"This page is Intentionally Left Blank"
Heat
, , ,
Hilary. D. Brewster
Oxford Book Company
Jaipur I India
ISBN: 9789380179087
First Edition 2009
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Preface
Heat is basic science that deals with energy and has long been
an essential part of Engineering Curricula all over the world. It
was developed during the eighteenth and nineteenth century during
a time when Temperature and Heat were not well understood yet.
Its development was driven by the need for an improved theoretical
understanding of Steam Engines invented at the same time. It
evolved as a rather formal and elegant theory that proved to be of
great importance to Engineers.
Thermodynamics is the science of Energy, Heat, Work,
Entropy and Spontaneity of processes. It is closely related to
Statistical Mechanics from which many Thermodynamic
relationships can be derived. While dealing with processes in
which systems exchange Matter or Energy, Classical Thermodyna
mics is not concerned with the rate at which such processes take
place, termed Kinetics.
The book contains detailed descriptions of Modern
Techniques in Thermodynamics. The aim of the book is to make
the subject matter broadly accessible to advanced students, whilst
at the same time providing a reference text for graduate scholars
and research scientists active in the field.
Prabhat Kumar Choudhary
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Contents
Preface v
1. Introduction 1
2. Heat transfer 21
3. Heat Conduction 56
4. The Behaviour of Gases 76
5. Specific Heat of Solids 85
6. Thermal Equilibrium and Zeroth Law 95
7. The First Law of Thermodynamics 116
8. The Second Law of Thermodynamics 177
9. Third Law of ThennodYD11mics 224
10. Entropy 229
11. Enthalpy Generating Heat 237
12. Isolated Paramagnets 249
13. Power Cycles with TwoPhase Media 289
Bibliography 314
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1
Introduction
HEAT
In physics, heat, symbolized by Q, is energy transferred from
one body or system to another due to a difference in temperature.
In thermodynamics, the quantity TdS is used as a representative
measure of heat, which is the absolute temperature of an object
multiplied by the differential quantity of a system's entropy
measured at the boundary of the object. Heat can flow
spontaneously from an object with a high temperature to an object
with a lower temperature.
The transfer of heat from one object to another object with
an equal or higher temperature can happen only with the aid of a
heat pump. High temperature bodies, which often result in high
rates of heat transfer, can be created by chemical reactions (such
as burning), nuclear reactions (such as fusion taking place inside
the Sun), electromagnetic dissipation (as in electric stoves), or
mechanical dissipation (such as friction).
Heat can be transferred between objects by radiation,
conduction and convection. Temperature is used as a measure of
the internal energy or enthalpy, that is the level of elementary
motion giving rise to heat transfer. Heat can only be transferred
between objects, or areas within an object, with different
temperatures (as given by the zeroth law of thermodynamics), and
then, in the absence of work, only in the direction of the colder
body (as per the second law of thermodynamics). The temperature
and phase of a substance subject to heat transfer are determined
Heat and Thermodynamics
by latent heat and heat capacity. A related term is thermal energy,
loosely defined as the energy of a body that increases with its
temperature. The first law of thermodynamics states that the energy
of a closed system is conserved. Therefore, to change the energy
of a system, energy must be transferred to or from the system.
Heat and work are the only two mechanisms by which energy can
be transferred to or from a control mass. Heat is the transfer of
energy caused by the temperature difference. The unit for the
amount of energy transferred by heat in the International System
of Units SI is the joule (1), though the British Thermal Unit and
the calorie are still occasionally used in the United States. The
unit for the rate of heat transfer is the watt (W = J/s),
Surroundings
r .. :::· ........ '.. .. .
~ : ~ ~ ~ : ~ ............... )
Heat Q can flow across the boundary of the system and thus
change its internal energy U. Heat transfer is a path function
(process quantity), as opposed to a point function (state quantity).
Heat flows between systems that are not in thermal equilibrium
with each other; it spontaneously flows from the areas of high
temperature to areas of low temperature. When two bodies of
different temperature come into thermal contact, they will
exchange internal energy until their temperatures are equalized;
that is, until they reach thermal equilibrium.
The adjective hot is used as a relative term to compare the
object's temperature to that of the surroundings (or that of the
person using the term). The term heat is used to describe the flow
of energy. In the absence of work interactions, the heat that is
transferred to an object ends up getting stored in the object in the
form of internal energy 
Specific heat is defined as the amount of energy that has to
be transferred to or from one unit of mass or mole of a substance
to change its temperature by one degree. Specific heat is a property,
3 Introduction
which means that it depends on the substance under consideration
and its state as specified by its properties. Fuels, when burned,
release much of the energy in the chemical bonds of their
molecules. Upon changing from one phase to another, a pure
substance releases or absorbs heat without its temperature
changing. The amount of heat transfer during a phase change is
known as latent heat and depends primarily on the substance and
its state.
THERMAL ENERGY
Thermal energy is a term often confused with that of heat.
Loosely speaking, when heat is added to a thermodynamic system
its thermal energy increases and when heat is withdrawn its thennal
energy decreases.
In this point of view, objects that are hot are referred to as
being in possession ofa large amount of thermal energy, whereas
cold objects possess little thermal energy. Thermal energy then is
often mistakenly defined as being synonym for the word heat. This,
however, is not the case: an object cannot possess heat, but only
energy.
The tenh "thermal energy" when used in conversation is often
not used in a strictly correct sense, but is more likely to be only
used as a descriptive word. In physics and thermodynamics, the
words "heat", "internal energy", "work", "enthalpy" (heat content),
"entropy", "external forces", etc., which can be defined exactly,
i.e. without recourse to internal atomic motions and vibrations,
tend to be preferred and used more often than the term "thermal
energy", which is difficult to define.
NOTATION
The total amount of energy transferred through heat transfer
is conventionally abbreviated as Q. The conventional sign
convention is that when a body releases heat into its surroundings,
Q < 0 (); when a body absorbs heat from its surroundings, Q> 0
(+). Heat transfer rate, or heat flow per unit time, is denoted by:
. dQ
Q=.
dt
Heat and Thermodynamics 4
It is measured in watts. Heat flux is defined as rate of heat transfer
per unit crosssectional area, and is denoted q, resulting in units
of watts per square metre, though slightly different notation
conventions can be used.
ENTROPY
In 1854, German physicist Rudolf Clausius defined the second
fundamental theorem (the second law of thermodynamics) in the
mechanical theory of heat (thermodynamics): "if two
transformations which, without necessitating any other permanent
change, can mutually replace one another, be called equivalent,
then the generations of the quantity of heat Q from work at the
temperature T, has the equivalencevalue:"
Q
T
In 1865, he came to define this ratio as entropy symbolized
by S, such that, for a closed, stationary system:
Q
!J.S =
T
and thus, by reduction, quantities of heat oQ (an inexact
differential) are defined as quantities of TdS (an exact differential):
8Q= TdS
In other words, the entropy function S facilitates the
quantification and measurement of heat flow through a
thermodynamic boundary,.
DEFINITIONS
In modern terms, heat is concisely defined as energy in transit.
Scottish physicist James Clerk Maxwell, in his 1871 classic Theory
of Heat, was one of the first to enunciate a modern definition of
"heat". In short, Maxwell outlined four stipulations on the
definition of heat. One, it is "something which may be transferred
from one body to another", as per the second law of
thermodynamics.
Two, it can be spoken of as a "measurable quantity", and
thus treated mathematically like other measurable quantities.
5 Introduction
Three, it "can not be treated as a substance"; for it may be
transformed into something which is not a substance, e.g.
mechanical work.
Lastly, it is "one of the forms of energy". Similar such
modern, succinct definitions of heat are as follows:
• In a thermodynamic sense, heat is never regarded as
being stored within a body. Like work, it exists only as
energy in transit from one body to another; in
thermodynamic terminology, between a system and its
surroundings. When energy in the form of heat is added
to a system, it is stored not as heat, but as kinetic and
potential energy of the atoms and molecules making up
the system .
• The noun heat is defined only during the process of
energy transfer by conduction or radiation
• Heat is defined as any spontaneous flow of energy from
one object to another, caused by a difference in
temperature between two objects
Heat may be defined as energy in transit from a high
temperature object to a lowertemperature object
Heat as an interaction between two closed systems
without exchange of work is a pure heat interaction when
the two systems, initially isolated and in a stable
equilibrium, are placed in contact.
The energy exchanged between the two systems is then
called heat
• Heat is a form of energy possessed by a substance by
virtue of the vibrational movement, i.e. kinetic energy,
of its molecules or atoms
• Heat is the transfer of energy between substances of
different temperatures.
THERMODYNAMICS
INTERNAL ENERGY
Heat is related to the internal energy U of the system and
work W done by the system by the first law of thermodynamics:
tl.U= Q W
which means that the energy of the system can change either
Heat and Thermodynamics 6
via work or via heat flows across the boundary of the
thermodynamic system. In more detail, Internal eI).ergy is the sum
of all microscopic fonns of energy of a system.
It is related to the molecular structure and the degree of
molecular activity and may be viewed as the sum of kinetic and
potential energies of the molecules; it comprises the following
types of energies:
Type
Sensible energy
Latent energy
Chemical energy
Nuclear energy
Energy interactions
Thermal energy
Composition of Internal Energy (U)
The portion of the internal energy of a system
associated with kinetic energies (molecular translation,
rotation, and vibration; electron translation and spin;
and nuclear spin) of the molecules.
The internal energy associated with the phase of a
system.
The internal energy associated with the atomic bonds
in a molecule
The tremendous amount of energy associated wit)t the
strong bonds within the nucleus of the atom itself
Those types of energies not stored in the system (e.g.
heat transfer, mass transfer, and work), but which are
recognized at the system boundary as they cross it,
which represent gains or losses by a system during a
process
The sum of sensible and latent forms of internal energy.
The transfer of heat to an ideal gas at constant pressure
increases the internal energy and perfonns boundary work (Le.
allows a control volume of gas to become larger or smaller),
provided the volume is not Returning .to the first law
equation and separating the work tenn into two types, "houndary
work" and "other" (e.g. shaft wo.r.k perfonned by a COmpressor
fan), yields the following:
!l.U + Wboundary = Q  .Wother
This combined 9uanti.ty + Wbounc/ary is H, one
of the thennodynrulllc potentials. Both e1,1Jhalpy, H, and mternal
energy, U are state (uncti<;lns. State functions ,return to their initial
values upon· completion of each c·ycle in cyclic processes such as
that of a l:leat engine.
In contrast, neither Q nor Ware .properties of a system and
need not sum to zero over the steps of a cycle. The infinitesimal
7 Introduction
expression for heat, oQ, forms an inexact differential for processes
involving work. However, for processes involving no change in
volume, applied m?gnetic field, or other external parameters, oQ,
forms an exact differential. Likewise, for adiabatic processes (no
heat transfer), the for work forms an exact differential,
but for processes involving transfer of heat it forms an inexact
differential.
HEAT CAPACITY
For a simple compressible system such as an ideal gas inside
a piston, the changes in enthalpy and internal energy can be related
to the heat capacity at constant pressure and volume, respectively.
Constrained to have constant volume, the heat, Q, required to
change its temperature from an initial temperature, To, to a final
temperature, T
f
is given by:
Q= r: CvdT=flU
Removing the volume constraint and allowing the system to
expa»d or contract at constant pressure:
Q = flU t: PdT = !ill = r: CpdT
For inconwressible substances, such as solids and liquids, the
distin.ction between the two types of heat cl;lpacity disappears, as
no work is performed. Heat capacity is an extensive quantity and
as such is dependent on the number of molecules in the system. It
can be represented as the product of mass, m , and specific heat
capacity, csaccordjng to:
C
p
= mc
s
or is dependelLt on the number of mqles and the molar heat
capacity, c
n
ac.corc!i,ng to:
C
p
=nc
n
The lJlolar and specific :heat are dependent upon the
inter,nal of freedom of the systep1 and not on any ext.ernal
prQpel1<\es as volume.and A':llllher of molecules.
rh,e specific heats of monatom:ic ,gage,s (e.g., he1il,l,lll) are
,constant with tell,lperature. Pi/itomic such as hydrogen
display some temperature de,pe.odence, and triatomic gases (e.g.,
Heat and Thermodynamics 8
carbon dioxide) still more in liquids at sufficiently low
temperatures, quantum effects become significant. An example is
the behaviour of bosons such as helium4. For such substances,
the behaviour of heat capacity with temperature is discontinuous
at the BoseEinstein condensation point.
The quantum behaviour of solids is adequately characterized
by the Debye model. At temperatures well below the characteristic
Debye temperature of a solid lattice, its specific heat will be
proportional to the cube of absolute temperature. For low
temperature metals, a second term is needed to account for the
behaviour of the conduction electrons, an example of FermiDirac
statistics.
CHANGES OF PHASE
The boiling point of water, at sea level and normal
atmospheric pressure a!1d temperature, will always be at nearly
100°C, no matter how much heat is added.
The extra heat changes the phase of the water from liquid
into water vapour. The heat added to change the phase of a
substance in this way is saio to be "hidden" and thus it is called
latent heat (from the Latin latere meaning "to lie hidden"). Latent
heat is the heat per unit mass necessary to change the state of a
given substance, or:
11m
and
Q= rM Ldm.
JMo
Note that, as pressure increases, the L rises slightly. Here,
Mo is the amount of mass initially in the new and M is the
amount of mass that ends up in the new phase. Also,L generally
does not depend on the amount of mass that changes phase, so
the equation can normally be written:
Q=L!:l.m.
Sometimes L can be timedependent if pressure and volume
are changing with time, so that the integral can be written as:
Q= fL dm dt.
dt
9
Introduction
HEAT TRANSFER MECHANISMS
Heat tends to move from a hightemperature region to a low
temperature region. This heat transfer may occur by the
mechanisms of conduction and radiation. In engineering, the term
convective heat transfer is used to describe the combined effects
of conduction and fluid flow and is regarded as a third mechanism
of heat transfer.
Conduction
Conduction is the most significant means of heat transfer in
a solid. On a microscopic scale, conduction occurs as hot, rapidly
moving or vibrating atoms and molecules interact with neighboring
atoms and molecules, transferring some of their energy (heat) to
these neighboring atoms. In insulators the heat flux is carried
almost entirely by phonon vibrations.
The "electron fluid" of a conductive metallic solid conducts
nearly all of the heat flux through the solid. Phonon flux is still
present, but carries less than 1 % of the energy. Electrons also
conduct electric current through conductive solids, and the thermal
and electrical conductivities of most metals have about the same
ratio. A good electrical conductor, such as copper, usually also
conducts heat well. The PeltierSeebeck effect exhibits the
propensity of electrons to conduct heat through an electrically
conductive solid. Thermoelectricity is caused by the relationship
between electrons, heat fluxes and electrical currents.
Convection
Convection is usually the dominant form of heat transfer in
liquids and gases. This is a term used to characterize the combined
effects of conduction and fluid flow. In convection, enthalpy
transfer occurs by the movement of hot or cold portions of the
fluid together with heat transfer by conduction. Commonly an
increase in temperature produces a reduction in density. Hence,
when water is heated on a stove, hot water from the bottom of the
pan rises, displacing the colder more dense liquid which falls.
Mixing and conduction result eventually in a nearly homogenous
density and even temperature. Two types of convection are
Heat and Thermodynamics 10
commonly distinguished, free convection, in which gravity and
buoyancy forces drive the fluid movement, and forced convection,
where a fan, stirrer, or other means is used to move the fluid.
Buoyant convection is due to the effects of gravity, and hence
does not occur in microgravity environments.
Radiation
Radiation is the on;y form of heat transfer that can occur in
the absence of any form of medium; thus it is the only means of
heat transfer through a vacuum. Thermal radiation is a direct result
of the movements of atoms and molecules in a material. Since
these atoms and molecules are composed of charged particles
(protons and electrons), their movements result in the emission
of electromagnetic radiation, which carries energy away from the
surface. At the same time, the surface is constantly bombarded by
radiation from the surroundings, resulting in the transfer of energy
to the surface. Since the amount of emitted radiation increases
with increasing temperature, a net transfer of energy from higher
temperatures to lower temperatures results.
The power that a black body emits at various frequencies is
described by Planck's law. For any given temperature, there is a
frequency f
max
at which the power emitted is a maximum. Wien's
displacement law, and the fact that the frequency of light is
inversely proportional to its wavelength in vacuum, mean that the
peak frequency j ~ a x is proportional to the absolute temperature T
of the black body. The photosphere of the Sun, at a temperature
of approximately 6000 K, emits radiation principally in the visible
portion of the spectrum. The earth's atmosphere is partly
transparent to visible light, and the light reaching the earth's
surface is absorbed or reflected. The earth's surface emits the
absorbed radiation, approximating the behaviour of a black body
at 300 K with spectral peak atfmax' At these lower frequencies,
the atmosphere is largely opaque and radiation from the earth's
surface is absorbed or scattered by the atmosphere. Though some
radiation escapes into space, it is absOl bed and subsequently re
emitted by atmospheric gases. It is this spectral selectivity of the
atmosphere that is responsible for the pl:inetary greenhouse effect.
11
Introduction
The commOn household lightbulb has a spe<.:trum overlapping
the blackbody spectra of the Sun and the earth. A portion of the
photons emitted by a tungsten light bulb filament at 3000K are in
the visible spectrum. However, most of the energy is associated
with photons of longer wavelengths; these will not help a person,
but will still transfer heat to the environment, as can be deduced
empirically by observing a household incandescent lightbulb.
Whenever EM radiation is emitted and then absorbed, heat is
transferred. This principle is used in microwave ovens, laser
cutting, and RF hair removal.
Other Heat Transfer Mechanisms
• Latent heat: Transfer of heat through a physical change
in the medium such as watertoice or watertosteam
involves significant energy and is exploited in many
ways: steam engine, refrigerator etc.
• Heat pipes: Using latent heat and capillary action to move
heat, heat pipes can carry many times as much heat as a
similarsized copper rod. Originally invented for use in
satellites, they are starting to have applications in
personal computers.
HEAT DISSIPATION
In cold climates, houses with their heating systems form
dissipative systems. In spite of efforts to insulate such houses to
reduce heat losses to their exteriors, considerable heat is lost, or
dissipated, from them, which can 'make their interiors
uncomfortably cool or cold. For the comfort of its inhabitants,
the interior of a house must be maintained out of thermal
equilibrium with its external surroundings. In effect, domestic
residences are oases.of warmth in a sea of cold and the thermal
gradient between the inside and outside is often quite steep.
This can lead to problems such as condensation and
uncomfortable draughts (drafts) which, if left unaddressed, can
cause structural damage to the property. This is why modern
insulation techniques are required to reduce heat loss.
In such a house, a thermostat is a device capable of starting
the heating system when the house's interior falls below a set
Heat and Thermodynamics 12
temperature, and of stopping that same system when another
(higher) set temperature has been achieved. Thus the thermostat
controls the flow of energy into the house, that energy eventually
being dissipated to the exterior.
TEMPERATURE MEASUREMENT
Temperature is the most commonly measured parameter, yet
in many respects it is the least understood. It is a surprisingly
difficult parameter to measure with the precision that one might
reasonably expect.
To obtain accuracies better than O.2°C (O.4°F) great care in
needed. Errors occur due to the presence of temperature gradients,
drafts, sensor nonlinearities, poor thermal contact, calibration
drifts, radiant energy and sensor self heating. Generally the
accuracy of all sensor types can be greatly improved by individual
calibration.
The information in this section is oriented towards electronic
thermometers those with an electrical output that can be connected
to a measuring instrument, such as: a data acquisition system, a
data logger, a control system or a chart recorder. However, there
is also a wide range of thermometers that can be used for manual
temperature measurement. These include: the glass thermometer,
various gas thermometers, pressure based thermometers, bimetallic
thermometers and temperature sensitive paint or film
thermometers.
IS TEMPERATURE MEASUREMENT DIFFICULT?
The answer depends on the temperature, the material being
measured and your expectations of accuracy. The table below
summarises the difficulty of temperature measurement over a range
of temperatures:
Accuracy Required
Temperature ±5°e
±]Oe
±O.5°e
±o.]Oe
200°C care needed difficult difficult very difficult
O°C to 50°C easy care needed difficult very difficult
IOOO°C care needed very difficult extremely almost
difficult impossible
2000°C very difficult extremely almost don"t
difficult impossible even try
13 Introduction
In a laboratory with appropriate standards and equipment, it
is possible to measure temperature to O.OOloC (l°mC) or even
better. This is typically done by interpolation (estimation of the
values) between two standards, using a quality platinum
temperature sensor and / or a Type S thermocouple.
When measuring temperature it is important to keep your
goals in mind. Identify exactly what is to be measured and the
accuracy needed. If accurate temperature differences are of prime
importance, then consider using the thermopile to avoid the need
for closely matched sensors.
SOURCES OF TEMPERATURE MEASUREMENT ERROR
In using temperature sensor3 it is helpful to think of where
heat flows. This applies to both sheathed and unsheathed sensors.
Understanding the thermal resistances and where they are located
is especially useful in identifying potential errors sources.
The following diagram indicates some of the complexity in
temperature measurement. Note the presence of thermal gradients
in the material being measured. These gradients can be particularly
troublesome when measuring the materials with poor thermal
conductivity, such a:. plastics and even stainless steel.
Gradient Iron, surface Sensor
to sensor 9:nlment )
f i "L:;;:;O
1il ::2: Conducbon In w ,
2 .
Gradient in thick Temperature gradient
ness of material to environment
Thermal Flows To and From a Temperature Sensor
Below is a description of temperature measurement error
sources and some suggestions on minimising these errors.
SENSOR CALIBRATION
Sensors calibration errors can be due to offset, scale and
linearity errors. In addition, each of these errors can drift with
time and temperature cycling. Hysteresis (where a value depends
on the direction from whjch it was approached) can be noticed
Heat and Thermodynamics 14
with some sensors, but the effect is usually small with the
exception of the bimetallic strip where it may be several degrees.
Platinum RTD's are considered the most accurate and stable of
standard sensors. However, individually calibrated thermocouples
can come close over the same temperature range. The platinum
based thermocouples can be just a stable as platinum RTD's and
cover a higher temperature range.
Sensor interchangeability is often the decisive factor. It refers
to the maximum temperature reading error likely to occur in
replacing a sensor with another of the same type without
recalibrating the system. Choosing a practical calibration reference
can be an issue. For professional purposes, a high quality platinum
RTD is best, along with an appropriate indicator. Other references
include iced water bath, traditional glass thermometers (especially
laboratory grade) and medical thermometers. In general, the
defining reference points of the ITS':90 are not practical for routine
calibration purposes.
THERMAL GRADIENTS
Thermal gradients are often a major source of measurement
error. This is especially true when measuring materials with poor
thermal conductivity such as: air, most liquids and nonmetallic
solids. In the case of fluids it important that the fluid be stirred.
An unstirred ice bath (a mixture of ice and water) can have a
vertical temperature gradient of several degrees. If stirring is not
practical, gradients can be minimised by insulating the system
b ~ i n g measured, to prevent heat transfer :nto or out of, the system.
Employing multiple sensors for spatial diversity and averaging
the readings is another solution.
HEAT CONDUCTION IN SENSOR LEADS
All sensors \\lith the exception of noncontact and maybe the
fibre optic types require that wires be brought to the sensor. These
wires are usually copper, an excellent heat conductor. The
placement of these wires can have a significant impact on accuracy.
The wires allow heat flow into or out of the sensor lJoQ.y,
requiring the sensing element to be in better thermal contact with
15 Introduction
the material being measured than would otherwise be needed.
When measuring the temperature of thermal insulation materials,
this can be a major source of error.
There are three solutions, all of which are good standard
practice:
• Use as thin wires as is practical for sensor hookup.
(Note: this contradicts good practice for high temperature
thermocouple measurement where the reverse rule
appliesuse the thickest wire that is practical)
• Place the wires in or against the material being measured,
so that they actually assist in transferring the temperature
of the material into the sensor
Good Wring Poor Wiring
Heat Conductance in leads
• Attempt to minimise the thermal gradient along the
sensor wires by placing the wires at an angle to the
gradient. This ensures a higher thermal resistance because
of a longer length of wire.
RADIATION
Radian heat can be a major source of error in measuring air
temperature.
A sensor in sunlight is almost certain to read significantly
higher than the actual air temperature.
To avoid this error the sensor must be shielded from source
of radiant energy.
The sun is the most obvious source, however just about any
object that is at a different temperature to the air is a potential
source (or sink) of troublesome radiant energy.
The best solutions are the following:
• Ensure that the sensor's outside surface is highly
reflective of infrared radiation (i.e.it is painted white or
has a bright metal finish)
Heat and Thermodynamics 16
• Ensure the sensor is thermally 'well connected' to the
air by having a good surface areatovolume ratio. Small
sensors are generally better.
Place the sensor in a vented radiation shield that also
has a highly reflective surface on the outside and inside
Ensure the sensor has a high surface areatovolume ratio
to ensure good thermal 'contact' with the air.
Radiant heat loss can be a source of sensor error when
measuring elevated temperature. Again, the same rules apply. Use
reflective surface finish on the sensor, shield the sensor if possible,
and ensure a good thermal contact with the medi urn being measured.
SENSOR SELFHEATING
Thermistors, RTDs and semiconductor sensors require the
application of an excitation power in order that a reading may be
taken. This power can heat the sensor, causing a high reading.
The effect depends on the size of the sensing element and the level
of power. Typically, the magnitude of the self heating effect is
between 0.1 °C and I.SoC.
The best solutions are the following:
• Calibrate out the selfheating effect. This is perhaps the
easiest solution. However, the equipment must be
allowed time to 'warm up', and different calibrations
are required for mediums with different thermal
characteristics e.g. air and water
• Use the lowest possible excitation power. However, a
compromise between selfheating and sensitivity (and
signaltonoise ratio) must be made
Avoid unnecessarily small sensing elementsthey will
selfheat more than larger elements
Switch the excitation power off between readings. This
is the best solution if the readings can be made quickly,
befOIe the sensor has time to warm, and if there is
adequate time between readings for cooling
• Avoid selfheating sensor typesuse thermocouples. How
ever this is not necessary as simple as that, as the
measuring device is likely to use a reference junction
temperature sensor that is itself prone to selfheating.
17 Introduction
THERMAL CONTACT
Obviously, thermal contact with the material being measured
is important, but the degree of contact required is dependent on
other parasitic thermal connections to the surroundings which are
likely to have a significant impad on heat flow. These parasitics
include: lead conduction, direct contact with other material (e.g.
air) and radiant energy transfers.
If there is no temperature gradient in the vicinity of the sensor,
the thermal contact of the sensor can be poor and the sensor will
still provide accurate readings.
THERMAL TIME CONSTANT
When the temperature changes, it takes time for a sensor to
respond. Some sensors respond quickly, some in less than a second,
while others take minutes or even hours.
The time taken to reach 63% of the way to the new
temperature is referred to as the 'thermal time constant'. Most
sensors have one dominant time constant. However, sometimes,
there are minor, but longer, time constants present that can confuse
the measurement process.
Obviously if the temperature is changing more quickly than
a sensor is able to track, the measurement wil1 be in error.
The best solutions include the following:
• Use a more rapidly responding sensor
• Improve thermal contact
• Reduce the sensors thermal mass, by minimising material
in contact with the sensing element that is not associated
with improving thermal contact
• Compensate the readings using an inverse matching filter.
If the thermal characteristics of the system are constant
and known, it is possible to predict the temperature
dynamical1y.
Sometimes long time constants are useful in providing an
averaging effect on a rapidly fluctuating temperature. If this effect
is to be exploited, care needs to be taken to compensate for the
phase (time) delay in the response.
Heat and Thermodynamics 18
READOUT ERRORS
The measuring device connected to the sensor is never perfect.
The measuring device, be it a: meter, chart recorder, data
acquisition board or data logger, can have calibration, linearity
and temperature dependent errors.
These errors can be reduced by:
• Calibration of the readout device against known
references
Calibration of the total sensor  readout system, using a
reference temperature or against a precision thermometer
(glass or RTD+readout).
Temperature effects on the readout device can be a subtle
source of error. It is recommended that a test be conducted where
the temperature of the sensor is held constant, but the readout
device be placed in an oven or freezer. This is particularly
important for thermocouple readout devices, as their performance
can be greatly impacted by temperature gradients and the quality
of the internal reference junction sensing.
ELECTRICAL NOISE OR INTERFERENCE
Electrical noise can induce errors in systems with poor noise
rejection. Use the standard procedures as described in the
Measurements Methods section to minimise the impact. These
include the following:
Use shielded twisted pair cable
Keep wiring away from power cables, transformers and
electrical machinery
• Install low pass filters into the measuring device
• Avoid ground loops.
In some industrial processes, electrical noise can be so intense
that noncontact or fibreoptic sensors are the only option.
CONDENSATION
Sometimes in situations where temperatures are frequently
cycled through the dew point, condensation in the sensor and
wiring can collect and become an electrical leakage path, causing
errors. Prevention is better than cure.
19 Introduction
Preventative measures include the following:
Ensure that the sensor and its wiring is sealed. When an
air volume is sealed, ensure that the air is dry
• Moisture can wick along wires by capillary action. This
can be inhibited by sealing wires at the sensor end, with
a mediumviscosity super glue, or using a penetrating
oil from both ends.
Condensation can be a s o u r c ~ of intermittent errors and may
go unrecognized for a long time. It also can lead to corrosion,
accelerated by sensor excitatio!l power, ultimately leading to
complete failure. Semiconductor sensors can be particularly prone
to moisture penetrating the metalplastic interface of plastic
packages. Evaporating condensation can also lead to measurement
errors due to evaporative cooling effects  a subtle but real error
source.
SENSOR MECHANICAL STRESS
Many temperature sensor elements can respond to mechanical
stress. film type RTD has the appearance of a strain gauge and
will behave like one given the opportunity. Again, prevention is
better than cure.
Preventative measures include:
• Ensure that sensing elements are not subjected to
deformation in the way they are mounted
• Avoid using adhesives in attaching sensors to the surfaces
to be measured. The differences in the thermal
coefficients of linear expansion will induce mechanical
stress
• Use sensor that are less sensitive to stress  the
thermocouple
• Wound (as opposed to film) RTDs can be prone to
vibration damage. Take great care in the seft:ction and
mounting of sensors in highvibration environment
• Use grease in preference to adhesive to ensure thermal
connection. Avoid potting sensor elements in epoxy_
Calibration
If funds are available, special purpose temperature calibrators
Heat and Thermodynamics 20
can be purchased. However, these are expensive and not always
as accurate as one might expect
To calibrate over normal environment range, there are
two low cost standards that can be effectively employed to
achieve O.2°C accuracy. These are icewater mix made from
distilled water and a standard medical thermometer. These
points (O.O°C and about 37°C) are sufficiently far apart to
provide a useful calibration o'ver the 20
o
e to +60"C range
REFERENCES
A Guide to Physics: Thermodynamics. Statistical
Physics, and Quantum Mechanics by Gerald D.
Mahan. Boris E. Nadgorny, and Max
The Language of Science by Sidney B. ('ahn.
Introduction to Thermal Sciences: Thermodynamics
Fluid Dynamics Heat Transfer by Fnn'k W. Schmidt,
Robert E. Henderson. and Carl H. V. •. llgemuth.
• Thermodynamics In Materials Science by Robert T.
Dehoff.
Heat and Thermodynamics: A Historical Perspective
(Greenwood Guides to Great Ideas in Science) by
Christopher J. T. Lewis.
2 ______________________________ ___
Heat Transfer
CONDUCTIVE HEAT TRANSFER
HEAT TRANSFER MODES
Heat "flows" to right ( q)
Fig. Conduction Heat Transfer
Heat transfer processes are classified into three types. The
first is conduction, which is defined a ~ lransfer of heat
occurring through intervening matter with0ut bulk motion of
the matter. The process pictorially. A solid (a block of metal.
say) has one surface at a high temperature and one at a lower
temperature. This type of heat conduction can occur, through
a turbine blade in a jet engine. The outside surface. whIch is
exposed to gases from the combustor, is at a higher
temperature than the inside surface, which has cooling air next
to it. The level of the wall temperilture is critical for a turbine
blade.
The second heat transfer process is convection. or heat
transfer due to a flowing fluid. The fluid can he a gas or a liquid:
Heat and Thermodynamics 22
both have applications in aerospace technology. In convection heat
transfer, the heat is moved through bulk transfer of a nonun iform
temperature fluid.
The third process is radiation or transmission of energy
through space without the necessary presence of matter. Radiation
is the only method for heat transfer in space. Radiation can be
important even in situations in which there is an intervening
medium; a familiar example is the heat transfer from a glowing
piece of metal or from a fire.
Conduction
We will start by examining conduction heat transfer. We must
first determine how to relate the heat transfer to other properties
(either mechanical, thermal, or geometrical). The answer to this
is rooted in experiment, but it can be motivated by considering
heat flow along a "bar" between two heat reservoirs at T
A
, T
B
• It
is plausible that the heat transfer rate, Q, is a function of the
temperature of the two reservoirs, the bar geometry and the bar
properties. (Are there other factors that should be considered? If
so, what?). This can be expressed as
Q= 11(T
A
, T
B
, bar geometry, bar properties) .
..... __ L __ .....,
Fig. Heat transfer along a bar
It also seems reasonable to postulate that Q should depend on
the temperature difference TA  T
B
. TAT
B
If is zero, then the heat
transfer should also be zero. The temperature dependence can
therefore be expressed aSQ= 12 [TA  T
B
, T
A
, bar geometry, bar
properties] .
An argument for the general form of 12 can be made from
physical considerations. One requirement, as said, is if 12 = o.
TA = TB Using a Mac Laurin series expansion, as follows,
23
f(!:'T) = f(O) + ~ I !:'T + ...
c(!:'T) 0
Heat Transfer
Ifwe define !1T= TA  TB andf= f2' we find that (for small
c f ~ I
TA TB),fiTA TB)= Q=h(O)+ oCT ~ T ) (TAT
B
)
A B TATJl=O
+ ...
We know thatfiO) = 0. The derivative evaluated at TA = TB
(thermal equilibrium) is a measurable property of the bar. In
addition, we know that Q> ° ifTA>TB or 8i/8(TA  T
B
) > 0. It
also seems reasonable that if we had two bars of the same area,
we would have twice the heat transfer, so that we can postulate
that Q is proportional to the area.
Finally, although the argument is by no means rigorous,
experience leads us to believe that as L increases Q should get
smaller. All of these lead to the generalization that, for the bar,
the derivative in Equation has the form
Of2 I
O(TA  TB ) TrTJl=O
kA
L
In Equation, k is a proportionality factor that is a function of
the material and the temperature, Ais the crosssectional area and
Lis the length of the bar. In the limit for any temperature difference
!1T across a length ~ as both L, TA  TB ~ 0, we can say
Q = kA (TA  TB ) = kA (TB  TA) = kA dT .
L L dx
A more useful quantity to work with is the heat transfer per
unit area, defined as
iF"Q.
A
The quantity If is called the heat flux and its ",nits are Watts/
m
2
. The expression in can be written in terms of heat flux as
If = _k
dT
.
dx
Heat and Thermodynamics 24

