
system remains constant. Since the volume does not change, no work is done by or on the system.

Work in an Isochoric Process: recall from thermodynamics work done equation

Where W is the work, P is the pressure, and dV is the change in volume.

For an isochoric process, since the volume remains constant dV=0 meaning:
 ∫

Thus:
 No work is done in an isochoric process because there is no change in volume.
 Even though no work is done, heat can still be transferred, and this heat transfer will result in a
change in the system's internal energy according to the First Law of Thermodynamics: ( )
where ( )is the change in internal energy and Q is the heat added to or removed from the system.
 In an isochoric process, any energy added to or removed from the system will result in a change in
its internal energy but not through work, since the volume is constant.

6. Non-Mechanical Work: While the most common type of work in thermodynamics is mechanical
(pressure-volume work), work can also take other forms, such as:

 Electrical Work: Involving movement of charge in an electric field.

 Surface Work: If surface area changes in systems involving surface tension.
 Magnetic Work: In systems involving magnetic fields

1.2.8. ENTROPY

In thermodynamics, entropy is a fundamental concept that measures the level of disorder or randomness in a system.
It is a state function, meaning it depends only on the current state of the system and not on the path taken to reach
that state. Entropy is often interpreted as a measure of the unavailable energy in a system that cannot be used to do
useful work.

Key Points:

1. Second Law of Thermodynamics: Entropy is central to the second law of thermodynamics, which
states that the total entropy of an isolated system always increases or remains constant over time.
This means that natural processes tend to move toward a state of maximum entropy, or disorder,
indicating that energy is gradually dissipated.
2. Heat Transfer: When heat is added to a system, the entropy increases because the system‟s
molecules gain energy and move more chaotically. Conversely, removing heat decreases entropy.
3. Reversibility and Irreversibility: In an ideal reversible process ie a complete cycle, the change in
entropy is zero, but in real (irreversible) processes, entropy always increases. This increase in
entropy reflects energy losses due to friction, heat dissipation, or inefficiencies in energy
transformations.

Notably, when a fluid system changes from state A to state B by an irreversible process, then the
change of its entropy is be 𝜟S= SB - SA. The entropy of a system is the sum of the entropies of all
changes within the system. While for a system undergoing a reversible process, the change in
entropy, ΔS, is given by:

Where:
ΔS = change in entropy
Qrev = heat added in a reversible process
T = absolute temperature at which the heat is transferred
 4. Entropy in Statistical Mechanics: From a molecular perspective, entropy is linked to the number
of microscopic configurations that correspond to a thermodynamic system's macroscopic state. The
more ways the system‟s particles can be arranged, the higher the entropy.

Importance:
Entropy is crucial in understanding the direction of natural processes, energy efficiency in systems, and the
concept of equilibrium in thermodynamics. It provides insight into why certain processes are irreversible
and why perpetual motion machines are impossible.

1.2.9. HEAT

In thermodynamics, heat refers to the transfer of thermal energy between systems or bodies due to a
temperature difference. Unlike work, which involves mechanical or electrical energy transfer, heat is the
energy that spontaneously flows from a hotter object to a cooler one when they are in thermal contact. It is
a path-dependent quantity, meaning its value depends on the specific process through which energy is
transferred.

Key Points:

1. Definition of Heat: Heat, symbolized as Q, is the energy transferred between systems or bodies due
to a temperature gradient. It is not a property of a system but rather the energy in transit between
systems.
2. Temperature and Heat: Heat always flows from a body or system at a higher temperature to one
at a lower temperature until thermal equilibrium (same temperature) is reached. The higher the
temperature difference, the greater the potential for heat transfer.
3. Unit of Heat: The SI unit of heat is the joule (J), but calories (cal) are also commonly used, where
1cal = 4.184 J.
4. Forms of Heat Transfer: There are three primary mechanisms by which heat is transferred:

 Conduction: Heat transfer through direct contact of particles or molecules, typically in solids.
 Convection: Heat transfer by the movement of a fluid (liquid or gas) where warmer portions
rise and cooler portions sink.
 Radiation: Heat transfer in the form of electromagnetic waves, which can occur even in a
vacuum (e.g., the heat from the Sun reaching Earth).

5. First Law of Thermodynamics: The first law of thermodynamics relates heat to changes in
internal energy and work done by or on a system. Mathematically:

ΔU = Q - W,

Where:
ΔU = change in internal energy of the system
Q = heat added to the system
W = work done by the system

This law implies that heat added to a system can increase its internal energy or be used to do work.
1.2.10. POWER

In thermodynamics, power refers to the rate at which energy is transferred or converted from one form to
another in a system. Specifically, it measures how fast work is done or how quickly heat is transferred over
time. Power is an important concept in thermodynamic systems, especially when evaluating engines,
turbines, and other machines that convert energy into useful work.

