APJ Abdul Kalam Technological

University Module I
ME 205 Thermodynamics

Topics

Role of Thermodynamics in Engineering and Science --

Applications of Thermodynamics Basic Concepts -
Macroscopic and Microscopic viewpoints, Concept of
Continuum, Thermodynamic System and Control Volume,
Surrounding, Boundaries, Types of Systems, Universe,
Thermodynamic properties, Process, Cycle,
Thermodynamic Equilibrium, Quasi – static Process, State,
Point and Path function. (Review only; self-study)

Zeroth Law of Thermodynamics, Measurement of

Temperature- Thermometry, Reference Points, Temperature
Scales, Ideal Gas Temperature Scale, Comparison of
Thermometers - Gas Thermometers, Thermocouple,
Resistance thermometer

Energy - Work - pdV work and other types of work transfer,

Free Expansion Work, Heat and Heat Capacity.

Noel Joseph Gomez (+91 8129422545)

DEPARTMENT OF MECHANICAL ENGINEERING, SSET, KARUKUTTY
ME 205 Thermodynamics Module 1

Table of Contents

Introduction: ................................................................................................................................ 3
Role of Thermodynamics in Engineering and Science ............................................................... 3
Thermodynamic System ............................................................................................................. 4
Types of Thermodynamic Systems ............................................................................................. 4
Properties of A System............................................................................................................. 4
State of A System ..................................................................................................................... 5
Change of State ........................................................................................................................ 5
Path ......................................................................................................................................... 5
Process..................................................................................................................................... 5
Thermodynamic Cycle ............................................................................................................. 5
Types of Properties .................................................................................................................. 5
Macroscopic and Microscopic Analysis ..................................................................................... 6
Continuum................................................................................................................................... 6
Thermodynamic Equilibrium ...................................................................................................... 7
Quasi-Static Process.................................................................................................................... 8
Zeroth Law of Thermodynamics ................................................................................................ 9
Temperature Scales ..................................................................................................................... 9
Celsius Scale ............................................................................................................................. 10
Fahrenheit Scale ........................................................................................................................ 10
Thermodynamic Temperature Scales ....................................................................................... 10
Ideal Gas Temperature Scale .................................................................................................... 10
Constant Volume Gas Thermometer .................................................................................... 10
Constant Pressure Gas Thermometer .................................................................................... 15
Thermocouple ........................................................................................................................... 16
Resistance Thermometer ........................................................................................................... 16
Temperatures of Fixed Points ................................................................................................... 17
Work Transfer ........................................................................................................................... 17
pdV Work – Displacement Work ............................................................................................. 18
pdV-Work in various quasi-static processes ............................................................................ 18

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Path Function & Point Function ............................................................................................ 19

Other types of work transfer ..................................................................................................... 19
Shaft Work ............................................................................................................................. 19
Flow Work ............................................................................................................................. 20
Free Expansion with Zero Work Transfer.............................................................................. 20
Heat Transfer ............................................................................................................................ 20
Specific Heat and Latent Heat .................................................................................................. 21
Specific Heats ........................................................................................................................ 21
University Questions ................................................................................................................. 24

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

Thermodynamics deals with four laws, viz.

• 0th law – Temperature measurement
• 1st law – Conservation of energy
• 2nd law – Kelvin Planck Statement (Heat Engine) and Clausius Statement (Refrigerator or Heat
Pump)
• 3rd law –Entropy
Fortunately, there is no mathematical proof for any of these laws, but they are deduced from
experimental observations.

Role of Thermodynamics in Engineering and Science

Thermodynamics is the branch of physics concerned with heat and temperature and their
relation to energy and work. Thermodynamics applies to a wide variety of topics in science and
engineering, especially physical chemistry, chemical engineering and mechanical engineering.

