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CHAPTER 1
Basic Concepts and
Definitions
1.1 INTRODUCTION
Engineering is nothing but the application of knowledge of science and mathematics gained by study,
experience and practice to develop ways to utilize, the materials and forces of nature economically for
the benefit of mankind. The knowledge of engineering science gives solutions to various engineering
problems, which are not necessarily beneficial to mankind. To decide whether our solution is good for
mankind or not, the knowledge of social science and humanities is essential.
Thermodynamics is the study of energy and its transformation. It is one of the most fascinating
branch of science. Thermodynamics discusses the relationship between heat, work and the physical
properties of working substance. It also deals with equilibrium and feasibility of a process. The
science of thermodynamics is based on observations of common experience which have been formulated
into laws which govern the principle of energy conversion. Application of thermodynamic principles
in practical design tasks, may be that of a simple pressure cooker or of a complex chemical plant. The
applications of the thermodynamic laws and principles are found in all fields of energy technology,
say in steam and nuclear power plants, gas turbines, internal combustion engines, air conditioning,
refrigeration, gas dynamics, jet propulsion, compressors, etc. It is really difficult to identify any area
where there is no interaction in terms of energy and matter. It is a science having it’s relevance in
every walk of life. Thermodynamics can be classified as classical thermodynamics and statistical
thermodynamics. The classical thermodynamics is applied in engineering problems.
The word thermodynamics derives from two Greek words “therme” which means “heat” and
“dynamikos” which means “power”.
Thus, study of heat related to matter in motion is called “Thermodynamics”. The study of engineering
thermodynamics is mainly concerned with work producing or utilizing machines such as engines,
turbines and compressors together with working substances used in such machines.
Another definition of thermodynamics is that, it is the science that deals with the various phenomena
of energy transfer and its effects on the physical properties of substances. Energy transfer means
conversion of heat into mechanical work as in the case of internal combustion engines employed in
automobiles.
According to Van Wylen, “Thermodynamics is the science of energy, equilibrium and entropy”
(3 E’S). He treated the subject in such a way that, it deals with energy, matter and the laws governing
their interactions.
Hatsopoulos and Keenan defined the thermodynamics as the “science of states and changes in state
of physical systems and the interactions between systems which may accompany changes in state.”
The thermodynamic principles are embodied in two laws commonly called ‘the first law’ and ‘the
second law’ both of which deals with energy transformations. The first law is nothing but the
restatement of the law of conservation of energy and the second law puts a restriction on certain
possible energy transformations.
2 Basic Thermodynamics
A device involves many substances like gases and vapours while transforming and utilizing the
energy.
The study and analysis of system can be done by considering system in two approaches. One is
called microscopic approach in which the matter i.e. gases and vapour is composed of several molecules
and behaviour each individual molecule is studied and the analysis is applied to collective molecular
action by statistical methods and hence this approach is known as statistical approach or microscopic
study. In statistical approach, average behaviour of molecules based on statistical behaviour of a
system is considered. In the macroscopic approach, a certain quantity of matter composed of large
number of molecules is considered without the events occurring at the molecular level being taken
into account. Generally, we consider the behaviour of finite quantity of matter. This approach is also
known as classical approach.
In general, we can say that macroscopic approach analysis = S (microscopic approach analysis).
1.2 MICROSCOPIC AND MACROSCOPIC DESCRIPTION OF MATTER
There are two approaches in the study of thermodynamics from which the working or behaviour of a
system can be studied.
(1) microscopic or statistical approach.
(2) macroscopic or classical approach.
In microscopic approach, the knowledge of structure of matter is considered and a large number of
variables are needed to describe the state of matter. The matter is composed of several molecules and
behaviour of each individual molecule is studied. Each molecule is having certain position, velocity
and energy at a given instant. The velocity and energy change very frequently due to collision of
molecules. The analysis is made on the behaviour of individual atoms and molecules, for example,
some studies in nuclear physics such as the atomic structure of a fissionable material like uranium.
Example
The gas in a cylinder is assumed to contain a large number of molecules each having same mass and
velocity independent of each other. In order to describe the thermodynamic system in view of
microscopic approach, it is necessary to describe the position of each and every molecule which is
very complicated. Hence, this approach is rarely employed but, has become more important in recent
years. The behaviour of gas is to be described by summing up the behaviour of each molecule.
In macroscopic approach the structure of matter is not considered, in fact it is simple, and only few
variables are used to describe the state of matter. In this approach, a certain quantity of matter
composed of large number of molecules is considered without the events occurring at the molecular
level being taken into account. In this case, the properties of a particular mass of substance, such as
it’s pressure, temperature and volume are analysed. Generally, in engineering, this analysis is used for
study of heat engines and other devices. This method gives the fundamental knowledge for the
analysis of a wide variety of engineering problems.
Example
(1) Consider a piston and cylinder arrangement of an internal
combustion engine as a thermodynamic system. At any instant,
the system has certain volume depending upon the position of
piston. At this volume, different pro-perties such as pressure,
temperature, chemical composition can be easily described.
Fig. 1.1 Piston-cylinder machine
Cylinder
Gas
Piston
Basic Concepts and Definitions 3
(2) Distance measurement in metre.
(3) Time measurement in seconds.
The results of macroscopic thermodynamics are obtained from microscopic study of matter.
For example, consider a cube of 25 mm side and containing a monatomic gas at atmospheric
pressure and temperature.
Suppose, this volume contains 1020
atoms. In order to describe position and velocity of each atom,
three co-ordinates and velocity components are required. Therefore in view of microscopic approach,
at least 6 ´ 1020
equations are required to describe the behaviour of system. Even for a large digital
computer, computation task would become difficult. However, to reduce complexity of the problem,
two approaches have been adopted. In one approach, the average values of all the particles in the
system are considered and the analysis is applied to collective molecular action by statistical methods.
In the other approach, number of variables that can be handled are reduced to few only. Here, the
gross or average effects of many molecules is considered.
1.3 CONCEPT OF CONTINUUM
According to macroscopic point of view, the substance is considered to be continuous and molecules
are considered only in large volumes. The behaviour of individual molecule can be neglected. This
concept is known as “continuum”. The assumption of continuum is best suited for macroscopic
approach where discontinuity at molecular level can be easily ignored as the scale of analysis is quite
large.
1.4 THERMODYNAMIC SYSTEMS
In order to analyse the problem, it is necessary to specify objects which are under consideration. In
thermodynamics, this is done by considering an imaginary envelope around the objects, thereby
restricting the study to a specified region.
A thermodynamic system is defined as a quantity of matter of fixed mass or region in the space
whose volume need not be constant and where energy changes are to be analysed. The attention is
focussed on this region for study. The matter or region in the space is bounded by a closed surface or
wall, which may be actual one (ex: tank containing fluid) or hypothetical one (boundary of some
amount of fluid flowing in a pipe). It may change in shape and size.
Everything external to the system or real/hypothetical boundary is termed as the surroundings or
the environment. The envelope which separates the system and surrounding is called boundary of the
system. The boundary may be either fixed or moving. A system and its surroundings together is
termed as universe.
 Universe = System + Surroundings
Sometimes, a system can be defined as the ‘control system’ and boundary of which may be treated
as ‘control boundary’. The ‘control volume’ is the volume enclosed within this boundary and the
space within the boundary is called ‘control space’.
Consider a piston and cylinder arrangement as a thermodynamic system as shown in figure 1.2.
The gas temperature in the cylinder can be raised by external heating and this causes the piston to
move and also changes the system boundary size. It means, both heat and work crosses boundary of
the system during this process, but the matter that comprises the system can always be identified. It is
essential that position of boundary be specified very carefully. For example, a system in which gas
contained in a cylinder, boundary is to be specified within the cylinder to restrict the system under
consideration to the gas itself.
4 Basic Thermodynamics
Surrounding
Piston
Cylinder
Thermodynamic system
Fig. 1.2 Thermodynamic system
Boundary
Weights
Gas
System
boundary
Thermodynamic
system
If the boundary is located outside the cylinder, the system includes both the gas and the cylinder. In
case of a steam turbine, steam will cross the boundary as it enters and leaves the turbine and it is
desirable to place the boundary outside the turbine.
The thermodynamic systems are classified based on energy and mass interactions of the system
with surroundings or other systems into
(1) closed system (non-flow system)
(2) open system (flow system)
(3) isolated system
1.4.1 Closed System
The closed system is a system of fixed mass. In this system, energy may cross the boundary, and the
total mass within the boundary is fixed. The system and it’s boundary may contract or expand in
volume.
Boundary
Thermodynamic
system
Gas
WEnergy in
Mass interaction = 0
Energy out
Fig. 1.3 Closed System
Surrounding
Example
(1) Boiling water in a closed pan.
(2) Consider gas contained in a cylinder as shown in figure 1.3. The addition of heat to cylinder will
raise the gas temperature and causes the piston to move. This changes the system boundary.
This means, both heat and work crosses the boundary of system. But the original mass of
working substance (gas) remain unchanged.
Q
Basic Concepts and Definitions 5
1.4.2 Open System
The open system is one in which matter crosses the boundary of the system. There may be energy
transfer also. i.e. both energy and mass crosses the boundary of the system. Most of the engineering
devices belongs to this type.
M
boundaryair out
mass
out
energy
out
energy in
system
surrounding
air in Q
Both mass and energy interaction ¹ 0.
mass in
Fig. 1.4 Open system
If the inflow of mass is equal to out flow of mass, then the mass in the system is constant and the
system is known as steady flow system.
Example
(1) Air compressor.
In an air compressor, air enters at low pressure and leaves at high pressure. The working
substance (gas) crosses the boundary of the system. In addition to this mass transfer, heat and
work interactions take place across the system boundary.
(2) Automobile engine.
1.4.3 Isolated System
In an isolated system, neither mass nor energy crosses the system boundary. It is of fixed mass and
energy. The system is not affected by the surrounding i.e. there is no interaction between the system
and surroundings. Ex: flow through pipe.
Flow through pipe
System
Surroundings
Mass and energy interaction = 0
1 2 3 4 5
Fig. 1.5 Isolated system
1.5 CONTROL VOLUME AND CONTROL SURFACE
In a closed system, our attention is focussed on a fixed mass of matter for the analysis, whereas in the
open system, the analysis is concentrated on the region in the space through which matter flows.
The space volume through which matter, momentum and energy flows is termed as ‘control
volume’ and the surface or envelope of this control volume is known as ‘control surface’. Mass,
energy and work (momentum) can flow across the control surface.
work in
6 Basic Thermodynamics
The fluid flows through pipes can be analysed by using the concept of control volume. The control
volume may be stationary or may be contracted/expanded to change in size and position as in the case
of open systems. In closed systems, no mass transfer take place across the control surface.
Consider an air compressor, that involves flow of mass into/out of the device as shown in figure
1.6. For the analysis, it is required to specify a control volume that surrounds the device under
consideration. The surface of the control volume is called control surface. Mass, heat and work can
flow across the control surface.
Fig. 1.6 Air Compressor
Motor
Win
High pressure
air out
Q out
Control surface
(Both mass and
energy transfer across
the control surfaces)
Air compressor
Low pressure air in
1.6 HOMOGENEOUS AND HETEROGENEOUS SYSTEMS
If the substance within the system exists in a single phase like air, steam, liquids then the system is
called Homogeneous system. In these systems, the substance exists in only one phase.
If the substance within the system exists in more than one phase, then the system is called
Heterogeneous. (Ex: water and steam, immiscible, liquids)
1.7 THERMODYNAMIC PROPERTIES
The distinguishing characteristics of a system by which it’s physical condition may be described are
called properties of the system. They describe state of a system. The condition of a system can be
specified by mentioning it’s properties, i.e. the state of a system is described by specifying it’s
thermodynamic coordinates. Ex: temperature, volume, pressure, chemical energy content etc. These
co-ordinates are usually denoted as properties which are macroscopic in nature. The property must
have a definite value when the system is at a particular state and the value of which should not depend
upon the past history of the system.
A property can also be defined as any quantity that depends on state of the system and is independent
of the path by which the system has reached the given state. The change in value of a property is
dependent only on the end states of the system. It’s differential must be exact.
The property which is dependent upon the physical and chemical structure of the substance is
called an internal or thermostatic property.
In classical thermodynamics there are two types of properties:
(i) Intensive property
(ii) Extensive property
Properties which are independent of mass such as pressure and temperature, are known as intensive
properties. Some of the other examples are density, velocity, specific volume.
Basic Concepts and Definitions 7
Properties which are dependent upon mass, such as volume and energy in its various forms are
called extensive properties. Some of the other examples are internal energy etc.
If mass is increased, the values of extensive properties also increases.
Specific extensive properties i.e. extensive properties per unit mass are intensive properties. Ex:
specific volume, specific energy, density etc.
If a property can be varied at will, quite independently of other properties, then the property is
termed as an “independent property”. Ex: Temperature or pressure of a gas can be varied quite
independently of each other.
Some of the properties cannot be varied independently, those properties are termed as dependent
properties. Ex: While discussing vapour formation, temperature at which liquid vapourises depends
on the pressure. Here pressure is an independent property, but temperature is a dependent property.
1.8 THERMODYNAMIC STATE OF A SYSTEM
The state of a system at any instant is it’s condition or
configuration of existence at that instant. The various properties
of a system defines the state of the system. At any equilibrium
condition, the state of a system can be described by few
properties like pressure, temperature, specific volume, internal
energy etc. The state of a system can be represented by a point
on the diagram whose co-ordinates are thermodynamic
properties. When a system changes from one equilibrium state
(state 1) to another (state 2), due to energy interaction, the
system attains a new state which is shown by point ‘2’ on the
property diagram.
Example
Consider a given mass of water, which may become vapour or solid (ice) by heating or cooling. Each
phase of water may exist at different pressures and temperatures or we can say water may exist in
different states.
1.9 THERMODYNAMIC PROCESS
Whenever a system undergoes a change of state, then it is said to execute a process.
When the state of a system is changed by a number of operations
(or one operation) having been carried out on the system, then the
system is said to be undergone a process.
For example, consider a piston and cylinder arrangement in which
some weights are placed on the piston. If one of the weight is removed,
the piston rises and that changes the state of the system. Let P1, V1 be
the initial values of pressure and specific volume, before removing
the weight and P2, V2 are the corresponding values after the system
has attained a new state.
From the diagram, it is clear that pressure decreases and specific
volume increases during the change of state from 1 to 2 or else the
system is said to have undergone a process ‘1-2’.