Equation is the onedimensional fonn of Fourier's law of heat
conduction. The proportionality constant k is called the thermal
conductivity. Its units are W/mK. Thennal conductivity is a well
tabulated property for a large number of materials. Some values
for familiar materials are given in Table; others can be found in
the references. The thermal conductivity is a function of
temperature and the values shown in Table are for room
temperature.
Metals
Non
metals
Table: Thermal conductivity at room temperature for
some metals and nonmetals (W/mK)
Ag Cu Al Fe Steel
420 390 200 70 50
H
2
O Air Engine H2 Brick Wood
oil
0.6 0.026 0.15 0.18 0.40.5 0.2
SteadyState OneDimensional Conduction
j
lnsulalcd
(no beat transfer)
~
Q{x) 1.. L. <Xx + u)
I I
I I
~
. U .
       ~ . x
Fig. Onedimensional Heat Conduction
Cork
0.04
For onedimensional heat conduction (temperature depending
on one variable only), we can devise a basic description of the
process. The first law in control volume form (steady flow energy
equation) with no shaft work and no mass flow reduces to the
statement that LQ for all surfaces = 0 (no heat transfer on top or
bottom ). From Equation, the heat transfer rate in at the left (at x)
IS
. ( dT)
Q(x)=k A dx x'
25 Heat Transfer
The heat transfer rate on the right is
. . dQI
Q(x+dx) =Q(x) + dx dx+ ....
x
Using the conditions on the overall heat flow and the
expressions
Q(x)  ( Q(x) + 1; (x)dx + .... ) = o.
Taking the limit as dx approaches zero we obtain
dQ(x) =0,
dx
or
!( kA:)=O.
If is constant (i.e. ifthe properties of the bar are independent
of temperature), this reduces to
d_(AdT)=o
dx dx '
or (USiilg the chain rule)
d
2
T +(ldA)dT =0.
dx
2
A dx dx
Equation or describes the temperature field for quasione
dimensional steady state (no time dependence) heat transfer. WI.'
now apply this to an example.
Heat Transfer Through a Plane Slab
T'" T,
X'" 0 X'" L
.X
Fig. Temperature Boundary Conditions for a Slab
Heat and Thermodynamics 26
For this configuration, the area is not a function of x, i.e. A.
Equation, thus becomes
d
2
T
=0
dx
2
.
Equation, can be integrated immediately to yield
dT
=a
dx
and
T=a'C+b.
Equation is an expression for the temperature field where a
and b are constants of integration. For a second order equation,
such as, we need two boundary conditions to determine and . One
such set of boundary conditions can be the specification of the
temperatures at both sides of the slab ItO) = T
J
; T(L) = T
2
.
The condition ItO) = T
J
implies that b = T
J
• The condition
T2 = T(L) implies that T2 = aL + T
J
, or a= (T
2
 TJ)/L. With these
expressions for and (he temperature distribution can be written as
T(x)=l1 +(T2 ~ 1 1 )x.
This linear variation in temperature for a situation in which
T
J
> T
2
·
T
.c
Fig. Temperature Distribution Through a Slab
The heat flux ij is also of interest. This is given by
ij = k dT = _ k (T2 11) = constant.
dx L
Thermal Resistance Circuits
There is an electrical analogy with conduction heat transfer
that can be exploited in problem solving. The analog of Q is
current, and the analog of the temperature difference, T
J
 T
2
, is
27
Heat Transfer
voltage differt;nce. From this perspective the slab is a pure
resistance to heat transfer and we can define
Q = 'rt T2
R
where R = LlkA, the thermal resistance. The thermal resistance
Rincreases as Lincreases, as Adecreases, and as kdecreases.
R/ 1<.:
Fig. Heat Transfer Across a Composite Slab (Series Thermal Resistance)
The concept of a thermal resistance circuit allows ready
analysis of problems such as a composite slab (composite planar
heat transfer surface). In the composite slab, the heat flux is
constant with. The resistances are in series and sum to R = RI
R
2
. If TL is the temperature at the left, and TR is the
temperature at the right, the heat transfer rate is given by
. TL TR TL TR
Q= = .
model
c::::>
R R( +R2
Fig. Heat Transfer for a Wall with Dissimilar Materials
(Parallel Thermal Resistance)
Another example is a wall with a dissimilar material such as
a bolt in an insulating layer. In this case, the heat transfer
resistances are in parallel. The physical configuration, the heat
transfer paths and the thermal resistance circuit.
Heat and Thermodynamics 28
For this situation, the total heat flow Q is made up of the heat
flow in the two parallel paths, Q = QI + Q2' with the total resistance
given by
1 1 1
=+.
R RI R2
More complex configurations can also be examined; a brick
wall with insulation on both sides.
Brid<
14 0. 1111
=l • t ./ «/ «,
";,""
0.03111
Fig. Heat Transfer Through an Insulated Wall
The overall thermal resistance is given by
R = RI + R2 + R3 = k A + k A + k A .
I 1 2 2 3 3
Some representative values for the brick and insulation
thermal conductivity are:
kbrick = k2 = 0.7 W/mK
kinsulation = kl = k3 = 0.07 W/mK
Using these values, and noting that Al = A2 = A3 = A, we
obtain
ARI = AR3 = = 0.03 m = 0.42 m
2
K/W
kl 0.07 W/m K
O.lm =0.14m
2
K/W.
k2 0.7 W/mK
This is a series circuit so
Q . T.  T, 140 K
q =  = constant throughout = _1 __ 4 = 2 = 142 W/m
2
.
A RA 0.98 m K/W
29
Heat Transfer
I 2
4
1.0
TT.
7;T.
0
"
Fig. Temperature Distribution Through an Insulated Wall
The temperature is continuous in the wall and the intermediate
temperatures can be found from applying the resistance equation
across each slab, since Q is constant across the slab. to find T
2
:
q = 11 T2 =142 W/m
2
•
RIA
This yields T
1
T
2
= 60 K or T2 = 90°C.
The same procedure gives T3 = 70°C. As sketched, the larger
drop is across the insulating layer even though the brick layer is
much thicker.
Steady QuasiOneDimensional Heat Flow in NonPlanar
Geometry
The quasi onedimensional equation that has been developed
can also be applied to nonplanar geometries, such as cylindrical
and spherical shells.
Cylindrical Shell
An important case is a cylindrical shell, a geometry often
encountered in situations where fluids are pumped and heat is
transferred.
~ __ control volume
Fig. Cylindrical Shell Geometry Notation
For a steady axisymmetric configuration, the temperature
depends only on a single coordinate (r) and Equation, can be
written as
Heat and Thermodynamics 30
k = ~ ( A ( r ) dT) = 0,
dr dr
or, since A = 21tr,
~ ( r dT)=O.
dr dr
The steadyflow energy equation (no fluid flow, no work)
tells us that ~ n = Q..{)ut, or
dQ =0.
dr
The heat transfer rate per unit length is given by
. dT
Q=k21tr.
dr
Equation is a second order differential equation for T.
Integrating this equation once gives
dT
r=a
dr '
where a is a constant of integration. Equation, can be
written as
dT=a
dr
r
where both sides of Equation are exact differentials. It is
useful to cast this equation in terms of a dimensionless normalized
spatial variable so we can deal with quantities of order unity. To
do this, divide through by the inner radius, r
l
,
Integrating, yields
dT=ad(rlrl).
(r I 1j)
T = a In (r) + b.
(r1)
To find the constants of integration a and b, boundary
conditions are needed. These will be taken to be known
temperatures TI and T2 at rland r
2
respectively. Applying T= TI
r = rlat gives TI = b. Applying T= T2 at r = r
2
yields
31 Heat Transfer
or
T2 1J
a= .
In(r2 / rl)
The temperature distribution is thus
T
 (T '1') In(r / rl ) '1'
 2 I, +1,.
In(r2 / 'i)
As said, it is generally useful to put expressions into non
dimensional and normalized form so that we can deal with numbf:rs
of order unity (this also helps in checking whether results are
consistent). If convenient, having an answer that goes to zero at
one limit is also useful from the perspective of ensuring the answer
makes sense. Equation can be put in nondimensional form as
T 1J In(r / r,)
='"'
T2 1J In(r2 / 'i )
The heat transfer rate, Q, is given by
Q = leA dT = 21tr,k (T2 1J) 1 = 21t k(1J  T
2
)
dr In(r2 / 'i)'i 'i In(r2 / 'i )
per unit length. When the heat flow rate is written so as to
incorporate our definition of thermal resistance,
. 1JT
2
Q=R'
comparison with, reveals the thermal resistance R to be
R = In ('i /1j ) .
21tk
The cylindrical geometry can be viewed as a liqtiting case of
the planar slab problem. To make the connection, consider the
case when (r
2
 r1)/r, « 1. From the series expansion for In (1 + x)
we recall that
x
2
x
3
In (l+x) ~ x ++ ...
2 3
Heat and Thermodynamics 32
(Look it up, try it numerically, or use the binomial theorem
on the series ( 11x = 1 x + X
2
+ .... ) and integrate term by term.)
The logarithms in Equation, can thus be written as
In(I + r 1j ) == r 1j
1j 1j
and
== r2  rl
rl 1j
in the limit of (r2  r
l
)« r
l
. Using these expressions in
Equation, gives
T
_T T (rrl) T
(r2 lj)
With the substitution of r  r
l
= x, and r
2
 r
l
= L we obtain
x
T=1) +(T2 1),
L
which is the same as Equation. The plane slab is thus the
limiting case of the cylinder if (r2  rl)/R
t
« 1, where the heat
transfer can be regarded as taking place in (approximately) a planar
slab.
To see when this is appropriate, consider the expansion In
(I + x)/x, which is the ratio of heat flux for a cylinder and a plane
slab.
For <10% error, the ratio of thickness to inner radius should
be less than 0.2, and for 20% error, the thickness to inner radius
should be less than 0.5.
Table: Utility of plane slab approximation
x 0.1 0.2 0.3 0.4 0.5
10(1 + x)
0.95 0.91 0.87 0.84 0.81
x
Spherical Shell
A second example is the spherical shell with specified
temperatures T(r
l
) = T
J
and 1(r
2
) = T
2
.
33
Heat Transfer
T,
Fig. Spherical Shell
The area is now A(r) = 47tr
2
, so the equation for the
temperature fieid is
~ ( r 2 dT)=o.
dr dr
Integrating Equation, once yields
Integrating again gives
dT a
dr = r
2
'
a
T=+b,
r
or, normalizing the spatial variable
at
T=+b,
(r I Ij)
where a' and b are constants of integration. As before, we
specify the temperatures at r = r
l
and r = r
2
• Use of the first
boundary condition gives T(r
l
) = TI = d+ b. Applying the second
boundary condition gives
at
T(r2) = T2 + b.
(r2 11j)
Solving for d and b,
1i T2
a'=
1 rl Ir2
'7' 1i  T2
b' =11
lrl I r2
In nondimensional form the temperature distribution is thus
1i  T 1  (r 1 / r)
= '''
1i  T2 1  (Ij / r2)
Heat and Thermodynamics 34
CONVECTIVE HEAT TRANSFER
The secocnd type of heat transfer to be examined is
convection, where a key problem is determining the boundary
conditions at a surface exposed to a flowing fluid. An example is
the wall temperature in a turbine blade because turbine
temperatures are critical for creep (and thus blade) life. A view of
the problem is given which shows a crosssectional view of a
turbine blade.
There are three different types of cooling indicated, all meant
to ensure that the metal is kept at a temperature much lower than
that of the combustor exit flow in which the turbine blade operates.
In this case, the turbine wall temperature is not known and must
be found as part of the solution to the problem.
(2) convection cooling
3) film cooling
y
(I) jet impinging on
insidcof
Iu.binc blade
lurbine blade
Fig. Turbine Blade Heat Transfer Configuration
y
T
T. T ..
Velocity
distributioa;
c  0 at sur&cc
c (velocity)
Fig. Temperature and Velocity Distributions near a Surface
To find the turbine wall temperature, we need to analyze
convective heat transfer, which means we need to examine some
features of the fluid motion near a surface. The conditions near a
surface are illustrated schematically. In a region of thickness 0,
there is a thin "film" of slowly moving fluid through which most
of the temperature difference occurs. Outside this layer, T is
roughly uniform (this defines 0'). The heat flux can thus be
expressed as
35 Heat Transfer
. _ Q _ k(T.,v Too)
q _. A  0' .
It cannot be emphasized enough that this is a very crude
picture. The general concept, however, is correct, in that close to
the wall, there is a thin layer in which heat is transferred basically
by conduction. Outside of this regiun is high mixing. The difficulty
is that the thickness of the layer is not a fluid property.
It depends on velocity (Reynolds number), structure ofthe wall
surface, pressure gradient and Mach number. Generally 0' is not
known and needs to be found and it is customary to calculate the heat
transfer using kfluiio' .
This quantity has the symbol h and is known as the convective
heat transfer coefficient. The units of hare W Im
2
K. The convective
heat transfer coefficient is defined by
q = Q = h(Tw  Too).
A
Equation is often called Newton's Law of Cooling. For many
situations of practical interest, the quantity is still known mainly
through experiments.
THE REYNOLDS ANALOGY
We describe the physical mechanism for the heat transfer
coefficient in a turbulent boundary layer because most aerospace
vehicle applications have turbulent boundary layers. The treatment
closely follows that in Eckert and Drake. Very near the wall, the
fluid motion is smooth and laminar, and molecular conduction
and shear are important. The shear stress, 't, at a plane is given by
de
~ = dY = 't (where ~ is the dynamic viscosity), and the heat flux
l,y q = k ~ ~ . The latter is the same expression that was used for
a solid. The boundary layer is a region in which the velocity is
lower than the free stream. In a turbulent boundary layer, the
dominant mechanisms of shear stress and heat transfer change in
nature as one moves away from the wall.
Heat and Thermodynamics 36
plane
~       ~  
Fig. Velocity Profile Near a Surface
As one moves away from the wall (but still in the boundary
layer), the flow is turbulent. The fluid particles move in random
directions and the transfer of momentum and energy is mainly
through interchange of fluid particles.
m'c,T'
:f):
l    ~   I
m'c,T
" , , , " ; ; ,. ,. ,
Fig. Momentum and Energy Exchanges in Turbulent Flow
With reference to Figure, because of the turbulent velocity
field, a fluid mass tn' penetrates the plane aa per unit time and
unit area. In steady flow, the same amount crosses aa from the
other side. Fluid moving up transports heat m'epT. Fluid moving
down transports m' cpT downwards. If T' > T, there is a turbulent
downwards heat flow if turbulent' given by if turbulent = m' e
p
(T  1),
that results.
Fluid moving up also has momentum m' e and fluid moving
down has momentum m' e'. The net flux of momentum down per
unit area and time is therefore m' (e' c). This net flux of
momentum per unit area and time is a force per unit area or stress,
given by
'turbulent = m'(e'  C).
Based on these considerations, the relation between heat flux
and shear stress at plane aa is
37
Heat Transfer
(
T'T)
q turbulent = 'tturbulent e p e ,_ c '
or (again approximately)
. (dT)
q turbulent = 'tturbulent e p de '
since the locations of planes 11 and 22 are arbitrary.
For the laminar region, the heat flux towards the wall is q =
kdTldy and dividing by the expression for the shear stress, 't =
~ c 1 d y , yields
. kdT
q='t.
Il dc
The same relationship is applicable in laminar or turbulent
flow if klJl = e
p
or, expressed slightly differently,
J.lCp Illp _v_l
T k/pc
p
 a  ,
where v is the kinematic viscosity, and a is the thermal diffusivity.
The quantity J.lCJk is known as the Prandtl number (Pr), "fier
the man who first presented the idea of the boundary layer and
was one of the pioneers of modern fluid mechanics. For gases,
Prandtl numbers are in fact close to unity and for air Pr = 0.71 at
room temrerature. The Prandtl number varies little over a wide
range of temperatures: approximately 3% from 3002000 K.
We want a relation between the values at the wall (at which
T = T wand e = 0) and those in the free stream. To get this, we
integrate the expression for dT from the wall to the free stream
lq
dT=dc,
cp't
where the relation between heat transfer and shear stress has been
taken as the same for both the laminar and the turbulent portions
of the boundary layer. The assumption being made is that the
mechanisms of heat and momentum transfer are similar.
Equation can be integrated from the wall to the freestream
(conditions "at 00"):
Heat and Thermodynamics 38
r dT= r(
where C] IT. and c
p
are assumed constant.
Carrying out the integration yields
T T = C]w
c
""
woo'
"wcp
where Coo is the velocity and c
p
is the specific heat. In Equation,
C] IV is the heat flux to the wall and "w is the shear stress at the wall.
'The relation between skin friction (shear stress) at the wall and
heat transfer is thus
The quantity
C]w
PooC p (Tw  Too) Coo  .
"w
1 2
i
Poocoo
is known as the skin friction coefficient and is denoted by C
j
The
skin friction coefficient has been tabulated (or computed) for a
large number of situations. If we define a nondimensional quantity
C]W h(Too  = h = St,
Poocp(Tw  Too)coo Poocp(Tw  Too)c
oo
Poocpc
oo
known as the Stanton Number, we can write an expression for the
heat transfer coefficient, h as
C
f
h Poocpc
oo
.
2
Equation provides a useful estimate of h, or C] w' based on
knowing the skin friction, or drag. The direct relationship between
the Stanton Number and the skin friction coefficient is
Sf= C
f
.
2
The relation between the heat transfer and the skin friction
coefficient
39 Heat Transfer
is known as the Reynolds analogy between shear stress and heat
transfer. The Reynolds analogy is extremely useful in obtaining a
first approximation for heat transfer in situations in which the shear
stre5s is "known."
An example of the use of the Reynolds analogy is in analysis
of a heat exchanger. One type of heat exchanger has an array of
tubes with one fluid flowing inside and another fluid flowing
outside, with the objective of transferring heat between them. To
begin, we need to examine the flow resistance of a tube. For fully
developed flow in a tube, it is more appropriate to use an average
velocity e and a bulk temperature T
B
• Thus, an approximate
relation for the heat transfer is
. T8 Tw
qw ~ 'twcp _
C
The tluid resistance (drag) is all due to shear forces and is given
by 'tw4w = D, where Aw is the tube "wetted" area (perimeter length).
The total heat transfer, Q, is if w4w' so that
Q
. =D TB Tw
c
p
_ •
C
The power, P, to drive the flow through a resistance is given
by the product of the drag and the velocity, Dc , so that
Q = cp(TB Tw)
P e
2
The mass flow rate is given by m = peA, where is the cross
sectional area. For a given mass flow rate and overall heat transfer
rate, the power scales as c
2
or as lIA2, i.e.,
Qriz2
Poc 2 2'
P cp(TBTw)A
Equations shows that to decrease the power dissipated, we
need to decrease e, which can be accomplished by increasing the
crdsssectional area. Two possible heat exchanger configurations
the one on the right will have a iower loss.
Heat and Thermodynamics
beat exchanger
~
high loss
kwerloss
Fig. Heat Exchanger Configurations
40
To recap, there is an approximate relation between skin
friction (momentum flux to the wall) and heat transfer called the
Reynolds analogy that provides a useful way to estimate heat
transfer rates in situations in which the skin friction is known.
The relation is expressed by
or
or
C
Sf =1
2 '
heat flux to wall momentum flux to wall
convected heat flux convected momentum flux '
tlw 'w
=2'
Pa:,caJcp(T
aJ
 Tw) paJCaJ
The Reynolds analogy can be used to give information about
sc.aling of various effects as well as initial estimates for heaL
transfer. It is emphasized that it is a useful tool based on a
hypothesis about the mechanism of heat transfer and shear stress
and not a physical law.
COMBINED CONDUCTION AND CONVECTION
We can now analyze problems in which both conduction and
convection occur, starting with a wall cooled by flowing fluid on
each side. A description of the convective heat transfer can be
given explicitly as
Q =ij=h(TwTaJ)'
A
This could represent a model of a turbine blade with internal
cooling.
41
Heat Transfer
Fig. Conducting Wall with Convective Heat Transfer
The heat transfer in fluid 1 is given by
Q
  ~ (Twl 1)).
A
which is the heat transfer per unit area to the fluid. The heat transfer
in fluid 2 is similarly given by
Q =h2 (T2 Tw2)'
A
Across the wall, \\' e have
Q k
=(T. 2 T. I)'
A L W W
The quantity Q fA is the same in all of these expressions.
Putting them all together to write the known overall temperature
drop yields a relation between heat transfer and overall temperature
drop, T2  T
I
:
T2  TI = (T2  T wl2) + (T w2  Tw 1) + (T wi  T
I
) = ~ [ ~ I + ~ + ;J.
We can derine a thermal resistance, R, as before, such that
. (T2 1))
Q= R '
where R is given by
1 L 1
R=++.
~ A AK ~ A
Equation is the thermal resistance for a solid wall with
convection heat transfer on e.ach side.
For a turbine blade in a gas turbine engine, cooling is a critical
Heat and Thermodynamics 42
consideration. In terms of Figure, T2 is the combustor exit (turbine
inlet) temperature and TI is the temperature at the compressor exit.
We wish to find Tw2 because this is the highest metal temperature.
From, the wall temperature can be written as
Q T
2
1J 1
=T
2
 Ah2 =T
2
RAh
2
·
Using the expression for the thermal resistance, the wall
temperatures can be expressed in terms of heat transfer coefficients
and wall properties as
T2 1J
= T2  h, Lh .
=+_2 +1
hi k
Equation provides some basic design guidelines. The goal is
to have a low value of T w2. This means h/h2 should be large, k
should be large (but we may not have much flexibility in choice
of material) and L should be small. One way to achieve the first
of these is to have h2 low.
A second example of combined conduction and convection
is given by a cylinder exposed to a flowing fluid.
:>
Fig. Cylinder in a Flowing Fluid
For the cylinder the heat flux at the outer is given by
q = Q = h(T.,y  TrJeJ atr = r2·
A
The boundary condition at the inner surface could be either
a heat flux condition or a temperature specification; we use the
latter to simplify the algebra. Thus, T = TI at r = r
l
. This is a
model for the heat transfer in a pipe of radius r I surrounded by
insulation of thickness r
2
 r I. The solution for a cylindrical region
was given as T(r) = a + h.
43
Heat Transfer
Use of the boundary condition T(r
l
) = TI yields b = T
1
•
At the interface between the cylinder and the fluid, r = r
2
,
the temperature and the heat flow are continuous.
q = _ _ k
dT
dr
~
heart flux
inside cylinder
= k;' :h[[atn(;, ) + ~ )  T ~ ]
, " I
surface heat flux to flu id
Plugging the form of the temperature distribution in the cylinder
into Equation yields
a[:, +htn(;, )):h(1i  T ~ )
The constant of integration, a, is
and the expression for the temperature is, in normalized non
dimensional form,
1) T In(l"lrl)
= k .
1) Too +In(r21'i)
hr2
The heat flow per unit length, Q, is given by
Q = 21(1)  Too )k .
k
 + In (r2 Irl)
hr2
The units in Equation are W 1mso
A problem of interest is choosing the thickness of insulation
to minimize the heat loss for a fixed temperature difference TI 
Too between the inside of the pipe and the flowing fluid far away
from the pipe. (TI Too is the driving temperature distribution for
the pipe.) To understand the behaviour of the heat transfer we
examine the denominator in Equation as r
2
varies. The thickness
of insulation that gives maximum heat transfer is given by
Heat and Thermodynamics
In(rz J] = o.
dr2 hrz lj
From Equation, the value of r
2
for maximum Q is thus
k
(rZ)maximum heat transfer = ;;.
44
If r 2 is less than this, we can add insulation and increase heat
loss. To understand why this occurs, which shows a schematic of
the thermal resistance and the heat transfer. As r
2
increases from a
value less than r
2
= klh, two effects take place. First, the thickness
ofthe insulation increases, tending to drop the heat transfer because
the temperature gradient decreases.
Secondly, the area of the outside surface of the insulation
increases, tending to increase the heat transfer. The second of these
is (loosely) associated with the klhrs
z
term, the first with the In (ri
r 1 ) term. There are thus two competing effects which combine to give
a maximumQ at r
z
= klh.
k
Ii
Fig. Critical Radius of Insulation
DIMENSIONLESS NUMBERS AND ANALYSIS OF RESULTS
Phenomena in fluid flow and heat transfer depend on
dimensionless parameters. The Mach number and the Reynolds
number are two you have already seen. These parameters
information as to the relevant flow regimes of a given solution.
Casting equations in dimensionless form helps show the generality
of application to a broad class of situations (rather than just one
set of dimensional parameters).
It is generally good practice to use nondimensionaI numbers,
45
Heat Transfer
forms of equations, and results presentation whenever possible.
The results for heat transfer from the cylinder are already in
dimensionless form but we can carry the idea even further. For
the cylinder, we had in Equation,
T Ii In (r / rj )
Too Ii = ~ + In (r2 /1j) .
hr2
The parameter hr21k or hLlk, where L is a relevant length for
the particular problem of interest, is called the Biot number,
denoted by Hi. In terms of this parameter,
T Ii In (r / rj )
:...=
1 .
Too Ii Hi + In (r2 /1j)
The size of the Biot number gives a key to the regimes in which
different features are dominant. For Bi » I the convection heat
transfer process offers little resistance to heat transfer. There is
thus only a small L\Toutside (i.e. T(r
2
) close to Too) compared to
the L\T through the solid with a limiting behaviour of
T Ii In (r / 1j )
  =  ~ ~
Too  T In (r2 /1j)
as Hi goes to infinity. This is much like the situation with an
external temperature specified.
For Bi « 1 the conduction heat transfer process offers little
resistance to heat transfer. The temperature difference in the body
(i.e. from rjto r
2
) is small compared to the external temperature
difference, T
j
 Too' In this situation, the limiting case is
T Tj = Bi In (!...).
Too Ii 1j
In this regime there is approximately uniform temperature in
the cylinder. The size of the Biot number thus indicates the regimes
where the different effects become important.
RADIATION HEAT TRANSFER
All bodies radiate energy in the form of photons moving in a
random direction, with random phase and frequency. When
Heat and Thermodynamics 46
radiated photons reach another surface, they may either be
absorbed, reflected or transmitted. The behaviour of a surface with
radiation incident upon it can be described by the following
quantities:
• a = absorptance  fraction of incident radiation absorbed
• p = reflectance  fraction of incident radiation reflected
• t = transmittance  fraction of incident radiation
transmitted.
Figure shows these processes graphically.
~
Incident radiation
''\N<i'\,.Radi tion absorbed, a
I....J\MJ\.04. Radiation transmitted, 't
Radiation reflected. P _VVOil\#1
Fig. Radiation Surface Properties
From energy considerations the three coefficients must sum
to unity
a+p+t=l.
Reflective energy may be either diffuse or specular (mirror
like). Diffuse reflections are independent of the incident radiation
angle. For specular reflections, the reflection angle equals the angle
of incidence.
IDEAL RADIATORS
An ideal thermal radiator is called a "black body." It has
several properties:
• It has a = 1, and absorbs all radiation incident on it.
• The energy radiated per unit area is Eb = (J]4 where (J is
the StefanBoltzmann constant,
(J = 5.67 x 108 W/m
2
K4.
The units of Eb are therefore W/m
2
The energy of a black body, E
b
, is distributed over a range of
wavelengths of radiation. We can define e').. = dEJdA ~ M/!lA,
the energy radiated per unit area for a range of wavelengths of
width !lA. The behaviour of eA
47
Heat Transfer
e
0
·s
.
...
0.2898 emoK
J!
=
.:
u
:r
8
·S
u
;;
E
]
8
3
.!:
1 234 I • 7
Fig. Emissive Power of a Black Body at Several Temperatures,
Predicted and Observed; (A. T)eA.
max
= 0.2898 cm K
The distribution of eA varies with temperature. The quantity
AT at the condition where eA is a maximum is given by (AneAmax
= 0.2898 cm K. As T increases, the wavelength for maximum
energy emission shifts to shorter values. The frequency of the
radiation, j, is given by f = ciA so high energy means short
wavelengths and high frequency.
Fig. A Cavity with a Small hole (Approximates a Black Body)
I
Heat and Thermodynamics
Temperature T
Cavity
Blackbody
Fig. A Small Black Body Inside a Cavity
48
A physical real ization of a black body is a cavity with a small
hole. There are many reflections and absorptions. Very few
entering photons (light rays) will get out. The inside of the cavity
has radiation which is homogeneous and isotropic (the same in
any direction, uniform everywhere).
Suppose we put a small black body inside the cavity. The
cavity and the black body are both at the same temperature.
The radiant energy absorbed by the black body per second
and per m
2
is all!, where H is the irradiance, the radiant energy
falling on any surface inside the cavity. The radiant energy emitted
by the black body is E
B
. Since aB = 1 for a black body, H= E
B
.
The irradiance within a cavity whose walls are at temperature T
is therefore equal to the radiant emittance of a black body at the
same temperature and irradiance is a function of temperature only.
KIRCHHOFF'S LAW AND "REAL BODIES"
Real bodies radiate less effectively than black bodies. The
measurement of this is the emittance, e, defined by
E
. E
mlttance : e = ,
Eb
where Eis radiation from the real body at T, and Eb is radiation
from a black body at T.
Values of emittance vary greatly for different materials. They
are near unity for rough surfaces such as ceramics or oxidized
metals, and roughly 0.02 for polished metals or silvered reflectors.
The level of the emittance can be related to the absorptance
using the following arguments. Suppose we have a small nonblack
body in the cavity. The power absorbed per unit area is equal to
49 Heat Transfer
aH. The power emitted is equal to E. An energy balance gives
E= EbE = aH= aE
b
. Thus
E
=U=E.
Eb
Equation, the relation 0.= E, is known as Kirchhoffs Law. It
implies that good radiators are good absorbers. It was derived for
the case when T
body
= Tsurroundings (cavity) and is not strictly true for
all circumstar.ces when the temperature of the body and the cavity
are different, but it is true if at.. = a, Et.. = E, so the absorptance
and emittance are not functions of A. This situation describes a
"gray body." Also, since at.' Et.. are properties of the surface,
at.. = Et...
Radiation Heat Transfer Between Planar Surfaces
Surface 2
Surface: I
Fig. Path of a Photon between Two Gray Surfaces
Consider the two infinite gray surfaces. We suppose that the
surfaces are thick enough so that a + p = 1 (no radiation transmitted
so = 0). Consider a photon emitted from Surface 1 (remembering
that the reflectance p = 1  a):
Surface 1 emits E1
Surface 2 absorbs E1 0.
2
Surface 2 reflects E1 (1  0.
1
)
Surface 1 absorbs E1 (1  0.
2
) 0.
1
Surface 1 reflects E1 (1  0.
2
)(1  0.
1
)
Surface 2 absorbs E\ (l  0.
2
) (1  0.
1
) 0.
2
Surface 2 reflects E1 (1  0.
2
) (l  0.
1
) (1  0.
2
)
Surface 1 absorbs E
1
(1  0.
2
)(1  0.
1
)(1  0.
2
) 0.
1
The same can be said for a photon emitted from Surface 2:
Surface 2 emits E2
Surface 1 absorbs E
2
o.
1
Heat and Thermodynamics 50
Surface I reflects E
2
(l  a\)
Surface 2 absorbs E
2
( 1  a
2
)a
2
Surface 2 reflects Ei1  a\)(l  a
2
)
We can add up all the energy E\ absorbed in 1 and all the
energy E2 absorbed in 2. In doing the bookkeeping, it is helpful to
define 13 = (I  a\)(l  a
2
). The energy E\ absorbed in I is
E( (la2)a\ + E((1a2)a( (la2)(1 a\) + ....
This is equal to
However
1=(113)( =1+13+13
2
+ ....
113
We thus observe that the radiation absorbed by surface 1 can be
written as
Likewise
E\(Ia\)a2
113
is the radiation generated at 2 and absorbed there as well. Putting
th is all together we find that
E2 _(E
2
(1 a\) a2) = E
2
a\
113 113
is absorbed by 1. The net heat flux from 1 to 2 is
or
= E\ _ E\(la2)a\ E2a\
qnetlto2 113 113
Qnetlto2
E\E\(lala2 +ala2)E
1
a
l +E
1
a
la2 E
2
a
l
l(la( a2 +a,a2)
al +a2 a
1
a2
If TI = T
2
, we would have Q = 0, so from Equation,
EI = E2 = J(T).
a( a2
51
If body 2 is black, a
2
= 1, and E2 = art.
El = crT4,
('(.1
4
El
crT
= crT4.
a)
Heat Transfer
Therefore, again, E) = a
1
for any gray surface (Kirchhoffs
Law).
Using Kirchhoffs Law we find,
. Ela1l4E2  E2
aT
2
4E
I
qnetlto2 =
E) +E2 EIE2
or, as the final expression for heat transfer between gray, planar,
surfaces,
4 4
. s(lI  T2 )
qnet lto 2 = 1 1 .
+1
El E2
USE OF A THERMOS BOTTLE TO REDUCE HEAT
TRANSFER
Inside oflhennos
(hot fluid)
Silvered Walls
I '2
OulSidc ofl1lennos
(Cold)
Fig. Schematic of a Thermos Wall
El = E2 = 0.02 for silvered walls. Tl = 100°C = 373 K T2 = 20°C
= 293K.
cr(1I
4
 T24) .
Qnetlto2 = 1 1 = qnet lto 2
+1
El E2
= (5.1)7 x 10
8
W/m2K4)«373 K)4  (293 K)4) = 69 WI 2
1 1 . m.
+1
0.02 0.02
Heat and Thermodynamics 52
For the same I:!T, if we had cork insulation with k = 0.04 WI
mK, what thickness would be needed?
. kl:!T . L _ kflT _ (0.04 W/m K)(80 K)  047
q=Tsoathlckness T 6.9W/m . m
would be needed! The thermos is indeed a good insulator.
TEMPERATURE MEASUREMENT ERROR DUE TO
RADIATION HEAT TRANSFER
metal I mccal2
Fig. Thermocouple Used to Measure Temperature. Note: The Measured
Voltage is Related to the Difference between T) and T2
(the Latter is a known Temperature).
Thermocouples are commonly used to measure temperature.
There can be errors due to heat transfer by radiation. Consider a
black thermocouple in a chamber with black walls.
Suppose the air is at 20°C, the walls are at 100°C, and the
convective heat transfer coefficient is h = 15 Wmf2K.
What temperature does the thermocouple read?
Heal in (radiation) I Hcal oul (convection)
.... ,/
, ><
t Tie ,: Control \·olumc
' ... ,., ...  "
TwoIl
Fig. Effect of Radiation Heat Transfer on Measured Temperature
53 Heat Transfer
We use a heat (energy) balance on the control surface. The
heat balance states that heat convected away is equal to heat
radiated into the thermocouple in steady state. (Conduction heat
transfer along the thermocouple wires is neglected here, although
it would be included for accurate measurements.)
The heat balance is
 ) = 
where A is the area of the thermocouple. Substituting the numerical
values gives
(15 Wm
2
K)T
tc
293 K) = (5.67 x 10
8
W/m2K4) ((373 K)4_
from which we find = 51°C = 324 K. The thermocouple thus
sees a higher temperature than the air. We could this error
by shielding the thermocouple.
Radialionshicld
1000<:
Fig. Shielding a Thermocouple to Reduce Radiation Heat Transfer Error
RADIATION HEAT TRANSFER BETWEEN BLACK
SURFACES OF ARBITRARY GEOMETRY
In general, for any two objects in space, a given object 1
radiates to object 2, and to other places as well.
Fig. Radiation hetween Two Bodies
Heat and lherrnodynamics 54
Pody2
Body I
Fig. Radiation between Two Arbitrary Surfaces
We want a general expression for energy interchange
between two surfaces at different temperatures. This is given
by the radiation shape factor or view factor, F
i
_/ For the
situation in figure,
F
I
_
2
= fraction of energy leaving I which reaches 2
F
2
_
1
= fraction of energy leaving 2 which reaches I
F
I
_
2
' F
2
_
1
are functions of geometry only
For body 1, we know that Eb is the emissive power of a black
body, so the energy leaving body I is EblA I. The energy leaving
body I and arriving (and being absorbed) at body 2 is Ebl A IFI_
2. The energy leaving body 2 and being absorbed at body 1 is
Eb2A2F2_1. The net energy interchange from body 1 to body 2 is
Ebl
A
I
F
I_2  Eb2A2F2_1 = QI2·
Suppose both surfaces are at the same temperature so there
is no net heat exchange. If so,
Ebl
A
I
F
I_2  Eb2A2F2_1 = 0,
but also Ebl = E
b2
. Thus
A
1
F
I
_
2
= A
2
F
2
_
1
•
Equation is the shape factor reciprocity relation. The net
heat exchange between the two surfaces is
g2 = A
1
Fi2(E
bl
E
b2
) [or A2F2_1(F2_1Eb2)]
Concentric cylinders or concentric spheres
(SfT'
T,
Fig. Radiation Heat Transfer for Concentric Cylinders or Spheres
55 Heat Transfer
The net heat transfer from surface I to surface 2 of figure
is
G2 = A
1
Fi2(E
bl
 E
b2
)
We know that F
I
_
2
= I, i.e., that all of the energy emitted
by I gets to 2. Thus
G2 = Al (Ebl  E
b2
)·
This can be used to find the net heat transfer from 2 to I.
G2 = A
2
F
2