Historically, thermodynamics developed out of a desire to increase the efficiency of early steam
engines, particularly through the work of French physicist Nicolas Léonard Sadi Carnot (1824) who
believed that engine efficiency was the key that could help France win the Napoleonic Wars. Scottish
physicist Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854 which
stated, "Thermo-dynamics is the subject of the relation of heat to forces acting between
contiguous parts of bodies, and the relation of heat to electrical agency."

The initial application of thermodynamics to mechanical heat engines was extended early on
to the study of chemical compounds and chemical reactions. Chemical thermodynamics studies the
nature of the role of entropy in the process of chemical reactions and has provided the bulk of
expansion and knowledge of the field. Other formulations of thermodynamics emerged in the
following decades. Statistical thermodynamics, or statistical mechanics, concerned itself with statistical
predictions of the collective motion of particles from their microscopic behavior. In 1909, Constantin

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Carathéodory presented a purely mathematical approach to the field in his accepted formulation of
thermodynamics, a description often referred to as geometrical thermodynamics.

Thermodynamic System
A thermodynamic system is defined as a quantity of matter or a region in space upon which
attention is concentrated in the analysis of a problem.
• Everything external to the system is called the Surroundings or Environment.
• System is separated from its surroundings by the System Boundary, which may be either
fixed or moving.
• A system and its surroundings together comprises The Universe.

Types of Thermodynamic Systems

Thermodynamic systems are classified into three types, viz.
1. Closed System
2. Open System
3. Isolated System

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

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

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

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

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

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

Types of Properties

Properties Intensive
Independent Of The Mass Of The System

Eg. Pressure, temperature, etc

Dependent Of The Mass Of The System

Extensive Eg. Volume, energy etc

If the mass is increased, the values of extensive properties also increases.

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

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Macroscopic and Microscopic Analysis

Macroscopic Approach
– A certain quantity of matter is considered
– The events occurring at the molecular level is not taken into account
– Only concerned with the effects of the action of many molecules.
– These effects can be perceived by human senses.

Microscopic approach
– Matter is composed of many molecules
– Each molecule at a given instant has a certain position, velocity and energy (in the case of a
gas) and for each molecule these change very frequently as a result of molecular collisions.
– The behavior of the gas is then described by summing up the behavior of each molecule.

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

In thermodynamics, matter is made up of atoms that are widely spaced in the gas phase. Yet
it is very convenient to disregard the atomic nature of a substance and view it as a continuous,
homogeneous matter with no holes, that is, a continuum.
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The continuum idealization allows us to treat properties as point functions and to assume the
properties vary continually in space with no jump discontinuities. This idealization is valid as long as
the size of the system we deal with is large relative to the space between the molecules.

Thermodynamic Equilibrium
A system is said to exist in a state of thermodynamic equilibrium when no change in any
macroscopic property is registered, when the system is isolated from its surroundings.

An isolated system always reaches a state of thermodynamic equilibrium in the course of time
and can never depart from it spontaneously.

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

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

Thermodynamic
Equilibrium

Mechanical Chemical Thermal

Equilibrium Equilibrium Equilibrium

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Quasi-Static Process
In thermodynamics, a quasistatic process is a thermodynamic process that happens "infinitely
slowly". No real process is quasistatic, but such processes can be approximated by performing them
very slowly.
“Quasi” means “almost”
Infinite slowness is the characteristic feature of a quasi-static process. A quasi static process is a
succession of equilibrium states.
Consider a system of gas contained in a cylinder. The system initially is in equilibrium state.
The weight on the piston just balances the upward force exerted by the gas. If the weight is removed,
there will be an unbalanced force between the system and surroundings, and under gas pressure, the
piston will move up till it hits the stops. The system again comes to an equilibrium state, being
described by the properties p2, v2, t2. But the intermediate states passed through by the system are non-
equilibrium states which cannot be described by thermodynamic coordinates.
Now if the single weight on the piston is made up of many very small pieces of weights and
these weights are removed one by one very slowly from the top of the piston, at any instant of the
upward travel of the piston, the departure of the state of the system from the thermodynamic
equilibrium state will be infinitesimally small. So every state passed through by the system will be an
equilibrium state. Such a process, which is but locus of all the equilibrium points passed through by
the system is known as a quasi-static process.

