Unit 1

Introduction - Definition and Basic Concepts

Thermodynamics can be defined as the study of energy, its transformations, and its relation to
the matter.
Different Branches of Thermodynamics:
Thermodynamics is classified into the following four branches:
● Classical Thermodynamics
● Statistical Thermodynamics
● Chemical Thermodynamics
● Equilibrium Thermodynamics

Classical Thermodynamics
In classical thermodynamics, the behaviour of material is analyzed with a macroscopic
approach. Units such as temperature and pressure are taken into consideration, which helps
the individuals calculate other properties and predict the characteristics of the matter
undergoing the process.
Statistical Thermodynamics
In statistical thermodynamics, every molecule is under the spotlight, i.e. the properties of
every molecule and how they interact are taken into consideration to characterize the behavior
of a group of molecules.
Chemical Thermodynamics
Chemical thermodynamics is the study of how work and heat relate to each other in chemical
reactions and in changes of states.
Equilibrium Thermodynamics
Equilibrium thermodynamics is the study of transformations of energy and matter as they
approach the state of equilibrium.

Energy

Energy is the capacity to do work. If a system has the capacity to do work, it possesses at
least one form of energy that is available for transformation to another form of energy.
Energy can exist in many forms. For thermodynamic analysis, energy is classified into
two broad categories:
 i. macroscopic energy
ii. microscopic energy
Macroscopic forms of energy: forms of energy that a whole system possesses with
respect to some outside reference frame, such as kinetic and potential energy. The
macroscopic energy of a system is related to motion and the influence of some external
effects such as gravity, magnetism, electricity, and surface tension.
Kinetic energy: energy that a system posses as a result of its relative motion relative to
some reference frame, KE
𝑚𝑉
𝐾𝐸 = 2
( 𝑘𝐽)

where V is the velocity of the system in (m/s).

Potential energy: It is the energy that has the potential to become another form of energy. An
object’s potential energy depends on its physical properties and position in a system.
In thermodynamics, there are primarily two forms of potential energy, elastic potential energy
and gravitational potential energy.
Elastic potential energy is the energy stored in a deformable body such as an elastic solid or
a spring.
Gravitational potential energy is the energy that a system possesses by virtue of its
elevation with respect to a reference in a gravitational field. It is the energy that a system
posses as a result of its elevation in a gravitational field, PE
𝑃𝐸 = 𝑚𝑔𝑧
where g is the gravitational acceleration and z is the elevation of the center of gravity of the
system relative to some arbitrary reference plane.
Microscopic forms of energy: Energy relate to the system on a molecular or atomic level.
There are several types of microscopic energies, which is grouped together into a single
category referred to as internal energy. A system’s internal energy is defined as the sum of
the random internal kinetic energies of the atoms and the total internal potential energies due
to the bonds between atoms.
Internal energy is the sum of all the various forms of microscopic energies possessed by the
molecules and atoms in the system.
It is the total energy of a system consists of the kinetic, potential, and internal energies:
𝐸 = 𝐾𝐸 + 𝑃𝐸 + 𝑈
The internal energy associated with the atomic bonds in a molecule is called chemical or bond
energy. The tremendous amount of energy associated with the bonds within the nucleolus of
atom itself is called atomic energy.
 ● if heat flows out of the system, then Q will be negative
● if heat flows into the system, then Q will be positive
● if work is done by the system, then W will be negative
● if work is done on the system, then W will be positive
Closed and Open Systems

A system is defined as a quantity of matter or a region in space chosen for study. The mass or
region outside the system is called the surroundings.