1
(Eb2  E
bl
) = AlFi2 (Fb2  E
bl
) = At (Eb2  E
bl
)·
REFERENCES
• Introduction to Metallurgical Thermodynamics by
David R. Gaskell.
• Schaum's Outline of Thermodynamics for Engineers,
2nd edition (Schaum's Outlines) by Merle Potter and
Ph.D., Craig Somerton.
• Mixing and Excess Thermodynamic Properties
(Physical sciences data) by Jaime Wisniak and
Abraham Tamir.
• Thermodynamics by J.P. Holman.
• Schaum Engineering Thermodynamics (Schaum's
Outlines) by Merle Potter.
3 ______________ _
Heat Conduction
TEMPERATURE DISTRIBUTIONS
IN THE PRESENCE OF HEAT SOURCES
There are a number of situations in which there are sources
of heat in the domain of interest. Examples are:
• Electrical heaters where electrical energy is converted
resistively into heat.
Nuclear power supplies.
• Propellants where chemical energy is the source.
These situations can be analyzed by looking at a model
problem of a slab with heat sources (W/m3) distributed throughout.
We take the outside walls to be at temperature Tw and we will
determine the maximum internal temperature.
T.
beac
sour<:eI
W
a m'
... t
Sli(c III.t. x
t
dot
[InfiniteSimal slice] x x + dx
Fig. Slab with Heat Sources
With reference to Figure, a steadystate energy balance yields
an equation for the heat flux, :
q + adx  ( q + ~ ! ax) = o.
57 Heat Conduction
or
dq _
a.
dx
There is a change in heat flux with x due to the presence of
the heat sources. The equation for the temperature is
d
2
T a
+=0.
dx
2
k
Equation can be integrated once,
and again to give
dT a
=x+a
dx k '
a 2
T=x +ax+b,
2k
where and are constants of integration. The boundary conditions
imposed are T(O) = T(L) = Tw' Substituting these into
Equation gives b = Tw and a = aLl2k. The temperature distribution
is thus
.
2k 2k w
Writing in a normalized, nondimensional fashion gives a
form that exhibits in a more useful manner the way in which the
different parameters enter the problem:
T Tw
aL2 I k  2 L L2 .
)
o 0.5 1.0
X
I.
Fig. Temperature Distribution for Slab with Distributed Heat Sources
It is symmetric about the midplane at x = Ll2, with half the energy
due to the sources exiting the slab on each side.
Heat and Thermodynamics
58
The heat flux at the side of the slab, x = 0, can be found by
differentiating the temperature distribution and evaluating at x = 0:
_kdTI = k aL2 != _ aL
dx x=o 2k L 2
This is half of the total heat generated within the slab. The
magnitude of the heat flux is the same at x = L, although the
direction is opposite.
A related problem would be one in which there were heat
flux (rather !han temperature) boundary conditions at x = 0 and
x = L, so that T w is not known. We again determine the maximum
temperature. At x = 0 and L, the heat flux and temperature are
continuous so
dT
k  = h(T  T.
oo
) at x = 0 L
dx '
Referring to the temperature distribution of Equation gives for the
two terms in Equation,
dT (ax )
k dx =k T+
a
= (ax + ka).
h(TT.l=h( a;: +ax+hT.)
Evaluating Equation at x = 0 and L allows determination cf the
two constants a and b. This is left as an exercise for the reader.
HEAT TRANSFER FROM A FIN
Fins are used in a large number of applications to increase
the heat transfer from surfaces. Typically, the fin material has a
high thermal conductivity. The fin is exposed to a flowing fluid,
which cools or heats it, with the high thermal conductivity allowing
increased heat being conducted from the wall through the fin. The
design of cooling f i n ~ is encountered in many situations and we
thus examine heat transfer in a fin as a way of defining some
criteria for design.
59 Heat Conduction
T,,(wall)
y
Fig. Geometry of Heat Transfer Fin
The fin is of length L. The other parameters of the problem
are indicated. The fluid has velocity cooand temperature Too. We
assume (using the Reynolds analogy or other approach) that the
heat transfer coefficient for the fin is known and has the value h.
The end of the fin can have a different heat transfer coefficient,
which we can call h L.
The approach taken will be quasionedimensional, in that
the temperature in the fin will be assumed to be a function of only.
This may seem a drastic simplification, and it needs some
explanation. With a fin crosssection equal to A and a perimeter
P, the characteristic dimension in the transverse direction is AlP
(For a circular fin, AlP = rl2). The regime of interest will be taken
to be that for which the Biot number is much less than unity, Bi = h
(AIPlk« 1), which is a realistic approximation in practice.
The physical content of this approximation can be seen from
the following. Heat transfer per unit area out of the fin to the fluid
is roughly of magnitude ~ h( T w  TOO> per unit area. The heat
transfer per unit area within the fin in the transverse direction is
(again in the same approximate terms) ~
k (1;  ~ v )
AlP , .
where T} is an internal temperature. These two quantities must be
of the same magnitude. If h(AIP)lk« I, then (T}  Tw)/(Tw  Too).
In other words, if Bi « 1, there is a much larger capability for
heat transfer per unit area across the fin than there is between the
Heat and Thennodynamics 60
· .
· .
· .
Q +! ! + Q
: + :
% x+tbc
Fig. Element of Fin Showing Heat Transfer
If there is little variation in temperature across the fin, an
appropriate model is to say that the temperature within the fin is
a function of x only, T = T(x), and use a quasionedimensional
approach. To do this, consider an element, dx, of the fin. There is
heat flow of magnitude Qin at the lefthand side and heat flow out
of magnitude Qout = Qin + 1; dx at the right hand side.
There is also heat transfer around the perimeter on the top,
bottom, and sides of the fin. From a quasionedimensional point
of view, this is a situation similar to that with internal heat sources,
but here, for a cooling fin, in each elemental slice of thickness
there is essentially a heat sink of magnitude Pdxh(T  T
rr
), where
Pdx is the area for heat transfer to the fluid.
The heat balance for the element in Figure can be written in
terms of the heat flux using Q = irA, for a fin of constant area:
rjA = Ph(T  Too)dx + (rjA + : dxA )
From Equation we obtain
A
drj
+Ph(TToo)=O.
dx
In terms of the temperature distribution, T(x):
.,
dT _ Ph (T T )=0.
dx2 Ak 00
The quantity of interest is the temperature difference (T  Too)'
and we can change variables to put Equation in terms of this
quantity using the substitution
61 Heat Conduction
!!.(T  T ) = dT .
dx 00 dx
Equation can therefore be written as
d
2
Ph
(TT )(TT )=0.
dx2 00 Ak 00
Equation describes the temperature variation along the fin. It is a
second order equation and needs two boundary conditions. The
first of these is that the temperature at the end of the fin that joins
the wall is equal to the wall temperature. (Does this sound
plausible? Why or why not?)
(T  Too)x=O = To  Too'
The second boundary conditicn is at the other end of the fin.
We will assume that tht: heat transfer from this end is negligible.
The boundary condition at x = L is
!!.(T  T
oo
)/ = o.
dx x=L
The last step is to work in terms of nondimensional variables to
obtain a more compact description. In this we define as (T  Too)1
(T
o
 Too), as!1T where the values of!1T range from zero to one.
We also define ~ = xl L, where ~ also ranges over zero to one. The
relation between derivatives that is needed to cast the equation in
terms of ~ is
d d ~ dId
==
dx dx d ~ L d ~
Equation can be written in this dimensionless form as
d
2
!1T _(hP L2)!1T = O.
d ~ 2 kA
There is one nondimensional parameter in Equation, which we
will call m and define by
m
2
L2 = hPL
2
kA
The equation for the temperature distribution we have obtained is
2 
d !1T _m
2
L2!1T = O.
d ~ 2
Heat and Thermodynamics
This second order equation has the solution
td = + be .
The boundary condition at = 0 is
LlT(O) = a + b = 1.
62
The boundary condition = 1 at is that the temperature
gradient is zero or
dllT (L) = mLae
mL
_ mLbe
mL
= o.
Solving the two equations given by the boundary conditions
for a and b gives an expression for LlT in terms of the hyperbolic
cosine or:
(eX +e
X
)
cosh X= ,
2
llT = cosh mL (1 .
cosh mL
This is the solution to Equation for a fin with no heat transfer
at the tip. In terms of the actual heat transfer parameters it is written
as
T Too cosh ( (li)JgL )
=
To  Too cosh ( JgL )
The amount of heat removed from the wall due to the fin,
which is the quantity of interest, can be found by differentiating
the temperature and evaluating the derivative at the wall, :
Q = kA(T  Too)
. d I
dx x=o
or
kA(To Too)
_ dllTI = mL sin h(mL) = mL tanh (mL),
x=o cosh (mL)
QL = tanh (mL).
Too)
63 Heat Conduction
The solution is plotted in Figure, which is taken from the
book by Lienhard. Several features of the solution should be noted.
First, one does not need fins which have a length such that is much
greater than 3. Second, the assumption about no heat transfer at
the end begins to be inappropriate as gets smaller than 3, so for
very short fins the simple expression above would not be a good
estimate. We will see below how large the error is.
Dimcnsionlcu heat
flow into the fin.
Q
Diml:nsionlcss
temperature
(T T.)I(7"o T.)
Dimensionless axial posilion ~  xII.
Dmsionless
temperalUI'C
.. tip
(T T.)I(T. T.)
Fig. The Temperature Distribution, Tip Temperature and Heat Flux in a
Straight Onedimensional Fin with the Tip Insulated.
TRANSIENT HEAT TRANSFER
All the heat transfer problems we have examined have been
steady state, but there are often circumstances in which the
transieni: response to heat transfer is critical. An example is the
heating up of gas turbine compressors as they are brought up to
speed during takeoff.
The disks that hold the blades are large and take a long time
to come to temperature, while the casing is thin and in the path of
high velocity compressor flow and thus comes to temperature
Heat and Thermodynamics 64
rapidly. The result is that the case expands away from the blade
tips, sometimes enough to cause serious difficulties with
aerodynamic performance.
To introduce the topic as well as to increase familiarity with
modeling of heat transfer problems, we examine a lumped
parameter analysis of an object cooled by a stream. This will allow
us to see what the relevant nOlldimensional parameters are and,
at least in a qualitative fashion, how more complex heat transfer
objects will behave. We want to view the object as a "lump"
described by a single parameter. We need to determine when this
type of ana,lysis would be appropriate. To address this, consider
the temperature difference TI  Tw between two locations in the
object.
c
T
Fig. Temperature Variation in an Object Cooled by a Flowing Fluid
If the heat transfer within the body and from the body to the
fluid are of the same magnitude,
k
h(Tw
L
where L is a relevant length scale, say half the thickness of the
object. The ratio of the temperature difference is
11 Tw hL
TwToo
If the Biot number is small the ratio of temperature differences
described in Equation is also (T
1
 Tw)/(Tw  T
rL
)« 1. We can thus
say (T
1
 Tw) « Tw  Too and neglect the temperature non
uniformity within the object.
The approximation made is to view the object as having a
spatially uniform temperature that is a function of time only.
Explicitly, T = T(t). The first law applied to the object is (using
the fact that for solids c
p
= C
v
= c),
65
Heat Conduction
. dT
Qin =pVc
dt
,
where p is the density of the object and is its volume. In terms of
heat transferred to the fluid, Qout =  pVcdTldt. The rate of heat
transfer to the fluid is Ah(T  Too, so the expression for the time
evolution of the temperature is
dT
Ah(TTCX»)=pVc.
dt
The initial temperature, ItO), is equal to some known value, which
we can canT
r
Using this, Equation can be written in terms of a
nondimensional temperature difference (T  Too)/(Tj  TCX»),
~ ( ~ = ;: ) + ~ c ( ~ = ~ : ) = O.
At time t = 0, this nondimensional quantity is equal to one.
Equation is an equation you have seep. before, (: + ~ = 0) which
has the solution x = ae
tir
• For the present problem the form is
T TCX) hAt/pVc
"'=ae .
1'; TCX)
The constant can be seen to be equal to unity to satisfy the
initial condition. This form of equation implies that the solution
has a heat transfer "time constant" given by 't = pVclhA.
The time constant, 't, is in accord with our intuition, or
experience; high density, large volume, or high specific heat all
tend to increase the time constant, while high heat transfer
coefficient and large area will tend to decrease the time constant.
This is the same form of equation and the same behaviour you
have seen for the RC circuit, as shown schematically in Figure.
The time dependence of the voltage in the RC circuit when the
switch is opened suddenly is given by the equation
dE E
+=0.
dt RC
There are, in fact, a number of physical processes which have
(or can be modeled as having) this type of exponentially decaying
behaviour.
Heat and Thermodynamics 66
R
Fig. Voltage Change in an RC Circuit
MODELING COMPLEX PHYSICAL PROCESSES
A number of assumptions were made about the processes that
we were attempting to describe. These are all part of the general
approach to modeling of physical systems. The main idea is that
for engineering systems, one almost always cannot compute the
process exactly, especially for fluid flow problems. At some level
of detail, one generally needs to model, i.e. to define some
plausible behaviour for attributes of the system that will not be
computed.
Modeling can span an enormous range from the level of our
assumption of uniform temperature within the solid object to a
complex model for the small scale turbulent eddies in the flow
past a compressor blade.
In carrying out such modeling, it is critical to have a clear
idea of just what the assumptions really mean, as well as the
fidelity that we ascribe to the descriptions of actual physical
phenomena, and we thus look at the statements we have made in
this context.
One assertion made was that because hLlk« 1 and on the
basis of a heat balance,
we could assume
k
 (Tc  Tw):::; h(Tw  Too),
L
(T
body
interior  Tw) 1
«.
(TwToo)
Based on this, we said that T
body
is approximately uniform
and T w :::; T
body
interior. Another aspect is that setting erases any
geometrical detail of the fin cross section. The only place where
67 Heat Conduction
P and A enter the problem is in a nondimensional combination.
A third assumption, made in the fin problem, was that the heat
transfer at the far end can be neglected. The solution including
this effect, where hLLlk is an axial Biot number is given as
Equation. If the quantity hLLlk is small, you can see that
Equation reduces to the previous result.
and
T  Too = cosh (mL(l1;)) + (Biaxial / m) sin h(mL(I1;))
ToToo cosh(mL)+(Biaxial/mL)sin h(mL)
Q _ BiaxIal / mL + tan h (mL)
.JkAhP(T
o
 Too)  1 + Biaxial tan h (mL)
mL
HEAT EXCHANGERS
The general function of a heat exchanger is to transfer heat
from one fluid to another. The basic component of '1 heat exchanger
can be viewed as a tube with one fluid running through it and
another fluid flowing by on the outside. There are thus three heat
transfer operations that need to be described:
• Convective heat transfer from fluid to the inner wall of
the tube,
1 Conductive heat transfer through the tube wall, and
• Convective heat transfer from the outer tube wall to the
outside fluid.
Heat exchangers are typically classified according to flow
arrangement and type of construction. The simplest heat exchanger
is one for which the hot and cold fluids move in the same or
opposite directions in a concentric tube (or doublepipe)
construction.
In the parallelflow arrangement of Figure, the hot and cold
fluids enter at the same end, flow in the same direction, and leave
at the same end. In the counterflow arrangement of Figure, the
fluids enter at opposite ends, flow in opposite directions, and leave
at opposite ends.
Heat and Thermodynamics
It

...

[Parallel flow] [Counter flow]

T=ftr •• ,·/
Fig. Concentric Tubes heat Exchangers
T=/1Jl)
' ... ..! .:
Tube flow
[Finned with both fluids unmixed]
[Unfinned with one
fluid mixed and the
other unmixed]
Fig. Crossflow Heat Exchangers
68

