Basic Thermodynamics Notes Prepared by Prof.V.G.

P Module 01

BASIC THERMODYNAMICS

1. MODULE 01: FUNDAMENTAL CONCEPTS AND DEFINITIONS

1.1 Definition
It is the science of the interactions among the systems and the consequent changes experienced by the
interacting systems. The interactions occur by exchange of heat and/or work. These interactions result
in changes of the properties of the systems. Thus, thermodynamics is the science that deals with the
study of heat and work interactions and their effects on the properties of the interacting systems. It
deals with energy conversion, energy exchange and direction of exchange.

Thermodynamics basically governs the following:

i. Energy and its transformation

ii. Feasibility of processes involved in Energy Transformation
iii. Feasibility of processes involved in Transfer of Energy
iv. Equilibrium processes.

Engineering Thermodynamics: it is the science that deals with design and analysis of practical energy
conversion devices that develop power from heat or do work to produce heat.

1.2 Scope of Thermodynamics

 Thermodynamics is concerned with the states of the system before and after a certain interaction.
 The changes in the properties of the system at the end of the interaction depends upon magnitudes
and direction of interaction and not their rate of occurrence, i.e. if one unit of heat/work is
transferred to a system, the resulting changes in the properties are proportional to the unit of heat
and not to the rate of transfer of heat/work.

1.3 Approaches to study Thermodynamics

Two different approaches are used for study of thermodynamics namely:

i. Macroscopic Approach
ii. Microscopic Approach

Macroscopic Approach: certain amount of matter is considered for study without considering the
events occurring at molecular level. The macroscopic approach to thermodynamics doesn’t require
the understanding of individual particles, this approach is called Classical Thermodynamics.

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Microscopic Approach: in this approach matter is considered to be composed of myriads of

molecules and behavior of matter is described by summing up the behavior of each molecule. This
approach to thermodynamics where the average behavior of large group of particles is considered is
called Statistical Thermodynamics. The differences between the macroscopic and microscopic
approaches has been summarized in the Table 1.1.

Table 1.1 Difference between Macroscopic and Microscopic Approach

Macroscopic Approach Microscopic Approach

In this approach a certain quantity of matter is This approach considers that the systems is
considered without taking into account the made up of a very large numbers of the discrete
events occurring at molecular level. particle known as molecules.

Analysis of macroscopic systems requires Advanced statistical and mathematical

simple mathematical formulae. methods are needed to explain the changes in
the system

The values of the properties of system are their The overall behavior of the matter is predicted
average values. Example: pressure of the gas is by statistically averaging the behavior of
the average value of the pressure exerted by individual molecules. The values of these
millions of individual molecules . energies are constantly changing with time.

Ex: Pressure exerted by Gas in a container is Ex: Temperature of gas at microscopic level is
directly measured by a pressure gauge without a function of velocity of molecules.
considering the action of individual gas
molecules.

Simple approach as few properties are required Complicated approach as large number of
to describe the system. Macroscopic properties variables are required to describe system.
Can be measured and perceived by human Microscopic properties cannot be perceived by
senses human senses.

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Continuum: a continuum is a system whose size is more than the mean free path of the molecules.
A system is said to be a continuum if its size were to be either 10 times greater than the mean free
path or 10 times greater than the mean molecular path.

1.4 Some practical applications of Engineering Thermodynamic systems

1.4.1 STEAM POWER PLANT

Fig 1.1 Schematic of Steam Power Plant

A schematic diagram of the steam power plant is shown in Figure 1.1. High pressure, high
temperature superheated steam leaving the steam generator or boiler does work on the turbine that
drives the electric generator to produce electricity. The low pressure steam from the turbine is
condensed to water in the condenser by transferring the heat from the steam to the cooling water
circulated in the tubes. This low pressure water is then pumped back to the boiler for next cycle of
operations.

The thermodynamic analysis of the steam power plant involves:

a. Amount of fossil fuel that’s to be burned for generation of the steam required to do work on the
turbine. (Rate of Combustion)
b. Pressure and Temperature analysis for design of condenser, super-heater and economizer
devices.
c. Adoption of suitable pumps for pumping out the coolant based on flow rate of steam, design of
heat exchanger systems based on heat transfer rate.
d. Analysis of the exhaust gases that are released by the boiler to do the Environmental Impact
Assessment (EIA) of the overall plant.