1
2
Thermodynamic
property A
Fig. 1.7 Property Diagram
Thermo-
dynamic
property
B
2
b
c
a
B
A
1
Fig. 1.8(a)
8 Basic Thermodynamics
If the process goes on slowly that the equilibrium state exists at
every moments, then such a process is called as “Equilibrium
Process” otherwise it is referred as “Non Equilibrium Process”. A
process can change the system from one non-equilibrium state to
another by following a path of non-equilibrium states.
If the properties do not depend on the path followed in reaching
the state, but only on the equilibrium state itself, then the properties
are called “Point functions”. As in the figure 1.8(a), the change in
property ‘A’ between states ‘1’ and ‘2’ is same irrespective of the
path ‘a’, ‘b’ or ‘c’.
If the properties depends on the path followed in reaching the
state, then the properties are called “path functions”.
A Thermodynamic cycle is defined as a series of state changes such that the final and initial states
are same. Here the system in it’s given initial state goes through a number of different state changes
or processes and finally returns to it’s original state. Therefore, at the end of a cycle all the properties
have the same value they had at the original state, i.e. the net change in any property of the system is
zero for a cycle ( dxòÑ = 0).
Thermodynamic processes that are commonly experienced in engineering practice are:
(1) Constant pressure/Isobaric process
(2) Constant volume/Isochoric process
(3) Constant temperature/Iso-thermal process
(4) Reversible adiabatic/Isentropic process
(5) Polytropic process
(6) Throttling process/Iso-enthalpic process
The cycles are classified into
1.10 THERMODYNAMICCYCLE
During change of state, the working substance does not change its chemical composition.
Example
(1) Water circulation in steam power plant
(2) Refrigerant in refrigeration process
Mechanical Cycle
During change of state, the working substance changes its chemical composition.
Example
Automotive engines in which air and fuel mixture is supplied and burnt gases leaves the engine, i.e.
during a cycle, property of the working substance changes or their end states are not same.
1.11 REVERSIBLE AND IRREVERSIBLE PROCESS
A reversible process for a system is an ideal process which once having taken place can be reversed in
such a way that the initial state and all energies transformed during the process can be completely
regained in both systems and surroundings. This process does not leave any net change in the system
or in the surroundings. A reversible process is always, quasi-static.
1P1
P
V1
V
2
V2
P2
Fig. 1.8(b)
Basic Concepts and Definitions 9
Some of the examples for reversible processes are : Motion without friction, expansion or
compression with no pressure difference, heat transfer without temperature gradient, reversible adiabatic
process, etc.
If the process is not reversible, i.e. if the initial state and energies transformed cannot be restored
without net change in the system after the process has taken place, it is called irreversible. This
process leaves traces of changes in the system and environment.
Some of the examples for irreversible processes are: Motion with
friction, free expansion, compression or expansion due to finite pressure
difference, heat transfer with finite temperature gradient, mixing of
nonidentical gases, and all processes which involve dissipative effects.
Consider a process 1-2, i.e. expansion of gas in a cylinder. Let w12 be
the amount of work done and Q12 be the quantity of heat transferred
between system and surrounding.
If it is possible to change the system from state 2 to state 1 by
supplying back w12 and Q12, then process 1-2 is called reversible process.
If there is any change in the requirement of work and heat to bring back
the system from 2 to 1, then the process 1-2 is called “Irreversible process”.
A process is said to occur, when the system undergoes a change of state. The intermediate equilibrium
conditions of the process cannot be defined if it occurs at a faster rate and is difficult to calculate heat
and work transfer for such process.
1.12 QUASI-STATIC PROCESS
If a process take place at a faster rate, then the intermediate conditions cannot be defined. Therefore,
an assumption is made such that the process is taking place at such a rate that the intermediate
conditions can be defined and hence must be represented on a thermodynamic property diagram.
1
2
V
P
Fig. 1.9
1
P
P1
2
V2V1
P2
V
Fig. 1.10(a) Property diagram (transition between
two states)
Fig. 1.10(b) System which may undergo quasi-static
process
Gas
Piston
Weights
A quasi-static process is also known as quasi-equilibrium process in which the process is carried
out in such a manner that, at every instant the system departs only infinitesimally from an equilibrium
state. It is an ideal process in which the system changes very slowly it’s state, under the influence of
infinite simal pressure or temperature difference. Quasi means “almost”. Infinite slowness is the
characteristic feature of this process. It is also a reversible process.
Consider a system of gas contained in a cylinder. Initially at state 1 the system is in equilibrium and
state of the system is represented by the properties P1, V1 and T1. The upward force exerted by the gas
is balanced by weight on the piston. The unbalanced force will set up between system and surrounding
and under gas pressure by removing weights on the piston. As a result, piston will move up and as it
10 Basic Thermodynamics
hits the stops, the system regains equilibrium condition (state 2) and properties of the system are
represented by P2, V2 and T2. State 1 and state 2 are the initial and final equilibrium states. Let us
consider intermediate points between 1 and 2. These points represent the intermediate states passed
through by the system, and are called non-equilibrium states. These non-equilibrium states are not
definable on thermodynamic co-ordinates.
Assume the weight on piston consists of many small pieces and are removed slowly one by one,
the process could be considered as quasi-equilibrium. So every state passed through by the system
will be an equilibrium state.
1.13 THERMODYNAMICEQUILIBRIUM
In the figure shown, 1-2 is a quasi-static process in which at
points a, b, c and d etc., the system is very close to thermodynamic
equilibrium.
It is observed that, in some situations a collection of matter
experiences negligible changes. For example, temperature and
pressure of gas in a tank exposed to atmospheric temperature
will be essentially constant as the instruments measure these
properties are insensitive to fluctuations. So thermodynamic equi-
librium means, the collection of matter (system) experiences no
changes in all it’s properties. In other words, the system is said to
be in thermodynamic equilibrium, when it satisfies mechanical,
thermal and chemical equilibrium conditions.
When a system has no unbalanced force within it and when the force it exerts on it’s boundary is
balanced by external force, then the system is said to be in mechanical equilibrium. It ensures in the
system that pressure is same at all points and does not change with time. It is the state of a system at
which applied forces and developed stresses are fully balanced.
When the system ensures uniform temperature throughout and is equal to the temperature of the
surroundings, the system is said to be in thermal equilibrium. The thermal equilibrium condition in
the system ensures constant temperature at all points in that system and does not change with time.
Chemical equilibrium means, the system is chemically stable and chemical composition will remain
unchanged. There is no chemical reaction or transfer of matter from one part of the system to another.
1.14 TEMPERATURE
Temperature is man’s perceptions of ‘hotness’ or ‘coldness’ of a body. The hot body transfers energy
to the cold body as molecules in it vibrate at a faster rate than that of cold body. The feel of a hot
body is due to the impact of such vibration and energy transfer take place from hot body to the cold
one or fingers of the hand. The ability to transfer energy is taken as the measure of hotness of the
body.
When hot and cold bodies are brought into contact, the hot body becomes cooler and cold body
becomes warmer. After some time, they appear to have same hotness or coldness. It is also seen that,
different materials at the same temperature are appeared to be at different temperature. So it is very
difficult to give the exact definition of temperature. Temperature is a measure of hotness of a body
and may be defined as the ability of the body to transfer energy.
1
2
c
b
a
d
V
Fig. 1.11
P
Basic Concepts and Definitions 11
1.15 EQUALITY OF TEMPERATURE
Because of difficulty in defining temperature, we define equality of temperature. Consider two systems
A and B which are at different temperatures T1 and T2 and are perfectly insulated from surroundings.
When these two systems are in physical contact with each other, there will be heat exchange between
these two systems due to temperature difference and this alters the physical properties like length,
electrical resistance etc. of both the systems. After some period, when both the systems attain thermal
equilibrium condition, no change in physical properties will be observed. It means, both the systems
are at the same temperatures and the concept is known as “Equality of temperature”.
1.16 ZEROTH LAW OF THERMODYNAMICS STATEMENT
When two systems are each in thermal equilibrium with a third
system, they are also in thermal equilibrium with each other.
Consider three systems X, Y and Z. Let ‘X’ is in thermal
equilibrium with ‘Y’ and ‘Y’ is in thermal equilibrium with ‘Z’,
then we can say that, X is in thermal equilibrium with ‘Z’. Thermal
equilibrium means the systems X, Y and Z will be at same
temperature.
This law provides basis for temperature measurement. The temperature of a system may be
determined by bringing it into thermal equilibrium with a thermometer by adopting zeroth law.
This law is useful in comparing the temperature of two systems ‘X’ and ‘Z’ with the help of ‘Y’
(thermometer). This is done without actually bringing ‘X’ and ‘Z’ in contact with each other.
The temperature and it’s conversion factors are as follows:
°R = °F + 459.67
K = °C + 273.15
K = 1.8°R
where, °R = degree Rankine (absolute degree Fahrenheit)
°F = degree Fahrenheit
K = degree Kelvin (absolute degree Celsius)
The concept of temperature can also be explained by considering two systems ‘A’ and ‘B’ having
any two gases with thermodynamic properties P1, V1 and T1 and P2, V2 and T2 etc. When these two
systems are in communication with each other through an adiabatic wall, thermodynamic properties
of both the systems will remain unchanged even after a long period of time.
When a diathermic wall is placed between two systems, the thermodynamic properties of both the
systems rapidly change till the systems regains equilibrium conditions.
When both the systems are in equilibrium, one property acquires a common numerical value for
both of the systems. This property is called temperature. i.e. If T1 and T2 are the temperatures of
systems A and B, under equilibrium condition T1 become equal to T2.
1.17 TEMPERATURE MEASUREMENTS
A reference system known as “thermometer” is used to measure temperature and the physical property
that changes with temperature is called “thermodynamic property”. Temperature cannot be measured
directly. The change in temperature, causes the thermometric property to vary and this effect is used
as a measure of temperature. Some of the thermometric properties are:
(1) Length of liquid column in a capillary connected to a bulb.
(2) The pressure of a fixed mass of gas kept at constant volume.
X Y
Z
Fig. 1.12
12 Basic Thermodynamics
(3) Electric resistance of a metallic wire.
(4) Emf of a thermocouple.
Some different types of thermometers with their thermometric properties are given below.
Table 1.1 Types of Thermometers
Thermometers Thermometric property Symbol
1. Mercury-glass thermometer Length L
2. Constant pressure gas thermometer Volume V
3. Constant volume gas thermometer Pressure P
4. Electrical resistance thermometer Resistance R
5. Thermocouple Thermal emf E
6. Pyrometers Intensity of radiation J
For temperature measurement, a number of thermometers are available and all of them use different
thermometric properties like length, volume, pressure, resistance, etc.
1.17.1 Liquid Glass Thermometer
These thermometers uses liquids as the thermometric substance and change
in the length of liquid column in the capillary with heat interactions is the
characteristics used for temperature measurement. Usually mercury and
alcohol are used in these type of thermometers. The figure shows mercury in
glass thermometer. It consists of a vertical tube with graduations marked on
it to show the temperature, one end of which is connected to a thermometric
bulb. A small quantity of mercury is filled in a capillary tube. Mercury has
lower specific heat and hence absorbs little heat from the body or source.
When the bulb is brought in contact with a hot system, there is change in
volume of mercury which results in rise or fall of mercury level in the
capillary tube. The length of liquid column is used as a thermometric property
and is a measure of temperature.
Advantages of mercury over other thermometric liquids are:
(1) Lower specific heat, hence absorbs little heat from the source.
(2) It can be conveniently seen in the capillary tube.
(3) It is a good conductor of heat, does not adhere to the wall of tube.
(4) It has uniform coefficient of expansion over a wide range of
temperature.
In liquid-glass thermometer, the variation in temperature may not cause uniform change of properties.
Hence the various thermometers will not indicate the same temperature between ice and steam points
and in some cases they cannot be ignored. In such cases, gas thermometers are used.
1.17.2 Gas Thermometers
These thermometers are more sensitive and uses gaseous thermometric substance like Oxygen, Nitrogen,
Hydrogen, Helium, etc. These gases have high coefficient of expansion and even a small change in
temperature can also be recognised accurately.
Fig. 1.13 Mercury glass
thermometer
Capillary tube
of small
volume
Safety bulb
Bulb of large
volume having
mercury
Thick glass
wall
Basic Concepts and Definitions 13
(i) Constant Volume Gas Thermometers
This thermometer consists of a capillary tube (C), which connects
thermometer bulb with a U-tube manometer. A small amount of
helium gas is contained in the bulb ‘B’. The left limb of manometer
is kept open to atmosphere and can be moved vertically and
mercury level on the right limb can be adjusted so that it just touches
lip ‘L’ of the capillary. The pressure of the gas in the bulb is used as
a thermometric property and is given by
P = Patm + rmh
where, Patm = Atmospheric pressure
rm = density of mercury
When the bulb is brought in contact with the system whose temperature is to be measured, it comes
in thermal equilibrium with the system. The gas in the bulb will be heated and expanded, pushes the
mercury column downward on the right limb. This rises mercury column on the left limb. The flexible
limb is then adjusted so that the mercury again touches the lip ‘L’. The difference in mercury level ‘h’
is recorded and the pressure ‘P’ of the gas in the bulb is estimated. Since the gas volume in the bulb
is constant, from ideal gas equation we can write,
DT =
V
R
DP (Q PV = mRT)
(Q V is constant, R is constant)
DT µ DP
i.e. the temperature rise is proportional to pressure rise.
Since for an ideal gas at constant volume, T µ P
T
Ttp
=
P
Ptp
T = 273.16
P
Ptp
Ttp: Triple point temperature of water
or T = 273.16
0
lim
®
é ù
ê ú
ë ûPtp
P
Ptp
(ii) Constant Pressure Gas Thermometer
This thermometer is very similar to constant volume gas thermometer except change in thermometric
property. In this type, pressure of the gas is kept con-stant and volume is directly proportional to it’s
absolute temperature. It consists of a reservoir ‘R’ which is filled with mercury and is connected to a
silica bulb ‘B’ through a connecting tube. The bulb ‘C’ is called compensating bulb and is connected
with compensating tube and the volume of which is equal to that of connecting tube. The manometer
is usually filled with sulphuric acid.