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Zeroth Law of Thermodynamics

The zeroth law of thermodynamics states that “if two bodies are in thermal equilibrium
with a third body, they are also in thermal equilibrium with each other”. The zeroth law serves
as a basis for the validity of temperature measurement. By replacing the third body with a
thermometer, the zeroth law can be restated as two bodies are in thermal equilibrium if both have the
same temperature reading even if they are not in contact.

Temperature Scales
All temperature scales are based on some easily reproducible states such as the freezing and
boiling points of water, which are also called the ice point and the steam point, respectively.

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Ice Point
(Ice + Water + Air Saturated with Vapor)1atm pressure
Steam Point
(Liquid Water + Water Vapor)1 atm pressure

Celsius Scale (Formerly the centigrade scale – designed by Swedish Astronomer A. Celsius)
On the Celsius scale, the ice and steam points were originally assigned the values of 0°C and 100°C,
respectively.
• 0°C : Ice Point
• 100°C : Steam Point
Fahrenheit Scale (Named after German instrument maker G. Fahrenheit)
The corresponding values on the Fahrenheit scale for ice point and steam point are 32°F and 212°F.
• 0°F : Temperature of brine made from equal parts of ice and salt (-17.778°C)
• 100°F : Average human body temperature (37.778°C)
➢ Both the Celsius scale and Fahrenheit scale are two point scales

Thermodynamic Temperature Scales

A temperature scale that is independent of the properties of any substance or substances is called a
thermodynamic temperature scale.
The thermodynamic temperature scale in the SI is the Kelvin scale. The lowest temperature on the
Kelvin scale is absolute zero, or 0 K.
The thermodynamic temperature scale in the English system is the Rankine scale. The temperature
unit on this scale is the Rankine, which is designated by R.

Ideal Gas Temperature Scale

A temperature scale that turns out to be nearly identical to the Kelvin scale is the ideal-gas temperature
scale.

Constant Volume Gas Thermometer

A gas thermometer measures temperature by the variation in volume or pressure of a gas.

The temperatures on the ideal gas temperature scale are measured using a constant-volume gas
thermometer, which is basically a rigid vessel filled with a gas, usually hydrogen or helium, at low
pressure.

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This thermometer is based on the principle that at low pressures, the temperature of a gas is
proportional to its pressure at constant volume.
∝( )
That is, the temperature of a gas of fixed volume varies linearly with pressure at sufficiently low
pressures. Then the relationship between the temperature and the pressure of the gas in the vessel can
be expressed as
= +
Where the values of the constants a and b for a gas thermometer are determined experimentally. Once
a and b are known, the temperature of a medium can be calculated from this relation by immersing
the rigid vessel of the gas thermometer into the medium and measuring the gas pressure when thermal
equilibrium is established between the medium and the gas in the vessel whose volume is held
constant.
An ideal-gas temperature scale can be developed by measuring the pressures of the gas in the vessel
at two reproducible points (such as the ice and the steam points) and assigning suitable values to
temperatures at those two points. Considering that only one straight line passes through two fixed
points on a plane, these two measurements are sufficient to determine the constants a and b in Eq.
(1). Then the unknown temperature T of a medium corresponding to a pressure reading P can be
determined from that equation by a simple calculation. The values of the constants will be different
for each thermometer, depending on the type and the amount of the gas in the vessel, and the
temperature values assigned at the two reference points. If the ice and steam points are assigned the
values 0°C and 100°C, respectively, then the gas temperature scale will be identical to the Celsius scale.
In this case the value of the constant a (which corresponds to an absolute pressure of zero) is
determined to be −273.15°C regardless of the type and the amount of the gas in the vessel of the gas
thermometer. That is, on a P-T diagram, all the straight lines passing through the data points in this
case will intersect the temperature axis at −273.15°C when extrapolated, as shown in Figure 1. This is
the lowest temperature that can be obtained by a gas thermometer, and thus we can obtain an absolute
gas temperature scale by assigning a value of zero to the constant a in Eq. (1). In that case Eq. (1)
reduces to T = bP, and thus we need to specify the temperature at only one point to define an absolute
gas temperature scale.