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1.4.2 DOMESTIC REFRIGERATOR

A schematic diagram of the refrigerator is shown in the

Figure 1.2. The basic components include evaporator,
compressor, condenser and expansion device. The
evaporator where the refrigerant (working fluid)
evaporates absorbing the latent heat of vaporization is the
coldest part (freezer) of the system. The subsequent
compartments below the freezer are arranged in the order
of decreasing coldness. The cold air being denser flows
down from the freezer to the bottom of the refrigerator. The

Fig.1.2 Schematic of a Domestic Refrigerator warm air being lighter flows upward towards the freezer
and gets cooled again. Thus a natural convection current is
set which maintains the temperature gradient between the top and bottom of the refrigerator. The refrigerant
vapor is condensed with the help of the surrounding air that rises above by natural convection after
absorbing the latent heat of condensation from the refrigerant. After condensation, the refrigerant liquid at
high pressure is reduced to lower pressure of the evaporator by passing through an expansion valve and the
cycle is completed.
a. The thermodynamic analysis of the refrigerator system involves:
b. COP Analysis of refrigerants
c. Selection of suitable design for evaporator, compressor and condenser.
d. Analysis of temperature, pressure, electrical power consumption and mass flow
measurements in the system.
e. Pressure temperature analysis of refrigerants based on application.
f. Power optimization for compressor work.

1.5 Thermodynamic System and Surroundings

1.5.1 System

A thermodynamic system is defined as quantity of matter or region in a space on which the attention
is focused during the thermodynamic analysis of the problem. It is enclosed within an envelope called
system boundary, which can be fixed or moving, Real or imaginary, adiabatic or diathermic.

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1.5.2 Surroundings

The mass or the region external to the system with which it interacts is called the surroundings or the
environment. A system and a surrounding together comprise a universe.

1.5.3 Boundary

The real or the imaginary surface that separates the system form the surroundings is called the
boundary. The of the system can be fixed or movable, real or imaginary, adiabatic or diathermic. The
boundary is the surface that is shared by both system and surroundings, mathematically it has zero
thickness and thus it cannot contain any mass nor volume in space.

Surroundings

System
Boundary

Fig 1.3 Illustration of System, Surrounding and Boundary

1.5.4 Systems and its Types

Systems may be classified into three (Figure 1.4) based on the energy and mass transfer that occurs
across the boundary:

i. Closed systems
ii. Open systems
iii. Isolated systems
 Closed System (Control Mass): a closed system consists of a fixed amount of mass and doesn’t
allow the mass to transfer across its boundary, i.e. no mass can enter nor leave the boundary.
However, energy in the form of heat or work can cross the boundary and the volume of the closed
system isn’t fixed.
Ex: a certain quantity of fluid in a cylinder bounded by a piston constitutes a closed system.
 Open system (Control Volume): the open system is one which allows both the mass and energy
transfer across its boundaries. Most of the engineering devices allows the mass transfer and
energy transfer across a controlled volume as in case of air compressor where the air enters at
lower pressure and exits at higher pressure and also energy transfers across the boundary.
Ex: Water flow through nozzle.

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 Isolated system: the isolated system is one which doesn’t allow the energy as well as mass to be
transferred across its boundary. There is no notable interaction between the system and
surroundings. It’s of fixed mass and energy as there is no mass or energy transfer across the
system boundary.
Ex: Thermos Flask, UNIVERSE.

Fig 1.4 Types of Systems

1.5.5 Homogeneous and Heterogeneous Systems

A system composed of a single phase throughout is called a homogeneous system and a system
composed of one or more phase is known as heterogeneous phase.