Key Points:

1. Definition of Power: Power is the amount of energy transferred or converted per unit of time. It is
typically represented by the symbol P and is mathematically defined as:

Where:
P = power
W = work or energy transferred
t = time

2. Unit of Power: The SI unit of power is the watt (W), where:

In practical terms, power can also be expressed in kilowatts (k W), megawatts (MW), or
horsepower (hp), depending on the scale of the system.

3. Power in Heat Transfer: In thermodynamic systems involving heat transfer, power is related to the
rate at which heat is transferred. If a system transfers heat Q over time t, the power associated with
heat transfer is:

Where:
P = rate of heat transfer (thermal power)
Q = amount of heat transferred
t = time

Thermal power is important in heating and cooling systems, where we need to know how much heat
is being added or removed per unit of time.

4. Power in Mechanical Systems: In mechanical thermodynamic systems, power is related to the

amount of work performed by a machine or engine per unit of time. For example, in engines, the
power output is how fast the engine does work, and this can be calculated by:
Where:
P = mechanical power
F = force applied by the system
v = velocity at which the force is applied

This is particularly relevant for systems like turbines, where the power output depends on the force
generated by the fluid flow and the velocity of the turbine blades.

5. Power in Electric Systems: In electrical systems, power is the rate at which electrical energy is
converted into other forms of energy (such as heat, light, or mechanical energy). The electric power
can be calculated by:

Where:
P = electric power
V = voltage
I = current

6. Power in Thermodynamic Cycles: In thermodynamic cycles (such as those in power plants or

engines), power is often the measure of the useful work produced by the system over time. For
example, in a steam turbine, the power is a measure of how much mechanical energy the turbine
produces from the steam's thermal energy. The thermal efficiency of the cycle is also often
evaluated in terms of power output.
7. Efficiency and Power: Power is closely related to efficiency, which is the ratio of useful work
output to the energy input. The efficiency of a thermodynamic system (such as an engine) can be
defined as:

Where:
η = efficiency
Poutput = useful power output
Pinput = total energy input to the system

Power is a crucial concept for understanding how efficiently energy is utilized in machines and systems. It
helps engineers and scientists design and optimize engines, power plants, and other systems to ensure they
deliver maximum performance while minimizing energy losses. Understanding power in thermodynamics
allows for better management of energy resources, making processes more sustainable and cost-effective.

1.2.11. THE PHASE RULE

Phase rule states that “if the equilibrium between any number of phases is not influenced by gravity, or
electrical, or magnetic forces, or by surface action but are influenced only by temperature, pressure and
concentration, then the number of degrees of freedom (F) of the system is related to the number of
components (C) and number of phases (P) by the following phase rule equation:

[Link] WHAT IS PHASE (P)

A phase is defined as “an homogeneous, physically distinct and mechanically separated portion of system,
which is separated from other parts of the system by definite boundary surfaces” Example :
  Liquid phase: The number of liquid phase depends on the number of liquids present and their
miscibility.
i) If two liquids are immiscible, they will form two separate liquid phases. Example : benzene
and water
ii) ii) If two liquids are miscible they will form one liquid phase only. Example : alcohol and
water

 Solid phase: each solid forms a separate phase. The number of solid phase depends on the number
of solids present in it. Example: various forms of sulphur can exist together, but these are all
separate phases.
 Gaseous phase: a gaseous mixture is thoroughly miscible in all proportions, it will form one phase
only. Example: a mixture of N2 and H2 forms one phase only.
 A solution of a substance in a solvent consists of one phase only, e.g. glucose solution.
 A heterogeneous mixture like:

CaCO3(s) ⇌ CaO (s) + CO2 (g)

Consists of three phases (i.e., two solids and one gaseous). In the equilibrium reaction,

Fe(s) + H2O(g) ⇌ FeO(s) + H2(g)

There are two solid phases, Fe and FeO and one gaseous phase consisting of H2O (g) and H2(g).
Thus three phases exists in equilibrium.

 At freezing point, water consists of three phases:

Ice (s) ⇌ Water (l) ⇌ Water vapour (g)

 A homogeneous solid solution of a salt forms a single phase.

Example: Mohr‟s salt [FeSO4. (NH4)2SO4.6H2O] solution has a single phase.

[Link] Component (C)

Component is defined as “the smallest number of independently variable constituents, the composition of
each phase can be expressed in the form of a chemical equation”. Example:

 In the water system,

Ice (s) ⇌ Water (l) ⇌ Water vapour (g)
The chemical component of all the three phases is H2O and therefore it is one component
system.
 Sulphur exists in four phases namely rhombic, monoclinic, liquid and vapour, but the chemical
composition of all phases is S. Thus is a one component system.
 A system of saturated solution of NaCl consists of solid salt, salt solution and water vapour. The
chemical composition of all the three phases can be expressed in terms of NaCl and H2O.
Therefore, it is a two component system.