Initially, the bulbs ‘B’, ‘R’ and ‘C’ are immersed in melting ice. The mercury level in the reservoir
must be zero and the stop valve must be closed. The level of sulphuric acid in the limbs of manometer
Fig. 1.14 Constant volume gas
thermometer
Patm
h
M
B
L
Flexible
tubing
C
14 Basic Thermodynamics
Silica bulb
B
A
Manometer
C R Reservoir
Compensating bulb
Fig. 1.15 Constant pressure gas thermometer
will be same which indicates that the pressure in the bulb ‘B’ and ‘C’ are same. Hence the gas and air
are maintained at same pressure.
Now consider bulb ‘B’ which has definite number of air molecules and bulb ‘C’ and compensating
tube contain same number of molecules of air. If the bulb ‘B’ is placed in a bath whose temperature is
to be measured, then both connecting tube and compensating tubes are maintained at room temperature.
The air in bulb ‘B’ attain temperature equal to the temperature to be measured.
This thermometer is similar to constant volume gas thermometer, but change in volume of gas due
to temperature variation is used as a thermometric property. The height of mercury column, h is kept
constant and the volume of gas is used as a thermometric property.
At the limiting condition of temperature
T = 273.16 ×
V
Vtp
T = 273.16
0
lim
®
æ ö
ç ÷è øVtp
V
Vtp
1.17.3 Thermocouple
When two dissimilar metal wires are joined at their ends and the junctions are maintained at different
temperatures, an emf is generated. By knowing temperature at one junction, other junction temperature
can be measured in terms of emf.
A
1
T1
E B
2
T2
1
T1
A
2
T2
B
Fig. 1.16
When two dissimilar metals A and B are joined at the ends 1 and 2 with their temperatures ‘T1' and
‘T2', produces an emf E.
Then T(E) = 273.16
E
Etp
é ù
ê ú
ë û
where E and Etp are thermometric properties
B
Basic Concepts and Definitions 15
1.17.4 Electric Resistance Thermometer
It was first developed by Siemen in 1871 and is also known as “Platinum
resistance thermo-meter”. It works on the principle of Wheatstone
bridge.
In this thermometer, temperature change causes change in resistance
of a metal wire which is the thermometric property. It may also be
used as a standard for calibrating other thermometers, as it measures
temperature to a high degree of accuracy and is more sensitive.
We can write
R = R0 [1 + At + Bt2
]
where R0 = Platinum wire resistance when it is immersed in melting ice.
A and B = constants
1.18 INTERNATIONALTEMPERATURESCALE
It was adopted at the seventh general conference on weights and measures held in 1927. In 1968,
slight modifications were introduced into the scale and now it is well accepted standard scale of
practice. It is based on a number of fixed and easily reproducible, points that are assigned definite
values of temperatures.
Table 1.2 Temperatures of Fixed Points
Primary Points for the International Practical Temperature Scale of 1968
Temperature °C
Triple point of oxygen –218.78
Normal boiling point of oxygen –182.97
Triple point of water (standard) +0.01
Normal boiling point of water 100.00
Normal boiling point of sulphur 444.6
Normal freezing point of zinc 419.58
Normal melting point of antimony 630.56
Normal melting point of silver 960.80
Normal melting point of gold 1063.00
The means available for measurement and interpolation are as follows:
1. The range from –259.34°C – 0°C
R = R0 [1 + At + Bt2
+ C(t – 100) + t3
]
where R0, A, B and C are the constants obtained by finding resistance at oxygen, ice, steam and
sulphur points respectively.
2. The range from 0°C to 630.74°C
It is also based on platinum resistance thermometer
R = R0 (1 + At + Bt2
)
where R0, A and B are computed by measuring resistance at ice point, steam point and sulphur
point.
3. The range from 630.74°C – 1064.43°C. It is based on measurement of temperature on a standard
platinum against rhodium-platinum thermocouple, in terms of emf.
E = a + bt + ct2
G
Fig. 1.17 Wheat-stone bridge
Galvano-
meter
Resistance
(Platinum)
16 Basic Thermodynamics
where a, b and c are computed from measurements at antimony point, silver point and gold
point.
4. Above 1064.43°C
In this range, the temperature measurement is done by comparing intensity of radiation of any
convenient wave length with intensity of radiation of same wavelength emitted by a black body
at gold point and Planck’s equation is used to measure temperature.
1.19 TEMPERATURE SCALE
To perform the measurement of temperature it is required to set up standards which may be used for
calibration of different thermometers. The boiling and freezing points of water are two such “standards”,
but they do not cover the whole range of temperatures.
The two temperatures scale normally used for temperature measurements are Fahrenheit and Celsius
scales. Until 1954, the Celsius scale was based on two fixed points, ice point and steam point. The ice
point is defined as the temperature of mixture of ice and water which is in equilibrium with saturated
air at 1 atm pressure and is assigned a value of 0°C on Celsius scale and 32°F on Fahrenheit scale.
The steam point is the temperature of water and steam which are in equilibrium at 1 atmospheric
pressure. It is assigned a value of 100°C on Celsius scale and 212°F on Fahrenheit scale.
In 1954, single fixed point method was adopted and Celsius scale was defined in terms of the ideal
gas temperature scale. The triple point of water is used as a single fixed point (triple point means, it is
the state at which solid, liquid and vapour phases of water exist together in equilibrium). The
magnitude of degree is defined in terms of ideal gas temperature scale. A value of 0.01°C is assigned
to triple point of water and steam point is found to be 100.00°C by experimental methods.
The Celsius scale has 100 units between ice and steam points, whereas Fahrenheit scale has 180
units. The absolute temperature scale has only positive values. The absolute Celsius scale is termed as
Kelvin scale and absolute Fahrenheit scale is called as the Rankine scale. The same physical state
represents zero points on both of these absolute scales and gives same values for the ratio of two
temperature values, irrespective of the scale used, i.e.
2
1
æ ö
ç ÷è ø
T
T
Rankine = 2
1
æ ö
ç ÷è ø
T
T
Kelvin
The relationship between these two scales is given by
(1) °F = 32.0 +
9
5
°C
°F = 32.0 + 1.8°C
(2) °R =
9
5
K
°R = 1.8 K
°R = °F + 459.67
K = °C + 273.15
Basic Concepts and Definitions 17
K °C °F °R
2273.15 2000 3632 4091.67
1773.15 1500 2732 3191.67
1273.15 1000 1832 2291.67
773.15 500 932 1391.67
673.15 400 752 1211.67
573.15 300 572 1031.67
473.15 200 392 851.67
373.15 100 212.0 671.67
273.15 0 32.0 491.67
233.15 – 40 –40 419.67
173.15 –100 –148 311.67
Fig. 1.18
Kelvin Scale
This is an absolute scale. The ice point is assigned with a value of 273.15 K and steam point is
assigned with a value of 373.15 K. The triple point of water is 273.16 K.
Rankine Scale
This is also an absolute scale and the corresponding values are:
Ice point – 491.67 R
Steam point – 671.67 R
Triple point of water – 491.69 R
Celsius Scale
On this scale, the freezing point (ice point) corresponds to 0°C, and boiling point is referred as 100°C
(steam point). The scale has 100 divisions between these two, each representing 1°C. The corresponding
triple point of water is 0.01°C.
Fahrenheit Scale
Ice point – 32°F
Steam point – 212°F
Triple point of water – 32.02°F
The scale has 180 divisions each representing 1°F.
1.20 COMPARISON OF TEMPERATURE SCALES
Let us consider a thermometric property ‘L’, such that ‘t’ is in °C and ‘t’ is a linear function of ‘L’.
Then the general equation is
t = AL + B, where A and B are constants for Celsius scale.
At ice point, t = 0°C
L = LI [LI = Thermometric property at ice point]
18 Basic Thermodynamics
Substitute these, in the general equation, we get,
0 = ALI + B
B = –ALI
At steam point, t = 100°C
L = LS
 After substitution, we get
100 = ALs + B
100 = ALs – ALI [B = –ALI]
= A[LS – LI]
A =
100
-S IL L
Now
B = –ALI
B = –
100
-
I
S I
L
L L
Now t = AL + B
Substitute the values of A and B, we get,
t =
100
-S IL L
L +
100-æ ö
ç ÷-è ø
I
S I
L
L L
t =
100
-S IL L
(L – LI)
 t°C =
100( )
( )
-
-
I
S I
L L
L L
Fahrenheit scale;
we know that t = AL + B
At ice point, t = 32°F
L = LI
32 = ALI + B (1)
At steam point, t = 212°F
L = LS
 212 = ALS + B (2)
Solving (1) and (2), we get,
212 = ALS + B
(– )32 = ALI + B
180 = A(LS – LI)
A =
180
( )-S IL L
Basic Concepts and Definitions 19
Substitute the value of ‘A’ in eqn. (1), we get,
32 =
180
( )-S IL L
LI + B
B = 32 –
180
-
I
S I
L
L L
Now t = AL + B
t =
180æ ö
ç ÷-è øS IL L
L + 32 –
180
( )-
I
S I
L
L L
t =
180
-S IL L
(L – LI) + 32
 t °F = 32 + 180
-é ù
ê ú-ë û
I
S I
L L
L L
Similarly for Rankine scale,
T°R =
-é ù
ê ú-ë û
I
S I
L L
L L
× 180 + 491.67
TK =
-é ù
ê ú-ë û
I
S I
L L
L L
× 100 + 273.15
Relation between Celsius and Fahrenheit Scale
We know that,
t°C =
-æ ö
ç ÷-è ø
I
S I
L L
L L
× 100
C
100
t °
=
-æ ö
ç ÷-è ø
I
S I
L L
L L
(1)
also, t°F = 32 + 180
-é ù
ê ú-ë û
I
S I
L L
L L
(2)
from equations (1) and (2), we can write
t°F = 32 + 180
C
100
t °é ù
ê úë û
t°F = 32 +
9
5
t°C
and t°C = (t°F – 32) ×
5
9
20 Basic Thermodynamics
1.21 IDEAL GAS TEMPERATURE SCALE
We know that,
T = 273.16
P
Ptp
× (A)
Suppose a number of measurements were made with different amount of gas in the gas bulb of a
constant volume gas thermometer, depending on the amount of gas in the bulb, the pressure at triple
point (Ptp = 1000, 500, 250, 100 mm of Hg) and system temperature T will change. For different
gases, the graph shown in the figure can be obtained by plotting T verses Ptp. From the graph, it is
clear that, all gases indicate the same temperature as Ptp is decreased and approaches zero.
T
K
373.15
T (steam)
= 373.15 K
Ptp, mm of Hg
Fig. 1.19
0 1000500250
H2
N2
Air
O2
A similar type of test may be made with a constant pressure gas thermo-meter. The values of ‘P’
are taken as 1000 mm of Hg, 500 mm of Hg etc., and in each trial, V and Vtp may be recorded when
the bulb is surrounded by steam condensing at 1 atm and the triple point of water, respectively.
Then, T = 273.16
V
Vtp
Then, plot T v/s P, as shown in figure. It is clear from the experiments that all gases indicates same
value of T as P approaches zero.
Since the real gas in the bulb, behaves like an ideal gas as P ® 0, the ideal gas temperature T can
be defined by using any of these two equations
T = 273.16
0
lim
®
æ ö
ç ÷è øPtp
P
Ptp
or
T = 273.16
0
lim
®
æ ö
ç ÷è øPtp
V
Vtp
T = Ideal gas temperature scale expressed in K.
Formulae Used in Solving Problems
(1) t = AL + B
Basic Concepts and Definitions 21
(2) °R = °F + 459.67
(3) K = °C + 273.15
(4) K = 1.8°R
1.22 NUMERICALPROBLEMS
Problem 1 : In 1701, Newton proposed a linear temperature scale in which the ice point temperature
was taken as 0°N and the human body temperature was taken as 12°N. Find the conversion scale
between Newton scale of temperature and centigrade scale of temperature, if the temperature of
human body in centigrade scale is 37°C.
Solution :
We know that,
t = AL + B (1)
(a) For Newton scale
At Ice point, t = 0°N
L = LI [LI = Thermometric property at ice point]
The equation (1) becomes
0 = A LI + B
B = –ALI
At human body temperature, t = 12°N
L = Lh
[Lh = Thermometric property at human body temperature] Substitute
these values in equation (1)
12 = A × Lh + B
12 = A Lh – A LI [But B = –ALI]
= A [Lh – LI]
 A =
12
-h IL L
Now, B = –A LI
B =
12é ù
-ê ú-ë ûh IL L
LI
 B =
12-
-
I
h I
L
L L
We know that, t°N = AL + B
Substitute the values of ‘A’ and ‘B’
t°N =
12
–
æ ö
ç ÷è øh IL L
L +
12-æ ö
ç ÷-è ø
I
h I
L
L L
 t°N =
12
-h IL L
(L – LI)
22 Basic Thermodynamics
Repeat the same procedure for centigrade scale
At ice point, t = 0°C
L = LI
0 = ALI + B
B = –ALI
At human body temperature, t = 37°C
L = Lh
 37 = ALh + B
= ALh – ALI [B = –ALI]
37 = A[Lh – LI]
 A =
37
-h IL L
B = –ALI
=
37æ ö
-ç ÷-è øh IL L
LI =
37
-
-
I
h I
L
L L
 t°C = AL + B
=
37æ ö
ç ÷-è øh IL L
L +
37æ ö
-ç ÷-è ø
I
h I
L
L L
t°C =
37æ ö
ç ÷-è øh IL L
(L – LI)
Now,
N
C
°
°
t
t
=
12
( )
12
37 37
( )
-
-
=
æ ö
-ç ÷-è ø
I
h I
I
h I
L L
L L
L L
L L
 t°C =
37
12
t°N
 t°C = 3.083 t°N Ans.
Problem 2: A thermometer is calibrated with ice and steam points as fixed points referred to as 0°C
and 100°C respectively. The equation used to establish the scale is t = a loge x + b.
(a) Determine the constants ‘a’ and ‘b’ in terms of xS and xI.
(b) Prove that t°C =
æ ö
ç ÷è ø
æ ö
ç ÷è ø
e
I
S
e
I
x
log
x
100
x
log
x
Basic Concepts and Definitions 23
Solution : The given equation is
t = a loge x + b
At ice point, t = 0°C, x = xI
0 = a loge xI + b
b = – a loge xI
At steam point, t = 100°C, x = xS
100 = a loge xS + b
100 = a loge xS – a loge xI
100 = a loge
S
I
x
x
æ ö
ç ÷è ø
a =
100
log
æ ö
ç ÷è ø
S
e
I
x
x
Ans.