1.6 Control Volume and Control Surface

Any arbitrary region of space that is selected for study or
analysis is called a control volume and the boundaries of
a control volume is called a control surface (Figure 1.5).
The characteristics of a control volume are as follows:

i. It can be fixed or moving as in case of a piston cylinder

arrangement.
ii. It can be real or imaginary as in case of a nozzle. It can
also involve heat and work interactions across the control
surface (Figure 1.6).
Fig 1.5 Control Volume and Control
Surface

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Fig 1.6 Types of Boundaries/ Control Surface

1.7 Properties of a System

Any characteristic of a system that are measurable, observable is called its property. Some of the
familiar properties are pressure(p), temperature(T), volume (V), density (ρ), entropy (S) etc. They are
macroscopic in nature, a system with definite values of its properties is said to be in definite state.
Properties are the coordinates to measure the state of the system. Properties of a system can be
classified as:

i. Intensive and Extensive properties

ii. Specific properties
iii. Dependent and Independent properties
iv. Transport properties
 Extensive properties: are those that are dependent on the mass of the system such as volume,
energy, total momentum etc.
 Intensive properties: are those that aren’t dependent on the mass of the system such as
temperature, pressure etc.
 Specific Properties: Extensive properties per unit mass of the system are called specific
properties and are intensive properties. Ex: Specific gravity, specific energy, specific volume etc.
 Independent properties: If a property can be varied at will independently of other properties
then the property is said to be independent property. Temperature & pressure of the gas can be
varied independently.
 Dependent properties: If variation of a particular property affects the other property of the
system, then the property is said to be dependent. In vapor formation temperature at which liquid
boils depends upon pressure, hence temperature depends upon pressure.
 Transport property: property which is a function of time, that defines the rate at which an
interaction can occur. Ex: Viscosity, Thermal conductivity

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1.8 Thermodynamic State and Equilibrium

1.8.1 State
The condition of the system defined by the values of all its
properties at any instant of time is called the state of the
system. It gives the complete description of the system.
Any operations in which one or more properties of the
system changes results in ‘Change of the system’. The
figure illustrated shows the system at two different states
i.e. at different temperatures and volumes which are the
properties of the gas contained in the cylinder. The state of
the system containing a gas at two different properties that
define its state is illustrated in Figure 1.7.
Fig 1.7 State of a system 1.8.2 State Diagram

Process diagrams plotted by employing thermodynamic

properties as coordinates are called the state diagrams. It
represents the state of the system at different instant of time.
The commonly considered state diagrams include the P-V
diagrams and T-s Diagrams. A state diagram for variation of
volume with pressure is shown in Figure 1.8 for a cylinder-
piston system.

Fig 1.8 State Diagram for Cylinder-Piston 1.8.3 Process and Path
System Succession of states passed through during a change of state
of the system is called the path of the system. In the figure illustrated above, the path is the locus of
the point traversed from its state 1 to state 2. Any change in state, the system undergoes from one
state to another is called a process. To describe the process completely the initial and the final states
of the system, path followed and the interactions with the surroundings must be defined.
1.8.4 Thermodynamic Equilibrium
Thermodynamics deals with equilibrium states. Equilibrium implies state of balance. In an
equilibrium state there are no unbalanced potentials within the system. A system in equilibrium
experiences no changes (changes in macroscopic properties) when it is isolated form its surroundings.

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There are many types of equilibrium, and a system is not in thermodynamic equilibrium unless the
conditions of all the relevant types of equilibrium are satisfied. A system is said to be in
thermodynamic equilibrium if the conditions for following equilibriums are satisfied:
1. Mechanical Equilibrium (no unbalanced forces in the system)
2. Chemical Equilibrium (no chemical reaction such as diffusion within the system)
3. Thermal equilibrium (no temperature differential, temperature is same throughout the system)
4. Phase Equilibrium (indifference in the masses of each phase)

 Mechanical Equilibrium:

In the absence of any unbalanced force within the system and also the system and its surroundings
the system is said to be in mechanical equilibrium. Mechanical equilibrium is related to pressure
and a system is said to be in mechanical equilibrium if there is no change in pressure at any point
of the system.

 Chemical Equilibrium

A system is said to be in chemical equilibrium if its chemical composition does not change with
time i.e. no chemical reaction occurs.

 Thermal Equilibrium

A system is in thermal equilibrium if the temperature is the same throughout the entire system
and there is no temperature differential across the system and its surroundings.

 Phase Equilibrium

If a system involves two phases, it is in phase equilibrium when the mass of each phase reaches
an equilibrium level and stays there.