Alternatively, the fluids may be in cross flow (perpendicular
to each other), as shown by the finned and unfinned tubular heat
exchangers of Figure.
The two configurations differ according to whether the fluid
moving over the tubes is unmixed or mixed. The fluid is said to
be unmixed because the fins prevent motion in a direction (x) that
is transverse to the main flow direction (y).
In this case the fluid temperature varies with x and y. In
contrast, for the unfinned tube bundle of Figure, fluid motion,
hence mixing, in the transverse direction is possible, and
temperature variations are primarily in the main flow direction.
Since the tube flow is unmixed, both fluids are unmixed in the
finned exchanger, while one fluid is mixed and the other unmixed
in the unfinned exchanger.
To develop the methodology for heat exchanger analysis and
design, we look at the problem of heat transfer from a fluid inside
a tube to another fluid outside.
69 Heat Conduction
T.
Tl
Fig. Geometry for Heat Transfer between Two Fluids
We examined this problem before in Section and found that
the heat transfer rate per unit length is given by
Q= 2pk(TA T
B
) •
'ihl r2h2 rl
Here we have taken into account one additional thermal
resistance, the resistance due to convection on the interior, and
include in our expres')ion for heat transfer the bulk temperature
of the fluid, T
A
, rather than the interior wall temperature, T
I
•
It is useful to define an overall heat transfer coefficient ho
per unit length as
Q= 27tr2
h
O (T
A
 T
B
)
From Equations the overall heat transfer coefficient, ho' is
r2 In(r2
he k 'i h2
We will make use of this in what follows.
r :=J
n,
llr..J
t
T.,
Fig. Counterflow Heat Exchanger
Heat and Thennodynamics 70
A schematic of a counterflow heat exchanger. We wish to
know the temperature distribution along the tube and the amQunt
of heat transferred.
SIMPLIFIED COUNTERFLOW HEAT EXCHANGER
To address this we start by considering the general case of
axial variation of temperature in a tube with wall at uniform
temperature To and a fluid flowing inside the tube.
T, .+It. T,
x=O x=L
tbc
Fig. Fluid Temperature Distribution Along the Tube with
Uniform Wall Temperature
The objective is to find the mean temperature of the fluid at
x, T(x), in the case where fluid comes in at x = 0 with temperature
T
j
and leaves at x = L with temperature T
2
• The expected
distribution for heating and cooling are sketched in Figure.
For heating ero > 1), the heat flow from the pipe wall in a
length dx is
{J1tl1dx = h1tD(To  T)dt,
where D is the pipe diameter. The heat given to the fluid (the
change in enthalpy) is given by
1tD2 .
pumc
p
dT = mCpdT,
4
where p is the density of the fluid, urn is the mean velocity of the
fluid, c is the specific heat of the fluid and m is the mass flow
rate o{the fluid. Setting the last two expressions equal and
integrating from the start of the pipe, we find
71 Heat Conduction
,dT 1 4h
1 To T = pumcpD dx.
Carrying out the integration,
4hx =
pumcpD IToT IToT 1 TOT 1
I.e.,
In ( To  T ) _ _ 4hx
To Ii  7tu
m
c
p
D·
Equation can be written as
To T /h
=e ,
To 1]
where
B _ 4h _ 7thD
 pumcpD  lnc
p
.
This is the temperature distribution along the pipe. The exit
temperature at x = L is
or
nhDL
To T2 rirc
p
"== e
To Ii
The total heat transfer to the wall all along the pipe is
From Equation,
Q = mC
p
(1] T
2
)·
me
p
( hrtDL l
To Ii
To T2
The total rate of heat transfer is therefore
Q = hnDL(Ii  T
2
)
In (Ii To)
T2 To
Q = h7tDL!)'Tu,f'
where !)'T
LM
is the logarithmic mean temperature difference,
defined as
Heat and Thennodynamics 72
T2 11 L11\  L1T2
DTLM = = ';;=
In ( ~ = i ) In ( ~ ~ r
The concept of a logarithmic mean temperature difference is
useful in the analysis of heat exchangers. We will define a
logarithmic mean temperature difference for the general
counterflow heat exchanger below.
GENERAL COUNTERFLOW HEAT EXCHANGER
We return to our original problem, and write an overall heat
balance between the two counterflowing streams as
Q=maCpa(Tal Ta2)=mbcpb(Tb2 1[,1)'
From a local heat balance, the heat given up by ~ t r e a m in
length d
x
is macpadTao (There is a negative sign since Ta
decreases). The heat taken up by stream b is mbcpadTb. (There
is a negative sign because Tb decreases as x increases). The local
heat balance is
maC padTb = mbc pbdTb = qdA = q1CDx.
Solving for dT
a
and dT
b
, we find
dT = _ qdA . dT. = qdA .
a . , b 0
macpa macpb
d(Ta T
b
)=dL1T =_(_. _1 ___ . _l_]qdA =_(_1 __ 1 )q1CDd:"(,
maC pa mb
c
pb Wa Wb
where W = mc
p
' Also, q = hoL1T where ho is the overall heat
transfer coefficient. We can then say
dL1T =ho
1CL1
(_1 __ 1 )\dx.
L1T Wa Wb
Integrating from x = 0 to x gives
In(Ta2 Tbl)=_ho1CDL(_1 __ 1 ).
Tal  Tb2 Wa Wb
Equation can also be written as
73 Heat Conduction
where
a. = ho
7tDL
(_1 __ 1 ).
Wa Wb
We know that
Thus
. (1 1)
(Tal  T
b2
)  (T
a2
 T
bl
) = Q Wa  Wb .
Solving for the total heat transfer:
Q= (Tal T
b2
)(T
a2
T
bl
).
( ~ a ~ b )
Rearranging allows us to express ( ~ a ~ b ) in terms of other
parameters as
I (T
a2
T
bl
)
(
_1 ___ 1_) = n Tal  Tb2 .
Wa Wi, ho 7tDL
Substituting Equations we obtain a final expression for the total
heat transfer for a counterflow heat exchanger:
or
Q = ho
7tDL
(Tal  T
b2
)  (Ta2  T
bl
)
In(Tal  Tb2)
Ta2 Tbl
Heat and Thermodynamics 74
EFFICIENCY OF A COUNTERFLOW HEAT EXCHANGER
Suppose we know only the two inlet temperatures Tal' T
bl
,
and we need to find the outlet temperatures. From,
Ta2  Tbl = (Tal  T
b2
) ea.
or, rearranging,
Ta2  Tal = Tbl  Tal + (Tal  T
b2
) ea..
Eliminating Q from Equation,
Tb2 = Tbl + Wa (Tal  T
a2
).
Wb
We now have two equations, Equation and two
unknowns, Ta2 and T
b2
. Solving first for T
a2
,
or
Ta2  Tal = Tbl  Tal + (Tal  T
bl
) e
u
Wa (Tal  T
a2
) e
u
Wb
(Tal T
b2
{1 ~ e
u
) = (Tal T
a2
)(1e
U
).
(Tal  T
b2
) = 11 (Tal  Tal)'
where 11 is the efficiency of a counterflow heat exchanger:
1
u
e 1
u
e
11 = = :
1
Wa u maCpa_u
e le
Wb mbCpa
Equation=gives Ta2 in terms of known quantities. We can
use this result in to find T
b2
:
maCpa macpa
Tb2  Tbl = . (Tal  T
a2
) = . 11 (Tal  T
bl
)·
mbcpb mbcpb
We examine three examples.
•
mb
c
pb > maC pa
D T can approach zero at cvld end.
[
1 1)
rcDLho  .
macpa mbcpb
75
•
•
h ~ 1 as ho' surface area, .
Tal Ta2
Maximum value of ratio
Tal Tbl
Heat Conduction
Tb2  Tb2 maC pa
Maximum value of ratio =
Tal  Tbl mb
c
pb
mbCpb
a is negative, 11 ~ ~ as [] ® ¥ (Wb < W
a
)
a pa
Ta2  Ta2 mb
C
pb
Maximum value of ratio T  ~ = m C
al bl a pa
Ta2 Tal = 1
Maximum value of ratio
Tal T
bl
mb
c
pb < maC pa
d (Ta  T
b
) = 0
temperature difference remains uniform, 11 = 1.
References
• DK Science Encyclopedia by Susan McKeever and
Martyn Foote.
• Course in Thermodynamics. Revised Printing. Volume
II. (Series in Thermal and Fluids Engineering) by
Joseph Kestin.
• Essentials of Thermodynamics (Essentials) by Research
& Education Association, Rea, and Staff of Research
Education Association.
• Introductory Statistical Mechanics, R. Bowley and M.
Sanchez
• Equilibrium Statistical Physics, M. Plische and B.
Bergersen
4 ____________________________ __
The Behaviour of Gases
IDEAL GAS MODEL, HEAT, WORKAND HERMODYNAMICS
The Kinetic Theory picture of a gas (outlined in the previous
lecture) is often called the Ideal Gas Model. It ignores interactions
between molecules, and the finite size of molecules. In fact,
though, these only become important when the gas is very close
to the temperature at which it become liquid, or under extremely
high pressure.
In this lecture, we will be analyzing the behaviour of gases
in the pressure and temperature range corresponding to heat
engines, and in this range the Ideal Gas Model is an excellent
approximation. Essentially, our Programme here is to learn how
gases absorb heat and turn it into work, and vice versa. This heat
work interplay is called thermodynamics.
Julius Robert Mayer was the first to appreciate that there is
an equivalence between heat and mechanical work. The tortuous
path that led him to this conclusion is described in an earlier
lecture, but once he was there, he realized that in fact the numerical
equivalencehow many Joules in one calorie in present day
terminologycould be figured out easily from the results of some
measurements of gas specific heat by French scientists. The key
was that they had measured specific heats both at constant volume
and at constant pressure.
Mayer realized that in the latter case, heating the gas
necessarily increased its volume, and tne gas therefore did work
in pushing to expand its container.
77 The Behaviour of Gases
Having convinced himself that mechanical work and heat
were equivalent, evidently the extra heat needed to raise the
temperature of the gas at constant pressure was exactly the work
the gas did on its container. The simplest way to see what's going
on is to imagine the gas in a cylinder, held in by a piston, carrying
a fixed weight, able to move up and down the cylinder smoothly
with negligible friction. The pressure on the gas is just the total
weight pressing down divided by the area of the piston, and this
total weight, of course, will not change as the piston moves slowly
up or down: the gas is at constant pressure.
GAS
MOVEABLE PISTON
Moveable ~
piston 
Gas1 .....
The Gas Specific Heats C
v
and C
p
Consider now the two specific heats of this same sample of
gas, let's say one mole:
• Specific heat at constant volume, C
v
(piston glued in
place),
• Specific heat at constant pressure, C
p
(piston free to
rise, no friction).
In fact, we already worked out C v in the Kinetic Theory
lecture: at temperature T, recall the average kinetic energy per
molecule is 2kT, so one mole of gasAvogadro's number of
2
moleculeswill have total kinetic energy, which we'll label
internal energy,
Heat and Thermodynamics
78
EmdkT.NA =t
RT
.
That the internal energy is t RT per mole immediately gives us
the specific heat of a mole of gas in a fixed volume,
3
C
v
=R
2
that being the heat which must be supplied to raise the temperature
by one degree.
However, if the gas, instead of being in a fixed box, is held
in a cylinder at constant pressure, experiment confirms that more
heat must be supplied to raise the gas temperature by one degree.
As Mayer realized, the total heat energy that must be supplied
to raise the temperature of the gas one degree at constant pressure
is tk per molecule plus the energy required to lift the weight.
The work the gas must do to raise the weight is the force the gas
exerts on the piston multiplied by the distance the piston moves.
If the area of piston is A, then the gas at pressure P exerts force
PA. If on heating through one degree the piston rises a distance
1111, the gas does work
PA.l1h = PI1V.
Now, for one mole of gas, PV = RT, so at constant P
PI1V= RI1T.
Therefore, the work done by the gas in raising the weight is just
RI1T, the specific heat at constant pressure, the total heat energy
needed to raise the temperature of one mole by one degree,
C
p
= Cv+R.
In fact, this relationship is true whether or not the molecules
have rotational or vibrational internal energy. CIt's known as
Mayer's relationship.) The specific heat of oxygen at constant
volume
5
C
V
(0
2
) ="2 R
and this is understood as a contribution of t R from kinetic energy,
and R from the two rotational modes of a dumbbell molecule Gust
why there is no contribution form rotation about the third axis
can only be understood using quantum mechanics). The specific
heat of oxygen at constant pressure
79
7
C
p
(02) = R.
2
The Behaviour of Gases
It's worth having a standard symbol for the ratio of the specific
heats:
C
p
=y.
C
v
Tracking a Gas in the (P, V) Plane: Isotherms and
Adiabats
An ideal gas in a box has three thermodynamic variables: P,
V, T. But if there is a fixed mass of gas, fixing two of these
variables fixes the third from PV= nRT(for n moles). In a heat
engine, heat can enter the gas, then leave at a different stage. The
gas can expand doing work, or contract as work is done on it. To
track what's going on as a gas engine transfers heat to work, say,
we must follow the varying state of the gas. We do that by tracing
a curve in the (P, V) plane.
Supplying heat to a gas which consequently expands and does
mechanical work is the key to the heat engine. But just knowing
that a gas is expanding and doing work is not enough information
to follow its path in the (P, V) plane. The route it follows will
depend on whether or not heat is being supplied (or taken away)
at the same time.
There are, however, two particular ways a gas can expand
reversiblymeaning that a tiny change in the external conditions
would be sufficient for the gas to retrace its path in the (P, V)
plane backwards. It's important to concentrate on reversible paths,
because as Carnot proved they correspond to the most efficient
engines. The two sets of reversible paths are the isotherms and
the adiabats.
Isothermal be!7m'iour: The gas is kept at constant
temperature by allowing heat flow back and forth with a very large
object (a "heat reservoir") at temperature T. From PV = nRT, it is
evident that for a fixed mass of gas, held at constant T but subject
to (slowly) varying pressure, the variables P, V will trace a
hyperbolic path in the (P, V) plane.
Heat and Thermodynamics
80
This path, PV = nRTI' say is called the isotherm at
temperature T
1
• Here are two examples of isotherms:
Adiabatic behaviour: "Adiabatic" means "nothing gets
through", in this case no heat gets in or out of the gas through the
walls. So all the work done ion compressing the gas has to go into
the internal energy E
int
.
Adiabatic Compression
Cylinder of insulating material:
Isotherms PV = RT for One Mole at 273K. 373K
16
2
__
o 2 3 4 s 6 7 8 9 10
Volume In Ller.
As the gas is compressed, it follows a curve in the (P, V)
plane called an adiabat.
To see how an adiabat differs from an isotherm, imagine
beginning at some point on the blue 273K isotherm on the above
graph, and applying pressure so the gas moves to higher pressure
and lower volume.
Since the gas's internal energy is increasing, but the number
of molecules is staying the same, its temperature is necessarily
rising, it will move towards the red curve, taen above it. This
means the adiabats are always steeper than the isotherms.
In the diagram below, we've added a couple of adiabats to
the isotherms:
81
The Behaviour of Gases
I
Cylinder of insularing Material
...... ... .
....... .. .
•
...... ... .
•
Adiabatic Compression
Equation for an Adiabat
What equation for an adiabat corresponds to PV= nRT
J
for
an isotherm?
On raising the gas temperature by I:!..T, the change in the
internal energythe sum of molecular kinetic energy, rotational
energy and vibrational energy (if any),
Mint = CvA
T
.
This is always true: whether or not the gas is changing volume
is irrelevant, all that counts in E
int
is the sum of the energies of
the individual molecules (assuming as we do here that attractive
or repulsive forces between molecules are negligible).
In adiabatic compression, all the work done by the external
pressure goes into this internal energy, so
PI:!.. V = CvAT.
(Compressing the gas of course gives negative I:!.. V positive Mint.)
To find the equation of an adiabat, we take the infinitesimal
limit
PdV= C ~ T
Divide the lefthand side by PV, the righthand side by RT to
find
R dV dT
=
C
v
V T
Recall now that C p = C v + Rand C piC v = Y It follows that
Hence
R = C
p
C
v
=yl.
C
v
C
v
f
dV fdT
(yl) v= T
Heat and Thermodynamics
and integrating
In T+ (yl) In V= const.
from which the equation of an adiabat is
n>rl = const
82
From PV = RT, the P, V equation for an adiabat can be found by
multiplying the lefthand side of this equation by the constant PV/
T, giving
PvY = for an adiabat,
where y = % for a monatomic gas, Ys for a diatomic gas.
REAL GASES VS. IDEAL GASES
Most of the discussions of gases assume that the gases exhibit
ideal behaviour. Ideal behaviour involves two things: the first is
that the gas can be infinitely compressed or infinitely cooled and
the gas will not liquefy. The second is that the gas molecules have
no volume. With these assumptions, the ideal gas law, PV=nRT,
can be used.
In reality, however, if a gas is compressed enough the particles
will attract and will liquefy. Similarly if the gas is cooled to its
boiling point, it will liquefy. Therefore at low temperatures or high
pressures, the effect of the attractive forces becomes larger.
However, if the gas is moving fast enough, attractive forces
between the molecules that cause liquefaction are not a factor.
Gas molecules also definitely have a volume, small though it
may be, and the volume of the molecules playa factor under
conditions of large gas molecules and small container volumes.
Joseph van der Waals studied the behaviour of real gases and
made comparisons to the ideal gas law. He derived an equation to
account for the differences. The equation adds in two constants, a
and b, to the ideal gas law. These constants are derived to give
the best agreement between the observed behaviour and the
equation. Therefore each gas has its own values for the constants.
The van der Waals equation is stated as:
n ~ a
[
~ 1
p+ v
2
(Vnb)=nRT
83
The Behaviour of Gases
P + n
2
a/V2 deals with attractive forces between molecules
and how they reduce the ideal pres3ure. Vllb accounts for volume
of the particles, where the constant b is related to the size of the
molecule and since the molecules take up space, the effective size
of the container is decreased.
Van der Waals received a Nobel Prize in physics in 1910 for
his work in gases and liquids. Below is a table giving the a and b
constants for various gases. The a values are small for those gases
with small intermolecular attractions, such as He. In general the
larger molecules have a larger b constant, as can be seen for octane,
though this is not the only factor for determining b.
Gas Formula a [(L
2
. atm}/mole
2
J b [Llmole]
Helium He 0.03412 0.02370
Hydrogen H2 0.2444 0.02661
Nitrogen N2 1.390 0.03913
Oxygen 02 1.360 0.03183
Carbon dioxide CO
2
3.592 0.04267
Acetylene C
Z
H
2
4.390 0.05136
Chlorine Cl
z
6.493 0.05622
n  Butane C
4
HJO 14.47 0.122G
n  Octane CgH
lg
37.32 0.2368
To illustrate the differences between the two equations, an
example using acetylene and helium gas will be shown.
Example: One mole of acetylene gas is placed in a 20.0 L
container at 25°C.
The pressure using the Ideal Gas Law is shown to be:
nRT (1 mol)(0.0821 La\ )(298 K)
P = = rr:o :::: 1.223 atm
V 200L
The pressure using the van der Waals equation is shown
to be:
p = ( nRT _ \) _ (l n
2
a 1
V nb V
2
= (\ mol)(0.0821) K)]_ ((l mol)2 (4.390
20.0 L (l mo\)(0.05136 (20.0 L)2
= 1.215 atm
Heat and Thermodynamics 84
There is approximately a 0.66% difference between the two
values. If the same calcul
Isotherms and Adiabats for One Mole
2!'
20
e
)15
·i 10
a.
5
0
0 2 4 6 8 10
Volume in liter.
ation was done with helium gas, the difference would only be about
0.13%.
REFERENCE
• Equilibrium Thermodynamics, C. J. Adkins.
• Thermodynamics (and Introduction to Thermostatistics),
H. B. Callen.
• Statistical mechanics, R. P. Feynman, W. A. Benjamin.
An introduction to Statistical Thermodynamics, T.L. Hill
• Statistical Mechanics, K. Huang.
5 ____________________________ __
Specific Heat of Solids
Consider a simple solid containing atoms. Now, atoms in
solids cannot translate (unlike those in gases), but are free to
vibrate about their equilibrium positions. Such vibrations are called
lattice vibrations, and can be thought of as sound waves
propagating through the crystal lattice. Each atom is specified ty
three independent position coordinates, and three conjugate
momentum coordinates. Let us only consider small amplitude
vibrations. In this case, we can expand the potential energy of
interaction between the atoms to give an expression which is
quadratic in the atomic displacements from their equilibrium
positions.
It is always possible to perform a normal mode analysis of
the oscillations. In effect, we can find 3N independent modes of
oscillation of the solid. Each mode has its own particular
oscillation frequency, and its own particular pattern of atomic
displacements. Any general oscillation can be written as a linear
combination of these normal modes.
Let qi be the (appropriately normalized) amplitude of the ith
normal mode, and Pi the momentum conjugate to this coordinate.
In normal mode coordinates, the total energy of the lattice
vibrations takes the particularly simple form
I ~ 2 2 2
E=2L.)Pi +wi qi ),
i=1
where Wi is the (angular) oscillation frequency of the th normal
mode. It is clear that in normal mode coordinates, the linearized
Heat and Thermodynamics 86
lattice vibrations are equivalent to 3N independent harmonic
oscillators (of course, each oscillator corresponds to a different
normal mode).
The typical value of wi is the (anguiar) frequency of a sound
wave propagating through the lattice. Sound wave frequencies are
far lower than the typical vibration frequencies of gaseous
molecules. In the latter case, the mass involved in the vibration is
simply that of the molecule, whereas in the former case the mass
involved is that of very many atoms (since lattice vibrations are
nonlocalized).
The strength of interatomic bonds in molecules is
similar to those in solids, so we can use the estimate w  Jk! m (k
is the force constant which measures the strength of interatomic
bonds, and is the mass involved in the oscillation) as proof that
the typical frequencies of lattice vibrations are very much less
than the vibration frequencies of simple molecules. It follows from
/),.E = nw that the quantum energy levels of lattice vibrations are
far more closely spaced than the vibrational energy levels of
gaseous molecules.
Thus, it is likely (and is, indeed, the case) that lattice
vibrations are not frozen out at room temperature, but, instec..d,
make their full classical contribution to the molar specific heat of
the solid.
If the lattice vibrations behave classically then, according to
the equipartition theorem, each normal mode of oscillation has an
associated mean energy in kT equilibrium at temperature T[(l/
2)kT resides in the kinetic energy of the oscillation, and (l/2)kT
resides in the potential energy]. Thus, the mean internal energy
per mole of the solid is
E = 3N k T = 3vRT.
It follows th8t the molar heat capacity at constant volume is
1 (0£\
l =3R
for solids. This gins a value of 24.9 joules/mole/degree. In
fact, at room temperature most solids (in particular, metals) have
87
Specific Heat of Solids
heat capacities which lie remarkably close to this value. This fact
was discovered experimentally by Dulong and Petite at the
beginning of the nineteenth century, and was used to make some
of the first crude estimates of the molecular weights of solids (if
we know the molar heat capacity of a substance then we can easily
work out how much of it corresponds to one mole, and by weighing
this amount, and then dividing the result by Avogadro's number,
we can obtain an estimate of the molecular weight).
The experimental molar heat capacities c
p
at constant pressure
for various solids. The heat capacity at constant volume is
somewhat less than the constant pressure value, but not by much,
because solids are fairly incompressible.
It can be seen that Dulong and Petite's law (i. e., that all solids
have a molar heat capacities close to 24.9 joules/mole/degree)
holds pretty well for metals. However, the law fails badly for
diamond. This is not surprising. As is wellknown, diamond is an
extremely hard subshnce, so its intennolecular bonds must be very
strong, suggesting that the force constant k is large. Diamond is
also a fairly low density substance, so the mass involved in lattice
vibrations is comparatively small.
Both these facts suggest that the typical lattice vibration
frequency of diamond (w  ~ k / m ) is high. In fact, the spacing
between the different vibration energy levels (which scales like hW)
is sufficiently large in diamond for the vibrational degrees of
freedom to be largely frozen out at room temperature.
Table 4: Values of c
p
(joules/mole/degree) for some solids at
T = 298
0
K. From Reif.
~ ~ ~ ~ ~ c
Copper 24.5 Aluminium 24.4
Silver 25.5 Tin (white) 26.4
Lead 26.4 Sulphur (rhombic) 22.4
Zinc 25.4 Carbon (diamond) 6.1
Dulong and Petite's law is essentially a high temperature limit.
The molar heat capacity cannot remain a constant as the
temperature approaches absolute zero, since, by Equation, this
would imply S ~ 00, which violates the third law of
thermodynamics. We can make a crude model of the behaviour
Heat and Thermodynamics 88
of c
y
at low temperatures by assuming that all the normal modes
oscillate at the same frequency, w, say. This approximation was
first employed by Einstein in a paper published in 1907.
According to Equation, the solid acts like a set of 3N .
independent oscillators which, making use of Einstein's
approximation, all vibrate at the same frequency. We can use the
quantum mechanical result Equation for a single oscillator to write
the mean energy of the solid in the form
 (1 1 )
E =3Nliw + .
2 exp(phw)1
The molar heat capacity is defined
1 (aE) 1 (aE) ap 1 (aE)
cv =; aT y =; aT l' aT =  vkT2 ap y'
giving
r 1
C
y
= 3N
A
liw = l exp(pliw)liw J'
kT2 [exp(pliw) _1]2
which reduces to
Here,
c
y
= 3 R = (9
E
)2 exp(9E IT) .
T [exp(9
E
IT)1]2
n _liw
"'E
k
is called the Einstein temperature. If the temperature is sufficiently
high that T» 9
E
then kT» h w, and the above expression reduces
to c
y
= 3 R, after expansion of the exponential functions. Thus,
the law of Dulong and Petite is recovered for temperatures
significantly in excess of the Einstein temperature. On the other
hand, if the temperature is sufficiently low that T« 9 E then the
exponential factors in Equation become very much larger than
unity, giving
9
E
C
y
 3 Rexp (9 E IT).
T .
So, in this simple model the specific heat approaches zero
exponentially as T ~ o.
89
Specific Heat of Solids
In reality, the specific heats of solids do not approach zero
quite as quickly as suggested by Einstein's model when T O.
The experimentally observed low temperature behaviour is more
like C
v
ocT3. The reason for this discrepancy is the crude
approximation that all normal modes have the same frequency. In
fact, long wavelength modes have lower frequencies than short
wavelength modes, so the former are much harder to freeze out
than the latter (because the spacing between quantum energy
levels, liw, is smaller in the former case).
The molar heat capacity does not decrease with temperature
as rapidly as suggested by Einstein's model because these long
wavelength modes are able to make a significant contribution to
the heat capacity even at very low temperatures.
A more realistic model of lattice vibrations was developed
by the Dutch physicist Peter Debye in 1912. In the Debye model,
the frequencies of the normal modes of vibration are estimated by
treating the solid as an isotropic continuous medium. This
approach is reasonable because the only modes which really matter
at low temperatures are the long wavelength modes: i.e., those
whose wavelengths greatly exceed the interatomic spacing. It is
plausible that these modes are not particularly sensitive to the
discrete nature of the solid: i.e., the fact that it is made up of atoms
rather than being continuous.
Consider a sound wave propagating through an isotropic
continuous medium. The disturbance varies with position vector
r and time t like exp [ i.r  WI], where the wavevector k and the
frequency of oscillation satisfy the dispersion relation for sound
waves in an isotropic medium:
W = kcs'
Here, C
s
is the speed of sound in the medium. Suppose, for
the sake of argument, that the medium is periodic in the X, y,
and with periodicity lengths Lx' Ly and L
z
'
respectively. In order to maintain periodicity we need
ky (x + LX> = kxx + 21tn
x
'
where nx is an integer. There are analogous constraints on kyand k
z
.
It follows that in a periodic medium the components of the wave
vector are quantized, and can only take the values
Heat and Thermodynamics
21t
ky =n
y
,
Ly
21t
k
z
=n
z
'
L
z
90
where n
x
' ny, n
z
and are all integers. It is assumed that Lx' L
y
' and
L
z
are macroscopic lengths, so the allowed values of the
components of the wavevector are very closely spaced. For given
values of and k , the number of allowed values of kx which lie in
the range kx to kx + dk
x
is given by
Llnx = Lx dk
x
,
21t
It follows that the number of allowed values of k(i.e., the
number of allowed modes) when kx lies in the range kx to kx +
dh
x
' kv lies in the range to ky + dk
y
' and k
z
lies in the range k
z
to
+ dh_, is
"'
pd
3
k = (Lx dk
x
) (Ly dk
y
) (Lz dk
z
) =
21t 21t 21t (21t)
where V = is the periodicity volume, and d
3
k == dkxdkydk
z
.
The quantity p is called the density of modes. Note that this density
is independent of k, and proportional to the periodicity volume.
Thus, the density of modes per unit volume is a constant
independent of the magnitude or shape of the periodicity volume.
The density of modes per unit volume when the magnitude of k
lies in the range k to k + dk is given by multiplying the density of
modes per unit volume by the "volume" in kspace of the spherical
shell lying between radii and k + dk. Thus,
p dk = 4nk
2
dk
k (21t)3 21t2
Consider an isotropic continuous medium of volume V.
91 Specific Heat of Solids
According to the above relation, the number of normal modes
whose frequencies lie between wand w + dw (which is equivalent
to the number of modes whose kvalues lie in the range wlc
s
to wi
C
s
+ djc
s
) is
k
2
V V 2
crcCw)dw = 3
2
dk = 3
2

3
w dw.
21t 21t C
s
The factor of 3 comes from the three possible polarizations
of sound waves in solids. For every allowed wavenumber (or
frequency) there are two independent torsional modes, where the
displacement is perpendicular to the direction of propagation, and
one longitudinal mode, where the displacement is parallel to the
direction of propagation.
Torsion waves are vaguely analogous to electromagnetic
waves (these also have two independent polarizations). The
longitudinal mode is very similar to the compressional sound wave
in gases. Of course, torsion waves can not propagate in gases
because gases have no resistance to deformation without change
of volume.
The Debye approach consists in approximating the actual
density of normal modes cr(w) by the density in a continuous
medium cr
c
(w), not only at low frequencies (long wavelengths)
where these should be nearly the same, but also at higher
frequencies where they may differ substantially. Suppose that we
are dealing with a solid consisting of N atoms. We know that there
are only 3N independent normal modes.
It follows that we must cut off the density of states above
some critical frequency, w
D
say, otherwise we will have too many
modes. Thus, in the Debye approximation the density of normal
modes takes the form
crD(w) = crc(w) for w < w
D
crD(w) = 0 for w < w
D
.
Here, w
D
is the De bye frequency. This critical frequency is
chosen such that the total number of normal modes is 3N, so
Heat and Thermodynamics 92
Substituting Equation into the previous formula yields
3V ('"'D 2 V 3
2.b W dw=23 wD =3N.
21t 21t C
s
This implies that .
WD =C
s
( 61t
2
Thus, the Debye frequency depends only on the sound
velocity in the solid and the number of atoms per unit volume.
The wavelength corresponding to the Debye frequency is 21tCJ
w
D
' which is clearly on the order of the interatomic spacing a
(V /N)1I3. It follows that the cutoff of normal modes whose
frequencies exceed the Debye frequency is equivalent to a cutoff
of normal modes whose wavelengths are less than the interatomic
spacing. Of course, it makes physical sense that such modes should
be absent.
The actual density of normal modes in diamond \,/ith the
density predicted by Debye theory. Not surprisingly, there is not
a particularly strong resemblance between these two curves, since
Debye theory is highly Nevertheless, both curves exhibit
sharp cutoffs at high frequencies, and coincide at low frequencies.
Furthermore, the areas under both curves are the same. Sufficient
to allow Debye theory to cl)rrectly account for the temperature
variation of the specific heat of solids at low temperatures.
We can use the quantum mechanical expression for the mean
energy of a single oscillator, Equation, to calculate the mean energy
of lattice vibrations in the Debye approximation. We obtain
E = 1 )dw.
2 exp(l31iw)I
According to Equation, the molar heat capacity takes the form
 1 r ()1i [ exp(l31iw)1iw jdw
Cv   cr D W W •
vkT
2
[exp(l31iw) If
Substituting in Equation, we find that
93 Specific Heat of Solids
giving
3V k exp x 4dx
cv = 2n
2
v(C
s
Ph)3 .b (expxl)2 x ,
in terms of the dimensionless variable x = ph w. According to
Equation, the volume can be written
so the heat capacity reduces to
C
v
= 3 Rfo(!3hwo) = 3 RfD(edT)
where the Debye junction is defined
I" ( ) _ 3 £" exp x 4dx
JD Y = X •
l (expxl)
We have also defined the Debye temperature e
D
as
keo = hw
o
'
Consider the asymptotic limit in which T» eo. For small y, we
can approximate exp x as 1 + x in the integrand of Equation, so
that
.b
x2dx
=1.
Y
Thus, if the temperature greatly exceeds the Debye
temperature we recover the law of Dulong and Petite that C
v
= 3 R.
Consider, now, the asymptotic limit in which T« eo. For
large y,
4
r
y
exp x 4dx r exp x 4dx 4n
.b (expxl)2 x =.b (expxl)2 x =15
The latter integration is standard (if rather obscure), and can
be looked up in any (large) reference book on integration. Thus,
in the low temperature limit
Heat and Thermodynamics
This yields
C
v
= 12n4 R ( ~ ) 3
5 e
D
94
in the limit T« eD:i.e., C v varies with temperature like T3.
Table: Comparison of Debye temperatures (in degrees kelvin) obtained
from the low temperature behaviour of the heat capacity with those
calculated from the sound speed.
SolidS D from low temp S D from sound speed
NaCI 308
KCl 230
Ag 225
Zn 308
320
246
216
305
The fact that C v goes like 7
3
at low temperatures is quite
well verified experimentally, although it is sometimes necessary
to go to temperatures as low as 0.02 e
D
to obtain this
asymptotic behaviour. Theoretically, aD should be calculable
from Equation in terms of the sound speed in the solid and
the molar volume. Debye temperatures evaluated by this means
with temperatures obtained empirically by fitting the law
Equation to the low temperature variation of the heat capacity.
It can be seen that there is fairly good agreement between
the theoretical and empirical Debye temperatures. This
suggests that the Debye theory affords a good, thought not
perfect, representation of the behaviour of C v in solids over
the entire temperature range.
REFERENCES
• Statistical Physics, L. D. Landau and E. M. Lifshitz
• Statistical Mechanics, SK Ma
• Quantum Mechanics, E. Merzbacher
• The Cluster Expansion, W. J. Mullin
• A Modern Course in Statistical Physics, L. E. Reichl.
6 ______________ _
Thermal Equilibrium and
Zeroth Law
STATISTICAL DEFINITION
OF THERMODYNAMIC VARIABLES
Our starting point is the idea that one can count the
number of available states of a system. In principle, these are
discrete quantum states. For a large system the states will be
very closely spaced. The number of possible states with energy
between E and E + 3E is
Q(E) = g(E) 3E,
where g(E) is the density of states. Next, consider a dosed
system with fixed volume V, number of particles N, and energy
E. In order to avoid problems associated with the discreteness
of the quantum states we take the energy to be specified within
a tolerance 3E. This tolerance should be chosen so that for a
large system the precise value of 3E does not matter. We do
not know in which of the allowed states the system finds itself.
In fact, our fundamental assumption is that at equilibrium our
ignorance in this matter is complete, and that all the Q(E, V,
N)possible states are equally likely, i.e. all memory of how the
system was initially prepared is lost, except for the values of
the energy, volume, and number of particles. We define the
entropy as
S = kB In Q(E, N, V).
Consider next an infinitesimally small change from an
Heat and Thermodynamics 96
equilibrium state E, V,N to another, slightly different, equilibrium
state E + dE, V + dV, N + dN. The change in the entropy is then
dS = as dE + as dV + as dN.
aE av an
The change in energy in this process is given by
dE=dQ+dU,
We distinguish between two forms of energy heat and work.
Heat is a form of energy associated with random or thermal motion
of atoms and molecules. Consider a gas of low density. The
molecules will move in straight trajectories until they collide with
other molecules or the walls of the gas container. After a few
collisions it becomes practically impossible to relate the velocity
and position of the molecules to the corresponding quantities at
an earlier time.
The difficulty is not just the enormous amount of data
required to describe a large number of particles. A more
fundamental problem is the fact that after a few collisions the
positions and the velocities of the particles become extremely
sensitive to the initial conditions. A very similar situation occurs
when throwing an unbiased die or tossing a coin. In principle, it
should be possible to predict the outcome of the toss using
Newton's laws and the initial velocity and position. In practice,
the calculation will not be able to predict the behaviour of real
coins, because initial conditions that give rise to radically different
outcomes are so close together that the problem of specifying the
intial conditions and parameters of the problem with sufficient
accuracy becomes severe.
This type of motion has been described as chaotic. Each
particle is just as likely to move in any direction as in any other,
and the the speed of the particles is frequently changing. We also
distinguish between the random motion of a molecule and bulk
(ordered) movement.
An example of the latter is the flight of a solid object such as
a pebble thrown in the air. We refer to changes in energy associated
with bulk motion or transport of matter as work. In dQ is the heat
supplied to the system and dU the work done on the system. The
97 Thermal Equilibrium and Zeroth Law
internal energy E is a state variable and its differential is exact,
i.e. dE depends only on the initial and final state and is independent
of the process leading to the change.
On the other hand "heat" and "work" are not state variables
and the partition into heat and work depends on the process. Hence,
the difference in notation: dE, but dQ and dU We have not yet
defined the variables P, T and J..!. We want to do this in such a
way as to allow us to write
dE = TdS  PdV + J.ldN
or
dS + J..! dE +1:.dN + P dV.
T T T T
We now define the temperature, pressure, and chemical
potential as
(
8S)1
T = 8E
J..! __ T(8S) P_T(8S)
8N EV 8V N E
, ,
It is important to note that our basic assumption is that all
allowed states are equally likely. The second law of
thermodynamics now becomes the statement that a closed system
will tend to approach a macroscopic state which can be achieved
the most possible ways. The conventional mathematical
formulation of the second law on the other hand only becomes an
essentially trivial matter of definition. We must next show that
these definitions lead to familiar looking results otherwise they
would not be useful.
THE ZEROTH LAW OF THERMODYNAMICS
To establish the equivalence of our definitions and the
conventional thermodynamic we shall make contact with the
zeroth law of thermodynamics. This law has an analogy with
mechanics, where in equilibrium the forces are balanced. In
particular if two are in contact and in equilibrium:
TI = T2 thermal equilibrium
PI = P 2 mechanical equilibrium
J..!l = J..!2 T2 chemical equilibrium
Heat and Thermodynamics 98
The zeroth law has a fairly straightforward statistical
interpretation and this will allow us to begin to establish the
equivalence between the statistical definitions and the conventional
thermodynamic ones. Consider two systems that are free to
exchange energy but are isolated from the rest of the universe by
an ideal insulating surface. The particle numbers N
1
, N2 and
volumes VI' V
2
are fixed for each subsystem. The total energy
will be constant under our assumptions and we assume further
that the two subsystems are sufficiently weaklY interacting that
E=El +E
2
,
where El and E2 are the energies of the subsystems. Assume that
the densities of state g(E), g 1 (E),g2(E) are coarse grained so that
0= g(E)oE 01 = gl (E
1
) oE 02 = g2 (E
2
) oE, , . We then have
geE) = fdElg2 (E  EI )gl (E
I
),
If the subsystems are sufficiently large, the product giE
Ej)gl(E) will be a sharply peaked function of E
I
. From the
definition of the entropy we note that it is a monotonically
increasing function of g and that the product glg2 will be at a
maximum when the total entropy
SeE, E
I
) = SI(E
I
) + S2(EE
I
)
is at a maximum. The most likely value (E
I
) of EI is the one for
which
8S1 + aS2 aE2 = o.
aEI aE
2
aEI
Since aE/aE
I
we find using, that
1 1
=0,
1i T2
or TI = T
2
. The most probable partition of energy between the
two systems is the one for which the two temperatures are the
same. Consider next two subsystems that are separated by a
movable wall. The two systems are free to exchange energy, but
the number of particles is fixed in each subsystem and the total
volume V = VI + V
2
is constant. We write E = El + E
2
. The density
of allowed states for the total system is then
99 Thermal Equilibrium and Zeroth Law
g(E,V) = L JdE
1
g
1
(E
1
,f'i)g21(EE
l
,VVi)
volume settings
The integrand is sharply peaked for large systems and takes
on its maximum value when SI(El,vl)+SiEEl'VV1)=max.
Differentiation using
(
8S I' _ 1 . ( 8S) = P
8E )VN  T ' ~ 8 V EN T
implies that it is overwhelmingly probable that the system will be
near a state for which
1_1,ll_P
2
1J
T
2'1J
T
2
or TI = T
2
, PI = P 2' Conventionally, one would say that the pressure
in the two compartments must be equal at equilibrium because
the forces have to be in balance. The argument now being made
is quite different, there are no forces, instead the movable wall is
guided to its equilibrium by the invisible hand of the law of large
numbers. Similarly, consider two systems 1 and 2 which are free
to exchange particles and energy. It is easy to show that the most
probable configuration is the one for which TI = T
2
, III = 112.
BOLTZMANN FACTOR
Consider now a system in contact with a heat bath, or
reservoir. System 1 is the one we are interested in, and we want
to find the probability P(EI) that it has energy E
I
. We assume
that system 2 is much larger than 1, so that El« E = E
I
+ E
2
•
Another way of putting this is to say that the heat capacity C
2
of
system 2 is very large. We assume that all compatible microstates
are equally likely. We have
P(El)dE
I
= gl(EI )g2(E  EI)dEI
JdEIg
l
(E
1
)g2(E  E
1
)
From the definition of entropy
1 r S2(E  Ell
g2 = 8E eXPl kB
Heat and Thermodynamics
We expand in a Taylor series
8S
2
E18
2
s
2
S2(EE
1
)=S2(E)E
1
8E +2 8E
2
+ ....
100
With T the temperature of the heat bath and C its heat capacity,
the partial derivatives are given by
8S
2
1
=
8E T
8
2
S 81 1 8T 1
__ 2 =.L= ___ = __ _
8E
2
8E T2 8E T
2
C
Since E1«TC we neglect the last term in giving
g2 = const.exp[E
1
] =
kBT
where we define 13 = lI(k
B
1). We conclude
The factor is the Boltzmann factor. When a system is
in contact with a heat bath at a certain temperature, all possible
microstates of the system are no longer equally likely. Instead,
the Boltzmann factor acts as a weight factor biasing the distribution
towards states with lower energy.
PARTITION FUNCTION AND THE
CANONICALDISTRIBUTION
The constant in eqnaution can be determined by normalizing
the probability distribution i.e. requiring that
Jp(E)dE=1
Let us define the canonical partition function (a = microstate)
Zc = =
a
We find that the probability p( a) that a state is in a given microstate
p(a)=_l
Zc
If x( a) is the value of some physical property in microstate
101
Thermal Equilibrium and Zeroth Law
a, and E(a) the energy of this state then the canonical ensemble
average is given by
(x) = _I
Zc a
Equation is a very useful formula, and we will give many examples
of its use.
HELMHOLTZ FREE ENERGY
F or an isolated system S = SeE, V, N), with E, V, N independent
variables. For a system in contact with a heat bath at a given
temperature, T becomes an independent variable, or control
parameter. The energy E and entropy S will then fluctuate about
their mean values and. E and S become dependent variables given
by equations of state. The change of variables is handled most
efficiently by introducing he Helmholtz free energy. In
thermodynamics it is defined as
F=ETS
Imagine a reversible process which takes the system from one
equilibrium state to another
dE= TdSPdV+ V,N)
dF = dE  TdS  SdT =  PdV + IJdN = dF (T, V, N)
We see tilat the Helmholtz free energy is should be considered
to be dependent on the control variables T, V, N. We have
as
S=_oF
oT
p=_oF
aT
aF
J.1=
aN
In statistical mechanics we define the Helmholtz free energy
A = (E)  T (S) = (F)
We wish to show that for a large system
Zc JeEg(E)e
13E
Heat and Thermodynamics 102
Proof: The r,anonical partition function is
=  TS(E, V, N)]}
We evaluate this integral using the saddle point method.
Almost all the contribution to the integral will come from values
of E near E = (E) the value for which ET (S, E, V, N) = minimum.
We let S(E), V, N) = (5) and
1 28
2
S
ETS::::(E)T(s)T(E(E) 2 + ....
2 8E
Substituting Equation we obtain
Zc :::: exp[  T (S)  T (S)] IdE exp{(E 
BE 2Ck
B
T
U sing we find
T
2
C
Zc:::: B
BE
and from
[
J27tkBT
2
C 1
A =  kBT In Zc = (E)  T(5)  kBT In BE
The last term in will be small compared to the first two terms
for a large system, and it is possible to choose the tolerance 8E so
that it is identically zero.
BOLTZMANN DISTRIBUTIONS
We have gained some understanding of the macroscopic
properties of the air around us. For instance, we know something
about its internal energy and specific heat capacity. How can we
obtain some information about the statistical properties of the
molecules which make up air? Consider a specific molecule: it
constantly collides with its immediate neighbour molecules, and
occasionally bounces off the walls of the room.
These interactions "inform" it about the macroscopic state
of the air, such as its temperature, pressure, and volume. The
statistical distribution of the molecule over its own particular
microstates must be consistent with this macrostate. In other words,
103
Thermal Equilibrium and Zeroth Law
if we have a large group of such molecules with similar statistical
distributions, then they must be equivalent to air with the
appropriate macroscopic properties. So, it ought to be possible to
calculate the probability distribution of the molecule over its
microstates from a knowledge of these macroscopic properties.
We can think of the interaction ofa molecule with the air in
a classroom as analogous to the interaction of a small system A in
thermal contact with a heat reservoir A'. The air acts like a heat
reservoir because its energy fluctuations due to any interactions
with the molecule are far too small to affect any of its macroscopic
parameters. Let us determine the probability P
r
of finding system
A in one particular microstate r of energy Er when it is thermal
equilibrium with the heat reservoir A'.
As usual, we assume fairly weak interaction between A and A "
so that the energies ofthese two systems are additive. The energy
of A is not known at this stage. In fact, only the total energy of the
combined system A(O) = A + A'is known. Suppose that the total
energy lies in the range 8°) to 8°) + oE. The overall energy A(O) is
constant in time, since is assumed to be an isolated system, so
E + E' = 8°)
r '
where E' denotes the energy of the reservoir A'. Let 0' (E) be the
number of microstates accessible to the reservoir when its energy
lies in the range E' to E' + oE. Clearly, if system A has an energy
Er then the reservoir A' must have an energy close to E = 8°) 
E,.
Hence, since A is in one definite state (i.e., state r), and the total
number of states accessible to A' is 0' (8°)  E
r
), it follows that
the total number of states accessible to the combined system is
simply Q' (80)  Er)' The principle of equal a priori probabilities
tells us the the probability of occurrence of a particular situation
is proportional to the number of accessible microstates. Thus,
Pr = C' 0'(8°)  Er)
where is a constant of proportionality which is independent of r.
This constant can be determined by the normalization condition
~ ) ~ . =1,
r
Heat and 1bermodynamics 104
where the sum is over all possible states of system A, irrespective
of their energy.
Let us now make use of the fact that sygtem A is far smaller
than system A'. It follows that Er «Fj..o>, so the slowly varying
logarithm of P
r
can be Taylor expanded abcut E' = E<n). Thus,
r
81n O
']
Inp" = In C'+lnO'(E(O»)l ~ ° Er+···.
Note that we must expand In P, rather than P
r
itself, because
the latter function varies so rapidly with energy that the radius of
convergence of its Taylor series is far too small for the series to
be of any practical use. The higher order terms in Equation ~ a n
be safely neglected, because Er« E<0). Now the derivative
1
8InO
'] =
l 8E' ° p.
is evaluated at the fixed energy E'= E<0) and is, thus, a constant
independent of the energy Er of A. In fact, we know, that this
derivative is just the temperature parameter f3 = (kT)1
characterizing the heat reservoir A'. Hence, Equation becomes
In P
r
= In C' + In fl' (E<0»)  f3 E
r
,
giving
P
r
= C exp ( f3 E
r
),
where C is a constant independent of r. The parameter C is
determined by the normalization condition, which gives
r
so that the distribution becomes
p. _ exp( PEr)
r  Lr exp(pE
r
)·
This is known as the Boltzmann probability distribution, and
is undoubtably the most famous result in statistical physics.
The Boltzmann distribution often causes confusion. People
who are used to the principle of equal a priori probabilities, which
says that all microstates are equally probable, are understandably
105 Thermal Equilibrium and Zeroth Law
surprised when they come across the Boltzmann distribution which
says that high energy microstates are markedly less probable then
low energy states.
However, there is no need for any confusion. The principle
of equal a priori probabilities applies to the whole system, whereas
the Boltzmann distribution only applies to a small part of the
system. The two results are perfectly consistent. If the small system
is in a microstate with a comparatively high energy Er then the
rest of the system (i.e., the reservoir) has a slightly lower energy
E' than usual (since the overall energy is fixed).
The number of accessible microstates of the reservoir is a
very strongly increasing function of its energy. It follows that when
the small system has a high energy then significantly less states
than usual are accessible to the reservoir, and so the number of
microstates accessible to the overall system is reduced, and, hence,
the configuration is comparatively unlikely.
The strong increase in the number of accessible microstates
of the reservoir with increasing E' gives rise to the strong (i.e.,
exponential) decrease in the likelihood of a state of the small
system with increasing E
r
. The exponential factor exp (13 Er) is
called the Boltzmann factor.
The Boltzmann distribution gives the probability of finding
the small system A in one particular state of energy E
r
. The
probability peE) that A has an energy in the small range between
E and E + oE is just the sum of ail the probabilities of the states
which lie in this range. However, since each of these states has
approximately the same Boltzmann factor this sum can be written
peE) = c neE) exp ( I3E),
where neE) is the number of microstates of A whose energies lie
in the appropriate range. Suppose that system A is itself a large
system, but still very much smaller than system A'. For a large
system, we expect neE) to be a very rapidly increasing function
of energy, so the probability peE) is the product of a rapidly
increasing function of E and another rapidly decreasing function
(i.e., the Boltzmann factor).
This gives a sharp maximum of PCE) at some particular value of
the energy. The larger system A, the sharper this maximum
Heat and Thermodynamics
106