But b = –a loge xI = –
100
log
æ ö
ç ÷è ø
S
e
I
x
x
× xI
b =
100
log
-
æ ö
ç ÷è ø
I
S
e
I
x
x
x
Ans.
Now, t = a loge x + b
t =
100
log
æ ö
ç ÷è ø
S
e
I
x
x
× x +
100
log
-æ ö
ç ÷æ ö
ç ÷ç ÷è øè ø
I
S
e
I
x
x
x
t =
100
log
æ ö
ç ÷è ø
S
e
I
x
x
[loge x – loge xI]
 t°C =
100 log ( / )
log ( / )
e I
e S I
x x
x x
Ans.
Problem 3 : Define a new temperature scale say degree N, in which the freezing and boiling points of
water are 100°N and 300°N respectively. Correlate this temperature scale with centigrade scale.
Solution : We know that t = AL + B (1)
(i) For Newton Scale
24 Basic Thermodynamics
At freezing and boiling points of water,
100 = ALI + B (2)
300 = ALS + B (3)
(3) – (2) gives 200 = A(Ls – LI)
 A =
200
-S IL L
Substitute this value in equation 2, we get,
100 =
200æ ö
ç ÷-è øS IL L
LI + B
B = 100 –
200
-
I
S I
L
L L
 Substitute ‘A’ and ‘B’ in Eqn. (1), we get
t =
200
-S IL L
L + 100 –
200
-
I
S I
L
L L
t°N =
–
–
æ ö
ç ÷è ø
I
S I
L L
L L
200 + 100 Ans.
also we know that
t°C =
-æ ö
ç ÷-è ø
I
S I
L L
L L
100 + 0
 t°N =
-æ ö
ç ÷-è ø
I
S I
L L
L L
2 ´ 100 + 100
t°N = 2 ´ t°C + 100 Ans.
Problem 4 : Define a new temperature scale of °B in which the boiling and freezing points of water
are 500°B and 100°B respectively. Co-relate this temperature scale with centigrade scale of
temperature.
Solution : We know that, t = AL + B
for °B scale, at ice point, t = 100°B
L = LI
100 = ALI + B
B = 100 – ALI
At steam point, t = 500°B
L = LS
500 = ALS + B
500 = ALS + 100 – ALI (Q B = 100 – ALI)
400 = A (LS – LI)
Basic Concepts and Definitions 25
A =
400
-S IL L
 B = 100 –
400æ ö
ç ÷-è øS IL L
LI
 t°B =
400æ ö
ç ÷-è øS IL L
LI + 100 –
400æ ö
ç ÷-è ø
I
S I
L
L L
t°B =
400
-S IL L
(L – LI) + 100 (1)
for °C scale, at ice point, t = 0°C, L = LI
0 = ALI + B
B = –ALI
At steam point, t = 100°C, L = LS
100 = ALS + B
100 = ALS – ALI
 A =
100
-S IL L
B = –
100
-S IL L
LI
t°C =
100
-S IL L
L –
100
-S IL L
LI
t°C =
100
-S IL L
(L – LI) (2)
from equation (1)
t°B =
4 100( )
( )
´ -
-
I
S I
L L
L L
+ 100
 t°B = 4 ´ t°C + 100 Ans.
100( )
where C from equation (2)
( )
-é ù
° =ê ú-ë û
I
S I
L L
t
L L
Problem 5 : A centigrade and Fahrenheit thermometers are both immersed in a fluid, and the
numerical value recorded on both thermometers is same. Determine the temperature of the fluid
expressed as °K and °R and also find that identical value shown by thermometers.
26 Basic Thermodynamics
Solution : Given that, t°C = t°F
Writing °C and °F scale in terms of °K and °R scales, we get
T°K – 273.16 = T°R – 459.17
 T°R – T°K = 459.17 – 273.16
T°R – T°K = 186.54
But, T°R = 1.8 T°K
 1.8 T°K – T°K = 186.54
0.8 T°K = 186.54
T°K =
186.54
0.8
= 233.17°K
 T°K = 233.17°K Ans.
Now T°R = 1.8 T°K
= 1.8 ´ 233.17
T°R = 419.70°R Ans.
We know that T°C = T°K – 273.16
= 233.17 – 273.16
T°C = –39.99 » – 40°C Ans.
and, T°F = T°R – 459.7
= 419.7 – 459.7
T°F = – 40°F Ans.
Problem 6 : Fahrenheit and centigrade thermometers are both immersed in a fluid. If °F reading is
twice that of °C reading, what is the temperature of fluid in terms of °R and °K. (VTU, Aug. 2000)
Solution : For the given condition
T°F = 2 T°C
(T°R – 459.7) = 2 (T°K – 273.16)
1.8 T°K – 459.7 = 2 (T°K – 273.16) [Q T°R = 1.8 T°K]
2 T°K – 1.8 T°K = 546.32 – 459.7
 T°K =
86.62
0.2
= 433.1°K
T°K = 433.1°K
T°R = 1.8 T°K
= 1.8 ´ 433.1
T°R = 779.58°R
Hence temperature of the fluid is
433.1°K or
779.58°R Ans.
Basic Concepts and Definitions 27
Problem 7 : A thermometer using pressure as a thermo metric property gives values of 1.86 and 6.81
at ice and steam point respectively. If ice point and steam point are assigned the values 10 and 120
respectively, determine the temperature corresponding to P = 2.3. The equation corresponding to
temperature is t = a + b ln (P) (VTU, March, 2001)
Solution : Given t = a + b ln (P)
At t = 10, 10 = a + b ln (PI) (1)
At t = 120, 120 = a + b ln (PS) (2)
(2) – (1) gives
110 = b[ln PS – ln PI] = b ln S
I
P
P
 b =
110
ln /S IP P
from eqn (1)
a = 10 – b ln (PI)
= 10 –
110
ln /S IP P
× ln (PI)
 t = 10 –
110 ln( ) 110
ln /
ln
+I
SS I
I
P
PP P
P
P
t = 10 +
110 ln /
ln /
I
S I
P P
P P
given that, PI = 1.86, PS = 6.81, P = 2.3
 t = 10 +
2.3
110 ln
1.86
6.81
ln
1.86
t = 28°C Ans.
Problem 8 : Two Celsius thermometers ‘A’ and ‘B’ agree at the ice point (0°C) and steam point
(100°C) and the related equation is tA = L + m tB + n tB
2
, where tA and tB are thermometer readings
and L, m and n are constants. When both thermometers are immersed in an oil bath, thermometer A
indicates 51°C and B registers 50°C. Determine the reading of A, when B reads 30°C.
(VTU, Feb, 2002)
Solution :
At ice point, tA = tB = 0°C
28 Basic Thermodynamics
At ice point
t = 0°C
K = 1.83
At steam point
t = 100°C
K = 6.5
The two thermometers are related by
tA = L + m tB + n tB
2
0 = L + 0 + 0
L = 0
At steam point, tA = tB = 100°C
 100 = L + m(100) + n(100)2
 100 = 0 + m(100) + 10,000 n (1) [Q L = 0]
Given, when tA = 51°C, while tB = 50°C
51 = 0 + m(50) + n(50)2
51 = 50m + 2500n (2)
Solving equations (1) and (2) for constants m and n
100 = 100m + 10,000n
51 = 50m + 2,500n ´ 2 (multiply by 2)
 100 = 100m + 10,000n
(–)102 = 100m + 5,000n
–2 = 0 + 5000n
n = –4 ´ 10–4
, substitute in any one of equation, we get
102 = 100m + 5,000 (–4 ´ 10–4
)
 m = 1.04
When tB = 25°C
tA = L + m tB + n tB
2
= 0 + 1.04(30) + (–4 ´ 10–4
) (302
)
 tA = 30.84°C Ans.
Problem 9 : The relation between temperature ‘t’ and property ‘K’ on a thermometric scale is given
by t = a 1n k + b. The values of K are found to be 1.83 and 6.5 at the ice point and steam point.
Determine the temperature, when K reads 2.42 on the thermometer. Take temperature values as 0°
and 100°C at ice and steam point respectively
Solution : The given equation is
t = a ln k + b
0 = a ln 1.83 + b (1)
100 = a ln 6.5 + b (2)
(2) – (1) gives
a ln 6.5 – a ln 1.83 = 100 – 0
a =
100
1.267
= 78.92
from (1)
0 = 78.92 1n 1.83 + b
 b = –47.69
Basic Concepts and Definitions 29
We know that
t = a ln k + b
t = 78.92 1n 2.42 + (–47.69)
t = 22.056°C Ans.
Problem 10 : The resistance in the windings of a motor is 78 ohms at room tem-perature (25°C).
When operating at full load under steady conditions, the motor is switched off and the resistance of
windings is found to be 95 ohms. The resistance of windings at temperature t°C is given by Rt = R0[1
+ 0.00393 t], where R0 is the resistance at 0°C. Find the temperature of the coil at full load.
Solution : We know that,
Rt = R0 [1 + 0.00393 t]
At room temperature t = 25°C, resistance Rt = 78 ohms
78 = R0[1 + 0.00393 (25)]
R0 =
78
1.0982
= 71.025
R0 = 71.025 ohm
At full load, Rt = 95 ohms and t = ?
Rt = R0 (1 + 0.00393 t)
95 = 71.025 (1 + 0.00393 t)
t = 85.87°C Ans.
Problem 11 : The equation Rt = R0 (1 + at) is used to a resistance thermometer, in which Rt and R0
are the resistance values at t°C and 0°C respectively. The thermometer is calibrated by immersing in
boiling water (100°C) and boiling sulphur (445°C) and the indicated resistance values are 14.7 ohm
and 29.2 ohm respectively. Determine fluid temperature when resistance thermometer reads 25 ohm.
Solution : When thermometer is immersed in boiling water,
t = 100°C, Rt = 14.7 ohm
 14.7 = R0 [1 + a (100)] (1)
When the same thermometer is immersed in boiling sulphur,
t = 445°C and Rt = 29.2
 29.2 = R0 [1 + a (445)] (2)
By solving equations (1) and (2),
(2)-(1) gives
14.5 = 345 × a × R0
R0 × a = 0.042 [substitute this value in equation (1)]
14.7 = R0 + R0a ´ 100
= R0 + 0.042 ´ 100
 R0 = 10.5
When Rt = 25 ohm, the temperature ‘t’
Rt = R0(1 + at)
30 Basic Thermodynamics
25 = R0 + R0at
25 = 10.49 + 0.042 ´ t
t = 345.47°C Ans.
Problem 12 : The emf of a thermocouple having one junction kept at the ice point and test junction is
at the Celsius temperature t, is given by
e = at + bt2
, where a = 0.2 mv/deg, b = – –5.0 ´ 10–4
mv/deg.
(i)Sketch the graph of e against t.
(ii)Suppose the emf e is taken as a thermometric property and that a temperature scale t1
is defined
by the linear equation t1
= a1
e + b1
such that t1
= 0 at ice point and t1
= 100 at steam point. Find the
numerical values of a1
and b1
and plot a graph of e against t1
.
Solution : The temperature t in terms of emf is given by
e = at + bt2
[Q a = 0.2 mV/deg
b = –5.0 ´ 10–4
mV/deg]
(i) e = 0.2t + (–5.0 ´ 10–4
) t2
At ice point t = 0°C
e = 0 + 0 = 0
e = 0 mV
At steam point t = 100°C
e = 0.2 ´ 100 – 5 ´ 10–4
(100)2
e = 15 mV
The following values are obtained for different values of t.
t°C 0 10 20 30 40 50 60 70 80 90 100
e, mV 0 1.95 3.8 5.55 7.2 8.75 10.2 11.55 12.8 13.95 15
0
2
4
6
10
8
12
14
16
10
t °C
1009080706050403020
e, mV
(ii) The temperature scale t1
can be defined by taking e as the thermometric property
t1
= a1
e + b1
At ice point t1
= 0, e = 0
Basic Concepts and Definitions 31
0 = 0 + b  b1
= 0
At steam point t1
= 100°C, e = 15 [from graph]
100 = a1
´ 15 + 0 [Q b1
= 0]
 a1
=
100
15
= 6.66
 The equation becomes
t1
= 6.66 e + 0
 t1
= 6.66 e
The values of e for different values of t1
are tabulated as follows:
t1
, °C 0 10 20 30 40 50 60 70 80 90 100
e, mV 0 1.5 3.00 4.5 6.00 7.50 9.00 10.5 12.01 13.51 15.00
16
e, mV
00
02
04
06
08
10
12
14
100908010 20 30 40 50 60 70
t 1
°C
Problem 13 : The emf in a thermo couple with test junction at ice point is given by
e = 0.2t – 5 ´ 10–4
t2
mV.
The millivoltmeter is calibrated at ice point and steam points. What will this thermometer read in a
place where gas thermometer reads 50°C (VTU Feb. 2003)
Solution : At freezing or ice point
eI = 0.2 ´ 0 – 5 ´ 10–4
´ 0
= 0 mV
At boiling or steam point eS = 0.2 ´ 100 – 5 ´ 10–4
(1002
)
= 15 mV
At t = 50°C
e = 0.2 ´ 50 – 5 ´ 10–4
(502
)
e = 8.75 mV.
 The temperature ‘t’ can be calculated as
t = 100
e e
e e
é ù-
ê ú
-ë û
I
S I
32 Basic Thermodynamics
= 100
8.75 0
15 0
é ù-
ê ú
-ë û
t = 58.34°C Ans.
Problem 14 : A thermocouple with test junction at t°C on a gas thermometer and cold junction at
0°C gives output emf as per the following relation.
e = 0.20 t – 5 ´ 10–4
t2
, mV
where t is the temperature. The millivoltmeter is calibrated at ice and steam points. What temperature
would this thermometer show when gas thermometer reads 70°C (VTU, Feb. 2004)
Solution : Given e = 0.20 t – 5 ´ 10–4
t2
, mV
At ice point t = 0
eI = 0.20 ´ 0 – 5 ´ 10–4
´ 0 = 0 mV
At steam point, t = 100°C
eS = 0.20 ´ 100 – 5 ´ 10–4
(1002
)
eS = 15 mV
when t = 70°C
e = 0.20 ´ 70 – 5 ´ 10–4
´ 702
= 11.55 mV
when gas thermometer reads 70°C, thermocouple will read
t = 100
æ ö-
ç ÷-è ø
I
S I
e e
e e
=
11.55 0
100
15 0
æ ö-
ç ÷-è ø
t = 77°C Ans.