Boundary: the real or imaginary surface that separates the system from its surroundings.
The boundaries of a system can be fixed or movable. Mathematically, the boundary has zero
thickness, no mass, and no volume.
Closed system or control mass: consists of a fixed amount of mass, and no mass can cross
its boundary. But, energy in the form of heat or work, can cross the boundary, and the
volume of a closed system does not have to be fixed.
Open system or control volume: is a properly selected region in space. It usually encloses
a device that involves mass flow such as a compressor. Both mass and energy can cross the
boundary of a control volume.
Isolated system: A closed system that does not communicate with the surroundings by any
means.
Rigid system: A closed system that communicates with the surroundings by heat only.
Adiabatic system: Any system where no heat can be exchanged but work can be done on
the system. A closed or open system that does not exchange energy with the surroundings
by heat.
Properties of a System

Any characteristic of a system is called a property. In classical thermodynamics, the

substance or a system is assumed to be a continuum, homogenous matter with no
microscopic holes.
Intensive properties: are those that are independent of the size (mass) of a system, such as
temperature, pressure, and density. They are not additive.
Extensive properties: values that are dependent on size of the system such as mass, volume,
and total energy U.

Thermodynamic steady state

A steady state is basically a situation in which all state variables are constant despite ongoing
processes that attempt to change them. For an entire system to be at steady state, i.e. for all state
variables of a system to be constant, there must be a flow through the system.
Examples of steady state in a system is the case of a bathtub with the tap open but without the
bottom plug. After a certain time, the water flows in and out at the same rate, so the water level
(Volume) stabilizes and the system is at steady state. The Volume stabilizing inside the tub
depends on the size of the tub, the diameter of the exit hole and the flowrate of water in.

Equilibrium

The state of a system in which properties have definite, unchanged values as long as external
conditions are unchanged is called an equilibrium state.

At a given state, all the properties of a system have fixed values. Thus, if the value of even one
property changes, the state will change to different one.
In an equilibrium state, there are no unbalanced potentials (or driving forces) within the
system. A system in equilibrium experiences no changes when it is isolated from its
surroundings.

♦ Thermal equilibrium: when the temperature is the same throughout the entire system.
 ♦ Mechanical equilibrium: when there is no change in pressure at any point of the

system. However, the pressure may vary within the system due to gravitational effects.

♦ Phase equilibrium: in a two phase system, when the mass of each phase reaches an

equilibrium level.

♦ Chemical equilibrium: when the chemical composition of a system does not change

with time, i.e., no chemical reactions occur.

Thermal equilibrium is reached when two objects in contact with each other reach the same
temperature, and are therefore not exchanging heat.
For example, if a gallon of milk is taken out of a cold fridge and placed on the counter, the
counter and the milk are at thermal equilibrium when they reach the same temperature.

Zeroth law of thermodynamics

Zeroth Law of Thermodynamics states that when two bodies are in thermal equilibrium
with another third body then the two bodies are also in thermal equilibrium with each
other.
Ideal & Real Gases and Thermodynamic Relations
Three states of matter are recognized by their characteristics i.e. solids, liquids and gases. Solids
have definite mass and shape due to the strong molecular attraction. In liquids, the molecules are
moving so they result in taking the shape of the container. In gases, the molecules are free to
move anywhere in the container.
Two types of gases exist:

i. Real gas
ii. Ideal gas
As the particle size of an ideal gas is extremely small and the mass is almost zero and no volume
Ideal gas is also considered a point mass. The molecules of real gas occupy space though they
are small particles and have volume.
The properties of a mixture of as gas depends on the composition of the mixture as well as the
properties of the individual components.
There are two ways to describe the composition of a mixture: either by specifying the number of
moles of each component, called molar analysis,
or
by specifying the mass of each component, called gravimetric analysis.
Consider a gas mixture composed of k components. The mass of the mixture mm is the sum of
the masses of the individual components, whereas, the mole number of the mixture Nm is the sum
of the mole numbers of the individual components.
𝑘 𝑘
𝑚𝑚 = ∑ 𝑚𝑖 𝑁𝑚 = ∑ 𝑛𝑖
𝑖=1 𝑖=1

