ME201

Basics Engineering Thermodynamics (3-1-0) 4

Fundamental Concepts, system, temperature, Heat and Work, I law and II law of
Thermodynamics, applications, Pure
substance, Entropy, Available and unavailable energy , Analysis of cycles, Helmholtz
and Gibbs Functions and its
applications, Ideal and Real gases, Non reactive mixtures, properties of air and water
vapour.
Spalding and Cole, Engineering Thermodynamics, ELBS Edition Longmans,1987.
Arora C.P. Thermodynamics, TMH, 1998.
Gordan J. Van Wylen and Richard E.Sountag, Fundamentals of Classical
Thermodynamics, 4th Edition,Wiley, 1994.
P. K. Nag, Basic and Applied Thermodynamics, Tata McGraw Hill. 3rd Edition,
2005.
Yunus A Cengel and Michael A. Boles, Thermodynamics : An Engineering approach ,
Tata Mcgraw Hill,7th Edition
Evaluation plan

TQAS 30%
Midsem 20%
Endsem 50%
 Basic
Concepts of
Thermodynamics
Thermodynamics (TD): perhaps the most basic science
 One branch of knowledge that all engineers and scientists must have a grasp of
(to some extent or the other!) is thermodynamics.
 In some sense thermodynamics is perhaps the ‘most abstract subject’ and a
student can often find it very confusing if not ‘motivated’ strongly enough.
 Thermodynamics can be considered as a ‘system level’ science- i.e. it deals with
descriptions of the whole system and not with interactions (say) at the level of
individual particles.
 I.e. it deals with quantities (like T,P) averaged over a large collection of entities
(like molecules, atoms)*.
 This implies that questions like: “What is the temperature or entropy of an
atom?”; do not make sense in the context of thermodynamics (at lease in the usual way!).
 TD puts before us some fundamental laws which are universal** in nature (and
hence applicable to fields across disciplines).

* Thermodynamics deals with spatio-temporally averaged quantities.

** They apply to the universe a whole as well! (Though the proof is lacking!).
 What is thermodynamics?
• The study of thermodynamics is concerned with ways energy is
stored within a body and how energy transformations, which
involve heat and work, may take place.

• Approaches to studying thermodynamics

– Macroscopic (Classical thermodynamics)
• study large number of particles (molecules) that
make up the substance in question
• does not require knowledge of the behavior of
individual molecules
• The structure of the matter is not considered.
• A few variables are used to describe the state of the matter
under consideration.
• The values of these variables are measurable following the
available techniques of experimental physics
– Microscopic (Statistical thermodynamics)
• concerned within behavior of individual particles
(molecules)
• study average behavior of large groups of individual
particles
• A knowledge of the molecular structure of matter under
consideration is essential.
• A large number of variables are needed for a complete
specification of the state of the matter
 Applications of
Thermodynamics

The human body

Air-conditioning Airplanes
systems

Car radiators Power plants Refrigeration systems

Thermodynamic Systems
•Thermodynamic System
– quantity of matter or a region of
space chosen for study
•Boundary
– real or imaginary layer that
separates the system from its
surroundings
•Surroundings
– physical space outside the system
boundary
• Types of Systems
– Closed
– Open
 Closed Systems (fixed
masses)
Energy, not mass, crosses closed-system boundaries
Closed System with Moving
Boundry
 Open Systems (Control
Volumes)
Mass and Energy Cross Control Volume Boundaries
 Isolated System
• Closed system where no heat or work (energy) may cross the system boundary
– typically a collection of the a main system (or several systems) and
its surroundings is considered an isolated system

Isolated system boundary

work system
mass
Surr 1 heat

Surr 2 Surr 3
The language of TD
 To understand the laws of thermodynamics and how they work, first we need to get the
terminology right. Some of the terms may look familiar (as they are used in everyday
language as well)- but their meanings are more ‘technical’ and ‘precise’, when used in TD
and hence we should not use them ‘casually’.
 System is region where we focus our attention (Au block in figure).
 Surrounding is the rest of the universe (the water bath at constant ‘temperature’).
 Universe = System + Surrounding (the part that is within the dotted line box in the figure below)
 More practically, we can consider the ‘Surrounding’ as the immediate neighbourhood of the
system (the part of the universe at large, with which the system ‘effectively’ interacts).
In this scheme of things we can visualize: a system, the surrounding and the universe at
large.
 Things that matter for the surrounding: (i) T (ii) P (iii) ability to: do work, transfer heat,
transfer matter, etc. Parameters for the system: (i) Internal energy, (ii) Enthapy, (iii) T, (iv) P,
(v) mass, etc.