1.23 REVIEWQUESTIONS
1. Define thermodynamics and state its scope in the energy technology.
2. Distinguish between classical and statistical description of matter.
3. Explain the concept of macroscopic and microscopic view point as applied to stu dy of
thermodynamics.
4. Explain the concept of continuum.
5. What are the different thermodynamic systems? Explain them with examples.
6. Differentiate between
Homogeneous and Heterogeneous systems
Intensive and Extensive properties
Reversible and Irreversible processes
7. Define the following:
Thermodynamic state
Thermodynamic cycle and process
Quasi-static process
8. What do you mean by thermodynamic equilibrium? Explain; how does it differ from thermal
equilibrium.
Basic Concepts and Definitions 33
9. State the concept of temperature and equality of temperature.
10. State and explain zeroth law of thermodynamics.
11. Name and define the law that forms basis for temperature measurement.
12. Define thermometric property and thermometric substance.
13. What are the different types of thermometers used for temperature measurement?
14. Explain a liquid glass type thermometer.
15. Explain the working of a
(i) constant volume gas thermometer
(ii) constant pressure gas thermometer
16. Explain the working of electric resistance thermometer.
17. Establish a correlation between Centigrade and Fahrenheit scales.
18. What do you understand by the ideal gas temperature scale?
19. What is the significance of international temperature scale?

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Temperature scale

  • 1. CHAPTER 1 Basic Concepts and Definitions 1.1 INTRODUCTION Engineering is nothing but the application of knowledge of science and mathematics gained by study, experience and practice to develop ways to utilize, the materials and forces of nature economically for the benefit of mankind. The knowledge of engineering science gives solutions to various engineering problems, which are not necessarily beneficial to mankind. To decide whether our solution is good for mankind or not, the knowledge of social science and humanities is essential. Thermodynamics is the study of energy and its transformation. It is one of the most fascinating branch of science. Thermodynamics discusses the relationship between heat, work and the physical properties of working substance. It also deals with equilibrium and feasibility of a process. The science of thermodynamics is based on observations of common experience which have been formulated into laws which govern the principle of energy conversion. Application of thermodynamic principles in practical design tasks, may be that of a simple pressure cooker or of a complex chemical plant. The applications of the thermodynamic laws and principles are found in all fields of energy technology, say in steam and nuclear power plants, gas turbines, internal combustion engines, air conditioning, refrigeration, gas dynamics, jet propulsion, compressors, etc. It is really difficult to identify any area where there is no interaction in terms of energy and matter. It is a science having it’s relevance in every walk of life. Thermodynamics can be classified as classical thermodynamics and statistical thermodynamics. The classical thermodynamics is applied in engineering problems. The word thermodynamics derives from two Greek words “therme” which means “heat” and “dynamikos” which means “power”. Thus, study of heat related to matter in motion is called “Thermodynamics”. The study of engineering thermodynamics is mainly concerned with work producing or utilizing machines such as engines, turbines and compressors together with working substances used in such machines. Another definition of thermodynamics is that, it is the science that deals with the various phenomena of energy transfer and its effects on the physical properties of substances. Energy transfer means conversion of heat into mechanical work as in the case of internal combustion engines employed in automobiles. According to Van Wylen, “Thermodynamics is the science of energy, equilibrium and entropy” (3 E’S). He treated the subject in such a way that, it deals with energy, matter and the laws governing their interactions. Hatsopoulos and Keenan defined the thermodynamics as the “science of states and changes in state of physical systems and the interactions between systems which may accompany changes in state.” The thermodynamic principles are embodied in two laws commonly called ‘the first law’ and ‘the second law’ both of which deals with energy transformations. The first law is nothing but the restatement of the law of conservation of energy and the second law puts a restriction on certain possible energy transformations.
  • 2. 2 Basic Thermodynamics A device involves many substances like gases and vapours while transforming and utilizing the energy. The study and analysis of system can be done by considering system in two approaches. One is called microscopic approach in which the matter i.e. gases and vapour is composed of several molecules and behaviour each individual molecule is studied and the analysis is applied to collective molecular action by statistical methods and hence this approach is known as statistical approach or microscopic study. In statistical approach, average behaviour of molecules based on statistical behaviour of a system is considered. In the macroscopic approach, a certain quantity of matter composed of large number of molecules is considered without the events occurring at the molecular level being taken into account. Generally, we consider the behaviour of finite quantity of matter. This approach is also known as classical approach. In general, we can say that macroscopic approach analysis = S (microscopic approach analysis). 1.2 MICROSCOPIC AND MACROSCOPIC DESCRIPTION OF MATTER There are two approaches in the study of thermodynamics from which the working or behaviour of a system can be studied. (1) microscopic or statistical approach. (2) macroscopic or classical approach. In microscopic approach, the knowledge of structure of matter is considered and a large number of variables are needed to describe the state of matter. The matter is composed of several molecules and behaviour of each individual molecule is studied. Each molecule is having certain position, velocity and energy at a given instant. The velocity and energy change very frequently due to collision of molecules. The analysis is made on the behaviour of individual atoms and molecules, for example, some studies in nuclear physics such as the atomic structure of a fissionable material like uranium. Example The gas in a cylinder is assumed to contain a large number of molecules each having same mass and velocity independent of each other. In order to describe the thermodynamic system in view of microscopic approach, it is necessary to describe the position of each and every molecule which is very complicated. Hence, this approach is rarely employed but, has become more important in recent years. The behaviour of gas is to be described by summing up the behaviour of each molecule. In macroscopic approach the structure of matter is not considered, in fact it is simple, and only few variables are used to describe the state of matter. In this approach, a certain quantity of matter composed of large number of molecules is considered without the events occurring at the molecular level being taken into account. In this case, the properties of a particular mass of substance, such as it’s pressure, temperature and volume are analysed. Generally, in engineering, this analysis is used for study of heat engines and other devices. This method gives the fundamental knowledge for the analysis of a wide variety of engineering problems. Example (1) Consider a piston and cylinder arrangement of an internal combustion engine as a thermodynamic system. At any instant, the system has certain volume depending upon the position of piston. At this volume, different pro-perties such as pressure, temperature, chemical composition can be easily described. Fig. 1.1 Piston-cylinder machine Cylinder Gas Piston
  • 3. Basic Concepts and Definitions 3 (2) Distance measurement in metre. (3) Time measurement in seconds. The results of macroscopic thermodynamics are obtained from microscopic study of matter. For example, consider a cube of 25 mm side and containing a monatomic gas at atmospheric pressure and temperature. Suppose, this volume contains 1020 atoms. In order to describe position and velocity of each atom, three co-ordinates and velocity components are required. Therefore in view of microscopic approach, at least 6 ´ 1020 equations are required to describe the behaviour of system. Even for a large digital computer, computation task would become difficult. However, to reduce complexity of the problem, two approaches have been adopted. In one approach, the average values of all the particles in the system are considered and the analysis is applied to collective molecular action by statistical methods. In the other approach, number of variables that can be handled are reduced to few only. Here, the gross or average effects of many molecules is considered. 1.3 CONCEPT OF CONTINUUM According to macroscopic point of view, the substance is considered to be continuous and molecules are considered only in large volumes. The behaviour of individual molecule can be neglected. This concept is known as “continuum”. The assumption of continuum is best suited for macroscopic approach where discontinuity at molecular level can be easily ignored as the scale of analysis is quite large. 1.4 THERMODYNAMIC SYSTEMS In order to analyse the problem, it is necessary to specify objects which are under consideration. In thermodynamics, this is done by considering an imaginary envelope around the objects, thereby restricting the study to a specified region. A thermodynamic system is defined as a quantity of matter of fixed mass or region in the space whose volume need not be constant and where energy changes are to be analysed. The attention is focussed on this region for study. The matter or region in the space is bounded by a closed surface or wall, which may be actual one (ex: tank containing fluid) or hypothetical one (boundary of some amount of fluid flowing in a pipe). It may change in shape and size. Everything external to the system or real/hypothetical boundary is termed as the surroundings or the environment. The envelope which separates the system and surrounding is called boundary of the system. The boundary may be either fixed or moving. A system and its surroundings together is termed as universe. Universe = System + Surroundings Sometimes, a system can be defined as the ‘control system’ and boundary of which may be treated as ‘control boundary’. The ‘control volume’ is the volume enclosed within this boundary and the space within the boundary is called ‘control space’. Consider a piston and cylinder arrangement as a thermodynamic system as shown in figure 1.2. The gas temperature in the cylinder can be raised by external heating and this causes the piston to move and also changes the system boundary size. It means, both heat and work crosses boundary of the system during this process, but the matter that comprises the system can always be identified. It is essential that position of boundary be specified very carefully. For example, a system in which gas contained in a cylinder, boundary is to be specified within the cylinder to restrict the system under consideration to the gas itself.
  • 4. 4 Basic Thermodynamics Surrounding Piston Cylinder Thermodynamic system Fig. 1.2 Thermodynamic system Boundary Weights Gas System boundary Thermodynamic system If the boundary is located outside the cylinder, the system includes both the gas and the cylinder. In case of a steam turbine, steam will cross the boundary as it enters and leaves the turbine and it is desirable to place the boundary outside the turbine. The thermodynamic systems are classified based on energy and mass interactions of the system with surroundings or other systems into (1) closed system (non-flow system) (2) open system (flow system) (3) isolated system 1.4.1 Closed System The closed system is a system of fixed mass. In this system, energy may cross the boundary, and the total mass within the boundary is fixed. The system and it’s boundary may contract or expand in volume. Boundary Thermodynamic system Gas WEnergy in Mass interaction = 0 Energy out Fig. 1.3 Closed System Surrounding Example (1) Boiling water in a closed pan. (2) Consider gas contained in a cylinder as shown in figure 1.3. The addition of heat to cylinder will raise the gas temperature and causes the piston to move. This changes the system boundary. This means, both heat and work crosses the boundary of system. But the original mass of working substance (gas) remain unchanged. Q
  • 5. Basic Concepts and Definitions 5 1.4.2 Open System The open system is one in which matter crosses the boundary of the system. There may be energy transfer also. i.e. both energy and mass crosses the boundary of the system. Most of the engineering devices belongs to this type. M boundaryair out mass out energy out energy in system surrounding air in Q Both mass and energy interaction ¹ 0. mass in Fig. 1.4 Open system If the inflow of mass is equal to out flow of mass, then the mass in the system is constant and the system is known as steady flow system. Example (1) Air compressor. In an air compressor, air enters at low pressure and leaves at high pressure. The working substance (gas) crosses the boundary of the system. In addition to this mass transfer, heat and work interactions take place across the system boundary. (2) Automobile engine. 1.4.3 Isolated System In an isolated system, neither mass nor energy crosses the system boundary. It is of fixed mass and energy. The system is not affected by the surrounding i.e. there is no interaction between the system and surroundings. Ex: flow through pipe. Flow through pipe System Surroundings Mass and energy interaction = 0 1 2 3 4 5 Fig. 1.5 Isolated system 1.5 CONTROL VOLUME AND CONTROL SURFACE In a closed system, our attention is focussed on a fixed mass of matter for the analysis, whereas in the open system, the analysis is concentrated on the region in the space through which matter flows. The space volume through which matter, momentum and energy flows is termed as ‘control volume’ and the surface or envelope of this control volume is known as ‘control surface’. Mass, energy and work (momentum) can flow across the control surface. work in
  • 6. 6 Basic Thermodynamics The fluid flows through pipes can be analysed by using the concept of control volume. The control volume may be stationary or may be contracted/expanded to change in size and position as in the case of open systems. In closed systems, no mass transfer take place across the control surface. Consider an air compressor, that involves flow of mass into/out of the device as shown in figure 1.6. For the analysis, it is required to specify a control volume that surrounds the device under consideration. The surface of the control volume is called control surface. Mass, heat and work can flow across the control surface. Fig. 1.6 Air Compressor Motor Win High pressure air out Q out Control surface (Both mass and energy transfer across the control surfaces) Air compressor Low pressure air in 1.6 HOMOGENEOUS AND HETEROGENEOUS SYSTEMS If the substance within the system exists in a single phase like air, steam, liquids then the system is called Homogeneous system. In these systems, the substance exists in only one phase. If the substance within the system exists in more than one phase, then the system is called Heterogeneous. (Ex: water and steam, immiscible, liquids) 1.7 THERMODYNAMIC PROPERTIES The distinguishing characteristics of a system by which it’s physical condition may be described are called properties of the system. They describe state of a system. The condition of a system can be specified by mentioning it’s properties, i.e. the state of a system is described by specifying it’s thermodynamic coordinates. Ex: temperature, volume, pressure, chemical energy content etc. These co-ordinates are usually denoted as properties which are macroscopic in nature. The property must have a definite value when the system is at a particular state and the value of which should not depend upon the past history of the system. A property can also be defined as any quantity that depends on state of the system and is independent of the path by which the system has reached the given state. The change in value of a property is dependent only on the end states of the system. It’s differential must be exact. The property which is dependent upon the physical and chemical structure of the substance is called an internal or thermostatic property. In classical thermodynamics there are two types of properties: (i) Intensive property (ii) Extensive property Properties which are independent of mass such as pressure and temperature, are known as intensive properties. Some of the other examples are density, velocity, specific volume.