becomes. Eventually, the maximum becomes so sharp that the
energy of system A is almost bound to lie at the most probable
energy. As usual, the most probable energy is evaluated by looking
for the maximum of In P, so
alnP = alnn _p = 0
aE aE '
giving
alnn _p
aE
Of course, this corresponds to the situation in which the
temperature of A is the same as that of the reservoir. This is a
result which we have seen before. Note, however, that the
Boltzmann distribution is applicable no matter how small system
A is, so it is a far more general result than any we have previously
obtained.
PARAMAGNETISM
The simplest microscopic system which we can analyze using
the Boltzmann distribution is one which has only two possible
states (there would clearly be little point in analyzing a system
with only one possible state). Most elements, and some
compounds, are paramagnetic: i.e., their constituent atoms, or
molecules, possess a permanent magnetic moment due to the
presence of one or more unpaired electrons. Consider a substance
whose constituent particles contain only one unpaired electron.
Such particles have spin 112, and consequently possess an
intrinsic magnetic moment 11. According to quantum mechanics,
the magnetic moment of a spin 112 particle can point either parallel
or anti parallel to an external magnetic field B. Let us determine
the mean magnetic moment iTB (in the direction of B) of the
constituent particles of the substance when its absolute temperature
is T. We assume, for the sake of simplicity, that each atom (or
molecule) only interacts weakly with its neighbouring atoms. This
enables us to focus attention on a single atom, and treat the
remaining atoms as a heat bath at temperature.
Our atom can be in one of two possible states: the (+) state
107 Thermal Equilibrium and Zeroth Law
in which its spin points up (i.e., parallel to B), and the () state in
which its spin points down (i.e., antiparallel to B). In the (+) state,
the atomic magnetic moment is parallel to the magnetic field, so
thatJ..lB = J..l. The magnetic energy of the atom is E+ =  J..lB' In the
() state, the atomic magnetic moment is antiparallel to the
magnetic field, so that J..lB =  J..l. The magnetic energy of the atom
is E_= J..lB'
According to the Boltzmann distribution, the probability of
finding the atom in the (+) state is
p+ = C exp( [3E+) = C exp([3 J..l B),
where C is a constant, and [3 = (kn
1
. Likewise, the probability
of finding the atom in the () state is
p _ = C exp( [3E> = C exp([3 J..l B).
Clearly, the most probable state is the state with the lowest
energy [i. e., the (+) state]. Thus, the mean magnetic moment points
in the direction of the magnetic field (i.e., the atom is more likely
to point parallel to the field than antiparallel).
It is clear that the critical parameter in a paramagnetic system is
J..lB.
kT
This parameter measures the ratio of the typical magnetic
energy of the atom to its typical thermal energy. If the thermal
energy greatly exceeds the magnetic energy then y« 1, and the
probability that the atomic moment points parallel to the magnetic
field is about the same as the probability that it points antiparallel.
In this situation, we expect the mean atomic moment to be small,
so that B :: 0 .
On the other hand, if the magnetic energy greatly exceeds
the thermal energy then y» 1, and the atomic moment is far more
likely to point parallel to the magnetic field than antiparallel. In
this situation, we expect iT B = j..l •
Let us calculate the mean atomic moment iTB' The usual
definition of a mean value gives
 p+ + j..l+ P_(J..l)
J..lB = =J..l .
P+ + P_ J..l B) + exp( J..l B)
Heat and Thermodynamics
This can also be written
 h!J.B
IlB =Il
tan
,
kT
where the hyperbolic tangent is defined
h
_ exp(y)exp(y)
tan y= .
exp(y) + exp(y)
For small arguments, y <..'< 1,
y3
tan h y==+'"
3 '
whereas for large arguments, y» 1,
tanhy==l.
It follows that at comparatively high temperatures, kT» JlB'
_ 1l
2B
IlB == kT '
whereas at comparatively low temperatures, kT« J1B,
iIB == Il·
108
Suppose that the substance contains No atoms (or molecules) per
unit volume. The magnetization is defined as the mean magnetic
moment per unit volume, and is given by
Mo = NofiB'
At high temperatures, kT» /lB, the mean magnetic moment,
and, hence, the magnetization, is proportional to the applied
magnetic field, so we can write
Mo=X
B
,
where X is a constant of proportionality known as the magnetic
susceptibility. It is clear that the magnetic susceptibility of a spin
112 paramagnetic substance takes the form
Na/l
2
X=;;r'
The fact that X ex: r1is known as Curie's law, because it was
109
Thermal Equilibrium and Zeroth Law
discovered experimentally by Pierre Curie at the end of the
nineteenth century. At low temperatures, kT « J.!B,
Mo
so the magnetization becomes independent of the applied field.
This corresponds to the maximum possible magnetization, where
all atomic moments are lined up parallel to the The
breakdown of the Mo oc B law at low temperatures (or high
magnetic fields) is known as saturation.
The above analysis is only valid for paramagnetic substances
made up of spin onehalf (J = J /2) atoms or molecules. However,
the analysis can eas]y be generalized to take account of substances
whose constituent particles possess higher spin (i.e., J > 112). The
experimental and theoretical magnetization versus fieldstrength
curves for three different substances made up of spin 3/2, spin 5/
2, and spin 7/2 particles, showing the excellent agreement between
the two sets of curves. Note that, in all cases, the magnetization is
proportional to the magnetic fieldstrength at small fieldstrengths,
but saturates at some constant value as the fieldstrength increases.
The previous analysis completely neglects any interaction
between the spins of neighbouring atoms or molecules. It turns
out that this is a fairly good approximation for paramagnetic
substances. However, for ferromagnetic substances, in which the
spins of neighbouring atoms interact very strongly, this
approximation breaks down completely. Thus, the above analysis
does not apply to ferromagnetic substances.
MEAN VALUES
Consider a system in contact with a heat reservoir. The
systems in the representative ensemble are distributed over their
accessible states in accordance with the Boltzmann distribution.
Thus, the probability of occurrence of some state with energy Er
is given by
Heat and Thermodynamics 110
The mean energy is written
 L exp( Er )E
r
E  
 L r exp( Er) ,
where the sum is taken over all states of the system, irrespective
of their energy. Note that
where
Z = Er)
r
It follows that p
oZ =_ olnZ.
Z
The quantity Z, which is defined as the sum of the Boltzmann
factor over all states, irrespective of their energy, is called the
partition function. We have just demonstrated that it is fairly easy
to work out the mean energy of a system using its partition
function. In fact, as we shall discover, it is easy to calculate
virtually any piece of statistical information using the partition
function.
Let us evaluate the variance of the energy. We know that
(/ill)2 = E2 _ E2
Now, according to the Boltzmann distribution,
2 "exp( 2
E  L..J
r
r

However,
111
Hence,
Thermal Equilibrium and Zeroth Law
2" 1 a
2
z
E =
Z ap2·
We can also write
E2 aZ)+_l (az)2 =_ aE +E2
ap Z ap Z2 ap ap ,
where use has been made of Equation
 2
(b.E)2 = _ aE = a 1nZ.
ap ap2
Thus, the variance of the energy can be worked out from the
partition function almost as p.asily as the mean energy. Since, by
definition, a variance can never be negative, it follows that
aE / ap 0, or, equivalently, aE / aT O. Hence, the mean energy
of a system governed by the Boltzmann distribution always
increases with temperature.
Suppose that the system is characterized by a single external
parameter x (such as its volume). The generalization to the case
where there are several external parameters is obvious. Consider
a quasistatic change of the external parameter from x to x + dx.
In this process, the energy of the system in state changes by
8E
r
= aE dx.
ax
The macroscopic work dW done by the system due to this
parameter change is
L exp( p Er)( aEr / ax dx)
____________ _
Lrexp(P Er)
In other words, the work done is minus the average change
in internal energy of the system, where the average is calculated
using the Boltzmann distribution. We can write
![
Heat and Thermodynamics 112
which gives
dW = __ 1_8Z dx =}_ 81nZ,dx.
PZ ax P ax
We also have the following general expression for the work
done by the system
where
dW=x dx,
x= 8E
r
ax'
is the mean generalized force conjugate to x. It follows that
x = ~ 81nZ.
P ax
Suppose that the external parameter is the volume, so x = V.
It follows that
and
_ 181nZ
P=j3av'
Since the partition function is a function of /3 and V (the
energies Er depend on V), it is clear that the above equation relates
the mean pressure P to T (via /3 = lIk1) and V.
In other words, the above expression is the equation a/state.
Hence, we can work out the pressure, and even the equation of
state, using the partition function.
PARTITION FUNCTIONS
It is clear that all important macroscopic quantities associated
with a system can be expressed in terms cf its partition function
Z. Let us investigate how the partition function is related to
thermodynamical quantities. Recall that Z is a function of both /3
and x (where x is the single external parameter). Hence, Z = Z(/3,
x), and we can write
113 Thermal Equilibrium and Zeroth Law
dlnZ = olnZ dx+ olnZ
ax
Consider a quasistatic change by which x and b change so
slowly that the system stays close to equilibrium, and, thus,
remains distributed according to the Boltzmann distribution. If
follows from Equations that
dlnZ =/3dW
The last term can be rewritten
din Z = /3dW  +
giving
d (In Z + = P( 1iW + dE) == 13dQ.
The above equation shows that although the heat absorbed
by the system dQ is not an exact differential, it becomes one when
multiplied by the temperature parameter 13. This is essentially the
second law of thermodynamics. In fact, we know that
dS= dQ.
T
Hence,
S == k(ln Z + (3E).
This expression enables us to calculate the entropy of a system
from its partition function.
Suppose that we are dealing with a system A(O)consisting of
two systems A and A'which only interact weakly with one another.
Let each state of A be denoted by an index and have a
corresponding energy E
r
. Likewise, let each state of A' be denoted
by an index and have a corresponding energy E;. A state of the
combined systemA(O) is then denoted by two indices r and s. Since
A and A' only interact weakly their energies are additive, and the
energy of state is
(0) _ •
E
rs
Er+Ex·
By definition, the partition function of A(O) takes the form
Heat and Thermodynamics· 114
Z(O) = L exp[  p E ~ ~ ) ]
r,.s
= Lexp(p[E
r
+ E ~ ] )
r,s
r,s
Hence,
Z(O) = Z Z',
giving
InZ(O) =lnZ+lnZ',
where Z and Z' are the partition functions of A and A',
respectively. It follows from Equations that the mean energies
of A (0), A, and A' are related by
E(O) =E+E'.
It also follows from Equations that the respective entropies
of these systems are related via
SlO) =S+S'.
Hence, the partition function tells us that the extensive
thermodynamic functions of two weakly interacting systems
are simply additive. It is clear that we can perform statistical
thermodynamical calculations using the partition function Z
instead. of the more direct approach in which we use the density
of states n. The former approach is advantageous because the
partition function is an unrestricted sum of Boltzmann factors
over all accessible states, irrespective of their energy, whereas
the density of states is a restricted sum over all states whose
energies lie in some narrow range. In general, it is far easier to
perform an unrestricted sum than a restricted sum. Thus, it is
generally easier to derive statistical thermodynamical results
using Z rather than n, although n has a far more direct
physical significance than Z.
115 Thermal Equilibrium and Zeroth Law

