MODULE I

ME 010 506 Thermodynamics

Abstract
Fundamentals concepts – scope and limitations of thermodynamics. Thermodynamic systems –
different types of systems – macroscopic and microscopic analysis – continuum – properties –
state – processes. Thermodynamics equilibrium – Equation of state of an ideal gas – PVT system
– Real gas relations – Compressibility factor – Law of corresponding states.

Noel Joseph Gomez

noel@scmsgroup.org
ME 010 506 Thermodynamics Module 1

Table of Contents
Introduction: ................................................................................................................................ 2
Thermodynamic System ............................................................................................................. 2
Types of Thermodynamic Systems ............................................................................................. 2
Properties Of A System .......................................................................................................... 3
State Of A System ................................................................................................................... 3
Change of State ....................................................................................................................... 3
Path ......................................................................................................................................... 3
Process .................................................................................................................................... 3
Thermodynamic Cycle ............................................................................................................ 3
Types of Properties ................................................................................................................. 3
Macroscopic and Microscopic Analysis ..................................................................................... 4
Continuum................................................................................................................................... 4
Thermodynamic Equilibrium ...................................................................................................... 5
Quasi-Static Process.................................................................................................................... 5
Laws of Perfect Gases ................................................................................................................. 6
Boyle’s Law ............................................................................................................................ 6
Charles’s Law ......................................................................................................................... 7
Gay-Lussac's Law ................................................................................................................... 7
Avogadro's Law ...................................................................................................................... 7
Combined and Ideal Gas Laws ............................................................................................... 7
PVT System ................................................................................................................................ 8
Real Gas Relations ...................................................................................................................... 8
Compressibility Factor ................................................................................................................ 9
Critical Temperature ................................................................................................................... 9
Law of Corresponding States .................................................................................................... 10

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ME 010 506 Thermodynamics Module 1

Introduction:
Thermodynamics is the science of energy transfer and its effect on the physical properties of
substances. The alternate definition is: thermodynamics is the science that deals with work and
heat and these properties of substances that bear a relation to heat and work. Like all sciences,
the basis of thermodynamics is experimental observation.

Thermodynamics deals with four laws, viz.

 0th law – Temperature measurement

 1st law – Conservation of energy
 2nd law – Kelvin Planck Statement (Heat Engine) and Clausius Statement (Refrigerator or
Heat Pump)
 3rd law –Entropy

Fortunately, there is no mathematical proof for any of these laws, but they are deduced from
experimental observations.

Thermodynamic System
A thermodynamic system is defined as a quantity of matter or a region in space upon which
attention is concentrated in the analysis of a problem.

Everything external to the system is called the surroundings or environment.

System is separated from its surroundings by the system boundary, which may be either fixed
or moving.

A system and its surroundings together comprises the universe.

Types of Thermodynamic Systems

Thermodynamic systems are classified into three types, viz.

1. Closed System
2. Open System
3. Isolated System

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ME 010 506 Thermodynamics Module 1

Properties Of A System
Characteristics of a system by which its physical condition can be described are called as the
properties of the system. Eg. Volume, Temperature, Pressure, etc.

State Of A System
When all properties of a system have definite values, the system is said to exist at a definite state.

Change of State
Any operation in which one or more properties of a system changes is called a change of state of
the system.

Path
The succession of states passed through during a change of state is called as the path of the
change of state.

Process
When the path is completely specified, the change of state is called a process

Thermodynamic Cycle
It is defined as a series of state changes such that the final state is identical to the initial state.

Types of Properties

Properties

Intensive Extensive

Intensive properties are independent of the mass of the system eg. Pressure, temperature, etc.

Extensive properties are dependent of the mass of the system eg. Volume, energy etc. If the
mass is increased, the values of extensive properties also increases.

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ME 010 506 Thermodynamics Module 1

Specific extensive properties (extensive properties per unit mass) are also intensive properties.
Eg. Specific volume (m3/kg) specific energy (J/kg) etc.

Macroscopic and Microscopic Analysis

In Macroscopic approach, a certain quantity of matter is considered, without the events occurring
at the molecular level being taken into account. Macroscopic thermodynamics is only concerned
with the effects of the action of many molecules and these effects can be perceived by human
senses.