A system is said to be thermodynamic equilibrium if no change in property occurs when it is isolated

from its surroundings, i.e. there would be no unbalanced forces and temperature gradients within the
system, no chemical interaction or phase transfer within the system.

1.8.5 State Postulate

The state of a system is described by its properties. But we know from experience that we do not need
to specify all the properties in order to fix a state. Once a sufficient number of properties are specified,
the rest of the properties assume certain values automatically. That is, specifying a certain number of
properties is sufficient to fix a state.
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The number of properties required to fix the state of a system is given by the state postulate: “The
state of a simple compressible system is completely specified by two independent, intensive
properties”.

A system is called a simple compressible system in the absence of

electrical, magnetic, gravitational, motion, and surface tension effects.
These effects are due to external force fields and are negligible for most
engineering problems. Otherwise, an additional property needs to be
specified for each effect that is significant. If the gravitational effects
are to be considered, for example, the elevation z needs to be specified
in addition to the two properties necessary to fix the state. The state

Fig.1.9 State of N2 is fixed

postulate requires that the two properties specified be independent to
by two independent fix the state. Two properties are independent if one property can be
properties
varied while the other one is held constant. Temperature and specific
volume, for example, are always independent properties, and together they can fix the state of a simple
compressible system (Figure 1.9). Temperature and pressure, however, are independent properties
for single-phase systems, but are dependent properties for multiphase systems. At sea level (P=1 atm),
water boils at 100°C, but on a mountain top where the pressure is lower, water boils at a lower
temperature. That is, T=f(P) during a phase-change process; thus, temperature and pressure are not
sufficient to fix the state of a two-phase system.

1.8.6 Phase

When a substance is of the same nature throughout its mass, then it is said to be in phase. Based on
the phase the thermodynamic system is classified into Homogeneous (same mass composition) and
Heterogeneous (different mass composition) systems. Oxygen cylinder and an air fuel mixture in
combustion chamber are the respective examples.

1.8.7 Two Property Rule

If two independent properties of a pure substance are defined, then all the other properties or the state
of the substance is also defined. If the state of the system is known, then the phase or the mixture of
the phases is also known.

1.9 Process and its Types

Any change that a system undergoes from one equilibrium state to another is called a process.
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Types of Processes:

i. Isothermal Process: the process is carried out a constant temperature.

ii. Isochoric process: the process is carried out a constant volume.
iii. Isobaric process: the process is carried out a constant pressure.
iv. Adiabatic process: the process is said to be adiabatic if the process occurs within the system
enclosed by an adiabatic wall.
v. Isentropic: the process is carried out at constant entropy.
vi. Isenthalpic: the process is carried out at constant enthalpy.
vii. Reversible process: the process is said to be reversible if the system and its surroundings are
restored to their respective initial states by reversing the process.
viii. Irreversible process: the process is irreversible if the initial states of the system and
surroundings cannot be restored by reversing the process.
ix. Cyclic Process: a cyclic process is a series of state changes with the initial and final state being
identical. Ex: Carnot Cycle
x. Non-Cyclic Process: a cyclic process is a series of state changes with the initial and final state
not being identical. Ex: Boiling of water

In the Figure 1.10a, Process path is given as 1-A-2-B. The process is cyclic if state of 1 is same after
the cycle is completed and is non-cyclic if state 1 changes at the end of the process from its initial
state. Figure 1.10b different processes represented on P-v diagram.

Fig.1.10b Types of Process on a P-v Diagram

Fig.1.10a Process-Cyclic and Non-cyclic

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1.10 Quasi-Static Process

Quasi means ‘almost’, thus it literally means almost a static process.

A quasi-static process is one that that takes place infinitely slowly so that the system passes
successively through equilibrium states. When a process proceeds in such a manner that the system
remains infinitesimally close to an equilibrium state at all times, it is called a quasistatic, or quasi-
equilibrium process.