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Figure 1 P versus T plots of the experimental data obtained from a constant-volume gas thermometer using four different
gases at different (but low) pressures.

It should be noted that the absolute gas temperature scale is not a thermodynamic temperature scale,
since it cannot be used at very low temperatures (due to condensation) and at very high temperatures
(due to dissociation and ionization). However, absolute gas temperature is identical to the
thermodynamic temperature in the temperature range in which the gas thermometer can be used, and
thus we can view the thermodynamic temperature scale at this point as an absolute gas temperature
scale that utilizes an “ideal” or “imaginary” gas that always acts as a low-pressure gas regardless of the
temperature. If such a gas thermometer existed, it would read zero kelvin at absolute zero pressure,
which corresponds to −273.15°C on the Celsius scale (Figure 2).

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Figure 2 A constant-volume gas thermometer would read −273.15°C at absolute zero pressure.

The Kelvin scale is related to the Celsius scale by

T(K) = T(℃) + 273.15 (2)

The Rankine scale is related to the Fahrenheit scale by

T(R) = T(℉) + 459.67 (3)

The temperature scales in the two unit systems are related by

( ) = 1.8 ( )

(℉) = 1.8 (℃) + 32

A comparison of various temperature scales is given in Figure 3

• The two reference points used in the Kelvin scale are

▪ 0K : The absolute zero temperature (-273.15°C)
▪ 273.16 K : Triple point of water (0.01°C)

The reference temperature chosen in the Kelvin scale is the triple point of water (the state at which
all three phases of water coexist in equilibrium), which is assigned the value 273.16 K. The Celsius
scale was also redefined at this conference in terms of the ideal-gas temperature scale and a single
fixed point, which is again the triple point of water with an assigned value of 0.01°C. The boiling

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temperature of water (the steam point) was experimentally determined to be again 100.00°C, and thus
the new and old Celsius scales were in good agreement.

Figure 3 Comparison of various temperature scales

Figure 4 Comparison of temperature scales.

Problem 1

Consider a system whose temperature is 18°C. Express this temperature in R, K, and °F.

Answer

A temperature is given in °C. It is to be expressed in °F, K, and R.

Using the conversion relations between the various temperature scales,

T(K] = T(°C) + 273 = 18°C + 273 = 291 K

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T(°F] = 1.8T(°C) + 32 = (1.8)(18) + 32 = 64.4°F

T(R] = T(°F) + 460 = 64.4 + 460 = 524.4 R

Constant Pressure Gas Thermometer

In a constant pressure gas thermometer, the thermometric property is the “Volume” of the gas
keeping the pressure constant. (Figure 5)

Figure 5 Constant Pressure Gas Thermometer

A small about of gas is enclosed in the bulb which is in communication via the capillary tube with one
limb of the mercury manometer. The other limb of the mercury manometer is open to the atmosphere
and can be moved vertically to adjust the mercury levels so that the mercury just touches the lip of
the capillary.
When the bulb is brought in contact with the system whose temperature is to be measured, the bulb
comes in thermal equilibrium with the system.
The gas in the bulb expands, on heated pushing the mercury downward.
To keep the pressure inside the bulb constant, the mercury levels are adjusted by moving the capillary
tube vertically such that “h” is constant, and the volume “V” which would vary with the temperature
of the system becomes the thermometric property.