In TD we usually do not worry about

the universe at large!
 Type of boundary Interactions Mass
Open All interactions possible (Mass, Work, Heat)
Closed Matter cannot enter or leave
Interactions possible
Semi-permeable Only certain species can enter or leave Work
Insulated Heat cannot enter or leave
Rigid Mechanical work cannot be done* Heat
Isolated No interactions are possible**

* By or on the system
** Mass, Heat or Work
 Properties
• Any characteristic of a system in equilibrium is
called a property.
• Types of properties
– Extensive properties - vary directly with the
size of the system
Examples: volume, mass, total energy
– Intensive properties - are independent of the
size of the system
Examples: temperature, pressure, color
• Extensive properties per unit mass are intensive properties.
specific volume v = Volume/Mass = V/m
density r = Mass/Volume = m/V
 Continuum
The diameter of the oxygen
molecule is about 3X10-10 m and
its mass is 5.3X10-26 kg. Also, the
mean free path of oxygen at 1 atm
pressure and 20°C is 6.3X10-8 m.

Despite the large gaps between molecules, a substance can be

treated as a continuum because of the very
large number of molecules even in an extremely small
volume
 State & Equilibrium
• State of a system
– system that is not undergoing any change
– all properties of system are known & are not
changing
– if one property changes then the state of the
system changes
• The State Postulate:
• The number of properties required to fix the state of a system is
given by the state postulate:
• The state of a simple compressible system is completely
specified by two independent, intensive properties.
• “Simple” = no electrical, magnetic, kinetic, gravity, or surface
tension effects. If any of these must be considered, then one
additional property must be known for each added effect.
• Example: for motion (kinetic) effects, velocity must be known.
• “Compressible” = volume not fixed.
• “Independent” = one property of a pair can be changed without
affecting the other.
• Example: a. temperature and specific volume (density-1) are
always independent.
• b. Temperature and pressure are sometimes independent (in a
single - phase system) but not in a system undergoing phase
change. Temperature at which water boils varies with pressure
(100 C at sea level, ~93 C in Boulder).
• “Intensive” = the value of the property is not dependent on that
amount of material in the system.
• Thermodynamic equilibrium
– “equilibrium” - state of balance
– A system is in equilibrium if it maintains thermal
(uniform temperature), mechanical (uniform
pressure), phase (mass of two phases), and
chemical equilibrium
• When the property of a system is defined, it is understood that
the system is in equilibrium.
• If a system is in thermal equilibrium, the temperature will be same
throughout the system.
• If a system is in mechanical equilibrium, there is no tendency for
the pressure to change.
• In a single phase system, if the concentration is uniform and
there is no tendency for mass transfer or diffusion, the system is
said to be in chemical equilibrium.
• A system which is simultaneously in thermal, mechanical, and
chemical equilibrium is said to be in thermal equilibrium.
 Processes & Paths
• Process
– when a system changes from one equilibrium state to
another one
• Path
– series of states which a system passes through during a
process
Processes in TD We will deal with some of them in detail later on

 Here is a brief listing of a few kinds of processes, which we will encounter in TD:
 Isothermal process → the process takes place at constant temperature
(e.g. freezing of water to ice at –10C)
 Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
 Isochoric → constant volume
(e.g. heating of gas in a sealed metal container)
 Isentropic → constant entropy
 Reversible process → the system is close to equilibrium at all times (and infinitesimal
alteration of the conditions can restore the universe (system + surrounding) to the original
state.
 Cyclic process → the final and initial state are the same. However, q and w need not be
zero.
 Adiabatic process → dq is zero during the process (no heat is added/removed to/from the
system)
 A combination of the above are also possible: e.g. ‘reversible adiabatic process’.
Compression Process
 Quasi-Equilibrium
Processes
• System remains practically in
equilibrium at all times
• Easier to analyze (equations of state
can apply)
• Work-producing devices deliver the
most work
• Work-consuming devices consume
the least amount of work
 Cycles

A process (or a series of connected processes) with identical end

states

2
P
Process
B

1
Process
A

V
Temperature
 Though we all have a feel for temperature (‘like when we are feeling hot’); in the context
of TD temperature is technical term with ‘deep meaning’.
 As we know (from a commons sense perspective) that temperature is a measure of the ‘intensity of
heat’. ‘Heat flows’ (energy is transferred as heat) from a body at higher temperature to one at lower
temperature. (Like pressure is a measure of the intensity of ‘force applied by matter’→
matter (for now a fluid) flows from region of higher pressure to lower pressure).
 That implies (to reiterate the obvious!) if I connect two bodies (A)-one weighing 100kg at 10C
and the other (B) weighing 1 kg at 500C, then the ‘heat will flow’ from the hotter body to
the colder body (i.e. the weight or volume of the body does not matter).
 But, temperature comes in two important ‘technical’ contexts in TD:
1 it is a measure of the average kinetic energy (or velocity) of the constituent entities (say molecules)
2 it is the parameter which determines the distribution of species (say molecules) across
various energy states available.