Characteristics of a Quasi-Static Process:

 The departure of the state of the system from the thermodynamic equilibrium state will be
infinitesimally small.
 It is a succession of equilibrium states
 It is a reversible process
 It can be represented as a continuous line on a state diagram
 Infinite slowness is the main feature of the system

A quasi-equilibrium process is an idealized process and is not a true representation of an actual

process. But many actual processes closely approximate it, and they can be modeled as a quasi-
equilibrium process with negligible error. Engineers are interested in quasi-equilibrium processes for
two reasons. First, they are easy to analyze; second, work-producing devices deliver the most work
when they operate on quasi-equilibrium processes. Therefore, quasi-equilibrium processes serve as
standards to which actual processes can be compared.

Example of a Quasi-static process:

Fig. 1.11 Sudden and Quasi-static expansion of a Gas Fig. 1.12 Representation of a Quai-Static Process

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Consider a system of gas contained in a cylinder as shown in Figure 1.11. the system initially is at
equilibrium state represented by the properties p1, v1, T1. The weight (W) 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 the surroundings and the piston shall move upwards until it hits the stoppers.
The system again comes to equilibrium state with the properties being p2, v2, T2. The intermediate
states passed by the system are non-equilibrium states that cannot be described the thermodynamic
co-ordinates. The states 1 and 2 cannot be joined by a continuous line but a dotted line. Now if the
single weight on the piston is made up of many small pieces of weights as shown in Figure 1.11, and
these weights are removed one by one very slowly from the top of the piston, at any instant of upward
travel of the piston, if the gas system is isolated, the departure of the system from the thermodynamic
equilibrium state shall be infinitesimally small. So every state passed through by the system will be
in equilibrium state, such a process which is locus of all the equilibrium points passed through by the
system is known as a quasi-static process and can be represented as a continuous line on the state
diagram as shown in Figure 1.12.

1.11 Units and Dimensions

The system International (SI) system of units shall be used. Some of the basic units in this system are
given in Table 1.2. The standard list of multipliers used are given in Table 1.3.

Table 1.2 Basic Units Table 1.3 Standard Multipliers

Quantity Unit Symbol
Length (L) Metre M Factor Prefix
Mass (M) Kilogram kg 1012 tera, T
Time (t) Seconds s 109 giga, G
Temperature Kelvin K 106 mega, M
Amount of Substance Mole mol 103 kilo, K
Electric Current Ampere A 10-3 milli, m
Luminous Intensity Candela Cd 10-6 micro, μ
Plane Angle Radian Rad 10-9 nano, n
Solid Angle Steradian sr 10-12 pico, p

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1.12 Pressure
It is the normal component of the force exerted by the fluid against the unit area of the bounding
surface. SI unit for pressure is Pascal (Pa) which is the force of 1Newton (N) acting on an area of
1m2. Two other units not within the SI system of units used for measurement of pressure are:

 1bar =105Pa or 100kPa or 0.1MPa

 1atm=101.325kPa = 1.01325bar
1. Absolute Pressure: The pressure of a system measured with respect to zero datum (absolute
vacuum) is called the absolute pressure.
2. Gauge Pressure: when the absolute pressure of a system is greater than the atmospheric pressure
the difference between the absolute pressure and the atmospheric pressure is called the gauge
pressure of the system.
Pgauge=Paboslute - Patm
3. Vacuum Pressure: when the absolute pressure of a system is less than the atmospheric pressure
the difference between the atmospheric pressure and the absolute pressure is called the vacuum
pressure.
Pvaccum = Patm - Pabsolute

Pgauge
Atmospheric Pressure

Pvac
Pabs

Patm

Patm Pabs

Zero Pressure
Pabs =Patm +Pgauge Pabs =Patm – Pvac

Fig 1.13 Gauge and Absolute Pressure

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1.12.1 Variation of pressure with depth

Consider a rectangular fluid element of height ∆z, length

∆x and unit depth in equilibrium as shown in Figure
1.14, let 𝜌 be the density of the fluid i.e. constant, a force
balance equation in z-direction gives:

Σ𝐹𝑧=𝑚𝑎𝑧=0

𝑃2.Δ𝑥−𝑃1.Δ𝑥−𝜌𝑔Δ𝑥Δ𝑧=0

Dividing by Δ𝑥 throughout,

𝑃2−𝑃1−𝜌𝑔Δ𝑧=0
If P2-P1=∆P is the change in pressure, then

Δ𝑃−𝜌𝑔Δ𝑧=0
Fig 1.14 Fluid element in Equilibrium
Δ𝑃=𝜌𝑔Δ𝑧

Thus, pressure difference between two points in a constant density fluid is proportional to the vertical
distance between the two points. This vertical distance ∆z is used as a measure of pressure and is
called the vertical head.