  • 7. Basic Concepts and Definitions 7 Properties which are dependent upon mass, such as volume and energy in its various forms are called extensive properties. Some of the other examples are internal energy etc. If mass is increased, the values of extensive properties also increases. Specific extensive properties i.e. extensive properties per unit mass are intensive properties. Ex: specific volume, specific energy, density etc. If a property can be varied at will, quite independently of other properties, then the property is termed as an “independent property”. Ex: Temperature or pressure of a gas can be varied quite independently of each other. Some of the properties cannot be varied independently, those properties are termed as dependent properties. Ex: While discussing vapour formation, temperature at which liquid vapourises depends on the pressure. Here pressure is an independent property, but temperature is a dependent property. 1.8 THERMODYNAMIC STATE OF A SYSTEM The state of a system at any instant is it’s condition or configuration of existence at that instant. The various properties of a system defines the state of the system. At any equilibrium condition, the state of a system can be described by few properties like pressure, temperature, specific volume, internal energy etc. The state of a system can be represented by a point on the diagram whose co-ordinates are thermodynamic properties. When a system changes from one equilibrium state (state 1) to another (state 2), due to energy interaction, the system attains a new state which is shown by point ‘2’ on the property diagram. Example Consider a given mass of water, which may become vapour or solid (ice) by heating or cooling. Each phase of water may exist at different pressures and temperatures or we can say water may exist in different states. 1.9 THERMODYNAMIC PROCESS Whenever a system undergoes a change of state, then it is said to execute a process. When the state of a system is changed by a number of operations (or one operation) having been carried out on the system, then the system is said to be undergone a process. For example, consider a piston and cylinder arrangement in which some weights are placed on the piston. If one of the weight is removed, the piston rises and that changes the state of the system. Let P1, V1 be the initial values of pressure and specific volume, before removing the weight and P2, V2 are the corresponding values after the system has attained a new state. From the diagram, it is clear that pressure decreases and specific volume increases during the change of state from 1 to 2 or else the system is said to have undergone a process ‘1-2’. 1 2 Thermodynamic property A Fig. 1.7 Property Diagram Thermo- dynamic property B 2 b c a B A 1 Fig. 1.8(a)
  • 8. 8 Basic Thermodynamics If the process goes on slowly that the equilibrium state exists at every moments, then such a process is called as “Equilibrium Process” otherwise it is referred as “Non Equilibrium Process”. A process can change the system from one non-equilibrium state to another by following a path of non-equilibrium states. If the properties do not depend on the path followed in reaching the state, but only on the equilibrium state itself, then the properties are called “Point functions”. As in the figure 1.8(a), the change in property ‘A’ between states ‘1’ and ‘2’ is same irrespective of the path ‘a’, ‘b’ or ‘c’. If the properties depends on the path followed in reaching the state, then the properties are called “path functions”. A Thermodynamic cycle is defined as a series of state changes such that the final and initial states are same. Here the system in it’s given initial state goes through a number of different state changes or processes and finally returns to it’s original state. Therefore, at the end of a cycle all the properties have the same value they had at the original state, i.e. the net change in any property of the system is zero for a cycle ( dxòÑ = 0). Thermodynamic processes that are commonly experienced in engineering practice are: (1) Constant pressure/Isobaric process (2) Constant volume/Isochoric process (3) Constant temperature/Iso-thermal process (4) Reversible adiabatic/Isentropic process (5) Polytropic process (6) Throttling process/Iso-enthalpic process The cycles are classified into 1.10 THERMODYNAMICCYCLE During change of state, the working substance does not change its chemical composition. Example (1) Water circulation in steam power plant (2) Refrigerant in refrigeration process Mechanical Cycle During change of state, the working substance changes its chemical composition. Example Automotive engines in which air and fuel mixture is supplied and burnt gases leaves the engine, i.e. during a cycle, property of the working substance changes or their end states are not same. 1.11 REVERSIBLE AND IRREVERSIBLE PROCESS A reversible process for a system is an ideal process which once having taken place can be reversed in such a way that the initial state and all energies transformed during the process can be completely regained in both systems and surroundings. This process does not leave any net change in the system or in the surroundings. A reversible process is always, quasi-static. 1P1 P V1 V 2 V2 P2 Fig. 1.8(b)
  • 9. Basic Concepts and Definitions 9 Some of the examples for reversible processes are : Motion without friction, expansion or compression with no pressure difference, heat transfer without temperature gradient, reversible adiabatic process, etc. If the process is not reversible, i.e. if the initial state and energies transformed cannot be restored without net change in the system after the process has taken place, it is called irreversible. This process leaves traces of changes in the system and environment. Some of the examples for irreversible processes are: Motion with friction, free expansion, compression or expansion due to finite pressure difference, heat transfer with finite temperature gradient, mixing of nonidentical gases, and all processes which involve dissipative effects. Consider a process 1-2, i.e. expansion of gas in a cylinder. Let w12 be the amount of work done and Q12 be the quantity of heat transferred between system and surrounding. If it is possible to change the system from state 2 to state 1 by supplying back w12 and Q12, then process 1-2 is called reversible process. If there is any change in the requirement of work and heat to bring back the system from 2 to 1, then the process 1-2 is called “Irreversible process”. A process is said to occur, when the system undergoes a change of state. The intermediate equilibrium conditions of the process cannot be defined if it occurs at a faster rate and is difficult to calculate heat and work transfer for such process. 1.12 QUASI-STATIC PROCESS If a process take place at a faster rate, then the intermediate conditions cannot be defined. Therefore, an assumption is made such that the process is taking place at such a rate that the intermediate conditions can be defined and hence must be represented on a thermodynamic property diagram. 1 2 V P Fig. 1.9 1 P P1 2 V2V1 P2 V Fig. 1.10(a) Property diagram (transition between two states) Fig. 1.10(b) System which may undergo quasi-static process Gas Piston Weights A quasi-static process is also known as quasi-equilibrium process in which the process is carried out in such a manner that, at every instant the system departs only infinitesimally from an equilibrium state. It is an ideal process in which the system changes very slowly it’s state, under the influence of infinite simal pressure or temperature difference. Quasi means “almost”. Infinite slowness is the characteristic feature of this process. It is also a reversible process. Consider a system of gas contained in a cylinder. Initially at state 1 the system is in equilibrium and state of the system is represented by the properties P1, V1 and T1. The upward force exerted by the gas is balanced by weight on the piston. The unbalanced force will set up between system and surrounding and under gas pressure by removing weights on the piston. As a result, piston will move up and as it
  • 10. 10 Basic Thermodynamics hits the stops, the system regains equilibrium condition (state 2) and properties of the system are represented by P2, V2 and T2. State 1 and state 2 are the initial and final equilibrium states. Let us consider intermediate points between 1 and 2. These points represent the intermediate states passed through by the system, and are called non-equilibrium states. These non-equilibrium states are not definable on thermodynamic co-ordinates. Assume the weight on piston consists of many small pieces and are removed slowly one by one, the process could be considered as quasi-equilibrium. So every state passed through by the system will be an equilibrium state. 1.13 THERMODYNAMICEQUILIBRIUM In the figure shown, 1-2 is a quasi-static process in which at points a, b, c and d etc., the system is very close to thermodynamic equilibrium. It is observed that, in some situations a collection of matter experiences negligible changes. For example, temperature and pressure of gas in a tank exposed to atmospheric temperature will be essentially constant as the instruments measure these properties are insensitive to fluctuations. So thermodynamic equi- librium means, the collection of matter (system) experiences no changes in all it’s properties. In other words, the system is said to be in thermodynamic equilibrium, when it satisfies mechanical, thermal and chemical equilibrium conditions. When a system has no unbalanced force within it and when the force it exerts on it’s boundary is balanced by external force, then the system is said to be in mechanical equilibrium. It ensures in the system that pressure is same at all points and does not change with time. It is the state of a system at which applied forces and developed stresses are fully balanced. When the system ensures uniform temperature throughout and is equal to the temperature of the surroundings, the system is said to be in thermal equilibrium. The thermal equilibrium condition in the system ensures constant temperature at all points in that system and does not change with time. Chemical equilibrium means, the system is chemically stable and chemical composition will remain unchanged. There is no chemical reaction or transfer of matter from one part of the system to another. 1.14 TEMPERATURE Temperature is man’s perceptions of ‘hotness’ or ‘coldness’ of a body. The hot body transfers energy to the cold body as molecules in it vibrate at a faster rate than that of cold body. The feel of a hot body is due to the impact of such vibration and energy transfer take place from hot body to the cold one or fingers of the hand. The ability to transfer energy is taken as the measure of hotness of the body. When hot and cold bodies are brought into contact, the hot body becomes cooler and cold body becomes warmer. After some time, they appear to have same hotness or coldness. It is also seen that, different materials at the same temperature are appeared to be at different temperature. So it is very difficult to give the exact definition of temperature. Temperature is a measure of hotness of a body and may be defined as the ability of the body to transfer energy. 1 2 c b a d V Fig. 1.11 P
  • 11. Basic Concepts and Definitions 11 1.15 EQUALITY OF TEMPERATURE Because of difficulty in defining temperature, we define equality of temperature. Consider two systems A and B which are at different temperatures T1 and T2 and are perfectly insulated from surroundings. When these two systems are in physical contact with each other, there will be heat exchange between these two systems due to temperature difference and this alters the physical properties like length, electrical resistance etc. of both the systems. After some period, when both the systems attain thermal equilibrium condition, no change in physical properties will be observed. It means, both the systems are at the same temperatures and the concept is known as “Equality of temperature”. 1.16 ZEROTH LAW OF THERMODYNAMICS STATEMENT When two systems are each in thermal equilibrium with a third system, they are also in thermal equilibrium with each other. Consider three systems X, Y and Z. Let ‘X’ is in thermal equilibrium with ‘Y’ and ‘Y’ is in thermal equilibrium with ‘Z’, then we can say that, X is in thermal equilibrium with ‘Z’. Thermal equilibrium means the systems X, Y and Z will be at same temperature. This law provides basis for temperature measurement. The temperature of a system may be determined by bringing it into thermal equilibrium with a thermometer by adopting zeroth law. This law is useful in comparing the temperature of two systems ‘X’ and ‘Z’ with the help of ‘Y’ (thermometer). This is done without actually bringing ‘X’ and ‘Z’ in contact with each other. The temperature and it’s conversion factors are as follows: °R = °F + 459.67 K = °C + 273.15 K = 1.8°R where, °R = degree Rankine (absolute degree Fahrenheit) °F = degree Fahrenheit K = degree Kelvin (absolute degree Celsius) The concept of temperature can also be explained by considering two systems ‘A’ and ‘B’ having any two gases with thermodynamic properties P1, V1 and T1 and P2, V2 and T2 etc. When these two systems are in communication with each other through an adiabatic wall, thermodynamic properties of both the systems will remain unchanged even after a long period of time. When a diathermic wall is placed between two systems, the thermodynamic properties of both the systems rapidly change till the systems regains equilibrium conditions. When both the systems are in equilibrium, one property acquires a common numerical value for both of the systems. This property is called temperature. i.e. If T1 and T2 are the temperatures of systems A and B, under equilibrium condition T1 become equal to T2. 1.17 TEMPERATURE MEASUREMENTS A reference system known as “thermometer” is used to measure temperature and the physical property that changes with temperature is called “thermodynamic property”. Temperature cannot be measured directly. The change in temperature, causes the thermometric property to vary and this effect is used as a measure of temperature. Some of the thermometric properties are: (1) Length of liquid column in a capillary connected to a bulb. (2) The pressure of a fixed mass of gas kept at constant volume. X Y Z Fig. 1.12
  • 12. 12 Basic Thermodynamics (3) Electric resistance of a metallic wire. (4) Emf of a thermocouple. Some different types of thermometers with their thermometric properties are given below. Table 1.1 Types of Thermometers Thermometers Thermometric property Symbol 1. Mercury-glass thermometer Length L 2. Constant pressure gas thermometer Volume V 3. Constant volume gas thermometer Pressure P 4. Electrical resistance thermometer Resistance R 5. Thermocouple Thermal emf E 6. Pyrometers Intensity of radiation J For temperature measurement, a number of thermometers are available and all of them use different thermometric properties like length, volume, pressure, resistance, etc. 1.17.1 Liquid Glass Thermometer These thermometers uses liquids as the thermometric substance and change in the length of liquid column in the capillary with heat interactions is the characteristics used for temperature measurement. Usually mercury and alcohol are used in these type of thermometers. The figure shows mercury in glass thermometer. It consists of a vertical tube with graduations marked on it to show the temperature, one end of which is connected to a thermometric bulb. A small quantity of mercury is filled in a capillary tube. Mercury has lower specific heat and hence absorbs little heat from the body or source. When the bulb is brought in contact with a hot system, there is change in volume of mercury which results in rise or fall of mercury level in the capillary tube. The length of liquid column is used as a thermometric property and is a measure of temperature. Advantages of mercury over other thermometric liquids are: (1) Lower specific heat, hence absorbs little heat from the source. (2) It can be conveniently seen in the capillary tube. (3) It is a good conductor of heat, does not adhere to the wall of tube. (4) It has uniform coefficient of expansion over a wide range of temperature. In liquid-glass thermometer, the variation in temperature may not cause uniform change of properties. Hence the various thermometers will not indicate the same temperature between ice and steam points and in some cases they cannot be ignored. In such cases, gas thermometers are used. 1.17.2 Gas Thermometers These thermometers are more sensitive and uses gaseous thermometric substance like Oxygen, Nitrogen, Hydrogen, Helium, etc. These gases have high coefficient of expansion and even a small change in temperature can also be recognised accurately. Fig. 1.13 Mercury glass thermometer Capillary tube of small volume Safety bulb Bulb of large volume having mercury Thick glass wall