[Link] Degree of freedom

Degree of freedom is defined as the minimum number of independent variable factors such as temperature,
pressure and concentration of the phases, which must be fixed in order to define the condition of a system
completely. A system having 1,2,3 or 0 degrees of freedom is called univariant, bivariant, trivariant and
nonvariant respectively.

Example:

1. Consider the water system

Ice (s) ⇌ Water (l) ⇌ Water vapour (g)

The three phases can be in equilibrium only at particular temperature and pressure. Therefore, when all the
three phases are present in equilibrium, then no condition needs to be specified. The system is therefore
zero variant or invariant or has no degree of freedom. In this system if pressure or temperature is altered,
three phases will not remain in equilibrium and one of the phases disappears.

2. Consider a system consisting of water in contact with its vapour,

Water (l) ⇌Water vapour (g)
To define this system completely, we must state either the temperature or pressure Thus degree
of freedom is one and the system is univariant.
3) For a system consisting of water vapour phase only, we must state the values of both the temperature
and pressure in order to define the system completely. Hence the system is bivariant or has two degrees of
freedom.
4. Consider a system consisting of
NaCl (s) ⇌ NaCl-water (aq) ⇌ Water vapour (g)
we must state either the temperature or pressure, because the saturation solubility is fixed at a particular
temperature or pressure. Hence the system is univariant.

[Link] MERITS OF THE PHASE RULE:

 It is applicable to both physical and chemical equilibria.

 It requires no information regarding molecular/microstructure, since it is applicable to macroscopic
systems.
 It is a convenient method of classifying equilibrium states in terms of phases, components and
degrees of freedom.
 It helps us to predict the behaviour of a system, under different sets of variables.
 It indicates that different systems with same degree of freedom behave similarly.
 It helps in deciding whether under a given set of conditions:
a) Various substances would exist together in equilibrium (or)
b) Some of the substances present would be interconverted or
(c) Some of the substances present would be eliminated.

[Link] LIMITATIONS OF PHASE RULE:

 It can be applied only for system in equilibrium. Consequently, it is of little value in case of
very slow equilibrium state attaining system.
 It applies only to a single equilibrium system; and provide no information regarding any other
possible equilibria in the system.
 It requires at most care in deciding the number of phases existing in an equilibrium state, since
it considers only the number of phases, rather than their amounts. Thus even if a trace of phase
is present, it accounts towards the total number of phases.
 It conditions that all phases of the system must be present simultaneously under the identical
conditions of temperature and pressure.
  It conditions that solid and liquid phases must not be in finely-divided state; otherwise
deviations occur.
[Link] APPLICATIONS OF PHASE RULE TO ONE COMPONENT SYSTEM (WATER
SYSTEM)

The water system is a one component system

Ice (s) ⇌ Water (l) ⇌ Water vapour (g)

ice water exists in three possible phases such as solid, liquid and vapour, there are three forms of equilibria
: liquid - vapour , solid - vapour and solid - liquid i.e., liquid – vapour, solid –vapour, solid - liquid each
equilibrium involves two phases. The nature of these phases which exist in equilibrium at any time depends
on the conditions of temperature and pressure.

Considering the phase diagram for the water system in the figure below:

Figure 1: water system

1. Curves: There are three curves OA, OB and OC.
2. Areas: Three curves OA , OB and OC divide the diagram into three areas AOB, AOC and BOC.
3. Triple point: The above three curves meet at the point O and is known as triple point.
4. Metastable equilibrium: The curve OA represents the metastable equilibrium.

INTREPREPATION

1) Curve OA:

The curve OA is called vaporization curve, it represents the equilibrium between water and vapour. At
any point on the curve the following equilibrium will exist. The degree of freedom of the system is one,
i.e, univariant. Thus applying phase rule equation,

F = C – P + 2 = 1 – 2 + 2 ;F = 1

This equilibrium (i.e, line OA ) will extend upto the critical temperature ( 3740C). Beyond the critical
temperature the equilibrium will disappear only water vapour will exist.

2) Curve OB: The curve OB is called sublimation curve of ice, it represents the equilibrium between
ice and vapour. At any point on the curve the following equilibrium will exist. The degree of
 freedom of the system is one, i.e., univariant. This is predicted by the phase rule. F = C – P + 2 ; F =
1–2+2;F=1

This equilibrium line will extend up to the absolute zero(– 2730C ) where no vapour can be present and only
ice will exist.