1.13 Density and Specific Volume

 Density (𝜌): Mass (m in kg) per unit volume (V in m3), SI Unit is kgm-3

𝜌=𝑚/𝑉 kgm-3

Density of a substance usually depends on temperature and pressure. Density of gases is directly
proportional to pressure and inversely proportional to temperature.

 Specific Volume (v): it’s the reciprocal of density, i.e. the volume per unit mass

𝜗=𝑉/𝑚=1/𝜌 m3kg-1
 Specific Gravity or relative density: ratio of the density of a substance to the density of some
standard substance at a specified temperature.

𝑆𝐺=𝜌/𝜌𝑊𝑎𝑡𝑒𝑟

SG is a dimensionless quantity and its numerical value is exactly equal to its density in kgm-3

 Specific weight is the weight of a unit volume of a substance and is given by 𝛾𝑠=𝜌𝑔

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1.14 Temperature: Zeroth Law of Thermodynamics

Temperature is the property that distinguishes
thermodynamics from other branches of engineering. It is the
measure of degree of Hotness or Coldness of the Body. It’s a
property of a system that determines if the system is in thermal
equilibrium with the other system. When two bodies at
different temperatures are bought into contact with each other,
Fig 1.15 Thermal Equilibrium between they attain a common temperature and continue to exist in
Fe and Cu thermal equilibrium as shown in Figure 1.15.

Zeroth law of Thermodynamics states “If two bodies are in thermal equilibrium with a third body,
they are also in thermal equilibrium with each other, i.e. when a body A is in thermal equilibrium
with body B and also separately with body C, then B and C are said to be in thermal equilibrium with
each other”.

A C
A B

Body A in thermal equilibrium with Body B Body A in thermal equilibrium with Body C

B C

Body B and Body C also in thermal equilibrium

Explanation for Zeroth Law of Thermodynamics:

Consider three systems A, B and C as illustrated in figure such

that A is in thermal equilibrium with C, and B is in thermal
Equilibrium with C. The systems A and B are separated by an
adiabatic wall (transfers only work not heat) and are in
communication with the system C simultaneously through a
diathermic wall (transfers heat across the wall) as shown in
Figure a. After sometime A and B shall reach a thermal
equilibrium with system C. once thermal equilibrium is
reached there shall be no changes in the properties of A and B.
at this instant if the adiabatic and diathermic walls are swapped as shown in figure b, no changes in
properties of A and B shall be observed thereby proving the zeroth law of thermodynamics.

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Significance of Zeroth Law of Thermodynamics:

The significance of this law lies in the fact that it forms the basis for temperature measurement. It’s
not a mathematical proposition but represents the essence of empirical information on temperature
and thermal equilibrium.In the figure above let the system B be melting ice at a standard atmospheric
pressure, system C be a thermometer and System A be the one whose temperature is to be measured.
The temperature of the ice is universally assigned a value of 0℃ on the Celsius scale of the
temperature. When system C is in communication with system B the thermometer after some time
records a reading of 0℃ once the thermal equilibrium between B and C is reached. Now when system
A comes in communication with system C, the thermometer continues to record a reading of 0℃
thereby proving that system A is in thermal equilibrium wit System C. This proves the zeroth law of
thermodynamics.

1.15 Temperature scales

Temperature scales enable us to use a common basis for temperature measurements. All temperature
scales are based on some easily reproducible states such as the freezing and boiling points of water,
which are also called the ice point and the steam point respectively. A mixture of ice and water that
is in equilibrium with air saturated with vapor at 1 atm pressure is said to be at the ice point, and a
mixture of liquid water and water vapor (with no air) in equilibrium at 1 atm pressure is said to be at
the steam point.