  • 13. Basic Concepts and Definitions 13 (i) Constant Volume Gas Thermometers This thermometer consists of a capillary tube (C), which connects thermometer bulb with a U-tube manometer. A small amount of helium gas is contained in the bulb ‘B’. The left limb of manometer is kept open to atmosphere and can be moved vertically and mercury level on the right limb can be adjusted so that it just touches lip ‘L’ of the capillary. The pressure of the gas in the bulb is used as a thermometric property and is given by P = Patm + rmh where, Patm = Atmospheric pressure rm = density of mercury When the bulb is brought in contact with the system whose temperature is to be measured, it comes in thermal equilibrium with the system. The gas in the bulb will be heated and expanded, pushes the mercury column downward on the right limb. This rises mercury column on the left limb. The flexible limb is then adjusted so that the mercury again touches the lip ‘L’. The difference in mercury level ‘h’ is recorded and the pressure ‘P’ of the gas in the bulb is estimated. Since the gas volume in the bulb is constant, from ideal gas equation we can write, DT = V R DP (Q PV = mRT) (Q V is constant, R is constant) DT µ DP i.e. the temperature rise is proportional to pressure rise. Since for an ideal gas at constant volume, T µ P T Ttp = P Ptp T = 273.16 P Ptp Ttp: Triple point temperature of water or T = 273.16 0 lim ® é ù ê ú ë ûPtp P Ptp (ii) Constant Pressure Gas Thermometer This thermometer is very similar to constant volume gas thermometer except change in thermometric property. In this type, pressure of the gas is kept con-stant and volume is directly proportional to it’s absolute temperature. It consists of a reservoir ‘R’ which is filled with mercury and is connected to a silica bulb ‘B’ through a connecting tube. The bulb ‘C’ is called compensating bulb and is connected with compensating tube and the volume of which is equal to that of connecting tube. The manometer is usually filled with sulphuric acid. Initially, the bulbs ‘B’, ‘R’ and ‘C’ are immersed in melting ice. The mercury level in the reservoir must be zero and the stop valve must be closed. The level of sulphuric acid in the limbs of manometer Fig. 1.14 Constant volume gas thermometer Patm h M B L Flexible tubing C
  • 14. 14 Basic Thermodynamics Silica bulb B A Manometer C R Reservoir Compensating bulb Fig. 1.15 Constant pressure gas thermometer will be same which indicates that the pressure in the bulb ‘B’ and ‘C’ are same. Hence the gas and air are maintained at same pressure. Now consider bulb ‘B’ which has definite number of air molecules and bulb ‘C’ and compensating tube contain same number of molecules of air. If the bulb ‘B’ is placed in a bath whose temperature is to be measured, then both connecting tube and compensating tubes are maintained at room temperature. The air in bulb ‘B’ attain temperature equal to the temperature to be measured. This thermometer is similar to constant volume gas thermometer, but change in volume of gas due to temperature variation is used as a thermometric property. The height of mercury column, h is kept constant and the volume of gas is used as a thermometric property. At the limiting condition of temperature T = 273.16 × V Vtp T = 273.16 0 lim ® æ ö ç ÷è øVtp V Vtp 1.17.3 Thermocouple When two dissimilar metal wires are joined at their ends and the junctions are maintained at different temperatures, an emf is generated. By knowing temperature at one junction, other junction temperature can be measured in terms of emf. A 1 T1 E B 2 T2 1 T1 A 2 T2 B Fig. 1.16 When two dissimilar metals A and B are joined at the ends 1 and 2 with their temperatures ‘T1' and ‘T2', produces an emf E. Then T(E) = 273.16 E Etp é ù ê ú ë û where E and Etp are thermometric properties B
  • 15. Basic Concepts and Definitions 15 1.17.4 Electric Resistance Thermometer It was first developed by Siemen in 1871 and is also known as “Platinum resistance thermo-meter”. It works on the principle of Wheatstone bridge. In this thermometer, temperature change causes change in resistance of a metal wire which is the thermometric property. It may also be used as a standard for calibrating other thermometers, as it measures temperature to a high degree of accuracy and is more sensitive. We can write R = R0 [1 + At + Bt2 ] where R0 = Platinum wire resistance when it is immersed in melting ice. A and B = constants 1.18 INTERNATIONALTEMPERATURESCALE It was adopted at the seventh general conference on weights and measures held in 1927. In 1968, slight modifications were introduced into the scale and now it is well accepted standard scale of practice. It is based on a number of fixed and easily reproducible, points that are assigned definite values of temperatures. Table 1.2 Temperatures of Fixed Points Primary Points for the International Practical Temperature Scale of 1968 Temperature °C Triple point of oxygen –218.78 Normal boiling point of oxygen –182.97 Triple point of water (standard) +0.01 Normal boiling point of water 100.00 Normal boiling point of sulphur 444.6 Normal freezing point of zinc 419.58 Normal melting point of antimony 630.56 Normal melting point of silver 960.80 Normal melting point of gold 1063.00 The means available for measurement and interpolation are as follows: 1. The range from –259.34°C – 0°C R = R0 [1 + At + Bt2 + C(t – 100) + t3 ] where R0, A, B and C are the constants obtained by finding resistance at oxygen, ice, steam and sulphur points respectively. 2. The range from 0°C to 630.74°C It is also based on platinum resistance thermometer R = R0 (1 + At + Bt2 ) where R0, A and B are computed by measuring resistance at ice point, steam point and sulphur point. 3. The range from 630.74°C – 1064.43°C. It is based on measurement of temperature on a standard platinum against rhodium-platinum thermocouple, in terms of emf. E = a + bt + ct2 G Fig. 1.17 Wheat-stone bridge Galvano- meter Resistance (Platinum)
  • 16. 16 Basic Thermodynamics where a, b and c are computed from measurements at antimony point, silver point and gold point. 4. Above 1064.43°C In this range, the temperature measurement is done by comparing intensity of radiation of any convenient wave length with intensity of radiation of same wavelength emitted by a black body at gold point and Planck’s equation is used to measure temperature. 1.19 TEMPERATURE SCALE To perform the measurement of temperature it is required to set up standards which may be used for calibration of different thermometers. The boiling and freezing points of water are two such “standards”, but they do not cover the whole range of temperatures. The two temperatures scale normally used for temperature measurements are Fahrenheit and Celsius scales. Until 1954, the Celsius scale was based on two fixed points, ice point and steam point. The ice point is defined as the temperature of mixture of ice and water which is in equilibrium with saturated air at 1 atm pressure and is assigned a value of 0°C on Celsius scale and 32°F on Fahrenheit scale. The steam point is the temperature of water and steam which are in equilibrium at 1 atmospheric pressure. It is assigned a value of 100°C on Celsius scale and 212°F on Fahrenheit scale. In 1954, single fixed point method was adopted and Celsius scale was defined in terms of the ideal gas temperature scale. The triple point of water is used as a single fixed point (triple point means, it is the state at which solid, liquid and vapour phases of water exist together in equilibrium). The magnitude of degree is defined in terms of ideal gas temperature scale. A value of 0.01°C is assigned to triple point of water and steam point is found to be 100.00°C by experimental methods. The Celsius scale has 100 units between ice and steam points, whereas Fahrenheit scale has 180 units. The absolute temperature scale has only positive values. The absolute Celsius scale is termed as Kelvin scale and absolute Fahrenheit scale is called as the Rankine scale. The same physical state represents zero points on both of these absolute scales and gives same values for the ratio of two temperature values, irrespective of the scale used, i.e. 2 1 æ ö ç ÷è ø T T Rankine = 2 1 æ ö ç ÷è ø T T Kelvin The relationship between these two scales is given by (1) °F = 32.0 + 9 5 °C °F = 32.0 + 1.8°C (2) °R = 9 5 K °R = 1.8 K °R = °F + 459.67 K = °C + 273.15
  • 17. Basic Concepts and Definitions 17 K °C °F °R 2273.15 2000 3632 4091.67 1773.15 1500 2732 3191.67 1273.15 1000 1832 2291.67 773.15 500 932 1391.67 673.15 400 752 1211.67 573.15 300 572 1031.67 473.15 200 392 851.67 373.15 100 212.0 671.67 273.15 0 32.0 491.67 233.15 – 40 –40 419.67 173.15 –100 –148 311.67 Fig. 1.18 Kelvin Scale This is an absolute scale. The ice point is assigned with a value of 273.15 K and steam point is assigned with a value of 373.15 K. The triple point of water is 273.16 K. Rankine Scale This is also an absolute scale and the corresponding values are: Ice point – 491.67 R Steam point – 671.67 R Triple point of water – 491.69 R Celsius Scale On this scale, the freezing point (ice point) corresponds to 0°C, and boiling point is referred as 100°C (steam point). The scale has 100 divisions between these two, each representing 1°C. The corresponding triple point of water is 0.01°C. Fahrenheit Scale Ice point – 32°F Steam point – 212°F Triple point of water – 32.02°F The scale has 180 divisions each representing 1°F. 1.20 COMPARISON OF TEMPERATURE SCALES Let us consider a thermometric property ‘L’, such that ‘t’ is in °C and ‘t’ is a linear function of ‘L’. Then the general equation is t = AL + B, where A and B are constants for Celsius scale. At ice point, t = 0°C L = LI [LI = Thermometric property at ice point]
  • 18. 18 Basic Thermodynamics Substitute these, in the general equation, we get, 0 = ALI + B B = –ALI At steam point, t = 100°C L = LS After substitution, we get 100 = ALs + B 100 = ALs – ALI [B = –ALI] = A[LS – LI] A = 100 -S IL L Now B = –ALI B = – 100 - I S I L L L Now t = AL + B Substitute the values of A and B, we get, t = 100 -S IL L L + 100-æ ö ç ÷-è ø I S I L L L t = 100 -S IL L (L – LI) t°C = 100( ) ( ) - - I S I L L L L Fahrenheit scale; we know that t = AL + B At ice point, t = 32°F L = LI 32 = ALI + B (1) At steam point, t = 212°F L = LS 212 = ALS + B (2) Solving (1) and (2), we get, 212 = ALS + B (– )32 = ALI + B 180 = A(LS – LI) A = 180 ( )-S IL L
  • 19. Basic Concepts and Definitions 19 Substitute the value of ‘A’ in eqn. (1), we get, 32 = 180 ( )-S IL L LI + B B = 32 – 180 - I S I L L L Now t = AL + B t = 180æ ö ç ÷-è øS IL L L + 32 – 180 ( )- I S I L L L t = 180 -S IL L (L – LI) + 32 t °F = 32 + 180 -é ù ê ú-ë û I S I L L L L Similarly for Rankine scale, T°R = -é ù ê ú-ë û I S I L L L L × 180 + 491.67 TK = -é ù ê ú-ë û I S I L L L L × 100 + 273.15 Relation between Celsius and Fahrenheit Scale We know that, t°C = -æ ö ç ÷-è ø I S I L L L L × 100 C 100 t ° = -æ ö ç ÷-è ø I S I L L L L (1) also, t°F = 32 + 180 -é ù ê ú-ë û I S I L L L L (2) from equations (1) and (2), we can write t°F = 32 + 180 C 100 t °é ù ê úë û t°F = 32 + 9 5 t°C and t°C = (t°F – 32) × 5 9
  • 20. 20 Basic Thermodynamics 1.21 IDEAL GAS TEMPERATURE SCALE We know that, T = 273.16 P Ptp × (A) Suppose a number of measurements were made with different amount of gas in the gas bulb of a constant volume gas thermometer, depending on the amount of gas in the bulb, the pressure at triple point (Ptp = 1000, 500, 250, 100 mm of Hg) and system temperature T will change. For different gases, the graph shown in the figure can be obtained by plotting T verses Ptp. From the graph, it is clear that, all gases indicate the same temperature as Ptp is decreased and approaches zero. T K 373.15 T (steam) = 373.15 K Ptp, mm of Hg Fig. 1.19 0 1000500250 H2 N2 Air O2 A similar type of test may be made with a constant pressure gas thermo-meter. The values of ‘P’ are taken as 1000 mm of Hg, 500 mm of Hg etc., and in each trial, V and Vtp may be recorded when the bulb is surrounded by steam condensing at 1 atm and the triple point of water, respectively. Then, T = 273.16 V Vtp Then, plot T v/s P, as shown in figure. It is clear from the experiments that all gases indicates same value of T as P approaches zero. Since the real gas in the bulb, behaves like an ideal gas as P ® 0, the ideal gas temperature T can be defined by using any of these two equations T = 273.16 0 lim ® æ ö ç ÷è øPtp P Ptp or T = 273.16 0 lim ® æ ö ç ÷è øPtp V Vtp T = Ideal gas temperature scale expressed in K. Formulae Used in Solving Problems (1) t = AL + B
  • 21. Basic Concepts and Definitions 21 (2) °R = °F + 459.67 (3) K = °C + 273.15 (4) K = 1.8°R 1.22 NUMERICALPROBLEMS Problem 1 : In 1701, Newton proposed a linear temperature scale in which the ice point temperature was taken as 0°N and the human body temperature was taken as 12°N. Find the conversion scale between Newton scale of temperature and centigrade scale of temperature, if the temperature of human body in centigrade scale is 37°C. Solution : We know that, t = AL + B (1) (a) For Newton scale At Ice point, t = 0°N L = LI [LI = Thermometric property at ice point] The equation (1) becomes 0 = A LI + B B = –ALI At human body temperature, t = 12°N L = Lh [Lh = Thermometric property at human body temperature] Substitute these values in equation (1) 12 = A × Lh + B 12 = A Lh – A LI [But B = –ALI] = A [Lh – LI] A = 12 -h IL L Now, B = –A LI B = 12é ù -ê ú-ë ûh IL L LI B = 12- - I h I L L L We know that, t°N = AL + B Substitute the values of ‘A’ and ‘B’ t°N = 12 – æ ö ç ÷è øh IL L L + 12-æ ö ç ÷-è ø I h I L L L t°N = 12 -h IL L (L – LI)
  • 22. 22 Basic Thermodynamics Repeat the same procedure for centigrade scale At ice point, t = 0°C L = LI 0 = ALI + B B = –ALI At human body temperature, t = 37°C L = Lh 37 = ALh + B = ALh – ALI [B = –ALI] 37 = A[Lh – LI] A = 37 -h IL L B = –ALI = 37æ ö -ç ÷-è øh IL L LI = 37 - - I h I L L L t°C = AL + B = 37æ ö ç ÷-è øh IL L L + 37æ ö -ç ÷-è ø I h I L L L t°C = 37æ ö ç ÷-è øh IL L (L – LI) Now, N C ° ° t t = 12 ( ) 12 37 37 ( ) - - = æ ö -ç ÷-è ø I h I I h I L L L L L L L L t°C = 37 12 t°N t°C = 3.083 t°N Ans. Problem 2: A thermometer is calibrated with ice and steam points as fixed points referred to as 0°C and 100°C respectively. The equation used to establish the scale is t = a loge x + b. (a) Determine the constants ‘a’ and ‘b’ in terms of xS and xI. (b) Prove that t°C = æ ö ç ÷è ø æ ö ç ÷è ø e I S e I x log x 100 x log x
  • 23. Basic Concepts and Definitions 23 Solution : The given equation is t = a loge x + b At ice point, t = 0°C, x = xI 0 = a loge xI + b b = – a loge xI At steam point, t = 100°C, x = xS 100 = a loge xS + b 100 = a loge xS – a loge xI 100 = a loge S I x x æ ö ç ÷è ø a = 100 log æ ö ç ÷è ø S e I x x Ans. But b = –a loge xI = – 100 log æ ö ç ÷è ø S e I x x × xI b = 100 log - æ ö ç ÷è ø I S e I x x x Ans. Now, t = a loge x + b t = 100 log æ ö ç ÷è ø S e I x x × x + 100 log -æ ö ç ÷æ ö ç ÷ç ÷è øè ø I S e I x x x t = 100 log æ ö ç ÷è ø S e I x x [loge x – loge xI] t°C = 100 log ( / ) log ( / ) e I e S I x x x x Ans. Problem 3 : Define a new temperature scale say degree N, in which the freezing and boiling points of water are 100°N and 300°N respectively. Correlate this temperature scale with centigrade scale. Solution : We know that t = AL + B (1) (i) For Newton Scale
  • 24. 24 Basic Thermodynamics At freezing and boiling points of water, 100 = ALI + B (2) 300 = ALS + B (3) (3) – (2) gives 200 = A(Ls – LI) A = 200 -S IL L Substitute this value in equation 2, we get, 100 = 200æ ö ç ÷-è øS IL L LI + B B = 100 – 200 - I S I L L L Substitute ‘A’ and ‘B’ in Eqn. (1), we get t = 200 -S IL L L + 100 – 200 - I S I L L L t°N = – – æ ö ç ÷è ø I S I L L L L 200 + 100 Ans. also we know that t°C = -æ ö ç ÷-è ø I S I L L L L 100 + 0 t°N = -æ ö ç ÷-è ø I S I L L L L 2 ´ 100 + 100 t°N = 2 ´ t°C + 100 Ans. Problem 4 : Define a new temperature scale of °B in which the boiling and freezing points of water are 500°B and 100°B respectively. Co-relate this temperature scale with centigrade scale of temperature. Solution : We know that, t = AL + B for °B scale, at ice point, t = 100°B L = LI 100 = ALI + B B = 100 – ALI At steam point, t = 500°B L = LS 500 = ALS + B 500 = ALS + 100 – ALI (Q B = 100 – ALI) 400 = A (LS – LI)
  • 25. Basic Concepts and Definitions 25 A = 400 -S IL L B = 100 – 400æ ö ç ÷-è øS IL L LI t°B = 400æ ö ç ÷-è øS IL L LI + 100 – 400æ ö ç ÷-è ø I S I L L L t°B = 400 -S IL L (L – LI) + 100 (1) for °C scale, at ice point, t = 0°C, L = LI 0 = ALI + B B = –ALI At steam point, t = 100°C, L = LS 100 = ALS + B 100 = ALS – ALI A = 100 -S IL L B = – 100 -S IL L LI t°C = 100 -S IL L L – 100 -S IL L LI t°C = 100 -S IL L (L – LI) (2) from equation (1) t°B = 4 100( ) ( ) ´ - - I S I L L L L + 100 t°B = 4 ´ t°C + 100 Ans. 100( ) where C from equation (2) ( ) -é ù ° =ê ú-ë û I S I L L t L L Problem 5 : A centigrade and Fahrenheit thermometers are both immersed in a fluid, and the numerical value recorded on both thermometers is same. Determine the temperature of the fluid expressed as °K and °R and also find that identical value shown by thermometers.