3) Curve OC The curve OC is called melting point curve of ice, it represents the equilibrium between
ice and water. At any point on the curve the following equilibrium will exist. The curve OC is
slightly inclined towards pressure axis. This shows that melting point of ice decreases with increase
of pressure. The degree of freedom of the system is one. i.e., univariant.
4) Triple point (Point „O‟): At triple point all the three phases namely ice, water and vapour coexist.
Thus the value of P is 3. Applying phase rule equation, the degree of freedom at this point is zero. It
means that three phases can coexist in equilibrium only at a definite temperature and pressure. The
values are 0.00750C and 4.58 mm respectively. At this triple point, neither pressure nor temperature
can be altered even slightly without causing the disappearance of one of the phases. The triple point
is not the same as the ordinary melting point of ice ( i.e, 00C). It‟s value has been increased due to
the fact that 00C is the melting point of ice at 760mm of mercury and a decrease of 4.58 mm will
rise the melting point to 0.00750C.
5) Curve OB ( Metastable equilibrium) The curve OB is called vapour pressure curve of the super-cool
water or metastable equilibrium. Where the following equilibrium will exist. Super-cool water
Vapour Sometimes water can be cooled below 00C without the formation of ice, this water is called
super-cooled water. Supercooled water is unstable and it can be converted into solid by „seeding‟ or
by slight disturbance.
6) Areas Area AOC, BOC, AOB represents water ice and vapour respectively. In order to define the
system at any point in the areas, it is essential to specify both temperature and pressure. The degree
of freedom of the system is two. i.e., Bivariant. This is predicted by the phase rule F = C – P + 2; F
= 1 – 1 +2 ; F = 2

[Link] Phase Diagram

Phase diagram is a graph obtained by plotting one degree of freedom against another. If the phase diagram
is plotted between temperature against pressure, the diagram is called P-T diagram. P-T diagram is used for
one component system. If the phase diagram is plotted between temperature against composition, the
diagram is called T-C diagram. T-C diagram is used for two component system.
[Link] Uses of Phase diagram

1. From the phase diagram, it is possible to predict whether an eutectic alloy or a solid solution is
formed on cooling a homogeneous liquid containing mixture of two metals.

2. The phase diagrams are useful in understanding the properties of materials in the heterogeneous
equilibrium system.

3. The study of low melting eutectic alloys, used in soldering, can be carried out using phase diagrams.
[Link] APPLICATIONS OF PHASE RULE TO TWO COMPONENT SYSTEM

Reduced phase rule or condensed phase rule.

We know the phase-rule equation, F = C – P +2,

For a two component system, C = 2 and hence the above equation becomes, F = 2 – P + 2 = 4 – P
The minimum number of phases in any system at equilibrium is one. the maximum number of degree of
freedom is three.

In solid-liquid equilibrium of an alloy, practically there is no gaseous phase and the pressure will not have
much influence. In the case of solid-liquid equilibrium, the experiments are generally carried out at
constant pressure. Thus the system in which only the solid and liquid phases are considered and the gas
phase is ignored is called a condensed system.

This reduces the degree of freedom of the system by one. The phase rule equation is then written as F = C –
P + 1, this equation is called reduced phase rule or condensed phase rule.

For a two component system the phase rule equation is written as F = C – P + 1 = 2 – P +1 = 3 – P The
above equation is known as the reduced (condensed) form of phase rule for two component system. There
are various types of solid-liquid equilibria of which only two of them are tconsidered here.

 Those equlibria in which the components are completely miscible with one another in liquid state.
They do not form any compound on solidification.

They give rise to merely an intimate mixture known as eutectic. Some examples of this system are:

1) lead-silver system 2) Lead-Antimony system 3) Zinc-cadmium system 4) Potassium iodide- water

system
 Those equilibria in which the components enter into chemical combination .

They give rise to one or more compounds. Examples of this system are: 1) Zinc-magnesium system 2)
Calcium chloride – Potassium chloride system 3) Gold-Tellurium system.

[Link] CLASSIFICATION OF TWO COMPONENT SYSTEM

The two component systems are classified into the following three types:
i. Simple eutectic formation
ii. (a) Formation of compound with congruent melting point.
b) Formation of compound with incongruent melting point.
iii) Formation of solid solution.

EXPLANATION

i. Simple eutectic formation:

A system with two substances which are completely miscible in the liquid state, but completely immiscible
in the solid state is known as eutectic system. In this system the substances do not react chemically. Among
the mixtures of different proportions of two substances, the mixture which has the lowest melting point is
known as the eutectic mixture. The temperature and composition corresponding to the point eutectic point
is called eutectic temperature and eutectic composition respectively.

ii. (a) Formation of compound with congruent melting point : In this type of binary alloy system the
two substances form one or more compounds with definite proportions. Of the compounds, a
compound is said to possess congruent melting point, if it melts exactly at a constant temperature into
liquid, having the same composition as that of the solid.