Heat flow
A direction B
500C

10C
 Temperature and Zeroth Law of Thermodynamics

• We cannot assign numerical values to temperatures

based on our sensations alone. Furthermore, our senses
may be misleading.
• Several properties of material changes with temperature
in a repeatable and predictable way, and this forms the
basis of accurate temperature measurement.
• The commonly used mercury-in-glass thermometer for
example, is based on the expansion of mercury with
temperature.
• Temperature is also measured by using several other
temperature dependant properties.
• Two bodies (eg. Two copper blocks) in contact attain
thermal equilibrium when the heat transfer between them
stops.
• The equality of temperature is the only requirement for
thermal equilibrium.
The Zeroth Law of Thermodynamics
• If two bodies are in thermal equilibrium with a third
body, they are also in thermal equilibrium with each
other.
• This obvious fact cannot be concluded from the other
laws of thermodynamics, and it serves as a basis of
temperature measurement.
• By replacing the third body with a thermometer, the
zeroth law can be restated two bodies are in thermal
equilibrium if both have the same temperature
reading even if they are not in contact
• The zeroth law was first formulated and labeled by
R.H. Fowler in 1931
 Temperature Scales
• All temperature scales are based on some easily reproducible
states such as the freezing and boiling point of water, which are also
called the ice-point and the steam-point respectively.
• A mixture of ice and water that is in equilibrium with air saturated
with water vapour at 1atm pressure, is said to be at the ice-point,
and a mixture of liquid water and water vapour (with no air) in
equilibrium at 1atm is said to be at the steam-point.
• Celsius and Fahrenheit scales are based on these two points
(although the value assigned to these two values are different) and
are referred as two-point scales.
• In thermodynamics, it is very desirable to have a temperature scale
that is independent of the properties of the substance or
substances.
• Such a temperature scale is called a thermodynamic temperature
scale.(Kelvin in SI)
 Ideal gas temperature scale
• The temperatures on this scale are measured using a constant
volume thermometer.
• Based on the principle that at low pressure, the temperature of
the gas is proportional to its pressure at constant volume.
• The relationship between the temperature and pressure of the
gas in the vessel can be expressed as
• T = a + b.P
• 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 the relation above by immersing the rigid
vessel of the gas thermometer into the medium and measuring
the gas pressure.
• 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 steam points) and assigning
suitable values to temperatures those two points.
• If the ice and the steam points are assigned the values 0
and 100 respectively, then the gas temperature scale will
be identical to the Celsius scale.
• In this case, the value of the constant a (that
corresponds to an absolute pressure of zero) is
determined to be –273.150C when extrapolated.
• The equation reduces to T = bP, and thus we need to
specify the temperature at only one point to define an
absolute gas temperature scale.
• Absolute gas temperature is identical to thermodynamic
temperature in the temperature range in which the gas
thermometer can be used.
• We can view that thermodynamic temperature scale at
this point as an absolute gas temperature scale that
utilizes an ideal gas that always acts as a low-pressure
gas regardless of the temperature.
•
• At the Tenth international conference on weights and
measures in 1954, the Celsius scale has been redefined in
terms of a single fixed point and the absolute temperature
scale.
• The triple point occurs at a fixed temperature and pressure
for a specified substance.
• The selected single point is the triple point of water (the state
in which all three phases of water coexist in equilibrium),
which is assigned the value 0.01 C. As before the boiling point
of water at 1 atm. Pressure is 100.0 C. Thus the new Celsius
scale is essentially the same as the old one.
• On the Kelvin scale, the size of Kelvin unit is defined as “ the
fraction of 1/273.16 of the thermodynamic temperature of the
triple point of water, which is assigned a value of 273.16K”.
The ice point on Celsius and Kelvin are respectively 0 and
273.15 K.
Few points about temperature scales and their properties
 Celsius (Farenheit, etc.) are relative scales of temperature and zero of these scales do not have
a fundamental significance. Kelvin scale is a absolute scale. Zero Kelvin and temperatures
below that are not obtainable in the classical sense.
 Classically, at 0K a perfect crystalline system has zero entropy (i.e. system attains its minimum
entropy state). However, in some cases there could be some residual entropy due to degeneracy
of states.
 At 0K the kinetic energy of the system is not zero. There exists some zero point energy.
 Pressure
 Pressure* is force per unit area (usually exerted by a fluid on a wall**).
 It is the momentum transferred (say on a flat wall by molecules of a gas) per unit area, per unit time. (In
the case of gas molecules it is the average momentum transferred per unit area per unit time on to the flat wall).
 P = momentum transferred/area/time.
 Pressure is related to momentum, while temperature is related to kinetic energy.
Wall of a container

‘Crude schematic’
of particles
impinging on a
wall.

* ‘Normal’ pressure is also referred to as hydrostatic pressure.

** Other agents causing pressure could be radiation, macroscopic objects impinging on a wall, etc.