REFERENCES
• Heat and Thermodynamics, M. W. Zemansky
• Modern Thermodynamics, D. Kondepundi and I.
Prigogine
• Noise and Fluctuations, D. K. C. MacDonald
• Introduction to Metallurgic.al Thermodynamics by
David R. Gaskell.
• Introductory Statistical Mechanics, R. Bowley and M.
Sanchez.
7 ____________________________ __
The First Law of Thermodynamics
Thermodynamics is a science and, more importantly, an
engineering tool used to describe processes that involve changes
in temperature, transformation of energy, and the relationships
between heat and work.
It can be regarded as a generalization of an enormous body
of empirical evidence. It is extremely general: there are no
hypotheses made concerning the structure and type of matter that
we deal with.
It is used to describe the performance of propulsion systems,
power generation systems, and refrigerators, and to describe fluid
flow, combustion, and many other phenomena. The focus of
thermodynamics in aerospace engineering is on the production of
work, often in the form of kinetic energy or shaft power, from
different sources of heat.
For the most part the heat will be the result of combustion
processes, but this is not always the case. The course content can
be viewed in terms of a "propulsion chain", where a progression
from an energy source to useful propulsive work (thrust power of
a jet engine).
Energy souroe
chemical
nuclear, etc.
Heat
(combustion
process)
Mechanical Useful propulsive
work, work (thrust
+ ele(:lric power... + power)
Fig. The Propulsion Chain
117 The First Law of Thermodynamics
FUNDAMENTAL IDEAS OF THERMODYNAMICS
As with all sciences, thermodynamics is concerned with the
mathematical modeling of the real world. In order that the
mathematical deductions are consistent, we need some precise
definitions of the basic concepts. Several of these will be further
amplified in the lectures and in other handouts. If you need additional
information or examples concerning these topics, they are described
clearly and indepth. Thermodynamics plays an important role in
our understanding of electrochemical processes. It can tell us
whether a given redox reaction is spontaneous and therefore whether
it is able to provide useful electrical energy.
Thermodynamics also describes how to add reduction
potentials to determine the cell potential for a galvanic or electrolytic
cell. It also permits us to add reduction potentials of two reductions
to calculate the potential of a new, or even theoretical, reduction half
reaction. Thermodynamics provides further insight into electroche
mical cells at nonstandard conditions in its derivation of the N ernst
Equation. The Nernst Equation allows us to calculate the cell poten
tial at any conditions and suggests the construction of concentration
cells such as pH meters or other ionselective electrodes.
Combining ideas from thermodynamics, stoichiometry, and
basic electrical theory makes this section the most important to
understand if you wish to become proficient at doing
electrochemistry problems. Such problems tend to be among the
more difficult ones on any exam because they cut across many fields
in chemistry and require deep analytical thought and an thorough
understanding of electrochemical cells. In this section, you will get
to know and love such formulae as ~ G o = nFE
O
(useful for
converting free energy and potentials) and E = £0  (RT/nF) In Q
(the Nernst Equation).
THE CONTINUUM MODEL
Matter may be described at a molecular (or microscopic) level
using the techniques of statistical mechanics and kinetic theory.
For engineering purposes, however, we want "averaged"
information, i.e., a macroscopic, not a microscopic, description.
There are two reasons for this. First, a microscopic description of
Heat and Thermodynamics 118
an engineering device may produce too much information to
manage. 1 mm
3
of air at standard temperature and presscre
contains 10
16
molecules, each of which has a position and a
velocity.
Typical engineering applications involve more than 10
20
molecules. Second, and more importantly, microscopic positions
and velocities are generally not useful for determining how
macroscopic systems will act or react unless, for instance, their
total effect is integrated.
We therefore neglect the fact that real substances are
composed of discrete molecules and model matter from the start
as a smoothedout continuum. The information we have about a
continuum represents the microscopic information a v e r a ~ e d over
a volume. Classical thermodynamics is concerned only with
continya.
THE CONCEPT OF A "SYSTEM"
A thermodynamic system is a quantity of matter of fixed
identity, around which we can draw a boundary. The boundaries
may be fixed or moveable. Work or heat can be transferred across
the system boundary. Everything outside the boundary is the
surroundings.
When working with devices such as engines it is often useful
to define the system to be an identifiable volume with flow in and
out. This is termed a control volume.
A closed system is a special class of system with boundaries
that matter cannot cross. Hence the principle of the conservation
of mass is automatically satisfied whenever we employ a closed
system analysis. This type of system is sometimes termed a control
mass.
,',' , ,',',',' ,
,         .
: Gas. Fluid j.
• _________ • System
Boundary
Fig. Piston (Boundary) and Gas (System)
119 The First Law of Thermodynamics
System boundary
;
 ......
Electrical anergy \. _ _ _ _
(work)
Fig. Boundary Around Electric Motor (System)
s""em_
1
complex
process T
L____ :_tn. P2 ,l2
L ___ _
Fig. Sample Control Volume
THE CONCEPT OF A "STATE"
The thermodynamic state of a system is defined by specifying
values of a set of measurable properties sufficient to determine
all other properties. For fluid systems, typical properties are
pressure, volume and temperature. More complex systems may
require the specification of more unusual properties. As an
example, the state of an electric battery requires the specification
of the amount of electric charge it contains.
Properties may be extensive or intensive. Extensive properties
are additive. Thus, if the system is divided into a number of sub
systems, the value of the property for the whole system is equal
to the sum of the values for the parts. Volume is an extensive
property. Intensive properties do not depend on the quantity of
matter present. Temperature and pressure are intensive properties.
Heat and Thermodynamics 120
Specific properties are extensive properties per unit mass and
are denoted by lower case letters.
Specific volume = VIm = v.
Specific properties are intensive because they do not depend
on the mass of the system.
The properties of a simple system are uniform throughout.
In general, however, the properties of a system can vary from point
to point. We can usually analyze a general system by subdividing
it (either conceptually or in practice) into a number of simple
systems in each of which the properties are assumed to be uniform.
It is important to note that properties describe states only when
the system is in equilibrium.
THE CONCEPT OF "EQUILIBRIUM"
The state of a system in which properties have definite,
unchanged values as long as external conditions are unchanged is
called an equilibrium state. ~ o Mass A
t t f t
Gasal
Mg P. A _ PA Pressurlt. P
[Mechanical Equilibrium] • 0  [Thermal Equilibrium]
I )J ":: 1'.... •·
Copper PatIrtIon
Overtime. T,  T2
Fig Equilibrium
A system in thermodynamic equilibrium satisfies:
• Mechanical equilibrium (no unbalanced forces);
• Thermal equilibrium (no temperature differences);
Chemical equilibrium.
THE CONCEPT OF A "PROCESS"
If the state of a system changes, then it is undergoing a
process. The succession of states through which the system passes
defines the path of the process. If, at the end of the process, the
121
The First Law of Thermodynamics
properties have returned to their original values, the system has
undergone a cyclic process or a cycle. Note that even if a system
has returned to its original state and completed a cycle, the state
of the surroundings may have changed.
QUASIEQUILIBRIUM PROCESSES
We are often interested in charting thermodynamic processes
between states on thermodynamic coordinates. A state only when
a system is in equilibrium. If a process involves finite, unbalanced
forces, the system can pass through nonequilibrium states, which
we cannot treat. An extremely useful idealization, however, is that
only "infinitesimal" unbalanced forces exist, so that the process
can be viewed as taking place in a series of "quasiequilibrium"
states. (The term quasi can be taken to mean "as if;" it used in a
number of contexts such as quasionedimensional, quasisteady,
etc.) For this to be true the process must be slow in relation to the
time needed for the system to come to equilibrium internally.
For a gas at conditions of interest to us, a given molecule
can undergo roughly 10
10
molecular collisions per second, so that,
if ten collisions are needed to come to equilibrium, the
equilibration time is on the orde: of 10
9
seconds. This is generally
much shorter than the time scales associated with the bulk
properties of the flow (say the time needed for a fluid particle to
move some significant fraction of the length of the device of
interest). Over a large range of parameters, therefore, it is a very
good approximation to view the thermodynamic processes as
consisting of such a succession of equilibrium states, which we
can chart.
The figures below demonstrate the use of thermodynamics
coordinates to plot isolines, lines along which a property is
constant. They include constant temperature lines, or isotherms,
on a pv diagram, constant volume lines, or isochors on a Tp
diagram, and constant pressure lines, or isobars, on a Tv diagram
for an ideal gas.
Real substances may have phase changes which we can also
plot on thermodynamic coordinates.
Heat and Thermodynamics 122
300r;r,
50
0.5 0.75 1.0 1.25
Specific Volume (m3Ikg)
pv diagram
1.5
250
~ 2 o o
200 300 400 500
Temperature (Kelvin)
pTdiagram
~ r   7 7 ~ ~ ~   r _ ~   ~ ~
0.75 1.0 1.25 1.5
Specific Volume (m3/kg)
Tv diagram
Fig. Thermodynamics Coordinates and Isolines for an Ideal Gas
EQUATIONS OF STATE
600
It is an experimental fact that two properties are needed to
define the state of any pure substance in equilibrium or undergoing
a steady or quasisteady process. Thus for a simple compressibie
gas like air,
P = P (v, 1), or v = v (P, 1), or T= T(P, v),
where v is the volume per unit mass,lIp. In words, if we know v
and T we know P, etc .
. Any of these is equivalent to an equationj{P, v, 1) = 0, which is
known as an equation of state. The equation of state for an ideal
gas, which is a very good approximation to real gases at conditions
that are typically of interest for aerospace applications is
Pv =RT,
where V is the volume per mol of gas and n is the "Universal
Gas Constant," 8.31 kJ/kmolK.
123 The First Law of Thermodynamics
A form of this equation which is more useful in fluid flow
problems is obtained if we divide by the molecular weight, M:
Pv=RT, or P=pRT
where is RIM, which has a different value for different gases
due to the different molecular weights. For air at room conditions,
R = 0.287 kJ/kgK.
CHANGING THE STATE OF A SYSTEM WITH HEAT AND
WORK
Changes in the state of a system are produced by interactions
with the environment through heat and work, which are two
different modes of energy transfer. During these interactions,
equilibrium (a static or quasistatic process) is necessary for the
equations that relate system properties to oneanother to be valid.
HEAT
Heat is energy transferred due to temperature differences only:
• Heat transfer can alter system states;
• Bodies don't "contain" heat; heat is identified as it comes
across system boundaries;
• The amount of heat needed to go from one state to
another is path dependent;
• Adiabatic processes are ones in which no heat is
transferred.
ZEROTH LAW OF THERMODYNAMICS
With the material so far, we are now in a position to describe
the Zeroth Law. Like the other laws of thermodynamics the Zeroth
Law is based on observation. We start with two such observations:
• If two bodies are in contact through a thermalIy
conducting boundary for a sufficiently long time, no
further observable changes take place; thermal
equilibrium is said to prevail.
• Two systems which are individually in thermal
equilibrium with a third are in thermal equilibrium with
each other; all three systems have the same value of the
property called temperature.
These closely connected ideas of temperature and thermal
Heat and Thermodynamics 124
equilibrium are expressed formally in the "Zeroth Law of
Thermodynamics"
Zeroth Law: There exists for every thermodynamic system
in equilibrium a property called temperature. Equality of
temperature is a necessary and sufficient condition for thermal
equilibrium. The Zeroth Law thus defines a property (temperature)
and describes its behaviour.
Note that this law is true regardless of how we measure the
property temperature. (Other relationships we work with will
typically require an absolute scale, so in these notes we use either
the Kelvin K = 273.15 + °C or Rankine scales) The zeroth law is
depicted schematically.
WORK
[J
2
(thermometer)
3
j
t
lIIen ,QJ  0
Fig. The Zeroth Law Schematically
Heat is a way of changing the energy of a system by virtue of
a temperature difference only. Any other means for changing the
energy of a system is called work. We can have pushpull work
(e.g. in a pistoncylinder, lifting a weight), electric and magnetic
work (e.g. an electric motor), chemical work, surface tension work,
elastic work, etc. In defining work, we focus on the effects that
the system (e.g. an engine) has on its surroundings. Thus we define
work as being positive when the system does work on the
surroundings (energy leaves the system). If work is done on the
system (energy added to the system), the work is negative.
Consider a simple compressible substance, a gas (the system),
exerting a force on the surroundings via a piston, which moves
125 The First Law of Thermodynamics
through some distance, I. The work done on the surroundings,
WonsuIT,' is
dW
on
SUIT. = Force on SUIT. x dl
dW
= Force on SUIT. x (A x dl)
on SUIT. Ar rea
ea
dW
on
SUIT. = pressure of SUIT. x d Volume
dWonSUIT. = Px xdV
therefore
Won SUIT. = (2 PxdV.
Why is the pressure Px instead of p/ Consider Px = 0 (vacuum).
No work is done on the surroundings even though p s changes and
the system volume changes.
Use of Px instead of Ps is often inconvenient because it is
usually the state of the system that we are interested in. The
external pressure can only be related to the system pressure if
Px ~ px· For this to occur, there cannot be any friction, and the
process must also be slow enough so that pressure differences due
to accelerations are not significant. In other words, we require a
"quasistatic" process, Px ~ px· Consider Px = P
s
± dp
W= CPx
dV
= (\Ps±dp)dV = (2 PsdV±dpdV.
Therefore, when dp is small (the process is quasistatic),
W = 12 PsdV,
1
and the work done by the system is the same as the work done on
the surroundings
Under these conditions, we say that the process is
"reversible." The conditions for reversibility are that:
If the process is reversed, the system and the
surroundings will be returned to the original states.
To reverse the process we need to apply only an
infinitesimal dp. A reversible process can be altered in
direction by infinitesimal changes in the external
conditions.
Heat and Thermodynamics 126
Remember this result, that we can only relate work done on
surroundings to system pressure for quasistatic (or reversible)
processes. In the case of a "free expansion," where Px = 0
(vacuum),ps is not related to Px (and thus, not related to the work)
because the system is not in equilibrium.
We can write the above expression for work done by the
system in terms of the specific volume, v,
W = m (2 Psdv.
where is the mass of the system. Note that if the system volume expands
against a force, work is done by the system. If the system volume
contracts under a force, work is done on the system.
e:temaJ
I Fa I Px
J
Area
Fig. A Closed System (Dashed Box) Against a Piston,
which Moves Into the Surroundings
fp.dV .. 0 but fp. dV • 0
Fig. Work During an Irreversible Process '# JP.sdV.
For simple compressible substances in reversible processes,
the work done can be represented as the area under a curve in a
pressurevolume diagram .
. 11l
Vi Va
[Work is area under curve of P(V)] Volume [Work depends on path]
127 The First Law of Thermodynamics
·1 W"J,
v
Fig. Work in P  V coordinates
Key points to note are the following:
• Properties only depend on states, but work is path
dependent (depends on the path taken between states);
therefore work is not a property, and not a state variable.
When we say W
l
_
2
' the work between states 1 2,
we need to specify the path.
• For irreversible (nonreversible) processes, we cannot use
f pdV ; either the work must be given or it must be found
by another method.
Example: Work on Fwo Simple Paths
Consider Figure, which shows a system undergoing quasi
static processes for which we can calculate work interactions as
fpdV.
p
CD
2Po
0 Po
b Q)
Vo 2Vo
Fig. Simple processes
W = 2po (
2V
o  Vo) = 2poVo
Along Path a:
W = Po (
2V
o  Vo) = PoVo
Along Path b:
V
Heat and Thermodynamics 128
Practice Questions
Given a piston filled with air, ice, a bunsen burner, and a
stack of small weights, describe
• how you would use these to move along either path a or
path b above, and
• how you would physically know the work is different
along each path.
Example: Work Done During Expansion of a Gas
Consider the quasistatic, isothermal expansion of a thermally ideal gas
from PI' VI to P2' V
2
· To find the work we must know the path. Is it
specified? Yes, the path is specified as isothermal.
p
V
Fig. Quasistatic, Isothermal Expansion of an Ideal Gas
The equation of state for a thermally ideal gas is
pV=n'RT,
where n is the number of moles, 'R is the Universal gas constant,
and V is' the total system volume. We write the work as above,
substituting the ideal gas equation of state,
W = (2 n'RT dV = =n'RT (2 dV = n'RTln(V2)
1;v VI
also for T, = constant, p I VI = P2 V
2
, so the work done by the system
is
W =n'RTln(;:)
or in terms of the specific volume and the system mass,
W = mRT In ( ) = mRT In ).
129 The First Law of Thermodynamics
Work vs. Heat
We can have one, the other, or both: it depends on what
crosses the system boundary (and thus, on how we define our
system). Consider a resistor that is heating a volume of water:
rv
Fig. A resistor Heating Water
• If the water is the system, then the state of the system
will be changed by heat transferred from the resistor.
• If the system is the water and the resistor combined, then
the state of the system will be changed by electrical
work.
CONSERVATION OF ENERGY
FIRST LAW OF THERMODYNAMICS
Observation leads to the following two assertions:
• There exists for every system a property called energy,
E. The system energy ~ a n be considered as a sum of
internal energy, kinetic energy, potential energy, and
chemical energy.
Like the Zeroth Law, which defined a useful property,
"temperature," the First Law defines a useful property
called "energy."
The two new terms (compared to what you have seen
in physics and dynamics) are the internal energy and
the chemical energy. Fur most situations in this class,
we will neglect the chemical energy. We will
generally not, however, neglect the internal energy, .
It arises from the random or disorganized motion of
molecules in the system. Since this molecular motion
Heat and Thermodynamics 130
is primarily a function of temperature, the internal
energy is sometimes called "thermal energy."
TI Tl
add heat
(molecular 1IIOIion) (molecular moUOII)
Fig. Random Motion is the Physical Basis for Internal Energy
The internal energy, u, is a function ofthe state of the system.
Thus u = u (p, 1), or u = u (p, v), or u = u (p, 1). Recall that for
pure substances the entire state of the system is specified if any
two properties are specified.
• The change in energy of a system is equal to the
difference between the heat added to the system and the
work done by the system,
!ill = Q W (units are Joules, J),
where E is the energy of the system,
and
Q is the ijeat input to the system, and
W is the work done by the system.
E = U (thermal energy) + Ekinctic + Epotenlial + ...
• Like the Zeroth Law, the First Law describes the
behaviour of the new property.
• The equation can also be written on a per unit mass basis
tle = q  w (units are J/kg).
• In many situations the potential energy, kinetic energy,
and chemical energy of the system are constant or not
important. Then
!ill = tlU,
tlU=QW or tlu=qw.
• Note that Q and Ware not functions of state, but U,
which arises from mclecular motion, depends only on
the state of the system; does not depend on how the
system got to that state. We therefore have the striking
result that:
131 The First Law of Thermodynamics
I1U is independent of path even though Q and Ware not!
Sometimes this difference is emphasized by writing the First
Law in differential form,
dU =oQoW or du =oqow,
where the symbol "0" is used to denote that these are not exact
differentials but rather are dependent on path.
• Note that the signs are important: Q is defined to be
positive if it is transferred to the system; thus the numerical
value we substitute for Q will be positive if heat is
transferred to the system from the surroundings, and
negative if heat is transferred from the system to the
surroundings.
W is defined to be positive if it is done by the system;
thus the numerical value we substitute for W will be
positive if the system is doing work, and negative if work
is being done on the system.
• For quasistatic processes we can substitute W = psysdV,
dU = dQ  pdV or du = oq  pdv
To give an example of where the first law is applied. We
heat a gas, it expands against a weight, some force (pressure times
area) is applied over a distance, and work is done. The change in
energy of the system supplies the connection between the heat
added and work done. We will spend most of the course dealing
with various applications of the first law  in one form or another.
Pressure Area
Heat(Q)
Fig. The Change in Energy of a System Relates the
Heat Added to the Work Done
The form of the first law we have given here is sometimes
called the "control mass" form, because it is well suited to dealing
with systems of a fixed mass.
Heat and Thermodynamics 132
COROLLARIES OF THE FIRST LAW
• Work done in any adiabatic (Q = 0) process is a function
of state. We can write the first law, setting the heat
transfer term equal to zero, as
Since tlUdepends only on the state change, now W can be
found as a function of the state change .
.
Fig. The change in energy between two states is not path dependent.
• For a cyclic process heat and work transfers are
numerically equal
Fig. Since Energy is a Function of State Only, any Process that Returns a
System to its Original State Leaves its Energy Unchanged.
U final = Uinitial
therefore
tlU=O
and
Q=W or qOQ=q8W
APPLICATIONS OF THE FIRST LAW
ADIABATIC, STEADY, THROTILING OF A GAS
The configuration of interest. We wish to know the relation
between properties upstream of the valve, denoted by"!" and those
downstream, denoted by "2".
 P,. V,,",... (:g) PI' ", ... ,... _
Valve
Fig. Adiabatic flow Through a Valve, a Generic Throttling Process
133
\ ®I
\
system
The First Law of Thermodynamics
E?a {Z).,.I»l"' Initial
y Slale
"'" pislons
)1
\. 7
__ __
..
SYSleRI PlslOns
Fig. Equivalence of Actual System and Piston Model
To analyze this situation, we can defHle the system (choosing
the appropriate system is often a critical element in effective
problem solving) as a unit mass of gas in the following two states.
Initially the gas is upstream of the valve andjust through the valve.
In the final state the gas is downstream of the valve plus just before
the valve.
In terms of the system behaviour, however, we could replace
the fluid external to the system by pistons which exert the same
pressure that the external fluid exerts, as indicated schematically
on the right side.
The process is adiabatic, with changes in potential energy
and kinetic energy assumed to be negligible. The first law for the
system is therefore
!::.U=  W.
The work dene by the is
W = P
2
V
2
ljVj.
Use of the first law leads to
U
2
=P
2
V
2
=U
1
+ljVj.
In words, the initial and final states of the system have the
same value of the quantity U + PV. For the case examined, since
we are dealing with a unit mass, the initial and final states of the
system have the same value of u + Pv.
We define this quantity as the "enthalpy," usually denoted
byH,
H=U+PV.
In terms of the specific quantities, the enthalpy per unit
mass IS
h = u + Pv = u + Pip.
Heat and Thermodynamics 134
It is a function of the state ofthe system. Hhas units of Joules,
and has units of Joules per kilogram.
The utility and physical significance of enthalpy will become
clearer as we work with more flow problems. When you evaluate
the energy of an object of volume V, you have to remember that
the object had to push the surroundings out of the way to make
room for itself. With pressure P on the object, the work required
to make a place for itself is p V. This is so with any object or system,
and this work may not be negligible. The force of one atmosphere
!lressure on one square meter is equivalent to the force of a mass
of about 10 tons. Thus the total energy of a body is its internal
energy plus the extra energy it is credited with by having a volume
Vat pressure p. We call this total energy the enthalpy, H.
QUASISTATIC EXPANSION OF A GAS
Consider a quasistatic process of constant pressure
expansion. We can write the first law in terms of the states before·
and after the expansion as
Q = (V
2
 VI) + W,
and writing the work in terms of system properties,
= (V
2
 VI) + P(V2  VI) since PI = P2 = p.
By grouping terms we can write the heat input in terms of
the enthalpy change of the system:
Q = (V
2
+ pV
2
)  (VI + pV
I
)
=H
2
H
I
TRANSIENT FILLING OF A TANK
Another example of a flow process, this time for an unsteady
flow, is the transient process of filling a tank, initially evacuated,
from a surrounding atmosphere, which is at a pressure Po and a
temperature To .
" , ~       ...
Po.T. ViICuum "",
" \
, System \
: (all the g a . ~ that goc:s I
\ inco the lank) }
,
" "'>(
Po ' ....... ____  .. ;
Yo
Fig. A Transient Problemfilling of a Tank from the Atmosphere
135 The First Law of Thermodynamics
At a given time, the valve at the tank inlet is opened and the
outside air rushes in. The inflow stops when the pressure inside is
equal to the pressure outside. The tank is insulated, so there is no
heat transfer to the atmosphere. What is the final temperature of
the gas in the tank?
This time we take the system to be all the gas that enters the
tank. The initial state has the system completely outside the tank,
and the final state has the system completely inside the tank. The
kinetic energy initially and in the final state is negligible, as is the
change in potential energy, so the first law again takes the form
/).U =  W.
Work is done on the system, of magnitude Po Vo. where Vo is
the initial volume of the system, so
/).U= Po Vo·
In terms of quantities per unit mass (/).U = m/).u, Vo = mv
o
'
where m is the mass of the system),
flu = Urinal  Uj = Po Vo·
The final value of the internal energy is
ufinaI = Uj + Po Vo
=hj =110.
For a perfect gas with constant specific heats,
U =cvT, h = CpT,
cvT
flnal
= C pTo,
C
T
final
= 2.. To = yTo.
C
v
The final temperature is thus roughly 200°F hotter than the outside
air!
It may be helpful to recap what we used to solve this problem.
There were basically four steps:
• Definition of the system
• Use of the first law
• Equating the work to a "PdV" term
• Assuming the fluid to be a perfect gas with constant
specific heats.
Heat and Thermodynamics 136
A message that can be taken from both ofthese examples (as
well as from a large number of other more complex situations, is
that the quantity h = u + Pv occurs naturally in problems of fluid
flow. Because the combination appears so frequently, it is not only
defined but also tabulated as a function of temperature and pressure
for a number of working fluids.
THE FIRST LAW IN TERMS OF ENTHALPY
We start with the first law in differential form and substitute
pdV for dW by assuming a quasistatic or reversible process:
dU = oQ  0 W (true forany process, neglecting ME and f:.P E)
dU = oQ  pdV (true for any quasistatic process, no ME or
ME)
The definition of er.thalpy,
H=U+pV,
can be differentiated (applying the chain rule to the p V term) to
produce
dH=dU+pdV+ Vdp
Substituting the dU above for the dU in the First Law, we
obtain
dH = oQ  oW + pdV + Vdp (valid for any process)
or
dH = oQ + Vdp (valid for any quasistatic process)
THE RELATION BETWEEN TEMPERATURE
CHANGE AND HEAT
How much does a given amount of heat transfer change the
temperature of a substance? It depends on the substance. In general
Q=CtlT,
where C is a constant that depends on the substance. We can
determine the constant for any substance if we know how much
heat is transferred. Since heat is path dependent, however, we must
specify the process, i.e., the path, to find C.
Two useful processes are constant pressure and constant
volume, so we will consider these each in turn. We will call the
specific heat at constant pressure Cp, and that at constant volume
Cv, or cp and cv per unit mass.
137 The First Law of Thermodynamics
• The Specific Heat at Constant Volume
Remember that if we specify any two properties of the system,
then the state of the system is fully specified. In other words we
can write u = u (T, v) u = u (p, v) or u = u (p, 1).
Consider the form u = u (T, v), and use the chain rule to write
how changes with respect to T and v:
du =(00) dT +(au) dv.
aT v av T
For a constant volume process, the second term is zero since
there is no change in volume, dv = O. Now if we write the First
Law for a quasistatic process, with dW = pdv,
du= 8qpdv,
we see that again the second term is zero if the· process is also
constant volume. Equating Equation with dv canceled in each,
8q=(:;1 dT,
and rearranging
(:l ~ ( : ~ l ·
In this case, any energy increase is due only to energy transfer
as heat. We can therefore use our definition of specific heat from
Equation to define the specific heat for a constant volume process,
C
v
=(:; l·
• The Specific Heat at Constant Pressure
If we write h = h (T, p), and consider a constant pressure
process, we can perform a similar derivation to the one above and
show that
c
p
=(:;)p'
In the derivation of c
v
' we considered only a constant volume
process, hence the name, "specific heat at constant volume." It is
more useful, however, to think of c
n
in terms of its definition as a
certain partial derivative, vvhich is a thermodynamic property,
Heat and Thermodynamics 138
rather than as a quantity related to heat transfer in a special process.
In fact, the derivatives above are defined at any point in any quasi
static process whether that process is constant volume, constant
pressure, or neither.
The names "specific heat at constant volume" and "specific
heat at constant pressure" are therefore unfortunate misnomers;
C
v
and c
p
are thermodynamic properties of a substance, and by
definition depend only the state. They are extremely important
values, and have been experimentally determined as a function of
the thermodynamic state for an enormous number of simple
compressible substances.
To recap:
or
(
ah \
c =1
P aT)
p
and C
v
= ( au) .
aT v
c =(aH) andC =(au) .
p aT v aT
P v
Practice Questions Throw an object from the top tier of the
lecture hall to the front of the room. Estimate how much the
temperature of the room has changed as a result. Start by listing
what information you need to solve this problem.
SPECIFIC HEATS OF AN IDEAL GAS
The equation of state for an ideal gas is
PV=NRT
where N is the number of moles of gas in the volume V. Ideal gas
behaviour furnishes an extremely good approximation to the
behaviour of real gases for a wide variety of aerospace
applications. It should be remembered, however, that describing
a substance as an ideal gas constitutes a model of the actual
physical situation, and the limits of model validity mUSt always
be kept in mind.
One of the other important features of an ideal gas is that its
internal energy depends only upon its temperature. (For now, this
can be regarded as another aspect nfthe model of actual systems
that the ideal gas represents, but it can be shown that this is a
139 The First Law of Thermodynamics
consequence of the form of the equation of state.) Since u depends
only Oil T,
or
du = cv (1)dT.
In the above equation we have indicated that C
v
can depend
on T. Like the internal energy, the enthalpy is also only dependent
on T for an ideal gas. (If u is a function of T, then, using the ideal
gas equation of state, u + Pv is also.) Therefore,
dh = ( fJh) dT + ( fJl/r dp,
fJT y JP )T
and
dh = c
p
(1)dT.
If we are interested in finIte changes of internal energy or
enthalpy, we integrate,
rT2
L\ul_2 = 1ft cy(T)dT
and
r
T2
L\h
l
_
2
= Jr
t
cp(T)dT
Over small temperature changes (DT :::0 200), it is often
assumed that c
y
and c
p
are constant. Furthermore, there are wide
ranges over which specific heats d ~ not vary greatly with respect
to temperature. It is thus often useful to treat them as constant.
If so
dh=cpdT,
U2  UI = c
v
(T2 11),
U2  hI = C P (T2 11),
These equations are useful in calculating internal energy or
enthalpy differences, but it should be remembered that they hold
only if the specific heats are constant. We can relate the specific
Heat and Thermodynamics 140
heats of an ideal gas to its gas constant as follows. We write the
first law in terms of internal energy,
oq=du+dW,
and assume a quasistatic process so that we can also write it in
terms of enthalpy,
oq =dhvdp.
Equating the two first law expressions above, and assuming
an ideal gas, we obtain
C pdT  vdp = cvdT + pdv.
Combining terms,
(c
p
c
v
) dT = d(pv)
Since pv = RT,
d(pv)
c c =
p v dT'
c c =R
p v
An expression that will appear often is the ratio of specific
heats, which we will define as
c
p
y=.
C
v
Below we summarize the important results for all ideal gases,
and give some values for specific types of ideal gases.
• All ideal gases:
• The specific heat at constant volume (c
v
for a unit mass
or Cv for one kmol) is a function of T only.
• The specific heat at constant pressure (c
p
for a unit mass
or Cp for one kmol) is a function of T only.
• A relation that connects the specific heats c
p
' c
v
' and the
gas constant is
CpCv=R,
where the units depend on the mass considered. For a unit mass
of gas, e.g., a kilogram, c
p
and C
v
woulci be the specific heats for
one kilogram of gas and R is as defined above. For one kmol of
gas, the expression takes the form
CpCv=R,
141 The First Law of Thermodynamics
where C p and C v have been used to de note the specific heats
for one kmol of gas and R is the universal gas constant.
• The specific heat ratio, y = c/c
v
(or C piC v), is a function
of T only and is greater than unity
• An ideal gas with specific heats independent of
temperature, c
p
= const and C
v
= const, is referred to as
a perfect gas. Monatomic gases and diatomic gases at
ordinary temperatures are considered perfect gases. To
make this distinction the terminology "a perfect gas with
constant specific heats" is used throughout the notes. In
some textbooks perfect gases are sometimes also referred
to as ideal gases, and to avoid confusion we use the
stated terminology.
• Monatomic gases, such as He, Ne, Ar, and most metallic
vapors:
• C
v
(or C v) is constant over a wide temperature range and
is very nearly equal to (3/2)R[or (3/2)R, for one kmol].
• c
p
(or C p) is constant over a wide temperature range and
is very nearly equal to (5/2)R[or (5/2)R, for one kmol].
• y is constant over a wide temperature range and is very
nearly equal to 5/3 [y = 1.67].
• Socalled permanent diatomic gases, namely H
2
, 02' N
2
,
Air, NO, and CO:
• C
v
(or C
v
) is nearly constant at ordinary temperatures,
being approximately (5/2)R [(5/2)R, for one kmol], and
increases slowly at higher temperatures.
• c
p
(or C
p
) is nearly constant at ordinary temperatures,
ocing approximately (7/2) R[(7/2)R, for one kmol], and
increases slowly at higher temperatures.
• y is constant over a temperature range of roughly to and
is very nearly equal to 7/5[y = 1.4]. It decreases with
temperature above this.
• Polyatomic gases and gases that are chemically active,
such as CO
2
' NH
3
, CH
4
, and Freons:
The specific heats, C
v
and c
p
' and g vary with the temperature,
the variation being different for each gas. The general trend is
that heavy molecular weight gases (i.e., more complex gas
molecules than those listed in 2 or 3), have values of g closer to
Heat and Thermodynamics 142
unity than diatomic gases, which, are closer to unity than
monatomic gases. Values of g below 1.2 are typical of Freons
which have molecular weights of over one hundred.
In general, for substances other than ideal gases, u and h
depend on pressure as well as on temperature, and the above
relations will not all apply. In this respect, the ideal gas is a very
special model.
In summary, the specific heats are thermodynamic properties
and can be used even if the processes are not constant pressure or
constant volume. The simple relations between changes in energy
(or enthalpy) and temperature are a consequence of the behaviour
of an ideal gas, specifically the dependence of the energy and
enthalpy on temperature only, and are not true for more complex
substances.
REVERSIBLE ADIABATIC PROCESSES FOR AN IDEAL GAS
From the first law, with Q = 0 du = cvdT, and Wor = pdv,
du+ pdv=O
Also, using the definition of enthalpy,
dh = du + pdv + vdp.
The underlined terms are zero for an adiabatic process. Rewriting
equations,
ycvdT =  ypdv
cvdT = vdp.
Combining the above two equations we obtain
ypdv=vdp or ydv!v = dp! p.
Equation can be integrated between states 1 an? 2 to give
'I! n(v2!vl) = In (P2! PI), or equivalently,
(P2 vi) !(PI v{) = 1.
For an ideal gas undergoing a reversible, adiabatic process,
the relation between pressure and volume is thus:
pv
Y
= constant, or
143 The First Law of Thermodynamics
p = constant x pY.
We can substitute for p or v in the above result using the
ideal gas law, or carry out the derivation slightly differently, to
also show that
( )
..L ( )Y_I
P2 = T2 yl and T2 = ~
PI 11 11 v2
We will use the above equations to relate pressure and
temperature to one another for quasistatic adiabatic processes (for
instance, this type of process is our idealization of what happens
in compressors and turbines).
CONTROL VOLUME FORM OF THE SYSTEM LAWS
The thermodynamic laws (as well as Newton's laws) are for
a system, a specific quantity of matter. More often, in propulsion
and power problems, we are interested in what happens in a fixed
volume, a rocket motor or a jet engine through which mass is
flowing at a certain rate. We may also be interested in the rates of
heat and work into and out of a system.
For this reason, the control volume form of the system laws
is of great importance. Rather than focus on a particle of mass
which moves through the engine, it is more convenient to focus
on the volume occupied by the engine. This requires us to use the
control volume form of the thermodynamic laws, developed below.
9 ~ € J
Syslemat/, Syslem at lime I,
Fig. Control Volume and System for Flow Through a Propulsion Device
CONSERVATION OF MASS
For the control volume shown, the rate of change of mass
inside the volume is given by the difference between the mass
flow rate in and the mass flow rate out. For a single flow coming
in and a single flow coming out this is
dmcv . .
= min  m
out
dt
Heat and Thermodynamics 144
If the mass inside the control volume changes with time it is
because some mass is added or some is taken out. In the special
case of a steady flow, dId! = 0, therefore
iii.. + control
volume
Fig. A Control Volume used to Track Mass Flows
CONSERVATION OF ENERGY
The first law of thermodynamics Chfl be written as a rate
equation:
where
de . .
=Q=W
dt '
. . (OQ)
Q = J:!o dt rate of total heat transfer to the system
. . (OW)
W = J:!o dt rate of total work done by the system.
To derive the first law as a rate equation for a control volume
we proceed as with the mass conservation equation. The physical
idea is that any rate of change of energy in the control volume
must be caused by the rates of energy flow into or out of the
volume.
The heat transfer and the work are already included and the
only other contribution must be associated with the mass flow in
and out, which carries energy with 'it.
The desired form of the equation will be (rate of change of
energy in cv) = (rate of heat added to C.V.)  (rate of work done)
+ (rate of energy flow into C.V.)  (rate of energy flow out C.V.).
145
[Simple]
t ·/
'IJi
'lot
The First Law of Thermodynamics
,
,
I
[More General]
 ..
, ...
~ ~ _ ~ _ ~ _ ~ __ ~ _ ~ _ ~ _ ~ _ ~ _ ~ _ ~ __ ~ J ~
....
o 0 Q
i
Fig. Schematic Diagrams Illustrating Terms in the Energy Equation
for a Simple and a more General Control Volume
The fluid that enters or leaves has an amount of energy per
unit mass given by
e=u+c
2
!2+gz,
where c is the fluid velocity relative to some coordinate
system, and we have neglected chemical energy. In addition,
whenever fluid enters or leaves a control volume there is a work
term associated with the entry or exit. The present derivation is
essentially an application of the ideas presented there. Flow exiting
at station "e" must push back the surrounding fluid, doing work
on it. Flow entering the volume at station "i" is pushed on by, and
receives work from the surrounding air.
The rate of flow work at exit is given by the product of the
pressure times the exit area times the rate at which the external
flow is "pushed back." The latter, however, is equal to the volume
per unit .nass times the rate of mass flow. Put another way, in a
time dt, the work done on the surroundings by the flow at the exit
station is
dW
flow
= pvdm
c
'
Heat and Thermodynamics 146
The net rate of flow work is
W
flow
= PeVeme  Pivjm
i
·
Including all possible energy flows (heat, shaft work, shear
work, piston work, etc.), the first law can then be written as:
~ LEcv = LOcv + LW
shaft
+ LWshcar + LWpiston + LWflow + Lm( u+ e; + gz )
where L includes the sign associated with the energy flow. Ifheat
is added or work is done on the system then the sign is positive, if
work or heat are extracted from the system then the sign is
negative. NOTE: this is consistent with M£ = Q  W, where W is
the work done by the system on the environment, thus work is
flowing out of the system.
We can then combine the specific internal energy term, U, in
e and the specific flow work term, pv, to make the enthalpy appear:
Total energy associated with mass flow:
e+ pv = U +c
2
/2+ gz+ [iv = h+c
2
/2 + gz.
Thus, the first law can be written as:
!LE
Cl
• = Lfkv + Lri;;haft + LW
shcar
+ LWpiston + Lm (h+ c; + gz)
For most of the applications in this course, there will be no
shear work and no piston work. Hence, the first law for a control
volume will be most often used as:
dE
ev
'Q' . . (h c; ). (h c ~ )
;It = cv  JYshaft + m
i
"i + 2" + gzi  me e + 2" + gZe .
Note how our use of enthalpy has simplified the rate of work
term. In writing the control volume form of the equation we have
assumed only one entering and one leaving stream, but this could
be generalized to any number of inlet and exit streams.
In the special case of a steadystate flow,
d
=0 and mi =m
e
=m.
dt
Applying this to Equation produces a form of the "Steady Flow
Energy Equation" (SFEE),
147 The First Law of Thermodynamics
Q" +m[( h, + c1 + gz}( hi + ct + gz,ll
which has units of Joules per second. We could also divide by the
mass flow to produce
. (h c; I (1. cf 1
qcvwcv+
m
which has units of Joules per second per kilogram. For problems
of interest in aerospace applications the velocities are high and
the term that is associated with changes in the elevation is small.
From now on, we will neglect the gz telms unless explicitly stated.
STAGNATION TEMPERATURE AND STAGNATION
ENTHALPY
iJ3r'""ii3.. __  