i. The temperature scales used in the SI and in the English system today are the Celsius scale in
1948 it was renamed after the Swedish astronomer A. Celsius, and the Fahrenheit scale, named
after the German instrument maker G. Fahrenheit, respectively. On the Celsius scale, the ice and
steam points were originally assigned the values of 0 and 100°C, respectively. The corresponding
values on the Fahrenheit scale are 32 and 212°F. These are often referred to as two-point scales
since temperature values are assigned at two different points.
ii. In thermodynamics, it is very desirable to have a temperature scale that is independent of the
properties of any substance or substances. Such a temperature scale is called a thermodynamic
temperature scale, which is developed later in conjunction with the second law of
thermodynamics. The thermodynamic temperature scale in the SI is the Kelvin scale, named after
Lord Kelvin. The temperature unit on this scale is the kelvin, which is designated by K.
iii. The thermodynamic temperature scale in the English system is the Rankine scale, named after
William Rankine. The temperature unit on this scale is the Rankine, which is designated by R.

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The relation between the three scales of temperature is given by the following equations:

a) The Celsius scale and the Fahrenheit scale are related by the equation:

T (°F) = 1.8T (°C) + 32

b) The Celsius scale is related to the Kelvin Scale by the equation:

T(K) = T (°C) + 273.15

c) The Rankine scale is related to Kelvin Scale by the equation:

T(R) = 1.8 T (K)

d) The Rankine scale is related to Fahrenheit scale by the equation:

T(R) =T(°F) +459.67

1.16 International Fixed Points

Temperature fixed points are well-defined and reproducible states of matter to which precise values
of temperature can be assigned. The International Temperature Scale of 1990 (ITS-90) specifies some
of the following temperature fixed points. Their primary purpose is to serve as standards or reference
temperature in calibrating thermometers in various ranges, these are listed in the table below with
their assigned temperature in degree Celsius.

Equilibrium State T (℃)

Normal Boiling point of Oxygen (Oxygen Point) -182.97
Triple point of water 0.01
Normal Boiling point of water (Steam Point) 100.00
Normal Boiling point of Sulphur (Sulphur point) 444.60
Normal Boiling point of antimony (Antimony point) 630.50
Normal Boiling point of silver (Silver Point) 960.80
Normal boiling point of gold (Gold Point) 1063.00

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1.17 Temperature Measurement- Thermometers

Thermometers are working examples of the zeroth law of thermodynamics. When a substance
receives heat the following effects are observed: Change in volume, Change in pressure, Change in
electric resistance, Change in thermo-electric e.m.f etc. Any of these changes can be used for the
measurement of temperature. The instrument used to measure the temperature by making use of
expansion of a substance is known as thermometer. The substance used is known as thermometric
substance.

1.17.1 Gas Thermometers

A gas thermometer measures temperature by the variation in volume or pressure of a gas. Gas is the
working fluid in such a thermometer and the types of gas thermometers in use include:

i. Constant Volume gas thermometer

ii. Constant Pressure Gas thermometer
i. Constant Volume Gas Thermometer

Construction: It consists of a tiny gas bulb ‘B’ connected to a U-Tube mercury manometer through a
capillary. The bulb contains a mass of permanent gas at a lower pressure, usually Helium or Hydrogen.
The bottom of the manometer is connected to a mercury reservoir through a flexible tube. This
manometer is used to measure the pressure. There is an indicating point marked at the top of the
manometer limb connected to the bulb. The open limb and the mercury reservoir are open to the
atmosphere. The bulb is exposed to the system whose temperature is to be measured.

Operation Principle: This thermometer is based on the principle that at low pressures, the temperature
of a gas is proportional to its pressure at constant volume. That is, the temperature of a gas of fixed
volume varies linearly with pressure at sufficiently low pressures. Then the relationship between the
temperature and the pressure of the gas in the vessel can be expressed as:

T=a + b. P

Where ‘a’ and ‘b’ are constants and their values are determined experimentally. Once ‘a’ and ‘b’ are
known, the temperature of a medium can be calculated from this relation by immersing the rigid
vessel of the gas thermometer into the medium and measuring the gas pressure when thermal
equilibrium is established between the medium and the gas in the vessel whose volume is held
constant.