(b) Formation of compound with incongruent melting point: a compound is said to possess
incongruent melting point, if it decomposes completely at a temperature below its melting point
yielding a new solid phase with a composition different from that of the original.
 iii) Formation of solid solution: In this type, when two substances, especially metals, are completely
miscible in both the solid and liquid states, they form solid solutions where mixing takes place in the
atomic levels. A solid solution can be formed only when the difference between the atomic radius of two
metals is not greater than 15%.

Figure 2: Lead-Silver System

i) The curve AC:

The curve AC is the freezing point curve of pure lead. The melting point of lead decreases gradually
along the curve AC, with the continuous addition of silver. Thus the curve AC is showing the effect of
addition of silver on the melting point of pure lead. All along the curve AC two phases –solid lead and
liquid are in equilibrium. According to reduced phase rule equation F = C – P + 1 = 2 – 2 + 1 = 1 i.e, F
= 1 i.e., the system is univariant.

i) The curve BC
Curve BC is the freezing point curve of pure silver and represents the effect of addition of pure
lead on the melting point of pure silver. All along the curve BC two phases –solid silver and
liquid are in equilibrium. According to reduced phase rule equation. F = C – P + 1 = 2 – 2 + 1 =
1, i.e. F = 1 (The system is univariant )
ii) Point C (Eutectic point) Point C is the eutectic point where solid silver, solid lead and their
solution coexist. The curves AC and BC meet at point C. Since the experiment is carried out at
constant pressure, the number of degree of freedom for the system at the eutectic point C is zero
on the basis of reduced phase rule.
F = C – P + 1 = 2 – 3 + 1 = 0; i.e., F = 0 The system is non-univariant. Eutectic composition is
2.6% silver and 97.4% lead and the corresponding temperature is 576 K.
iii) Areas The area above the line ACB has a single phase (molten Pb+Ag). According to reduced
phase rule equation,
F = C – P + 1 ; = 2 – 1 + 1 = 2 ; i.e., F = 2 The system is bivariant. Both the temperature and
composition have to be specified to define the system completely. The area below the line AC (
solid Ag + liquid melt), below the line BC ( solid Pb +liquid melt) and below the eutectic point
„C‟ have two phases and the system is univariant. According to reduced phase rule equation, F =
C – P + 1 ; = 2 – 2 + 1 = 1 i.e., F = 1
[Link] APPLICATION OF PATTINSON’S PROCESS

The phase diagram of lead-silver is useful in the extraction of silver from the argentiferous lead ore which
has a very small percentage of silver. This process is known as Pattinson‟s process. Let x represent the
molten argentiferous ( Pb + Ag alloy) lead containing very small amount of silver in it. It is a homogeneous
liquid and on cooling, the temperature falls but without change in concentration till any point y on the
curve AC is reached. On further cooling, lead begins to separate out and the solution becomes richer in
silver. Further cooling will shift the system along the line yc. More of lead separates as solid till the point C
is reached when the percentage of Ag rises to 2.6%. This process of increasing the relative proportion of
silver in the alloy is known as Pattinson‟s process of desilvering of lead.
[Link] USES OF EUTECTIC SYSTEM

1. Eutectic systems are useful in predicting the suitable alloy composition.

2. It is used in the preparation of solders which are used for joining two metal pieces together.
1.12. INTERNAL ENERGY (U)

Internal energy is a fundamental concept in thermodynamics that represents the total energy contained
within a system due to the microscopic motion and interactions of its particles. It encompasses the kinetic
energy of molecules (due to their motion) and potential energy (due to intermolecular forces) that constitute
a system. Internal energy is a state function, meaning its value depends only on the current state of the
system, not how it got there.

Key Points:

1. Definition: Internal energy (U) is the total energy contained within a system, primarily arising
from:

 Kinetic energy: The motion of molecules, including translational, rotational, and vibrational motion.
 Potential energy: The energy due to the interactions between molecules, such as intermolecular forces.

It can be written as:

Where:
KE = total kinetic energy of the molecules
PE = total potential energy due to molecular interactions

2. Microscopic Origins:

 Kinetic Energy: Molecules in a gas, liquid, or solid are in constant motion. This motion
includes translational movement (moving from place to place), rotational movement
(spinning), and vibrational movement (oscillating). These movements contribute to the
total internal energy of a system.
 Potential Energy: Molecules exert forces on each other due to attractions and repulsions
(like van der Waals forces, dipole interactions, and covalent bonds). These forces lead to
potential energy, which also contributes to the system's internal energy.

3. Internal Energy and Temperature: Internal energy is closely linked to the temperature of the
system:
  As the temperature increases, the average kinetic energy of the molecules increases, leading
to an increase in internal energy.
 However, temperature does not directly account for all potential energy within a system,
especially in phases like solids and liquids where intermolecular forces are significant.