The ratio of the mass of a component to the mass of the mixture is called the mass fraction mf,
and the ratio of the mole number of a component to the mole number of the mixture is called the
mole fraction.
𝑚1 𝑚𝑖
𝑀𝑎𝑠𝑠 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛: 𝑚𝑓𝑖 = 𝑚𝑚
𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛: 𝑁𝑖 = 𝑀𝑖

The average mass M of a substance can be expressed in terms of the mole number N and molar
mass M of the substance as m NM.
𝑚𝑚
𝑀𝑚 = 𝑁𝑚
P-v-T BEHAVIOR OF GAS MIXTURES:
IDEAL AND REAL GASES
There are two types of gases: real gas and ideal gas. Ideal gas, as the name suggests, adheres to
the Ideal Gas Law. This gas has negligible intermolecular forces. It also does not have a specified
volume as such. Real gas is the exact opposite of ideal gas. The molecules present in real gas
occupy space. They have intermolecular forces of attraction and even volume.

Ideal gas:

The ideal gas is assumed to lack any intermolecular forces of attraction. It is also assumed to
have no volume of its own and can expand infinitely to fill up any volume or be compressed
infinitely into any volume.
For example, assume that spherical balls are present closely with each other. But, they do not
have any contact with each other. They may collide with each other but bear no contact still. The
particles of the ideal gas have the liberty to move freely. They are elastic and do not accept any
limitations imposed on them by the cruel world. They also don’t have any volume since they are
assumed to be perfect points.
Further, the Ideal Gas Law also states that any change that takes place in the overall temperature
of the gas also causes a change in the internal temperature of the ideal gas. This, in turn, causes a
change in the kinetic energy and is followed by a change in temperature.
An ideal gas depends on:
P: Absolutely Pressure
T: Absolute Temperature
V: Volume
The relationship between them looks like:
Ideal Gas Law: PV = nRT = NkT
Herein, R = Universal Gas Constant = 8.3145 J/mol K
● n = number of moles
● k = Boltzmann Constant 1.38066 x 10-23 J/K = 8.617385 x 10-5 eV/K
● k = R/NA
● NA = Avagadro’s Number = 6.0221 x 1023 /mol
● N = number of molecules
Real gas:

As opposed to an ideal gas, real gas does not adhere to any of the gas laws. It has no relation to
the Ideal Gas Law. Unlike ideal gas, real gas has both mass and volume. Real gas has mass,
velocity, and even volume. Equations for the ideal gas only approximate the behaviour followed
by a real gas.
The examples of an ideal gas and real gas can be traced as follows: no gas behaves as an ideal
gas. However, some real gas examples are ammonia, water vapour, and sulphur dioxide.

P-v-T BEHAVIOR
When two or more ideal gases are mixed, the behavior of a molecule normally is not influenced
by the presence of other similar or dissimilar molecules, and therefore a nonreacting mixture of
ideal gases also behaves as an ideal gas. Air, for example, is conveniently treated as an ideal gas
in the range where nitrogen and oxygen behave as ideal gases. When a gas mixture consists of
real (nonideal) gases, however, the prediction of the P-v-T behavior of the mixture becomes
rather involved. The prediction of the P-v-T behavior of gas mixtures is usually based on two
models: Dalton’s law of additive pressures and Amagat’s law of additive volumes. Both models
are described and discussed below.
Dalton’s law of additive pressures:
Dalton's law (also called Dalton's law of partial pressures) states that the total pressure exerted by
a gaseous mixture is equal to the sum of the partial pressures of each individual component in a
gas mixture. This empirical law was observed by John Dalton in 1801 and is related to the ideal
gas laws.
Mathematically, the pressure of a mixture of gases can be defined as the:
𝑛
𝑃𝑡𝑜𝑡𝑎𝑙 = ∑ 𝑝𝑖
𝑖=1

Amagat’s law of additive volumes:

Amagat's law or the Law of Partial Volumes of 1880 describes the behavior and properties of
mixtures of ideal (as well as some cases of non-ideal) gases. Of use in chemistry and
thermodynamics, Amagat's law states that the volume Vm of a gas mixture is equal to the sum of
volumes Vi of the K component gases, if the temperature T and the pressure p remain the same:
 𝑘
𝑉𝑚(𝑇, 𝑝) = ∑ 𝑉𝑖(𝑇, 𝑝)
𝑖=1

Both Amagat's and Dalton's Law predict the properties of gas mixtures. Their predictions are the
same for ideal gases. However, for real (non-ideal) gases, the results differ. Dalton's Law of
Partial Pressures assumes that the gases in the mixture are non-interacting (with each other) and
each gas independently applies its own pressure, the sum of which is the total pressure. Amagat's
Law assumes that the volumes of each component gas (same temperature and pressure) are
additive; the interactions of the different gases are the same as the average interactions of the
components.
The thermodynamic properties of an ideal gas can be described by these two equations:
The equation of state of a classical ideal gas is given by the ideal gas law. The internal energy at
constant volume of an ideal gas is given by:
𝑃𝑉 = 𝑁𝑘𝐵𝑇 = 𝑛𝑅𝑇

where:
P is the pressure
V is the volume
n is the chemical amount of the gas
R is the gas constant (8.314 J·K−1 mol-1 in SI units)
T is the absolute temperature
N is the number of gas particles
kB is the Boltzmann constant (1.381×10−23J·K−1 in SI units)

Graphical Representation
There is a straight-line relationship between the volume of a gas and the number of moles of gas
particles. At the same temperature and pressure, as the volume of gas goes up, so increases the
number of moles of gas.
Van der Waals Equation of State for Real Gases and its Derivation
In the year 1873, a scientist named Johannes Diderik Van der Waals gave an equation. Johannes
Diderik was a theoretical physicist and a Dutch thermodynamic scientist. In 1910, he won the
noble prize in physics.
The equation of Van der Waals of state for real gases does not follow ideal gas law. By the ideal
gas law, that is, PV = nRT.
The equation of Van der Waals is composed of non-interacting point particles which satisfies
ideal gas law.
This equation for a real gas:
The volume is given as (Vm – b)
b= volume occupied per mole
Thus, when we substitute the ideal gas law with Vm – b= V, it comes as
Nrt = P(Vm-b)
the value of P is modified due to intermolecular attraction as

𝑅𝑇 = 𝑃 + ( 𝑉𝑚
𝑎
2
) (𝑉𝑚 − 𝑏)

( )(𝑉 𝑛 − 𝑛𝑏)
2
𝑎𝑛
𝑛𝑅𝑇 = 𝑃 + 2
𝑚
𝑉

𝑉 = 𝑉𝑚𝑛
Here,
Vm: The molar volume of gas
R: The universal gas constant
T: The temperature
P: The pressure
V: The volume

Law of corresponding states

This law was then developed after scientists observed that the properties of pure substances
are identical when they are at the same reduced conditions. The reduced conditions being the
ratio in between the actual pressure and the critical pressure, and the actual temperature and the
critical temperature. 2 substances having the same reduced conditions are in corresponding
states.

With
PR = reduced pressure
P = actual pressure
PC = critical pressure of the substance (same unit as P)
TR = reduced temperature
T = actual temperature in K
TC = critical temperature of the substance in K
We know that :
Thermodynamic cycle

Thermodynamic cycle refers to any closed system that undergoes various changes due to
temperature, pressure, and volume, however, its final and initial state are equal. This cycle is
important as it allows for the continuous process of a moving piston seen in heat engines and the
expansion/compression of the working fluid in refrigerators.

Example of P-V diagram of a thermodynamic cycle.

Specific heat at constant volume and pressure:

The specific heat of a gas at constant volume is defined as the quantity of heat required to raise
the temperature of unit mass of the gas by 1 degree when it is heated at constant volume. It is
given the symbol cv.

The specific heat of a gas at constant pressure is defined as the quantity of heat required to raise
the temperature of unit mass of the gas by 1 degree when it is heated at constant pressure. It is
given the symbol cp.