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 Basic Thermodynamics Notes Prepared by Prof.V.G.P Module 01

Working: The bulb is made to communicate with the system whose temperature is to be measured.
When the bulb attains a thermal equilibrium with the system, the gas at a constant volume with
increased temperature results in the increased pressure (Gay-Lussac Law), the mercury reservoir is
moved up or down until the mercury meniscus in the left limb coincides with the indicating mark.
The difference in the heights between the mercury meniscus in the two limbs ‘h’ is the measure of
the gauge pressure. The absolute pressure of the gas is given by p = p0+ ρgh. This pressure is
proportional to the temperature of the gas which is given by the equation:

273.15 𝑝
𝜃=
𝑃𝑡𝑝

Where ptp is the pressure read by the constant gas volume thermometer while sensing the triple point
of water.

Figure 1.16 Schematic of Constant Volume Gas thermometer

 Merits and De-merits of a Constant Volume Gas Thermometer:

i. More sensitive compared to other thermometers
ii. Can work uniformly over a wide range of temperatures
iii. Since the expansion of glass is negligible when compared to the expansion of the gas the error
due to expansion of glass is negligible.
iv. Not easily portable
v. The construction of constant Volume gas thermometer requires high degree of precision.
vi. Takes some time to measure the temperature, not a quick thermometer
vii. Can measure the temperatures of the bodies which can be bought in contact with the bulb only.

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 Basic Thermodynamics Notes Prepared by Prof.V.G.P Module 01

ii. Constant Pressure Gas Thermometer

It is a thermometer in which the volume occupied by a given mass of gas at a constant pressure is used
to determine the temperature.

1.17.2 Mercury in Glass Thermometer

This consists of a tiny sensing element filled with a certain quantity of mercury. This mercury is in
communication with an evacuated capillary. The thermometric scale is marked on the glass stem
surrounding the capillary. When the sensing element is exposed to a system whose temperature is to be
measured the volume of mercury in the sensing bulb changes and accordingly the mercury level in the
capillary keeps changing and reaches as steady value once the thermal equilibrium is reached. The
temperature of the system is read from the scale. The length of expansion ‘L’ is the thermometric
property.

1.17.3 Resistance Thermometer

The sensing element in this thermometer happens to be a fine platinum resistance wire enclosed in a
suitable glass or metallic tube. Generally, the resistance of the wire selected to be around 100ohm at
0℃. The resistance of the wire at any other temperature t℃ in a restricted calibrated range is assumed
to be given by the relation:

Rt = Ro (1 + a.t + b.t2)
Where Ro is the resistance at 0 and ‘a’ and ‘b’ are calibration constants. The measure of the change in
the resistance is the measure of temperature. The change in resistance is normally measured by
connecting the sensing resistance to the one limb of a Wheatstone bridge as shown in the figure. The
resistors R1, R2 are fixed and the R3 is variable resistance and RT is the resistance of the sensing element
of the resistance thermometer. The bridge is connected to constant voltage source and a galvanometer.

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 Basic Thermodynamics Notes Prepared by Prof.V.G.P Module 01

The bridge is initially balanced by varying resistance R3 such that there is no current flow through the
galvanometer. Then,
𝑅1 𝑅3
=
𝑅2 𝑅𝑇
The value of RT keeps changing with the temperature that is to be measured. Whenever R4 changes there
is an imbalance in the bridge as indicated by the deflection in the galvanometer. This deflection is the
measurement of the temperature.

1.17.4 Thermocouple
A thermocouple circuit made by joining two wires A and B made of dissimilar metals is used to measure
the temperature. Due to the Seebeck effect a net e.m.f is generated in the circuit which depends upon the
difference in the temperature between the hot and cold junctions and is therefore a thermometric property
of the circuit. This e.m.f is measured by a micro voltmeter to a high degree of accuracy. The choice of
metals depends largely on temperature range to be investigated and Copper-constantan, chromel-alumel
and platinum-rhodium are typical combinations in use. The thermocouple is calibrated by measuring the
thermal e.m.f at various known temperatures, the reference in junction being kept at 0℃. The results of
such measurements on most thermocouples is represented by a cubic equation:
ℇ = a + b.t + c.t2+ d.t3

Where ℇ is the thermal e.m.f and the constants a, b, c and d are different for each thermocouple. The
advantage of a thermocouple is that it comes to thermal equilibrium with the system whose temperature
is to be measured quite rapidly as its mass is very small.

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