4. Change in Internal Energy (ΔU): The change in internal energy is central to the first law of
thermodynamics, which is the law of energy conservation:

( )

Where:

 ΔU = change in internal energy

 Q = heat added to the system
 W = work done by the system

This equation tells us that the internal energy changes when heat is added to or removed from the
system, or when work is done on or by the system.

5. Units of Internal Energy: The SI unit of internal energy is the joule (J). In practical
thermodynamic problems, internal energy is often expressed in kilojoules (kJ) or calories,
especially in chemistry and engineering.
6. Internal Energy as a State Function: Internal energy depends only on the state of the system, not
the path taken to reach that state. This means it is a function of variables such as temperature,
pressure, and volume. Changes in internal energy depend only on the initial and final states of the
system.
7. Internal Energy in Different Phases:
 Gases: For an ideal gas, internal energy depends solely on temperature, as there are no
intermolecular forces (so potential energy is zero). The internal energy of an ideal gas is
proportional to its temperature.
 Liquids and Solids: In liquids and solids, both kinetic and potential energy contribute to internal
energy, since molecules are not free to move as in gases, and intermolecular forces play a more
significant role.
8. Internal Energy in Thermodynamic Processes:
 Isothermal process: At constant temperature, the internal energy of an ideal gas does not change
because internal energy is a function of temperature.
 Adiabatic process: In an adiabatic process, there is no heat exchange with the surroundings (Q=0Q
= 0Q=0), so any change in internal energy is due to work done on or by the system.
 Isochoric process: In a process at constant volume, no work is done (W=0W = 0W=0), and any heat
added to the system results in a change in internal energy.

Examples of Internal Energy:

 Heating a Gas: When you heat a gas, its molecules move faster, increasing their kinetic energy, which
increases the internal energy.
 Phase Changes: During melting or vaporization, heat is added to the system, but the temperature doesn't
increase because the energy goes into breaking intermolecular forces, increasing potential energy rather
than kinetic energy.

Importance of Internal Energy:

 Energy Conservation: Internal energy is a key component of the energy balance in thermodynamic systems
and is fundamental to understanding the behavior of heat engines, refrigerators, and chemical reactions.
 Thermodynamic Cycles: In thermodynamic cycles like the Carnot or Rankine cycles, changes in internal
energy govern the work output and efficiency of the cycle.
Internal energy is the total energy contained within a system, derived from the molecular motion and
interactions. It is a state function and forms the basis of the first law of thermodynamics, helping to explain
how heat and work affect a system. Understanding internal energy is crucial for analyzing energy transfers
in a wide range of processes in thermodynamics.

The internal energy of a system is the energy of the molecules making up the system. The molecules of a
system are believed to be in constant motion and to possess kinetic energy of translation, rotation and
internal vibration (with the exception of monoatomic substance or molecules such as Helium). The addition
of heat to a system increase this molecular activity and thus causes an increase in its internal energy work
done on the system can have the same effect. in addition to K.E, the molecules of a system possess
potential energy, because of the interactions among their force fields. Hence internal energy, U of a
chemical system is the sum of all the energies such as the chemical or potential energy , K.E and bond
energy of the system. When conditions of the system change ie

1. Heat is evolved or absorbed and/or

2. If work is done on or by the system from the first law of thermodynamic such change in the internal
energy of a system may be represented by
𝜟U= Heat absorbed by the system (Q) + Work done by the system(W)

The direction of energy flow is indicated by specifying sign for Q and W.

Thus when the system
1. Absorbed energy as heat from the surrounding, Q is positive (+)
2. Evolves energy as heat to the surrounding , Q is negative (-)
3. Absorbed energy by having work done on it by the surrounding , W is (+)
4. Evolves energy by doing work on the surrounding, W is negative (-)

1.2.13. ENTHALPY

Enthalpy is a thermodynamic property that represents the total heat content of a system. It combines the
system's internal energy and the product of its pressure and volume. Enthalpy is particularly useful in
processes that occur at constant pressure, such as chemical reactions, where it helps quantify the heat
exchange between the system and its surroundings.

Key Points:

1. Definition of Enthalpy: Enthalpy (H) is defined as:

Where:
H = enthalpy
U = internal energy of the system
p = pressure of the system
V = volume of the system

Enthalpy accounts for both the internal energy of the system and the energy required to "make
room" for it by displacing its surroundings (via pressure-volume work).

2. Unit of Enthalpy: The SI unit of enthalpy is the joule (J), the same as energy. Other units
commonly used include kilojoules (kJ) or calories, depending on the context.
3. Change in Enthalpy (ΔH): The change in enthalpy (ΔH) is the most important aspect in
thermodynamics. It measures the heat absorbed or released during a process occurring at constant
 pressure. For example, in chemical reactions, the change in enthalpy indicates whether the reaction
is endothermic (absorbing heat) or exothermic (releasing heat).