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Thermocouple

Figure 6 Thermocouple

▪ A thermocouple circuit is made up from joining two wires A & B made of dissimilar metals.
▪ Due to the Seebeck effect, a net e.m.f is generated in the circuit with depends on the difference
in temperature between the hot and cold junctions and is, therefore, a thermometric property
of the circuit.
▪ This e.m.f can be measured by a microvoltmeter to a high degree of accuracy.
▪ A thermocouple is calibrated by measuring the thermal e.m.f at various known temperatures
– the reference points.
▪ The advantage of a thermocouple is that it comes to thermal equilibrium with the system,
whose temperature is to be measured, quite rapidly, because its mass is small.

Resistance Thermometer

Figure 7 Resistance Thermometer

In the resistance thermometer, the change in resistance of a metal wire due to its change in temperature
is the thermometric property. The wire, may be incorporated in a wheatstone bridge circuit.

The resistance thermometer measures temperature to a high degree of accuracy and sensitivity, which
makes it suitable as a standard for the calibration of other thermometers.

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Temperatures of Fixed Points

Some fixed temperatures normally used as reference points for various ranges are given in the table
below.

Reference Points Temperature °C

Normal boiling point of oxygen -182.97
Triple point of water +0.01
Normal boiling point of water 100.00
Normal boiling point of Sulphur 444.60
Normal melting point of zinc 419.50
Normal melting point of antimony 630.50
Normal melting point of silver 960.80
Normal melting point of gold 1063.00

Work Transfer
Physics
“Work is done by a force as it acts upon a body moving in the direction of the force”
Thermodynamics
“Work is said to be done by a system if the sole effect on things external to the system can
be reduced to the raising of a weight”

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pdV Work – Displacement Work

All the states passed through by the system as the volume changes from V1 to V2 must be
equilibrium states, and the path 1-2 must be quasi-static.

The integration ∫ can be performed only on a quasi-static path.

The area under the pv diagram will give the work transfer during the process.

pdV-Work in various quasi-static processes

Constant pressure process = ( − )
Constant Volume Process =0
Isothermal Process
= ln
= .
Polytropic Process −
=
= . −1

n = Polytropic Index

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Process Closed System Open System

Work Transfer =∫ = −∫

Const. Volume
0 ( − )
=
Const. Pressure
( − ) 0
=
Isothermal ln OR ln
=
Isentropic ( − )
=
Polytropic
( − )
=

Path Function & Point Function

The amount of work transfer involved during a process is not a function of the end states of the
process, but it depends on the path the system follows in going from state 1 to state 2.
Therefore, work is called a path function and dW is an inexact or imperfect differential
The change in thermodynamic property of a system is independent on the path of the system and
depends only on the final states of the system. Hence, Thermodynamic properties are point
functions.
The differentials of thermodynamic properties are exact or perfect differentials.
The cyclic integral of a thermodynamic property is always zero.
∮ = 0, ∮ = 0, ∮ =0

Other types of work transfer

Shaft Work
When a shaft is rotated by a motor, there is work transfer into the system
=
T= Torque applied to the shaft
dθ=angular displacement of the shaft

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= = = ( − )

If N is the number of revolutions rotated by the shaft, then

1 revolution = 360°=2π radians
= × (2 )

Flow Work

The flow work per unit mass is given by,

=

Free Expansion with Zero Work Transfer

Work is done by a system to overcome some resistance.
In free expansion of a gas, there is no resistance to the fluid at the system boundary as the volume of
the gas increases to fill up the vacuum space.
Since vacuum does not offer any resistance, there is no work transfer involved in free expansion.

Heat Transfer
Heat is defined as the form of energy that is transferred across a boundary by virtue of temperature
difference.
The temperature difference is the ‘potential’ or ‘force’ and heat transfer is the ‘flux’.
1. The transfer of heat between two bodies in direct contact is called conduction.
2. The transfer of heat between a wall and fluid system in motion is called convection.
3. The transfer of heat between two bodies separated by empty space or gases is called radiation.
Heat is a form of energy in transit (like work transfer).
It is a boundary phenomenon since it occurs only at the boundary of a system.