 
I
Stagnation
Fig. Streamlines and a Stagnation Region; a Control Volume can be
Drawn between the Dashed Streamlines and Points 1 and 2
The streamlines are stationary in space, so there is no external
work done on the fluid as it flows. If there is also no heat
transferred to the flow (adiabatic), then the steady flow energy
equation becomes
The quantity that is conserved is defined as the stagnation
temperature,
Heat and Thermodynamics 148
or
I; = 1 + Y 1 M2 using a = ./yRT
T 2
where M = cia is the Mach number. The stagnation temperature
is the temperature that the fluid would reach if it were brought to
zero speed by a steady adiabatic process with no external work.
Note that for any steady, adiabatic flow with no external work,
the stagnation temperature is constant.
It is also convenient to define the stagnation enthalpy,
c
2
h
t
=cpT+
2 .
which allows us to write the Steady Flow Energy Equation in a
simpler form as
ql2  w
s
,I2 = ht2  h
tl
·
Note that for a quasistatic adiabatic process
11 = (!!L)Y;I
T2 P2
so we can write
yI
i =(;)1
and define the relationship between stagnation pressure and static
pressure as
r
I
~ =(1+ y ~ 1 M2)1,
where, the stagnation pressure is the pressure that the fluid would
reach if it were brought to zero speed, via a steady, adiabatic, quasi
static process with no external work.
FRAME DEPENDENCE OF STAGNATION QUANTITIES
An area of common confusion is the frame dependence of
stagnation quantities. The stagnation temperature and stagnation
pressure are the conditions the fluid would reach if it were brought
to zero speed relative to some reference frame, via a steady
149 The First Law of Thermodynamics
adiabatic process with no external work (for stagnation
temperature) or a steady, adiabatic, reversible process with no
external work (for stagnation pressure). Depending on the speed
of the reference frame the stagnation quantities will take on
different values.
Consider a high speed reentry vehicle traveling through the
still atmosphere, which is at temperature, T. Let's place our
reference frame on the vehicle and stagnate a fluid particle on the
nose of the vehicle (carrying it along with the vehicle and thus
essentially giving it kinetic energy). The stagnation temperature
of the air in the vehicle frame is
c
2
1', =T+,
2c
p
where c is the vehicle speed. The temperature the skin reaches (to
first approximation) is the stagnation temperature and depends on
the speed of the vehicle. Since reentry vehicles travel fast, the
skin temperature is much hotter than the atmospheric temperature.
The atmospheric temperature, T, is not frame dependent, but the
stagnation temperature, T
t
, is.
The confusion comes about because T is usually referred to
as the static temperature. In common language this has a similar
meaning as "stagnation," but in fluid mechanics and
thermodynamics static is used to label the thermodynamic
properties of the gas (p, T, etc.), and these are not frame dependent.
Thus in our reentry vehicle example, looking at the still
atmosphere from the vehicle frame we see a stagnation temperature
hotter than the atmospheric (static) temperature. If we look at the
same still atmosphere from a stationary frame, the stagnation
temperature is the same as the static temperature.
Example
For the case shown below, a jet engine is sitting motionless
on the ground prior to takeoff. Air is entrained into the engine hy
the compressor. The inlet can be assumed to be frictionless and
'adiebatic.
Heat and Thermodynamics
Atrrosphere:
T"tm
P"lm
= 0
Inlet cP Exhaust jet,
M=O.8
+. u ... § 0
150
Fig. A Stationary Gas Turbine Drawing Air in from the Atmosphere
Considering the state of the gas within the inlet, prior to
passage into the compressor, as state (1), and working in the
reference frame of the motionless airplane:
• Is Ttl greater than, less than, or equal to T
atm
?
The stagnation temperature of the atmosphere, T
ratm
, is equal
to T
atm
since it is moving the same speed as the reference frame
(the motionless airplane). The steady flow energy equation tells
us that ifthere is nc heat or shaft work (the case for our adiabatic
inlet) the stagnation enthalpy (and thus stagnation temperature for
constant Cp) remains unchanged. Thus Ttl = Tt'atm = T
atm
• Is 1'1 greater than, less than, or equal to
If Ttl = T
t
'
atm
then TI < T
atm
since the flow is moving
at station 1 and therefore some of the total energy is composed
of kinetic energy (at the expense of internal energy, thus
lowering T
I
)
• Is P tl greater than, less than, or equal to P atm?
Equal, by the same argument as 1.
• Is PI greater than, less than, or equal to P atm?
Less than, by the same argument as 2.
Steady Flow Energy Equation in Terms of Stagnation
Enthalpy
The form of the "Steady Flow Energy Equation" (SFEE) that
we will most commonly use is Equation written in terms of
stagnation quantities, and neglecting chemical and potential
energies, Steady Flow Energy Equation: Qcv  W
shaft
= m (hI h
ti
).
c
The steady flow energy equation finds much use in the analysis
of power and propulsion devices and other fluid machinery. Note
the prominent role of enthalpy.
151 The First Law of Thermodynamics
EXAMPLE APPLICATIONS OF THE STEADY FLOW
ENERGY EQUATION
Tank Filling
Using what we have just learned we can attack the tank filling
problem solved from an alternate point of view using the control
volume form of the first law. In this problem the shaft work is
zero, and the heat transfer, kinetic energy changes, and potential
energy changes are neglected. In addition there is no exit mass
flow.
m (mass flow)
r'
1 control I
1 volume I
1
1
1
I
1 _____ 
control surface
Fig. A Control Volume Approach to the Tank Filling Problem
The control volume form of the first law is therefore
dU =m,h
i
•
dt
The equation of mass conservation is
dm .
Combining we have
=m·
dt ,.
dU =dm
h
dt dt"
Integrating from the initial time to the final time (the incoming
enthalpy is constant) and using U = mu gives the result l'flnal = hi
= ho as before.
Flow Through a Rocket Nozzle
A liquid hipropellant rocket consists of a thrust chamber and
nozzle and some means for forcing the liquid propellants into the
chamber where they react, converting chemical energy to thermal
energy.
Heat and Thermodynamics
fuel
f>
I chamber
+ C:C y __ _
\ hot. hiSh pressure
low \'1:locIlY gas
Fig. Flow Through a Rocket Nozzle
152
Once the rocket is operating we can assume that all of the
flow processes are steady, so it is appropriate to use the steady
flow energy equation. Also, for now we will assume that the gas
behaves as a perfect gas with constant specific heats, though in
general this is a poor approximation. There is no external work,
and we assume that the flow is adiabatic. We define our control
volume as going between location c, in the chamber, and location
, at the exit, and then write the First Law as
qcc  Ws ec = h
te
 h
te
which becomes h
te
= h
te
or
Therefore
C
e
Te).
If we assume quasistatic, adiabatic expansion then
so
Te and Pc' the conditions in the combustion chamber, are set by
propellants, and p e is the external sta.ic pressure.
153 The First Law of Thermodynamics
Power to Drive a Gas Turbine Compressor
The engine is designed to produce about 84,000 Ibs ofthrust
at takeoff. The engine is a twospool design. The fan and low
pressure compressor are driven by the low pressure turbine. The
high pressure compressor is driven by the high pressure turbine.
We wish to find the total shaft work required to drive the
compression system.
AlII
'IAn
·"fM1ilUST
... •
: ''''''SI
Fig. The Pratt and Whitney 4084 (drawing courtesy of Pratt and Whitney)
1t f = total pressure ratio across the fan . :::: 1.4
1t
c
= total pressure ratio across the fan + cinoressir :::: 45
mf =610kg/s
moore = 120 kg/s
1inlct = 300 K.
We define our control volume to encompass the compression
system, from the front of the fan to the back of the fan and high
pressure compressor, with the shaft cutting through the back side
of the control volume. Heat transfer from the gas streams is negligi
ble, so we write the First Law (steady flow energy equation) as:
1° Ws = m (ht2 h
tl
)·
For this problem we must consider two streams, the fan stream,/,
and the core stream, c:
Heat and Thennodynamics 154
w., = m [f..hl,f + mcM/,c
= m[c pf..7;,f + mc
c
pf..7;,c
We obtain the temperature change by assuming that the
compression process is quasistatic and adiabatic,
then
~ ~ ( ~ f
(
7;2 ) = 11: J' = 1.1 :::::> f..7;, fan = 30 K
7;1 fan
(
T. ) yl
;2 = 11:c6re = 3.0 => f..7;, core = 600 K
II core
Substituting these values into the expression for the first law above,
along with estimates of c
P
' we obtain
W".s = 610 kg/s x 30 K x 1008 J/kgK + 120 kg/s x 600 K x 1008
J/kgK
=91xl06J/s
=  91 Megawatts negative sign implies work done on the
fluid
Note that 1 Hp = 745 watts. If a car engine has ~ 110 Hp =
8.2 x 10
4
wa!ts, then the power needed to drive compressor is
equivalent to 1,110 automobile engines. All of this power is
generated by the low pressure and high pressure turbines.
APPLICATION OF FIRST LAW .
SOME PROPERTIES OF ENGINEERING CYCLES; WORK
AND EFFICIENCY
As preparation for our discussion of cycles (and as a
foreshadowing of the second law), we examine two types of
processes that concern interactions between heat and work. The
first of these represents the conversion of work into heat. The
second, which is much more useful, concerns the conversion of
heat into work. The question we will pose is how efficient can
this conversion be in the two cases.
155
The First Law of Thermodynamics
i
Block on rough surface
+ ~ R
 L ~
Viscous liquid Resistive heating
Fig. Examples of the Conversion of Work into Heat
The first is the pulling of a block on a rough horizontal surface
by a force which moves through some distance. Friction resists
the pulling. After the force has moved through the distance, it is
removed. The block then has no kinetic energy and the same
potential energy it had when the force started to act. Ifwe measured
the temperature of the block and the surface we would find that it
was higher than when we started. (High temperatures can be
reached if the velocities of pulling are high; this is the basis of
inertia welding.) The work done to move the block has been
converted totally to heat.
The second example concerns the stirring of a viscous liquid.
There is work associated with the torque exerted on the shaft
turning through an angle. When the stirring stops, the fluid comes
to rest and there is (again) no change in kinetic or potential energy
from the initial state. The fluid and the paddle wheels wilI be found
to be hotter than when we started, however.
The final example is the passage of a current through a
resistance. This is a case of electrical work being converted to
heat, indeed it models operation of an electrical heater. All the
examples in Figure have 100% conversion of work into heat. This
100% conversion could go on without limit as long as work were
supplied. Is this true for the conversion of heat into work?
To answer the last question, we need to have some basis for
judging whether work is done in a given process. One way to do
this is to ask whether we can construct a way that the process
could result in the raising of a weight in a gravitational field. If
so, w(:; can say "Work has been done." It may sometimes be
difficult to make the link between a complicated thermodynamic
process and the simple raising of a weight, but this is a rigorous
test for the existence of work.
Heat and Thermodynamics 156
One example of a process in which heat is converted to work
is the isothermal ( constant temperature) expansion of an ideal gas.
The system is the gas inside the chamber. As the gas expands, the
piston does work on some external device. For an ideal gas, the
internal energy is a function of temperature only, so that if the
temperature is constant for some process the internal energy
change is zero. To keep the temperature constant during the
expansion, heat must be supplied. Because flU = 0, the first law
takes the form Q = W. This is a process that has 100% conversion
of heat into work.
PoT
Palm
t
E
Work received. W
Fig. Isothermal Expansion
The work exerted by the system is given by
f
PdV
where 1 and 2 denote the two states at the beginning and end of
the process. The equation of state for an ideal gas is
P=NRTIV,
with Nthe number of moles of the gas contained in the chamber.
Using the equation of state, the expression for work can be written
as
Work during an isothermal expansion
= NRT f dV / V = NRT In ( ~ )
For an isothermal process, P V = constant, so that PI / P 2 = Vi
VI' The w0fk can be written in terms of the pressures at the
beginning and end as .
Work during a ~ isothermal expansion = NRTln( V2) .
~ V J
The lowest pressure to which we can expand and still receive
work from the system is atmospheric pressure. Below this, we
157 The First Law of Thermodynamics
would have to do work on the system to pull the piston out further.
There is thus a bound on the amount of work that can be obtained
in the isothermal expansion; we cannot continue indefinitely. For
a power or propulsion system, however, we would like a source
of continuous power, in other words a device that would give
power or propulsion as long as fuel was added to it. To do this,
we need a series of processes where the system does not progress
through a oneway transition from an initial state to a different
final state, but rather cycles back to the initial state. What is looked
for is in fact a thermodynamic cycle for the system.
We define several quantities for a cycle:
• QA is the heat absorbed by the system.
• QR is the heat rejected by the system.
• Wi s the net work done by the system.
The cycle returns to its initial state, so the overall energy
change, !:J.U, is zero. The net work done by the system is related
to the magnitudes of the heat absorbed and the heat rejected by
W = Net work = QA  QR'
The thermal efficiency of the cycle is the ratio of the work
done to the heat absorbed. (Efficiencies are often usefully
portrayed as "What you get" versus "What you pay for." Here
what we get is work and what we pay for is heat, or rather the fuel
that generates the heat.) In terms of the heat absorbed and rejected,
the thermal efficiency is
. Work done Q Q Q
l'\= thermal efficlency = = A R = 1  K..
Heat absorbed QA Q
A
The thermal efficiency can only be 100% (complete
conversion of heat into work) if Q
R
= 0; a basic question is what
is the maximum thermal efficiency for any arbitrary cycle? We
examine this for several cases, including the Carnot cycle and the
Brayton (or Joule) cycle, which is a model for the power cycle in
a jet engine.
GENERALIZED REPRESENTATION OF
THERMODYNAMIC CYCLES
Before we examine individual heat engines, note that all heat
engines can be represented generally as a transfer of heat from a
Heat and Thermodynamics 158
high temperature reservoir to a device, which does work on the
surroundings, followed by a rejection of heat from that device to .
a low temperature reservoir.
. .  _ ~ W
Fig. A generalized heat engine
THE CARNOT CYCLE
It has four processes. There are two adiabatic reversible legs
and two isothermal reversible legs. We can construct a Carnot
cycle with many different systems, but the concepts can be shown
using a familiar working fluid, the ideal gas. The system can be
regarded as a chamber enclosed by a piston and filled with this
ideal gas .
p
•
titta
Reservoir Insulating slalld Rcscnoir
v
Fig. Camot Cycle Thermodynamic Diagram on Left and Schematic
of the Different Stages in the Cycle for a System
Composed of an Ideal Gas on the Right
The four processes in the Carnot cycle are:
• The system is at temperature T2 at state a. It is brought
159
The First Law of Thermodynamics
in contact with a heat reservoir, which is just a liquid
or solid mass of large enough extent such that its
temperature does not change appreciably when some
amount of heat is transferred to the system. In other
words, the heat reservoir is a constant temperature source
( or receiver) of heat. The system then undergoes an
isothermal expansion from a to b, with heat absorbed
Q2·
• At state b, the system is thermally insulated (removed
from contact with the heat reservoir) and then let expand
to c. During this expansion the temperature decreases to
T
I
. The heat exchanged during this part of the cycle,
Q
be
= 0)
At state the system is brought in contact with a heat
reservoir at temperature T
I
. It is then compressed to state
d, rejecting heat Q
I
in the process.
• Finally, the system is compressed adiabatically back to
the initial state a. The heat exchange Q
da
= O.
The thermal efficiency of the cycle is given by the definition
11 = 1  QR = 1 + QJ .
QA Q2
In this equation, there is a sign convention implied. The
quantities QA' Q
R
as defined are the magnitudes of the heat
absorbed and rejected. The quantities Ql' Q
2
on the other hand
are defined with reference to heat received by the system. In this
example, the former is negative and the latter is positive. The heat
absorbed and rejected by the system takes place during isothermal
processes and we already know what their values are:
Q2 = Wab = }TRT2 [In (Vb IVa)],
QJ = Web =NRTj [In (Vd IVe)]=[ln(VcIVd)]. (QI is negative.)
The efficiency can now be written in terms ofthe volumes at
the different states as
11 = I + Tj [In (Vd IVc)].
T
2
[In (Vb IVa)]
The path from states b to c and from a to dare ?oth adiabatic
Heat and Thermodynamics 160
and reversible. For a reversible adiabatic process we know that
PVY = constant. Using the ideal gas equation of state, we have
TJIYI = constant. Along curve bc , therefore, T2 Vr
l
= T/ .
Along the curve da, T2 = TI Vrl. Thus,
(
Vd )"rI _ (T'J. /1\) (Va )YI. Vd Va
V  (T IT,) V, ,whIch means that =.
c 2' 1 b Vc Vb
Comparing the expression for thermal efficiency equations show
two consequences. First, the heats received and rejected are related
to the temperatures of the isothermal parts of the cycle by
QI + Q2 =0.
1\ T2
Second, the efficiency of a Camot cycle is given compactly by
1\
11 = 1 T2 . Camot cycle efficiency.
The efficiency can be 100% only if the temperature at which the
heat is ,ejected is zero. The heat and work transfers to and from
the system.
;_ /sYIIeIn
1'....... _+
I
QJ
Fig. Work and Heat Transfers in a Camot Cycle
between Two Heat Reservoirs
REFRIGERATORS AND HEAT PUMPS
The Camot cycle has been used for power, but we can also
run it in reverse. If so, there is now net work into the system and
161 The First Law of Thermodynamics
net heat out of the system. There will be a quantity of heat Q
2
rejected at the higher temperature and a quantity of heat Q)
absorbed at the lower temperature. The former of these is negative
according to our convention and the latter is positive. The result
is that work is done on the system, heat is extracted from a low
temperature source and rejected to a high temperature source.
The words "low" and "high" are relative and the low
temperature source might be a crowded classroom on a hot day,
with the heat extractioll being used to cool the room. In this mode
of operation the cycle works as a refrigerator or heat pump. "What
we pay for" is the work, and "what we get" is the amount of heat
extracted. A metric for devices of this type is the coefficient of
performance, defined as
Coefficient of performance = QI = QI
w (QI +Q2)
01
,. .
V 0,
"Fig. Operation of a Camot refrigerator
For a Camot cycle we know the ratios of heat in to heat out
when the cycle is run forward and, since the cycle is reversible,
these ratios are the same when the cycle is run in reverse. The
coefficient of performance is thus given in terms of the absolute
temperatures as
. 1J
Coefficlency of performance = ~ .
12 11
This can be much larger than unity.
The Camot cycles that have been drawn are based on ideal
gas behaviour. For different working media, however, they will
look different. We will see an example when twophase situations.
Heat and Thermodynamics 162
What is the same whatever the medium is the efficiency for all
Carnot cycles operating between the same two temperatures.
REFRIGERATOR HARDWARE
Typically the thermodynamic system in a refrigerator analysis
will be a working fluid, a refrigerant, that circulates around a loop.
The internal energy (and temperature) of the refrigerant is
alternately raised and lowered by the devices in the loop. The
working fluid is colder than the refrigerator air at one point and
hotter than the surroundings at another point. Thus heat will flow
in the appropriate direction, as shown by the two arrows in the
heat exchangers.
Electrical Energy
In
Fig. Schematic of a Domestic Refrigerator
Starting in the upper right hand corner of the diagram, we
describe the process in more detail. First the refrigerant passes
through a small turbine or through an expansion valve. In these
devices, work is done by the refrigerant so its internal energy is
lowered to a point where the temperature of the refrigerant is lower
than that of the air in the refrigerator.
A heat exchanger is used to transfer energy from the inside
of the refrigerator to the cold refrigerant. This lowers the internal
energy of the inside and raises the internal energy of the refrigerant.
Then a pump or compressor is used to do work on the refrigerant,
adding additional energy to it and thus further rai3ing its internal
163 The First Law of Thermodynamics
energy. Electrical energy is used to drive the pump or compressor.
The internal energy of the refrigerant is raised to a point where its
temperature is hotter than the temperature of the surroundings.
The refrigerant is then passed through a heat exchanger (often
coils at the back of the refrigerator) so that energy is transferred
from the refrigerant to the surroundings.
As a result, the internal energy of the refrigerant is reduced
and the internal energy of the surroundings is increased. It is at
this point where the internal energy of the contents of the
refrigerator and the energy used to drive the compressor or pump
are transferred to the surroundings.
The refrigerant then continues on to the turbine or expansion
valve, repeating the cycle.
THE INTERNAL COMBUSTION ENGINE (OTTO CYCLE)
The Otto cycle is a set of processes used by spark ignition
internal combustion engines (2stroke or 4stroke cycles). These
engines a) ingest a mixture offuel and air, b) compress it, c) cause
it to react, thus effectively adding heat through converting chemical
energy into thermal energy, d) expand the combustion products,
and then e) eject the combustion products and replace them with
a new charge of fuel and air.
Intake stroke, gasoline vapour and air drawn into engine
(5+ 1).
• Compression stroke, p, Tincrease (l+2).
• Combustion (spark), short time, essentially constant
volume (2 + 3). Model: heat absorbed from a series of
reservoirs at temperatures T2 to T
3
.
Power stroke: expansion (3 + 4).
• Valve exhaust: valve opens, gas escapes.
• (4 + I) Model: rejection of heat to series of reservoirs
at temperatures T4 to T
I
.
• Exhaust stroke, piston pushes remaining combustion
products out of chamber (I + 5).
We model the processes as all acting on a fixed mass of air
contained in a pistoncylinder arrangement.
Heat and Thennodynamics
p
p
3
V2 = vJ VI = V. V
Fig. The ideal Otto Cycle
Not
Exhaust
valve
opens
V
Fig. Sketch of an Actual Otto Cycle
t
~ t
(0
(9 0
164
Fig. Piston and Valves in a Fourstroke Internal Combustion Engine
EFFICIENCY OF AN IDEAL OTTO CYCLE
The starting point is the general expression for the thermal
efficiency of a cycle:
165 The First Law of Thermodynamics
" = work = QH + QL = 1 + QL .
heat input QH QH
The convention, as previously, is that heat exchange is
positive if heat is flowing into the system or engine, so Q
L
is
negative. The heat absorbed occurs during combustion when the
spark occurs, roughly at constant volume. The heat absorbed can
be related to the temperature change from state 2 to state 3 as:
QH = Q23 = D.U
23
(W
23
= 0)
=
The heat rejected is given by (for a perfect gas with constant
specific heats)
QL =Q41 =D.U
41
=C
v
(1J T
4
)·
Substituting the expressions for the heat absorbed and rejected
in the expression for thermal efficiency yields
,,=1_
T4

1J
.
T3 T
2
We can simplify the above expression using the fact that the
processes from 1 to 2 and from 3 to 4 are isentropic:
T v,yI  T v.
y

I
T.IV,IYI = T
2
V.
2
'Y
I
4 I  3 2 '
T4 1J _(V2 VI
13 T2 
The quantity V
1
iV
2
= r is called the compression ratio. In
terms of compression ratio, the efficiency of all ideal Otto cycle
IS:
Heat and Thermodynamics
70
,60
I:
J:
Fig. Ideal Otto Cycle Thermal Efficiency
166
The ideal Otto cycle efficiency is shown as a function of the
compression ratio. As the compression ratio, r, increases, l'Jo
tto
increases, but so does T
2
. If T2 is too high, the mixture will ignite
without a spark (at the wrong location in the cycle).
ENGINE WORK, RATE OF WORK
PER UNIT ENTHALPY FLUX
The nondimensional ratio of work done (the power) to the
enthalpy flux through the engine is given by
__ P_o_w_e_r _ = = (22i'otto
Enthalpy flux mc pTj
There is often a desire to increase this quantity, because it
means a smaller engine for the same power. The heat input is given
by
where
• L1h
fucI
is the heat of reaction, i.e. the chemical energy
liberated per unit mass of fuel,
• mfuel is the fuel mass flow rate.
The nondimensional power is
W _ mfucl Mrucl [1 1]
mcpTj  ;; cpTj  r
y