In Microscopic approach, matter is composed of many molecules. Each molecule at a given

instant has a certain position, velocity and energy (in the case of a gas) and for each molecule
these change very frequently as a result of molecular collisions. The behavior of the gas is then
described by summing up the behavior of each molecule.

Continuum
Google gives the definition of continuum as “a continuous sequence in which adjacent elements
are not perceptibly different from each other, but the extremes are quite distinct.”

In thermodynamics, matter is made up of atoms that are widely spaced in the gas phase. Yet it is
very convenient to disregard the atomic nature of a substance and view it as a continuous,
homogeneous matter with no holes, that is, a continuum.

The continuum idealization allows us to treat properties as point functions and to assume the
properties vary continually in space with no jump discontinuities. This idealization is valid as
long as the size of the system we deal with is large relative to the space between the molecules.

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Thermodynamic Equilibrium
A system is said to exist in a state of thermodynamic equilibrium when no change in any
macroscopic property is registered, when the system is isolated from its surroundings. An
isolated system always reaches a state of thermodynamic equilibrium in the course of time and
can never depart from it spontaneously.

A system is in a state of thermodynamic equilibrium, if the following three types of equilibria are
satisfied.

a) Mechanical Equilibrium
When there are no unbalanced forces within the system and between the system and
surroundings, the system is said to be in a state of mechanical equilibrium.
b) Chemical Equilibrium
If there is no chemical reaction or transfer of matter from one part of the system to
another, the system is said to exist in a state of chemical equilibrium
c) Thermal Equilibrium
When a system existing in mechanical and chemical equilibrium is separated from its
surroundings by a diathermic wall, and if there is no spontaneous change in any property
of the system, the system is said to exist in a state of thermal equilibrium.

Quasi-Static Process
In thermodynamics, a quasistatic process is a thermodynamic process that happens "infinitely
slowly". No real process is quasistatic, but such processes can be approximated by performing
them very slowly. Any reversible process is necessarily a quasistatic one.

Consider a system of gas contained in a cylinder. The system initially is in equilibrium state. The
weight on the piston just balances the upward force exerted by the gas. If the weight is removed,
there will be an unbalanced force between the system and surroundings, and under gas pressure,
the piston will move up till it hits the stops. The system again comes to an equilibrium state,
being described by the properties p2, v2, t2. But the intermediate states passed through by the
system are non-equilibrium states which cannot be described by thermodynamic coordinates.
Now if the single weight on the piston is made up of many very small pieces of weights and
these weights are removed one by one very slowly from the top of the piston, at any instant of
the upward travel of the piston, the departure of the state of the system from the thermodynamic
equilibrium state will be infinitesimally small. So every state passed through by the system will
be an equilibrium state. Such a process, which is but locus of all the equilibrium points passed
through by the system is known as a quasi-static process.

Infinite slowness is the characteristic feature of a quasi-static process. A quasi static process is a
succession of equilibrium states.

“Quasi” means “almost”

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Laws of Perfect Gases

Boyle’s Law
Boyle's Law, published in 1662, states that, at constant temperature, the product of the pressure
and volume of a given mass of an ideal gas in a closed system is always constant.

1
𝑝∝
𝑉

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Charles’s Law
Charles' Law, or the law of volumes, was found in 1787 by Jacques Charles. It states that, for a
given mass of an ideal gas at constant pressure, the volume is directly proportional to its absolute
temperature, assuming a closed system.

𝑉∝𝑇

Gay-Lussac's Law
Gay-Lussac's Law, or the Pressure Law, was found by Joseph Louis Gay-Lussac in 1809. It
states that, for a given mass and constant volume of an ideal gas, the pressure exerted on the
sides of its container is directly proportional to its absolute temperature.