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Heat is not that which inevitably causes a temperature rise. When heat is transferred into an ice-and-
water mixture, the temperature does not rise until all the ice has melted.
A process in which no heat crosses the boundary is called an adiabatic process.
A wall which does not allow heat transfer to take place is called an adiabatic wall, and a wall which
permits heat transfer is called a diathermic wall.
Heat flow Q, like W, depends on the process and is path dependent and not a property of the system.
Heat transfer is a path function, that is, the amount of heat transferred when a system changes from
state 1 to state 2 depends on the intermediate states through which the system passes.

Specific Heat and Latent Heat

Specific heat of a substance is defined as the amount of heat required to raise a unit mass of a
substance through a unit rise in temperature.

= J/kg-K
.∆
The product of mass and specific heat is called the heat capacity of a substance.
The specific heat of a substance depends on the process through which the exchange of heat is
made.
If the process is constant pressure, it is cp, if the process is constant volume, it is cv
The latent heat is the amount of heat transfer required to cause a phase change in unit mass of a
substance at a constant pressure and temperature.
➢ Latent heat of fusion – solid into liquid
➢ Latent heat of vaporization – liquid into vapor
➢ Latent heat of sublimation – solid to vapor

Specific Heats
The specific heat is defined as the energy required to raise the temperature of a unit mass of a substance
by one degree (Figure 8). In general, this energy depends on how the process is executed. In

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thermodynamics, we are interested in two kinds of specific heats: specific heat at constant volume c v
and specific heat at constant pressure cp.

Figure 8 Specific heat is the energy required to raise the temperature of a unit mass of a substance by one degree in a
specified way.

The amount of energy needed to raise the temperature of a unit mass of a substance by one degree is
called the specific heat at constant volume cv for a constant-volume process and the specific heat at
constant pressure cp for a constant pressure process. They are defined as

= and =

Specific Heat at constant volume

The specific heat of a substance at constant volume cv is defined as the rate of change of specific
internal energy with respect to temperature when the volume is held constant, i.e

For a constant volume process,

(∆ ) =

The first law may be written for a closed stationary system composed of a unit mass of a pure
substance

=∆ +

Or

= +

For a process in the absence of work other than pdV work,

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∴ = +

When the volume is held constant

( ) = (∆ )

∴( ) =

Heat transferred at constant volume increases the internal energy of the system.

If the specific heat of a substance is defined in terms of heat transfer, then

The product mcv = Cv is called the heat capacity at constant volume (J/K)

Specific heat at constant pressure

The specific heat at constant pressure cp is defined as the rate of change of enthalpy with respect to
temperature when the pressure is held constant

ℎ
=

Since h,T and p are properties, so cp is a property of the system. Like cv, cp should not be defined in
terms of heat transfer at constant pressure, although ( ) = ℎ

For a constant pressure process

(∆ℎ) =

The first law for a closed stationary system of unit mass

= +

Again

ℎ= +

∴ ℎ= + +

= +

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∴ = ℎ−

For constant pressure process, dp=0

∴( ) = ℎ

Or

( ) = (∆ℎ)

∴( ) =

The heat capacity at constant pressure Cp is equal to mcp (J/K)

University Questions
1) Explain thermodynamic equilibrium
2) What is quasi-static process? What is its characteristic feature?
3) What is the concept of continuum? How will you define density and pressure using this concept?
4) Write short notes on
a) Different forms of energy
b) System, boundary and surroundings.
c) Point and path functions.
5) Define property of a system with any two examples. Why thermodynamic properties are taken as
coordinates in thermodynamics?
6) Explain free expansion? Why is displacement work absent in free expansion?
7) List any six applications of thermodynamics.
8) Explain the working of thermocouple with a neat sketch.
9) What is total energy of a system? Prove that total energy is thermodynamic property of a system.

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