If we are dealing with a gas, it is most convenient to use forms of the thermodynamics equations
based on the enthalpy of the gas. From the definition of enthalpy:

h = e+ p * v

where h in the specific enthalpy, p is the pressure, v is the specific volume, and e is the specific
internal energy. During a process, the values of these variables change. Let's denote the change
by the Greek letter Δ which looks like a triangle. So "Δ h" means the change of "h" from state 1
to state 2 during a process. Then, for a constant pressure process the enthalpy equation becomes:

Δ h = Δ e+ p * Δ v

The enthalpy, internal energy, and volume are all changed, but the pressure remains the same.
From our derivation of the enthalpy equation, the change of specific enthalpy is equal to the heat
transfer for a constant pressure process:

Δ h = cp * Δ T
where Δ T is the change of temperature of the gas during the process,and c is the specific heat
capacity. We have added a subscript "p" to the specific heat capacity to remind us that this value
only applies to a constant pressure process.

The equation of state of a gas relates the temperature, pressure, and volume through a gas
constant R . The gas constant used by aerodynamicists is derived from the universal gas constant,
but has a unique value for every gas.

p * v = R *T

If we have a constant pressure process, then:

p * Δ v = R * ΔT

Now let us imagine that we have a constant volume process with our gas that produces exactly
the same temperature change as the constant pressure process that we have been discussing.
Then the first law of thermodynamics tells us:

Δ e= Δ q - Δ w

where q is the specific heat transfer and w is the work done by the gas. For a constant volume
process, the work is equal to zero. And we can express the heat transfer as a constant times the
change in temperature. This gives:
 Δ e = cv * Δ T

where Δ T is the change of temperature of the gas during the process,and c is the specific heat
capacity. We have added a subscript "v" to the specific heat capacity to remind us that this value
only applies to a constant volume process. Even though the temperature change is the same for
this process and the constant pressure process, the value of the specific heat capacity is different.

Because we have selected the constant volume process to give the same change in temperature as
our constant pressure process, we can substitute the expression given above for "Δ e" into the
enthalpy equation. In general, you can't make this substitution because a constant pressure
process and a constant volume process produce different changes in temperature If we substitute
the expressions for "Δ e", "p * Δ v", and "Δ h" into the enthalpy equation we obtain:

cp * Δ T = cv * Δ T + R * Δ T

dividing by "Δ T" gives the relation:

cp = cv + R

The specific heat constants for constant pressure and constant volume processes are related to the
gas constant for a given gas. This rather remarkable result has been derived from thermodynamic
relations, which are based on observations of physical systems and processes. Using the kinetic
theory of gases, this same result can be derived from considerations of the conservation of
energy at a molecular level.
We can define an additional variable called the specific heat ratio, which is given the Greek
symbol "gamma", which is equal to cp divided by cv:

gamma = cp / cv

Reversible and Irreversible thermodynamic reaction :

A thermodynamic process is said to be reversible if the process can be restored. The system and
surroundings return to their original states without producing any change in the universe.
Isothermal expansion and compression, electrolysis are some examples of reversible processes.

The changes which can be brought back to their original form are known as reversible changes.
For example, melting of ice, expansion, or compression of spring. And irreversible changes are
those changes in which the matter cannot be brought back to its original state. For example,
burning of fuel, etc.

In irreversible process is one in which the system and its surroundings do not revert to their
original state after the process has been started.

Consider the case of an automotive engine that has travelled a certain distance using a certain
amount of fuel. The fuel burns to generate energy to the engine, converting itself to smoke and
heat energy in the process. We will never be able to recover the energy lost by the fuel, nor will
we ever be able to return to its original state.
In thermodynamics, a reversible process is one in which the participants return to their original
state by introducing slight or negligible changes to their environment. An irreversible process, on
the other hand, is a naturally occurring phenomenon that does not return to its initial condition.