𝑝∝𝑇

Avogadro's Law
Avogadro's Law states that the volume occupied by an ideal gas is directly proportional to the
number of molecules of the gas present in the container. The relation is given by

𝑉1 𝑉2
=
𝑛1 𝑛2

Where n is equal to the number of molecules of gas (or the number of moles of gas)

Combined and Ideal Gas Laws

The Combined Gas Law or General Gas Equation is obtained by combining the three preceding
gas laws, and shows the relationship between the pressure, volume, and temperature for a fixed
mass (quantity) of gas:

𝑝1 𝑉1 𝑝2 𝑉2
=
𝑇1 𝑇2

With the addition of Avogadro's Law, the combined gas law develops into the Ideal Gas Law:

𝑝𝑉 = 𝑛𝑅𝑇

Where,

 p is pressure
 V is volume
 n is the number of moles
 R is the universal gas constant (8.314 J/mol.K)
 T is temperature (K)

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ME 010 506 Thermodynamics Module 1

PVT System
All the possible states of an ideal gas can be represented by a PVT surface as illustrated below.
The behavior when any one of the three state variables is held constant is also shown.

Real Gas Relations

The ideal gas equation follows two important assumptions.

1. There is little or no attraction between molecules of the gas

2. The volume occupied by the molecules themselves is negligible small compared to the
volume of the gas.

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When the pressure is very small or temperature is very large, the intermolecular attraction and
the volume of the molecules compared to the total volume of the gas are not of much
significance, and the real gas obeys very closely the ideal gas equation.

But as pressure increases, the intermolecular forces of attraction and repulsion increase and also
the volume of the molecules becomes appreciable compared to the total gas volume. Then the
real gases deviate considerably from the ideal gas equation.

Van der Waals introduced two correction terms in the equation of the ideal gas by applying the
laws of mechanics to individual molecules.
𝑎
(𝑝 + ) (𝑣 − 𝑏) = 𝑅𝑇
𝑣2
The coefficient “a” was introduced to account for the existence of mutual attraction between the
molecules. The term “a/v2” is called the force of cohesion. The coefficient “b” was introduced to
account for the volumes of the molecules and is known as co-volume.

Apart from van der Waals equation, three 2-constant equations of state are those of
𝑅𝑇 𝑎
Berthelot: 𝑝 = 𝑣−𝑏 − 𝑇𝑣2

−𝑎
𝑅𝑇
Dieterici: 𝑝 = (𝑣−𝑏) . 𝑒 (𝑅𝑇𝑣)

𝑅𝑇 𝑎
Redlich-Kwong: 𝑝 = 𝑣−𝑏 − 1
𝑇 ⁄2 𝑣(𝑣+𝑏)

Compressibility Factor
The compressibility factor (𝒁), also known as the compression factor, is the ratio of the molar
volume of a gas to the molar volume of an ideal gas at the same temperature and pressure. It is a
useful thermodynamic property for modifying the ideal gas law to account for the real gas
behavior. In general, deviation from ideal behavior becomes more significant the closer a gas is
to a phase change, the lower the temperature or the larger the pressure
𝑝𝑣
𝑍=
𝑅𝑇
For an ideal gas, Z=1. The magnitude of 𝑍 for a certain gas at a particular pressure and
temperature gives an indication of the extent of deviation of the gas from the ideal gas behavior.

Critical Temperature
Gases become more difficult to liquefy as the temperature increases because the kinetic
energies of the particles that make up the gas also increase. The critical temperature of a
substance is the temperature at and above which vapor of the substance cannot be liquefied, no
matter how much pressure is applied.

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ME 010 506 Thermodynamics Module 1

Law of Corresponding States

According to van der Waals, the theorem of corresponding states (or principle of
corresponding states) indicates that all fluids, when compared at the same reduced temperature
and reduced pressure, have approximately the same compressibility factor and all deviate from
ideal gas behavior to about the same degree.

For a certain gas, the compressibility factor 𝑍 is a function of 𝑝 and 𝑇. And so a plot can be made
of lines of constant temperature on coordinates of p and Z. Form this plot Z can be obtained for
any value of 𝑝 and 𝑇, and the volume can then be obtained from the equation, 𝑝𝑣 = 𝑍𝑅𝑇. The
advantage of using 𝑍 instead of a direct plot of 𝑣 is a smaller range of values in plotting.

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