 ΔH > 0, the process is endothermic.

 ΔH < 0, the process is exothermic.

4. Enthalpy in Chemical Reactions: Enthalpy is commonly used to describe heat changes in

chemical reactions. For example:

 Endothermic reactions: The system absorbs heat from its surroundings, resulting in a
positive ΔH. This is common in reactions such as the melting of ice or the decomposition of
a substance.
 Exothermic reactions: The system releases heat to its surroundings, resulting in a negative
ΔH. Combustion reactions are a typical example of exothermic processes.

5. Enthalpy and Heat at Constant Pressure: At constant pressure, the change in enthalpy is equal to
the heat transferred into or out of the system:

Where:
ΔH = change in enthalpy
qp= heat added to or removed from the system at constant pressure
This is particularly useful in understanding processes such as phase changes (melting, boiling) and
chemical reactions where pressure remains constant.

6. Specific Enthalpy: Specific enthalpy is the enthalpy per unit mass of a substance and is denoted
by h:

Where:
h = specific enthalpy (J/kg)
H = total enthalpy (J)
M = mass of the substance (kg)

7. Enthalpy in Thermodynamic Cycles: Enthalpy is extensively used in analyzing thermodynamic

cycles like the Rankine cycle (used in power plants) and refrigeration cycles. These cycles involve
heat exchange processes, and enthalpy helps track the energy transfers during heating, cooling,
compression, and expansion.

Applications of Enthalpy:

 Phase Transitions: During phase changes such as melting, boiling, or condensation, the enthalpy of the
system changes as heat is added or removed without changing the temperature. For example, the heat
required to melt ice or boil water is related to the enthalpy of fusion and enthalpy of vaporization,
respectively.
 Reactions in Chemistry: Enthalpy changes are critical for understanding chemical reactions, especially
when determining reaction spontaneity and heat release or absorption.
 Engineering: In mechanical systems like engines and heat exchangers, enthalpy changes are used to
calculate the efficiency and performance of energy transfer systems.
Enthalpy is crucial for understanding how heat and work interact in various processes, from chemical
reactions to phase changes, and is vital for designing efficient systems in engineering and chemistry. By
quantifying heat exchange at constant pressure, enthalpy simplifies the analysis of real-world
thermodynamic processes.

SOLVED EXAMPLES ON FUNDAMENTALS OF THERMODYNAMICS

1. A man circling the earth in a spaceship weighed 300 N at a location where the local gravitational
acceleration was 4.5 m/s2. Calculate the mass of the man and his weight on the earth where the
gravitational acceleration is 9.81 m/s2.
SOLUTION
Force is equal to the product of mass and acceleration, i.e. F = ma
300 = m x 9.81,

m = 66.67kg

The weight on the earth is the force acting on the object on the earth.
F = 66.67 x 9.81 = 654N

2. A special manometer fluid has a specific gravity of 2.95 and is used to measure a pressure of 1.15
bar at a location where the barometric pressure is 760 mm Hg. What height will the manometer
fluid indicate?
Hint: 1 bar = 105 Pa = 105 N/m2
SOLUTION
If h is the height of the manometer fluid, the mass of the fluid is
m = hrA where r is the density of the liquid and A is the area of cross-section of the column of
liquid.
The force exerted by the fluid is,
F = ma = hrAg where g is the acceleration due to gravity. The pressure exerted by the fluid is

where p = r x reference density (103m3)

This should be equal to the difference in pressures between the two ends of the manometer (DP)
when the manometer indicates a steady reading.
DP = hpg
DP = P1 – P2
P1 = 1.15 bar = 1.15x105 N/m2
P2 = 760 mm Hg = 1.01325 bar = 1.01325 x 105 N/m2
DP = 1.15 x105 – 1.01325 105 = 0.13675 x 105
 0.13675 x 105 = hpg = h x (2.95 x 103) x 9.8067

3. The potential energy of a body of mass 10.0 kg is 1.5 kJ. What is the height of the body from the
ground? If a body of mass 10 kg is moving at a velocity of 50 m/s, what is its kinetic energy?
SOLUTION
The potential energy (PE) is given by
PE = mgz
1.5 x 103 = 10 x 9.8067 x z
z= 15.3m
Thus the elevation z = 15.3 m.
Kinetic energy (KE) is given by:

4. A man whose weight is 600 N takes 2 min for climbing up a staircase. What is the power
developed in him, if the staircase is made up of 20 stairs each 0.18 m in height?
SOLUTION
Total vertical displacement = 20 x 0.18 = 3.6 m
Work done = Force x Displacement = 600 x 3.6 = 2160 N.m (= 2160 J)
Power developed = Work done/Time

5. Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained by a weight placed
on the piston. The mass of the piston and the weight together is 50 kg. The acceleration due to
gravity is 9.81 m/s2 and the atmospheric pressure is 1.01325 bar. Assume frictionless piston.
Determine:
(a) The force exerted by the atmosphere, the piston, and the weight on the gas if the piston is 100
mm in diameter. (b) The pressure of the gas. (c) If the gas is allowed to expand pushing up the
piston and the weight by 400 mm, what is the work done by the gas in J? (d) What is the change
in the potential energy of the piston and the weight after the expansion in part (c)?
SOLUTION

(a) Force exerted by the atmosphere = Pressure x Area = 1.01325 x 105 x x(100 x 10 –3) 2 =
795.805N Force exerted by the piston and weight = m x g = 50 x 9.81 = 490.5 N
Total force acting on the gas = 795.805 + 490.5 = 1286
 (b) Pressure = Force = = 1.6378 10 5 N/m2 (=1.6378 bars)
( – )

(c) Work done = Force x Displacement = 1286.305 x (400 x 10 –3) = 514.5 J

(d) Change in the potential energy, 𝜟(PE) = mg𝜟z = 50 x 9.81x (400 x 10-3) =196.2 J
6. A spherical balloon of diameter 0.5 m contains a gas at 1 bar and 300 K. The gas is heated and the
balloon is allowed to expand. The pressure inside the balloon is found to vary linearly with the
diameter. What would be the work done by the gas when the pressure inside reaches 5 bar?
SOLUTION
Since the pressure varies linearly with the diameter of the balloon,

D = constant, where P is the pressure inside the balloon and D is the diameter.
1 x 105 N/m2 and 0.5m initially, P/D = 1 x 105 N/m2 / 0.5m = 2 x 105 N/m2 or P = 2 x 105 x D.
the final pressure is 5 x 105; the final diameter would be 5 x 105/2 x 105 = 2.5m

work done = ∫ PdV= ∫ 2 x 10 x d ( ) x D3

3
work done = (2 x 105 ) x( ) ∫ = x 105 x ( 2.54 - 0.54)

= 30.6305 x105 Nm = 30.6305 x105J

7. Two kilograms of CO2 gas is contained in a piston–cylinder assembly at a pressure of 6.5 bar and a
temperature of 300 K. The piston has a mass of 5000 kg and a surface area of 1 m2. The friction of
the piston on the walls is significant and cannot be ignored. The atmospheric pressure is 1.01325
bar. The latch holding the piston in position is suddenly removed and the gas is allowed to expand.
The expansion is arrested when the volume is double the original volume. Determine the work
appearing in the surroundings. Will it be the same as the work done by the gas?
SOLUTION
The initial volume of the gas is evaluated assuming that the gas follows the ideal gas equation,
PV = nRT
Number of moles of the gas n = Mass/Molecular Weight = 2/44 = 0.0455 kmol
Initial volume, V = nRT/P = 0.0455 (8.314 x 103) x 300/6.5 x 105 = 0.1746m3
Final volume = 2V = 2 x 0.1746m3 = 0.3492m3
Change in the volume, 𝜟V = V2 – V1 = 2V – V = 0.174 m3
Pressure on the surroundings = Atmospheric pressure + Pressure due to the weight of the piston
= 1.01325 x 105 + 5000 x 9.8067 = 1.50359 x 105 N/m2
Work done on the surroundings = P𝜟V = (1.50359 x 105) x 0.1746 = 0.2625 x 105 J
Since the pressure of the gas is changing continuously, the work done by the gas cannot be
evaluated as ∫ PdV ; this work would be greater than the work appearing in the surroundings
because of the irreversible nature of the process.
8. A gas which occupies a volume of 0.2m3 at a pressure of 1 bar is expanded to a final pressure of 7.0
bar. The pressure of the gas varies according to the relation P = 1200 V + b, where P is in kPa, V is
in m3 and b is a constant. Calculate the work done by the gas.

SOLUTION
Initial conditions are P1 = 1 bar = 100 kPa and V1 = 0.2 m3.
The pressure and volume of the gas are related by P = 1200 V + b Therefore, P1 = 1200 V1 + b
100 = 120 x 0.2 + b
b = –140 kPa
Therefore, the pressure-volume relationship is P = 1200V – 140
The final pressure P2 = 7.0 bar = 700 kPa.
Therefore, the final volume V2 is given by 700 = 120 x V2 – 140
The work done by the gas is given by

work done = ∫ PdV= ∫ ( – ) = x ( 0.72 - 0.22) – 140 x ( 0.7 - 0.2)