  • 26. 26 Basic Thermodynamics Solution : Given that, t°C = t°F Writing °C and °F scale in terms of °K and °R scales, we get T°K – 273.16 = T°R – 459.17 T°R – T°K = 459.17 – 273.16 T°R – T°K = 186.54 But, T°R = 1.8 T°K 1.8 T°K – T°K = 186.54 0.8 T°K = 186.54 T°K = 186.54 0.8 = 233.17°K T°K = 233.17°K Ans. Now T°R = 1.8 T°K = 1.8 ´ 233.17 T°R = 419.70°R Ans. We know that T°C = T°K – 273.16 = 233.17 – 273.16 T°C = –39.99 » – 40°C Ans. and, T°F = T°R – 459.7 = 419.7 – 459.7 T°F = – 40°F Ans. Problem 6 : Fahrenheit and centigrade thermometers are both immersed in a fluid. If °F reading is twice that of °C reading, what is the temperature of fluid in terms of °R and °K. (VTU, Aug. 2000) Solution : For the given condition T°F = 2 T°C (T°R – 459.7) = 2 (T°K – 273.16) 1.8 T°K – 459.7 = 2 (T°K – 273.16) [Q T°R = 1.8 T°K] 2 T°K – 1.8 T°K = 546.32 – 459.7 T°K = 86.62 0.2 = 433.1°K T°K = 433.1°K T°R = 1.8 T°K = 1.8 ´ 433.1 T°R = 779.58°R Hence temperature of the fluid is 433.1°K or 779.58°R Ans.
  • 27. Basic Concepts and Definitions 27 Problem 7 : A thermometer using pressure as a thermo metric property gives values of 1.86 and 6.81 at ice and steam point respectively. If ice point and steam point are assigned the values 10 and 120 respectively, determine the temperature corresponding to P = 2.3. The equation corresponding to temperature is t = a + b ln (P) (VTU, March, 2001) Solution : Given t = a + b ln (P) At t = 10, 10 = a + b ln (PI) (1) At t = 120, 120 = a + b ln (PS) (2) (2) – (1) gives 110 = b[ln PS – ln PI] = b ln S I P P b = 110 ln /S IP P from eqn (1) a = 10 – b ln (PI) = 10 – 110 ln /S IP P × ln (PI) t = 10 – 110 ln( ) 110 ln / ln +I SS I I P PP P P P t = 10 + 110 ln / ln / I S I P P P P given that, PI = 1.86, PS = 6.81, P = 2.3 t = 10 + 2.3 110 ln 1.86 6.81 ln 1.86 t = 28°C Ans. Problem 8 : Two Celsius thermometers ‘A’ and ‘B’ agree at the ice point (0°C) and steam point (100°C) and the related equation is tA = L + m tB + n tB 2 , where tA and tB are thermometer readings and L, m and n are constants. When both thermometers are immersed in an oil bath, thermometer A indicates 51°C and B registers 50°C. Determine the reading of A, when B reads 30°C. (VTU, Feb, 2002) Solution : At ice point, tA = tB = 0°C
  • 28. 28 Basic Thermodynamics At ice point t = 0°C K = 1.83 At steam point t = 100°C K = 6.5 The two thermometers are related by tA = L + m tB + n tB 2 0 = L + 0 + 0 L = 0 At steam point, tA = tB = 100°C 100 = L + m(100) + n(100)2 100 = 0 + m(100) + 10,000 n (1) [Q L = 0] Given, when tA = 51°C, while tB = 50°C 51 = 0 + m(50) + n(50)2 51 = 50m + 2500n (2) Solving equations (1) and (2) for constants m and n 100 = 100m + 10,000n 51 = 50m + 2,500n ´ 2 (multiply by 2) 100 = 100m + 10,000n (–)102 = 100m + 5,000n –2 = 0 + 5000n n = –4 ´ 10–4 , substitute in any one of equation, we get 102 = 100m + 5,000 (–4 ´ 10–4 ) m = 1.04 When tB = 25°C tA = L + m tB + n tB 2 = 0 + 1.04(30) + (–4 ´ 10–4 ) (302 ) tA = 30.84°C Ans. Problem 9 : The relation between temperature ‘t’ and property ‘K’ on a thermometric scale is given by t = a 1n k + b. The values of K are found to be 1.83 and 6.5 at the ice point and steam point. Determine the temperature, when K reads 2.42 on the thermometer. Take temperature values as 0° and 100°C at ice and steam point respectively Solution : The given equation is t = a ln k + b 0 = a ln 1.83 + b (1) 100 = a ln 6.5 + b (2) (2) – (1) gives a ln 6.5 – a ln 1.83 = 100 – 0 a = 100 1.267 = 78.92 from (1) 0 = 78.92 1n 1.83 + b b = –47.69
  • 29. Basic Concepts and Definitions 29 We know that t = a ln k + b t = 78.92 1n 2.42 + (–47.69) t = 22.056°C Ans. Problem 10 : The resistance in the windings of a motor is 78 ohms at room tem-perature (25°C). When operating at full load under steady conditions, the motor is switched off and the resistance of windings is found to be 95 ohms. The resistance of windings at temperature t°C is given by Rt = R0[1 + 0.00393 t], where R0 is the resistance at 0°C. Find the temperature of the coil at full load. Solution : We know that, Rt = R0 [1 + 0.00393 t] At room temperature t = 25°C, resistance Rt = 78 ohms 78 = R0[1 + 0.00393 (25)] R0 = 78 1.0982 = 71.025 R0 = 71.025 ohm At full load, Rt = 95 ohms and t = ? Rt = R0 (1 + 0.00393 t) 95 = 71.025 (1 + 0.00393 t) t = 85.87°C Ans. Problem 11 : The equation Rt = R0 (1 + at) is used to a resistance thermometer, in which Rt and R0 are the resistance values at t°C and 0°C respectively. The thermometer is calibrated by immersing in boiling water (100°C) and boiling sulphur (445°C) and the indicated resistance values are 14.7 ohm and 29.2 ohm respectively. Determine fluid temperature when resistance thermometer reads 25 ohm. Solution : When thermometer is immersed in boiling water, t = 100°C, Rt = 14.7 ohm 14.7 = R0 [1 + a (100)] (1) When the same thermometer is immersed in boiling sulphur, t = 445°C and Rt = 29.2 29.2 = R0 [1 + a (445)] (2) By solving equations (1) and (2), (2)-(1) gives 14.5 = 345 × a × R0 R0 × a = 0.042 [substitute this value in equation (1)] 14.7 = R0 + R0a ´ 100 = R0 + 0.042 ´ 100 R0 = 10.5 When Rt = 25 ohm, the temperature ‘t’ Rt = R0(1 + at)
  • 30. 30 Basic Thermodynamics 25 = R0 + R0at 25 = 10.49 + 0.042 ´ t t = 345.47°C Ans. Problem 12 : The emf of a thermocouple having one junction kept at the ice point and test junction is at the Celsius temperature t, is given by e = at + bt2 , where a = 0.2 mv/deg, b = – –5.0 ´ 10–4 mv/deg. (i)Sketch the graph of e against t. (ii)Suppose the emf e is taken as a thermometric property and that a temperature scale t1 is defined by the linear equation t1 = a1 e + b1 such that t1 = 0 at ice point and t1 = 100 at steam point. Find the numerical values of a1 and b1 and plot a graph of e against t1 . Solution : The temperature t in terms of emf is given by e = at + bt2 [Q a = 0.2 mV/deg b = –5.0 ´ 10–4 mV/deg] (i) e = 0.2t + (–5.0 ´ 10–4 ) t2 At ice point t = 0°C e = 0 + 0 = 0 e = 0 mV At steam point t = 100°C e = 0.2 ´ 100 – 5 ´ 10–4 (100)2 e = 15 mV The following values are obtained for different values of t. t°C 0 10 20 30 40 50 60 70 80 90 100 e, mV 0 1.95 3.8 5.55 7.2 8.75 10.2 11.55 12.8 13.95 15 0 2 4 6 10 8 12 14 16 10 t °C 1009080706050403020 e, mV (ii) The temperature scale t1 can be defined by taking e as the thermometric property t1 = a1 e + b1 At ice point t1 = 0, e = 0
  • 31. Basic Concepts and Definitions 31 0 = 0 + b b1 = 0 At steam point t1 = 100°C, e = 15 [from graph] 100 = a1 ´ 15 + 0 [Q b1 = 0] a1 = 100 15 = 6.66 The equation becomes t1 = 6.66 e + 0 t1 = 6.66 e The values of e for different values of t1 are tabulated as follows: t1 , °C 0 10 20 30 40 50 60 70 80 90 100 e, mV 0 1.5 3.00 4.5 6.00 7.50 9.00 10.5 12.01 13.51 15.00 16 e, mV 00 02 04 06 08 10 12 14 100908010 20 30 40 50 60 70 t 1 °C Problem 13 : The emf in a thermo couple with test junction at ice point is given by e = 0.2t – 5 ´ 10–4 t2 mV. The millivoltmeter is calibrated at ice point and steam points. What will this thermometer read in a place where gas thermometer reads 50°C (VTU Feb. 2003) Solution : At freezing or ice point eI = 0.2 ´ 0 – 5 ´ 10–4 ´ 0 = 0 mV At boiling or steam point eS = 0.2 ´ 100 – 5 ´ 10–4 (1002 ) = 15 mV At t = 50°C e = 0.2 ´ 50 – 5 ´ 10–4 (502 ) e = 8.75 mV. The temperature ‘t’ can be calculated as t = 100 e e e e é ù- ê ú -ë û I S I
  • 32. 32 Basic Thermodynamics = 100 8.75 0 15 0 é ù- ê ú -ë û t = 58.34°C Ans. Problem 14 : A thermocouple with test junction at t°C on a gas thermometer and cold junction at 0°C gives output emf as per the following relation. e = 0.20 t – 5 ´ 10–4 t2 , mV where t is the temperature. The millivoltmeter is calibrated at ice and steam points. What temperature would this thermometer show when gas thermometer reads 70°C (VTU, Feb. 2004) Solution : Given e = 0.20 t – 5 ´ 10–4 t2 , mV At ice point t = 0 eI = 0.20 ´ 0 – 5 ´ 10–4 ´ 0 = 0 mV At steam point, t = 100°C eS = 0.20 ´ 100 – 5 ´ 10–4 (1002 ) eS = 15 mV when t = 70°C e = 0.20 ´ 70 – 5 ´ 10–4 ´ 702 = 11.55 mV when gas thermometer reads 70°C, thermocouple will read t = 100 æ ö- ç ÷-è ø I S I e e e e = 11.55 0 100 15 0 æ ö- ç ÷-è ø t = 77°C Ans. 1.23 REVIEWQUESTIONS 1. Define thermodynamics and state its scope in the energy technology. 2. Distinguish between classical and statistical description of matter. 3. Explain the concept of macroscopic and microscopic view point as applied to stu dy of thermodynamics. 4. Explain the concept of continuum. 5. What are the different thermodynamic systems? Explain them with examples. 6. Differentiate between Homogeneous and Heterogeneous systems Intensive and Extensive properties Reversible and Irreversible processes 7. Define the following: Thermodynamic state Thermodynamic cycle and process Quasi-static process 8. What do you mean by thermodynamic equilibrium? Explain; how does it differ from thermal equilibrium.
  • 33. Basic Concepts and Definitions 33 9. State the concept of temperature and equality of temperature. 10. State and explain zeroth law of thermodynamics. 11. Name and define the law that forms basis for temperature measurement. 12. Define thermometric property and thermometric substance. 13. What are the different types of thermometers used for temperature measurement? 14. Explain a liquid glass type thermometer. 15. Explain the working of a (i) constant volume gas thermometer (ii) constant pressure gas thermometer 16. Explain the working of electric resistance thermometer. 17. Establish a correlation between Centigrade and Fahrenheit scales. 18. What do you understand by the ideal gas temperature scale? 19. What is the significance of international temperature scale?