1
•
The quantities in this equation, evaluated at stoichiometric
conditions are:
mfucl 1
R::
m 15
167 The First Law of Thermodynamics
4xl07
cpIi 10
3
x 288'
so
DIESEL CYCLE
The Diesel cycle is a compression ignition (rather than spark
ignition) engine. Fuel is sprayed into the cylinder at P2 (high
pressure) when the compression is complete, and there is ignition
without a spark.
p
V
z
v,
Fig. The ideal Diesel cycle
The thermal efficiency is given by:
1
QL 1 C
v
(Ii
T
4)
TiD I
 +   + "''_.2.:
lese  QH  C P (T3  T2 )
= 1 _ Ii (T4 / Ii I) .
yT2(T31T2 I)
This cycle can operate with a higher compression ratio than
the Otto cycle because only air is compressed and there is no risk
of autoignition of the fuel.
Although for a given compression ratio the Otto cycle has
higher efficiency, because the Diesel engine can be operated to
higher compression ratio, the engine can actually have higher
efficiency than an Otto cycle when both are operated at
compression ratios that might be achieved in practice.
Heat and Thermodynamics 168
BRAYTON CYCLE
The Brayton cycle (or Joule cycle) represents the operation
of a gas turbine engine. The cycle consists of four processes,
alongside a sketch of an engine:
• a  b Adiabatic, quasistatic (or reversible) compression
in the inlet and compressor;
• b  c Constant pressure fuel combustion (idealized as
constant pressure heat addition);
• c  d Adiabatic, quasistatic (or reversible) expansion in
the turbine and exhaust nozzle, with which we
• Take some work out of the air and use it to drive the
compressor, and
• Take the remaining work out and use it to accelerate fluid
for jet propulsion, or to turn a generator for electrical
power generation;
• d  a Cool the air at constant pressure back to its initial
condition.
Compressor "lUrbine
H_!ejection
10 atmosphere
Fig. Sketch of the Jet Engine Components and
Corresponding Thermodynamic States
The components of a Brayton cycle device for jet propulsion.
We will typically represent these components schematically. In
practice, real Brayton cycles take one of two forms. "open" cycle,
where the working fluid enters and then exits the device.
This is the way ajet propulsion cycle works. The alternative,
a closed cycle, which recirculates the working fluid. Closed cycles
are used, in space power generation.
169 The First Law of Thermodynamics
2· .
'__ ..... ·3
w ...
4
Q EquiYllenl heat II'IIISrer
I IlCDDSWIl paalR
Fig. Thermodynamic model of gas turbine engine cycle for power
generation
[Open cycle operation]
elL
[Closed cycle operation]
Fig. Options for operating Brayton cycle gas turbine engines
WORK AND EFFICIENCY
The objective now is to find the work done, the heat absorbed,
and the thermal efficiency of the cycle. Tracing the path shown
around the cycle from abcd and back to a, the first law gives
(writing the equation in terms of a unit mass),
!J.uabcda = 0 = q2 + ql  w.
Here !J.u is zero because is a function of state, and any cycle
returns the system to its starting state. The net work done is
therefore w = q2 + ql' where q l' q2
are
defined as heat received by
the system (ql is negative). We thus need to evaluate the heat
transferred in processes bc and da.
For a constant pressure, quasistatic process the heat exchange
per unit mass is
Heat and Thermodynamics 170
dh = cpdT = dq, or [dq]constant P = dh.
We can see this by writing the first law in terms of enthalpy
or by remembering the definition of cpo The heat exchange can be
expressed in terms of enthalpy differences between the relevant
states. Treating the working fluid as a perfect gas with constant
specific heats, for the heat addition from the combustor,
q2 = hc  hb = C p (Tc  T
b
)·
The heat rejected is, similarly,
ql =ha hd =c
p
(Ta Td)·
The net work per unit mass is given by
Net work per unit mass = ql + q2 = cpr (Tc  T
b
) + (Ta  Td )].
The thermal efficiency of the Brayton cycle can now be
expressed in terms of the temperatures:
Net work cp[(Tc T,,)(Td Ta)
TJ= ='
Heat in c p (Tc  T
b
)
_1 _ (Ta  Ta) = 1 Ta (Td ITa 1) .
 (Tc  T
b
) Tb(Tc 1Tb 1)
To proceed further, we need to examine the relationships
between the different temperatures. We know that points a and d
are on a constant pressure process as are points band c, and
P a = P d; P b = Pc. The other two legs of the cycle are adiabatic
and reversible, so
P
d
= P
a
=> (Td )Y/(YI) = (Ta )Y/(YI)
~ P
b
Tc T"
Therefore T jTc = T/Tb' or, finally, T jTa = T jTb. Using this
relation in the expression for thermal efficiency, Equation yields
an expression for the thermal efficiency of a Brayton cycle:
Ta Tatmospheric
Ideal Bratyton cycle efficiency: l1B = 1T, = 1 T .
b compressor eXIt
The temperature ratio across the compressor, TblTa = TR. In
terms of compressor temperature ratio, and using the relation for
an adiabatic reversible process we can write the efficiency in terms
171 The First Law of Thermodynamics
of the compressor (and cycle) pressure ratio, which is th;:: parameter
commonly used:
1
l1B = 1 TR = 1 PR(yl)/y'
0.7 .....,
i 0.6
.!II 0.5
! 0.4
iii 0.3
~ 0.2
& 0.1
10 20 30 40
Compressor Pressure Ratio
Fig. Trend of Brayton Cycle Thermal Efficiency
with Compressor Pressure Ratio
50
Equation says that for a high cycle efficiency, the pressure
ratio of the cycle should be increased. The history of aircraft engine
pressure ratio versus entry into service, and it can be seen that
there has been a large increase in cycle pressure ratio. The thermo
dynamic concepts apply to the behaviour of real aerospace devices!
GAS TURBINE TECHNOLOGY AND THERMODYNAMICS
The turbine entry temperature, T
e
, is fixed by materials
technology and cost. (If the temperature is too high, the blades
fail.) The relation between the gas temperature coming into the
turbine blades and the blade melting temperature.
C y ~ l c with T.  T,
p
Cydc with lower T •
...
...   _T = T _ = r.
v
Fig. Efficiency and Work of Two Brayton Cycle Engines
Heat and Thermodynamics 172
The problem is posed which shows two Brayton cycles. For
maximum efficiency we would like TR as high as possible. This
means that the compressor exit temperature approaches the turbine
entry temperature. The net work will be less than the heat received;
as Tb ~ Tc the heat received approaches zero and so does the net
work.
The net work in the cycle can also be expressed as f
pdv
,
evaluated in traversing the cycle. This is the area enclosed by the
curves, which is seen to approach zero as Tb ~ Tc'
The conclusion from either of these arguments is that a cycle
designed for maximum thermal efficiency is not very useful in
that the work (power) we get out of it is zero.
A more useful criterion is that of maximum work per unit
mass (maximum power per unit mass flow). This leads to compact
propulsion devices. The work per unit mass is given by:
Work/unit mass =cp[(Tc Tb)(Td T
a
)],
where Tc is the maximum turbine inlet temperature (a design
constraint) and Ta is atmospheric temperature. The design variable
is the compressor exit temperature, T
b
, and to find the maximum
as this is varied, we differentiate the expression for work with
respect to:
dWork = Cp[dTc 1 dTd + dT
a
].
dTb dTb d1b dTb
The first and the fourth terms on the right hand side of the
above equation are both zero (the turbine entry temperature is
fixed, as is the atmospheric temperature). The maximum work
occurs where the derivative of work with respect to Tb is zero:
dWork =0=1 dT
d
.
dTb dTb
To use Equation, we need to relate Td and T
b
. We know that
173 The First Law of Thermodynamics
Hence,
dTd TaTe
dTb=Tl'
Plugging this expression for the derivative into Equation gives
the compressor exit temperature for maximum work as Tb = ~ T a T e .
In terms of temperature ratio,
Tb i
e
Compre!lsor temperature ratio for maximum work: T = T'
a a
The condition for maximum work in a Brayton cycle is
different than that for maximum efficiency. The role of the
temperature ratio can be seen if we examine the work per unit
mass which is delivered at this condition:
[
r;;:;;r TaTe 1
Work/unit mass = C P Te  "TaTe  r;;:;;r + Ta .
"TaTe
Ratioing all temperatures to the engine inlet temperature,
[
Te ie 1 Work/unit mass = C pTa   2  + 1 .
Ta Ta
To find the power the engine can produce, we need to multiply
the work per unit mass by the mass flow rate:
. [Te rr; l. .
Power = mCpTa Ta  2Vr: + 1 ,Maximum power for an
ideal Brayton cycle.
kg J J
(The units are k K K = = Watts.)
s g s
The trend of work output vs. compressor pressure ratio, for
different temperature ratios TR = T jTa'
Heat and Thermodynamics
Brayton Cycle Work
3 ~                         ~
25
t. 2 
i 1/
I I
~ 1.5 ! r
1 1/
I / •• __ ••••••
.
' ........... .... ..
, ......... .
.
05
O ~   ~      +     ~     r    ~
o 10 20 30 40 50
Compres5Of Plessure Ratio
•••••• TR" 4
···TR=S
TR=6
TR=r
Fig. Trend of Cycle work with Compressor Pressure Ratio,
for Different Temperature Ratios
Pen Core Drive
Fig. Aeroengine Core Power
174
The expression for power of an ideal cycle compared with
data from actual jet engines. The gas turbine engine layout
including the core (compressor, burner, and turbine). The
core power for a number of different engines as a function of the
turbine rotor entry temperature. The equation in the figure for
horsepower (HP) is the same as that which we just derived, except
for the conversion factors. The analysis not only shows the
qualitative trend very well but captures much of the quantitative
behaviour too. A final comment on Brayton cycles concerns the
175 The First Law of Thermodynamics
value of the thermal efficiency. The Brayton cycle thermal
efficiency contains the ratio of the compressor exit temperature
to atmospheric temperature, so that the ratio is not based on the
highest temperature in the cycle, as the Camot efficiency is. For a
given maximum cycle temperature, the Brayton cycle is therefore
less efficient than a Camot cycle.
Brayton Cycle for Jet Propulsion: The Ideal Ramjet
A schematic of a ramjet is given in Figure.
Station Numbers
t" If"
Fig. Ideal Ramjet
In the ramjet there are "no moving parts." The processes that
occur in this propulsion device are:
• 0 + 3 : Isentropic diffusion and compression, with a
decrease in Mach number, Mo + M3 « 1.
• 3 + 4 : Constant pressure combustion.
• 4 + 5 : Isentropic expansion through the nozzle.
The ramjet thermodynamic cycle efficiency can be written
in terms offlight Mach number, Mo, as follows:
and
so
llBrayton = 1  To = 1 _ To = 1 _ To
T compressor exit T3 ~ o
To
=
~ o 1+ yI MJ'
2
yl 2
MO
_ 2
llBrayton  y  1 2
I+MO
2
Heat and Thennodynamics 176
REFERENCES
• A Guide to Physics: Thermodynamics, Statistical
Physics, and Quantum Mechanics by Gerald D.
Mahan, Boris E. Nadgomy, and Max Dresden.
• Mixing and Excess Thermodynamic Properties
(Physical sciences data) by Jaime Wisniak and
Abraham Tamir.
• Statistical mechanics, R.P. Feynman, W. A. Benjamin.
• The Language of Science by Sidney B. Cahn.
• Statistical Mechanics, K. Huang,
8 ______ _
The Second Law of Thermodynamics
DIFFERENCE BETWEEN FREE EXPANSION OF A GAS
AND REVERSIBLE ISOTHERMAL EXPANSION
The difference between reversible and irreversible
processes is brought out through examination of the isothermal
expansion of an ideal gas. The question to be asked is what is
the difference between the "free expansion" of a gas and the
isothermal expansion against a piston? To answer this, we
address the steps that we would have to take to reverse, in other
words, to undo the process. By free expansion, we mean the
unrestrained expansion of a gas into a volume. Initially all the
gas is in the volume designated as VI with the rest of the
insulated enclosure a vacuum. The total volume (VI plus the
evacuated volume) is V
2
• At a given time a hole is opened in
the partition and the gas rushes through to fill the rest of the
enclosure.
(ill
s m;? Gas IGas
P,. TI'  P" T
,
;, ~  P TIP T
~ ~ ., .'
Fig. Free Expansion
GaS
p,. T,.
Gas
Pt' T,.
Fig. Expansion Against a Piston
Heat and Thermodynamics 178
During the expansion there is no work exchanged with the
surroundings because there is no motion of the boundaries. The
enclosure is insulated so there is no heat exchange.
The first law tells us therefore that the internal energy is
constant (IlU = 0). For an ideal gas, the internal energy is a function
of temperature only so that the temperature of the gas before the
free expansion and after the expansion has been completed is the
same. Characterizing the before and after states:
Before: State 1, V = VI' T = TI
• After: State 2, V = V
2
, T = TI
Q = W = 0, so there is no change in the surroundings.
To restore the original state, i.e., to go back to the original
volume at the same temperature (V2 ~ VI at constant T= T\) we
cali compress the gas isothermally (using work from an external
agency). We can do this in a quasiequilibrium manner, with Psystem
~ Pextemal' If so the work that we need to do is W = 12 PdV. We
have evaluated the work in a reversible isothermal expansion, and
we can apply the arguments to the case of a reversible isothermal
compression. The work done on the system to go from state "2"
to state" 1" is
W= Work done on system = NRT\ In ( ~ ) .
Psystem
II 
~ Pexternal = Psystem + dp
........... 
~ return to initial condition
Fig. Returning the Free Expansion to its Initial Condition
From the first law, this amount of heat must also be rejected
from:the gas to the surroundings if the temperature of the gas is to
remain constant. A schematic of the compression process, in terms
of ~ e a t and work exchanged.
179 The Second Law of Thermodynamics
Q(beaI out)
Fig. Work and Heat Exchange in the Reversible
Isothermal Compression Process
At the end of the combined process (free expansion plus
reversible compression):
The system has been returned to its initial state (no
change in system state).
• The surroundings (us!) did work on the system of
magnitude W.
The surroundings received an amount of heat, Q, which
is equal to W.
The sum of all of these events is that we have converted
an amount of work, W, into an amount of heat, Q, with
Wand Q numerically equal in Joules.
The net effect is the same as if we let a weight fall and pull a
block along a rough surface. There is 100% conversion of work
into heat.
/Weight
Fig. 100% conversion of work into heat
The results of the free expansion can be contrasted against a
process of isothermal expansion against a pressure which is slightly
different than that of the system.
P.T L
I....ttLr ........  Work roceived. IV
Q
Q
Fig. Work and Heat Transfer in Reversible Isothermal Expansion
Heat and Thermodynamics 180
During the expansion, work is done on the surroundings of
magnitude W = JPdV, where P can be taken as the system
pressure. As evaluated in Equation, the magnitude of the work
done by the system is W = NRT
J
In (V
2
IV
1
). At the end of the
isothermal expansion, therefore:
• The surroundings have received work W.
• The surroundings have given up heat, Q, numerically
equal to W.
We now wish to restore the system to its initial state, just as
we did in the free expansion. To do this we need to do w o ~ k on
the system and extract heat from the system, just as in the free
expansion. In fact, because we are doing a transition between the
same states along the same path, the work and heat exchange are
the same as those for the compression process examined just
above.
The overall result when we have restored the system to the
initial state, however, is quite different for the reversible expansion
than for the free expansion. For the reversible expansion, the work
we need to do on the system to compress it has the same magnitude
as the work we received during the expansion process. Indeed,
we could raise a weight during the expansion and then allow it to
be lowered during the compression process. Similarly the heat put
into the system by us (the surroundings) during the expansion
process has the same magnitude as the heat received by us during
the compression process. The result is that when the system has
been restored back to its initial state, so have the surroundings.
There is no trace of the overall process on either the system or the
surroundings. That is another meaning of the word "reversible."
FEATURES OF REVERSIBLE PROCESSES
Reversible processes are idealizations or models of real
processes. One familiar and widely used example is Bernoulli's
equation, which you saw in Unified. They are extremely useful
for defining limits to system or device behaviour, for enabling
identification of areas in which inefficiencies occur, and in giving
181 The Second Law of Thermodynamics
targets for design. An important feature of a reversible process is
that, depending on the process, it represents the maximum work
that can be extracted in going from one state to another, or the
minimum work that is needed to create the state change.
Let us consider processes that do work, so that we can show
that the reversible one produces the maximum work of all possible
processes between two states. Suppose we have a thermally
insulated cylinder that holds an ideal gas. The gas is contained by
a thermally insulated massless piston with a stack of many small
weights on top of it. Initially the system is in mechanical and
thermal equilibrium.
Air
Fig. A piston with weights on top
Let us consider the following three processes:
All of the weights are removed from the piston
instantaneously and the gas expands until its volume is
increased by a factor of four (a free expansion).
Half of the weight is removed from the piston
instantaneously, the system is allowed to double in
volume, and then the remaining half of the weight is
instantaneously removed from the piston and the gas is
allowed to expand until its volume is again doubled.
• Each small weight is removed from the piston one at a
time, so that the pressure inside the cylinder is always
in equilibrium with the weight on top of the piston. When
the last weight is removed, the volume has increased by
a factor of four.
Heat and Thermodynamics 182
"
.
".
... ...., .....
"
Fig. Getting the Most Work Out ofa System Requires
that the Work be Extracted Reversibly
Maximum work (proportional to the area under these
curves) is obtained for the quasistatic expansion.
To reiterate:
The work done by a system during a reversible process
is the maximum work we can get.
The work done on a system in a reversible process is
the minimum work we need to do to achieve that state
change.
A process must be quasistatic (quasiequilibrium) to be
reversible. This means that the following effects must be absent
or negligible:
• Friction: If Pextemal "/:. Psystem we would have to do net
work to bring the system from one volume to another
and return it to the initial condition
• Free (unrestrained) expansion.
• Heat transfer through a finite temperature difference.
Q1
Q,
Fig. Heat Transfer Across a Finite Temperature Difference
Suppose we have heat transfer from a high temperature to a
lower temperature. How do we restore the situation to the initial
conditions? One thought would be to run a Carnot refrigerator to
get an amount of heat, Q, from the lower temperature reservoir to
the higher temperature reservoir. We could do this but the
183 The Second Law of Thermodynamics
surroundings, again us, would need to provide some amount of
work (which we could find using our analysis of the Carnot
refrigerator). The net (and only) result at the end of the combined
process would be a conversion of an amount of work into heat.
For reversible heat transfer from a heat reservoir to a system,
the temperatures of the system and the reservoir must be T
heat
reservoir = Tsystem ± dT. In other words the difference between
the temperatures of the two entities involved in the heat transfer
process can only differ by an infinitesimal amount, dT.
While all natural processes are irreversible to some extent, it
cannot be emphasized too strongly that there are a number of
engineering situations where the effect of irreversibility can be
neglected and the reversible process furnishes an excellent
approximation to reality.
The second law, which is the next topic we address, allows
us to make a quantitative statement concerning the irreversibility
of a given physical process.
THE SECOND LAW OF THERMODYNAMICS
STATEMENTS OF THE LAWS OF THERMODYNAMICS
As a further aid in familiarization with the second law of
thermodynamics and the idea of entropy, we draw an analogy with
statements made previously concerning quantities that are closer
to experience. In particular, we wish to present once more the
Zeroth and First Laws of thermodynamics and use the same
framework for the Second Law. In this socalled "axiomatic
formulation," the parallels between the Zeroth, First and Second
Laws will be made explicit.
Zeroth Law
Zeroth Law: There exists for every thermodynamic system
in equilibrium a property called temperature. Equality of
temperature is a necessary and sufficient condition for thermal
equilibrium. The Zeroth law thus defines a property (temperature)
and describes its behaviour.
Heat and Thermodynamics 184
First Law
Observations also show that for any system there is a property
called the energy. The First Law asserts that one must associate
such a property with every system.
First Law: There exists for every thermodynamic system a
property called the energy. The change of energy of a system is
equal to the mechanical work done on the system in an adiabatic
process. In a nonadiabatic process, the change in energy is equal
to the heat added to the system minus the mechanical work done
by the system.
On the basis of experimental results, therefore, one is led to
assert the existence of two new properties, the temperature and
internal energy, which do not arise in ordinary mechanics. In a
similar way, a further remarkable relationship between heat and
temperature will be established, and a new property, the entropy,
defined. Although this is a much less familiar property, it is to be
stressed that the general approach is quite like that used to establish
the Zeroth and First Laws.
A general principle and a property associated with any system
are extracted from experimental results. Viewed in this way, the
entropy should appear no more mystical than the internal energy.
The increase of entropy in a naturally occurring process is no less
real than the conservation of energy.
Second Law
Although all natural processes must take place in accordance
with the First Law, the principle of conservation of energy is, by
itself, inadequate for an unambiguous description of the behaviour
of a system. Specifically, there is no mention of the familiar
observation that every natural process has in some sense a preferred
direction of action. The flow of heat occurs naturally from hotter
to colder bodies, in the absence of other influences, but the reverse
flow certainly is not in violation of the First Law. So far as that
law is concerned, the initial and final states are symmetrical in a
very important respect.
The Second Law is essentially different from the First Law;
185
The Second Law of Thermodynamics
the two principles are independent and cannot in any sense be
deduced from one another. Thus, the concept of energy is not
sufficient, and a new property must appear. This property can be
developed, and the Second Law introduced, in much the same way
as the Zeroth and First Laws were presented. By examination of
certain observational results, one attempts to extract from
experience a law which is supposed to be general; it is elevated to
the position of a fundamental axiom to be proved or disproved by
subsequent experiments. Within the structure of classical
thermodynamics, there is no proof more fundamental than
observations. A statement which can be adopted as the Second
Law of thermodynamics is:
Second Law: There exists for every thermodynamic system
in equilibrium an extensive scalar property called the entropy, S,
such that in an infinitesimal reversible change of state of the
system, dS = dQIT, where T is the absolute temperature and dQ is
the amount of heat ;·eceived by the system. The entropy of a
thermally insulated system cannot decrease and is constant if and
only if all processes are reversible.
As with the Zeroth and First Laws, the existence of a new
property is asserted and its behaviour is described.
REVERSIBLE PROCESSES
In the course of this development, the idea of a completely
reversible process is central, and we can recall the definition, "a
process is called completely reversible if, after the process has
occurred, both the system and its surroundings can be wholly
restored by any means to their respective initial states". Especially,
it is to be noted that the definition does not, in this form, specify
that the reverse path must be identical with the forward path. If
the initial states can be restored by any means whatever, the
process is by definition completely reversible.
If the paths are identical, then one usually calls the process
(of the system) reversible, or one may say that the state of the
system follows a reversible path. In this path between two
equilibrium states:
Heat and Thennodynamics 186
• The system passes through the path followed by the
equilibrium states only.
• The system will take the reversed path by a simple
reversal of the work done and heat added.
Reversible processes are idealizations not actually
encountered. However, they are clearly useful idealizations. For
a process to be completely reversible, it is necessary that it be
quasistatic and that there be no dissipative influences such as
friction and diffusion. The precise (necessary and sufficient)
condition to be satisfied if a process is to be reversible is the second
part of the Second Law.
The criterion as to whether a process is completely reversible
must be based on the initial and final states. In the form presented
above, the Second Law furnishes a relation between the properties
defining the two states, and thereby shows whether a natural
process connecting the states is possible.
COMBINED FIRST AND SECOND LAW EXPRESSIONS
The first law, written in a form that is always true:
dU=dQdW.
For reversible processes only, work or heat may be
rewritten as
dW=PdV,
dQ=TdS,
Substitution leads to other forms of the first law true for
reversIble processes only:
dU = dQ  PdV, substituted for a reversible dQ.
dQ = TdS  dW, substituted for a reversible dQ.
(If the substance has other work modes, e.g., stress, strain,
dU =dQPdV XdY,
where X is a pressurelike quantity, and Y is a volumelike
quantity.)
Substituting for both dWand dQ in terms of state variables,
dU = TdS  PdV Always true.
187 The Second Law of Thermodynamics
The above is always true because it is a relation between
properties and is now independent of process.
In terms of specific quantities:
dU = TdS  PdV Combined first and second law (a) or Gibbs
equation (a).
The combined first and second law expressions are often more
usefully written in terms of the enthalpy, or specific enthalpy,
h=u+Pv,
dh = du + Pdv + vdP
= Tds  Pdv + Pdv + vdP, using in the first law.
dh = Tds + vdP.
Or, since v = lip,
dP
dh = Tds + P Combined first and second law (b) or Gibbs
equation (b).
In terms of enthalpy (rather than specific enthalpy) the relation is
dH= TdS+ VdP.
ENTROPY CHANGES IN AN IDEAL GAS
Many aerospace applications involve flow of gases (e.g., air)
and we thus examine the entropy relations for ideal gas behaviour.
The starting point is form (a) of the combined first and second
law,
du = Tds  Pdv.
For an ideal gas, du = cvdT. Thus
dT P
Tds = cvdT+ Pdv or ds =cv+dv,
T T
Using the equation of state for an ideal gas (Pv = RD, we
can write the entropy change as an expression with only exact
differentials:
ds=c
v
dT +Rdv.
T v
We can think of Equation as relating the fractional change in
temperature to the fractional change of volume, with scale factors
Heat and Thermodynamics 188
C
v
and R; if the volume increases without a proportionate decrease
in temperature (as in the case of an adiabatic free expansion), then
increases. Integrating Equation between two states "1" and "2":
1
2 dT [2 dv
I1s =s2 sl = cv+R .
1 T 1 V
For a perfect gas with constant specific heats
I1s = S2  SI = Cl' In[ ~ ) + Rln[ : ~ )
In nondimensional form (using R/c
v
= (y  1»
~ = In[ i ) + (y  1) In( : ~ ). Entropy change of a perfect gas.
Equation is in terms of specific quantities. For N moles of gas,
I1s =N[ln[T
2
J' +(Y_I)ln[V
21
].
C
v
Ii Vi )
This expression gives entropy change in terms of temperature
and volume. We can develop an alternative form in terms of
pressure and volume. which allows us to examine an assumption
we have used. The ideal gas equation of state can be written as
In P + In v = In R + In T.
Taking differentials of both sides yields
dP dv dT
+=.
. P v T
Using the above equation in Equation, and making use of the
relations c
p
= C
v
+ R; cJc
v
= y, we find
dS=cv[dP + dV]+RdV,
P v v
or
ds dP dv
=+y.
C
v
P v
Integrating between two states 1 and 2
I1s = In(P
2
) + y In[V2) = Inl
r
P
2
(V2 )Y].
C
v
Ii VI Ii VI
189 The Second Law of Thermodynamics
Using both sides of Equation as exponents we obtain
P2
v
i = [Pv
Y
]? =e
tls1cv
.
~ v r
Equation describes a general process. For the specific
situation in which fls = 0, i.e., the entropy is constant: we recover
the expression Pv
Y
= constant. It was stated that this expression
applied to a reversible, adiabatic process. Through use of the
second law, a deeper meaning to the expression, and to the concept
of a reversible adiabatic process, in that both are characteristics
of a constant entropy, or isentropic, process.
CALCULATION OF ENTROPY CHANGE IN SOME BASIC
PROCESSES
• Heat transfer from, or to, a heat reservoir.
A heat reservoir is a constant temperature heat source or sink.
Because the temperature is uniform, there is no heat transfer across
a finite temperature difference and the heat exchange is reversible.
From the definition of entropy (dS = dQrejT),
!hl=Q
T'
where Q is the heat into the reservoir (defined here as positive if
heat flows into the reservoir.)
ITH i f
QII QII
Fig. Heat Transfer From/to a Heat Reservoir
• Heat transfer between two heat reservoirs
The entropy change of the two reservoirs in Figure is the sum
of the entropy change of each. If the high temperature reservoir is
at T H and the low temperature reservoir is at T
L
, the total entropy
change is
Heat and Thennodynamics
Cl
,
_I
Til
TL
Device (block of copper)
no wort
no c:han&e in stale
Fig. Heat Transfer between Two Reservoirs
190
The second law says that the entropy change must be equal
to or greater than zero. This corresponds to the statement that heat
must flow from the higher temperature source to the lower
temperature source.
• Possibility of obtaining work from ~ single heat reservoir
We can regard the process proposed in Figure as the
absorption of heat, Q, by a device or system, operating in a cycle,
rejecting no heat, and producing work. The total entropy change
is the sum of the change in the reservoir, the system or device,
and the surroundings. The entropy change of the reservoir is /l...f\ =
 QIT H' The entropy change of the device is zero, because we are
considering a complete cycle (return to initial state) and entropy
is a function of state. The surroundings receive work only so the
entropy change of the surroundings is zero. The total entropy
change is
ilStotal = Mreservoir + Mdevice + Msurroundings
=  QIT H + = 0 + 0
Q
I ~ T"I
Fig. Work from a single hel't reservoir
The total entropy change in the proposed process is thus less
than zero,
Mtotal <0,
which is not possible. The second law thus tells us that we cannot
191
The Second Law of Thermodynamics
get work from a single reservoir only. The "only" is important; it
means without any other changes occurring.
• Entropy changes in the "hot brick problem"
G GJ
[Temperature equalization of two bricks] [Reservoirs used In reversible state transformation]
C!iiJ DLl
TH·4T TL+4T
Fig. The "Hot Brick" Problem
We can examine in a more quantitative manner the changes
that occurred when we put the two bricks together, as depicted.
The process by which the two bricks come to the same temperature
is not a reversible one, so we need to devise a reversible path. To
do this imagine a large number of heat reservoirs at varying
temperatures spanning the range T H  dT, ... ,T
L
+ dT. The bricks
are put in contact with them sequentially to raise the temperature
of one and lower the temperature of the other in a reversible
manner. The heat exchange at any of these steps is dQ = CdT. For
the high temperature brick, the entropy change is:
M
hot
brick = rTM CdT =Cln(T
M
),
JrH T TH
where C is the heat capacity of the brick (Jlkg). This quantity is
less than zero. For the cold brick,
Mcold brick = (M C:T = Cln( )
The entropy change of the two bricks is
Mbriok
The process is not reversible.
• Difference between the free expansion and the reversible
isothermal expansion of an ideal gas
The essential difference between the free expansion in an
insulated enclosure and the reversible isothermal expansion of an
ideal gas can also be captured clearly in terms of entropy changes.
For a state change flOm initial volume and temperature VITI' to
Heat and Thermodynamics 192
final volume and (the same) temperature V
2
T
1
, the entropy change
IS
M= t dS= +
or, making use of the equation of state and the fact that dU = 6 for
an isothermal process,
).
This is the entropy change that occurs for the free expansion
as well as for the isothermal reversible expansion processes
entropy changes are state changes and the two system final and
end states are the same for both processes.
For the free expansion:
Msystem = NR In ); Msurrundings = o.
There is no change in the entropy ofthe surroundings because
there is no interaction between the system and the surroundings.
The total entropy change is therefore,
M
tota1
= Msystem + Msurroundings = NR In > o.
There are several points to note from this result:
• Mtotal > 0 so the process is not reversible.
• Msystem > 12 dQ I T = 0; the equality between M and
dQIT is only for a reversible process.
• There is a direct connection between the work needed
to restore the system to the original state and the entropy
change:
W = NRT In( = T M
2

1
•
The TM quantity has a physical meaning as "lost work" in
the sense of work which we lost the opportunity to utilize.
For the reversible isothermal expansion:
The entropy is a state variable so the entropy change of the
system is the same as before. In this case, however, heat is
193 The Second Law of Thermodynamics
transferred to the system from the surroundings (Qsurroundings < 0)
S'.) thatMsurroundings = Qsurrounding/T < O.
The heat transferred from the surroundings, however, is equal
to the heat received by the system: Qsurroundings = Qsystem = W.
M = Qsurroundings = _ W = _ NR In (V2 ).
surroundmgs T T Vi
The total change in entropy (system plus surroundings) is
therefore
Q Q
M tota1 = Msystem + Msurroundings = T  T = O.
The reversible process has zero total change in entropy.
APPLICATIONS OF THE SECOND LAW
THE THERMODYNAMIC TEMPERATURE SCALE
The considerations of Carnot cycles in this section have not
mentioned the working medium. They are thus not limited to an
ideal gas and hold for Carnot cycles with any medium. Earlier we
derived the Carnot efficiency with an ideal gas as a medium and
the temperature definition used in the ideal gas equation was not
essential to the thermodynamic arguments. More specifically, we
can define a thermodynamic temperature scale that is independent
of the working medium. To see this, which has three reversible
cycles. There is a high temperature heat reservoir at Tl and a low
temperature heat reservoir at T
3
. For any two temperatures T
1
, T
2
,
the ratio of the magnitudes of the heat absorbed and rejected in a
Carnot cycle has the same value for all systems.
'_______ .... TJ
Fig. Arrangement of Heat Engines to Demonstrate
the Thermodynamic Temperature Scale
Heat and Thermodynamics 194
We choose the cycles so Q! is the same for A and C. Also Q
3
is the same for Band C. For a Carnot cycle
11 = 1 + QL = F(TL' T
H
);" is only a function of temperature.
Also QH
But
Hence
QI = QIQ2
Q3 Q2Q3
F(1\,T
3
) = !(1\,T
2
) x
y
Not a fuction of T2 Cannot be a function of T2
We thus conclude that F(T!, T
2
) has the formj{T!)!f(T
2
),
and similarly F{T
2
, T
3
) = j(T
2
)Ij(T
3
). The ratio of the heat
exchanged is therefore
f1L = F(r. Y:) = f(Tj) .
Q3 I' 3 f(1)
In general,
QH f(T
H
)
=,
QL f(T
L
)
so that the ratio of the heat exchanged is a function of the
temperature. We could choose any function that is monotonic, and
one choice is the simplest: j(1) = T. This is the thermodynamic
scale oftemperature, QII'Q
L
= T Ii'TL. The temperature defined in
this manner is the same as that for the ideal gas; the thermodynamic
temperature scale and the ideal gas scale are equivalent.
REPRESENTATION OF THERMODYNAMIC PROCESSES IN
COORDINATES
It is often useful to plot the thermodynamic state transitions
and the cycles ir.. terms of temperature (or enthalpy) and entropy,T,
S, rather than P, V. The maximum temperature is often the
195 The Second Law of Thermodynamics
constraint on the process and the enthalpy changes show the work
done or heat received directly, so that plotting in terms of these
variables provides insight into the process.
A Carnot cycle is shown below in these coordinates, in which
it is a rectangle, with two horizontal, constant temperature legs.
The other two legs are reversible and adiabatic, hence isentropic
(dS= dQrejT= 0), and therefore vertical in Ts coordinates.
ISOIhermaI
T Adiabatic
s
Fig. Camot Cycle in Coordinates
If the cycle is traversed clockwise, the heat added is
Heat added: QH= QH = lTdS=TH(SbSa)=THM.
The heat rejected (from c to d) has magnitude IQL= TL MI.
The work done by the cycle can be fmmd using the first law
for a reversible process:
dU=4QdW
=TdSdW
(This form isonly true for a reversible process.)
We can integrate this last expression around the closed path
traced out by the cycle:
cjdU = cjTdS cjdW.
However dU is an exact differential and its integral around a
closed contour is zero:
0= cjTdS cjdW.
The work done by the cycle, which is represented by the term
1
dW
, is equal to cjTdS, the area enclosed by the closed contour
in the  plane. This area represents the difference between the heat
Heat and Thennodynamics 196
absorbed CC}TdS at the high temperature) and the heat rejected
( g TdS at the low temperature). Finding the work done through
evaluation of is an alternative to computation of the work in a
reversible cycle from gPdV. Finally, although we have carried
out the discussion in terms of the entropy, S, all of the arguments
carry over to the specific entropy, s; the work of the reversible
cycle per unit mass is given by gTds.
BRAYTON CYCLE IN COORDINATES
The Brayton cycle has two reversible adiabatic (i.e.,
isentropic) legs and two reversible, constant pressure heat
exchange legs. The former are vertical, but we need to define the
shape of the latter. For an ideal gas, changes in specific enthalpy
are related to changes in temperature by dh = cpdT, so the shape
of the cycle in an h  s plane is the same as in a T  s plane, with
a scale factor of c
p
between the two. This suggests that a place to
start is with the combined first and second law, which relates
changes in enthalpy, entropy, and pressure:
dP
dh=Tds+.
p
On constant pressure curves dP = 0 and dh = Tds. The quantity
desired is the derivative of temperature, T, with respectto entropy,
, at constant pressure: (8T/8s)p. From the combined first and
second law, and the relation between dh and dT, this is
T
C
p
The derivative is the slope of the constant pressure legs of
the Brayton cycle on a Ts plane. For a given ideal gas (specific c
p
)
the slope is positive and increases as T.
We can also plot the Brayton cycle in an hs plane. This has
advantages because changes in enthalpy directly show the work
of the compressor and turbine and the heat added and rejected.
The slope of the constant pressure legs in the hs plane is
(8hI8s)p = T.
197 The Second Law of Thermodynamics
Note that the similarity in the shapes of the cycles in Ts and
hs planes is true for ideal gases only. As we will see when we
examine twophase cycles, the shapes look quite different in these
two planes when the medium is not an ideal gas.
T .. _____________________ 3
T
s
Fig. Ideal Brayton Cycle as Composed of Many Elementary Carnot Cycles
Plotting the cycle in Ts coordinates also allows another way
to address the evaluation of the Brayton cycle efficiency which
gives insight into the relations between Camot cycle efficiency
and efficiency of other .::ycles. We can break up the Brayton cycle
into many small Camot cycles. The "ith" Camot cycle has an
efficiency of
C
 1 ( 1(ow,; )
11;,
Thigh,;
where the indicated lower temperature is the heat rejection
temperature for that elementary cycle and the higher temperature
is the heat absorption temperature for that cycle. The upper and
lower curves of the Brayton cycle, however, have constant
pressure. All of the elementary Camot cycles therefore have the
same pressure ratio:
P(T
high
)
=:... = P R = constant (the same for all cycles).
P(1(ow)
From the isentropic relatio\s for an ideal gas, we know
that pressure ratio, PR, and temperature ratio, TR, are related
by: PR(yl)/y = TR.
The temperature ratios ~ 1iow.IThigh, j)of any elementary cycle
"i" are 'therefore the same and each of the elementary cycles has
Heat and Thermodynamics 198
the same thermal efficiency. We only need to find the temperature
ratio across anyone of the cycles to find what the efficiency is.
We know that the temperature ratio of the first elementary cycle
is the ratio of compressor exit temperature to engine entry
(atmospheric for an aircraft engine) temperature, TiTo. If the
efficiency of all the elementary cycles has this value, the efficiency
of the overall Brayton cycle (which is composed of the elementary
cycles) must also have this value. Thus, as previously,
1
linlet
l'lBrayton = 
T compressor
T aE.:
"'III
s
Fig. Arbitrary Cycle Operating between T
min
, Tmax
A benefit of this view of efficiency is that it allows us J way
to comment on the efficiency of any thermodynamic cycle.
Consider the cycle, which operates between some maximum and
minimum temperatures.
We can break it up into small Carnot cycles and evaluate the
efficiency of each. It can be seen that the efficiency of any of the
small cycles drawn will be less than the efficiency of a Carnot
cycle between T max and T min'
This graphical argument shows that the efficiency of any other
thermodynamic cycle operating between these maximum and
minimum temperatures has an efficiency less than that of a Carnot
cycle.
NET WORK PER UNIT MASS FLOW IN A BRAYTON CYCLE
We found the net work of a Brayton cycle in terms of heat
transfer. Now that we have defined entropy, we can reexamine
the net work using an enthalpyentropy (h  s) diagram. The net
mechanical work of the cycle is given by:
Net mechanical work/unit mas') = Wturbine  wcompressor'
199 The Second Law of Thermodynamics
where, by the first law,
wcompressor = Mo3 = llh
comp
Wturbine = llh
45
= llhwrb
If kinetic energy changes across the compressor and turbine
are neglected, the temperature ratio, TR, across the compressor
and turbine is related to the enthalpy changes:
TR _ 1 = llh
comp
= I I
flo hs
= llhcomp •
The net work is thus
net work = llh
comp
 1 )
The turbine work is greater than the work needed to drive
the compressor, as is evident on the (h  s) diagram.
IRREVERSIBILITY, ENTROPY CHANGES, AND "LOST
WORK"
Consider a system in contact with a heat reservoir during a
reversible process. If there is heat Q absorbed by the reservoir at
temperature T, the change in entropy of the reservoir is I1S = QT.
In general, reversible processes are accompanied by heat
exchanges that occur at different temperatures. To analyze these,
we can visualize a sequence of heat reservoirs at different
temperatures so that during any infinitesimal portion of the cycle
there will not be any heat transferred over a finite temperature
difference.
During any infinitesimal portion, heat dQrev will be transferred
between the system and one of the reservoirs which is at T. If
dQrev is absorbed by the system, the entropy change of the system
is
dSsyMem = .
The entropy change of the reservoir is
Heat and Thermodynamics
dSreservOir = d ~ e v .
The total entropy change of system plus surroundings is
dS
total
= dSsystem + dSreservoir = O.
200
This is also true if there is a quantity of heat rej ected by the system.
The conclusion is that for a reversible process, no change
occurs in the total entropy produced, i.e., the entropy of the system
plus the entropy of the surroundings: Mtotal = O.
YfB
AU
Fig. Irreversible and Reversible State Changes
We now carry out the same type of analysis for an irreversible
process, which takes t!le system between the same specified states
as in the reversible process with and denoting the irreversihle and
reversible processes. In the irreversible process, the system
receives heat dQ and does work dW. The change in internal energy
for the irreversible process is .
dU = dQ  dW (Always true  first law).
For the reversible process
dU= TdS  dW
rev
'
Because the state change is the same in the two processes
(we specified that it was), the change in internal energy is the
same. Equating the changes in internal energy in the above two
expressions yields ~
dQactual dWactual = TdS  dW
rev
'
The subscript "actual" refers to the actual process (which is
irreversible). The entropy change associated with the state change
is
d'S
dQactual 1 [dW d ]
= +  rev  Wactual .
T T
Ifthe process is not reversible, we obtain less work than in a
reversible process, dWactual < dW
rev
' so that for the irreversible
process,
201 The Second Law of Thermodynamics
dS > dQactual .
T
There is no equality between the entropy change dS and the
quantity dQIT for an irreversible process. The equality is only
applicable for a reversible process.
The change in entropy for any process that leads to a
transformation between an initial state "a" and a final state "b" is
therefore
tlS = Sb Sa
where dQactual is the heat exchanged in the actual process. The
equality only applies to a reversible process.
The difference dW
rev
 dW
actual
represents work we could have
obtained, but did not. It is referred to as lost work and denoted by
Wiost. In terms of this quantity we can write,
dS = dQactual + dWiost .
T T
The content of Equation is that the entropy of a system can
be altered in two ways: (i) through heat exchange and (ii) through
irreversibilities. The lost work (dWlos
t
in Equation) is always
greater than zero, so the only way to decrease the entropy of a
system is through heat transfer.
To apply the second law we consider the total entropy change
(system plus surroundings). If the surroundings are a reservoir at
temperature T, with which the system exchanges heat,
dS ( dS : )  dQactual
reser voir   T .
The total entropy change is
d = dS T dS . = (dQactual + dWiost ) _ dQactual
Stotal system surroundings T T T'
dS = dWiost > 0
total T _.
The quantity (dWlos!T) is the entropy generated due to
irreversibility.
Heat and Thermodynamics 202
Yet another way to state the distinction we are making is
dSsystem = dSfrom heat transfer + dSgenerated due to irreversible processes
= dS
heat
transfer + dS
Gen
·
The lost work is also called dissipation and noted dcf> Using
this notation, the infinitesimal entropy change of the system
becomes:
or
dcD
dS,ystem = dS
heat
transfer + T
TdSsystem = dQ + dcD.
Equation can also be written as a rate equation,
dS . . .
 = S = Sheat transfer + SGen .
dt
Either of Equations can be interpreted to mean that the entropy
of the system, S, is affected by two factors: the flow of heat Q and
the appearance of additional entropy, denoted by dS
Gen
, due to
irreversibility. This additional entropy is zero when the process is
reversible and always positive when the process is irreversible.
Thus, one can say that the system develops sources which
create entropy during an irreversible process. The second law
asserts that sinks of entropy are impossible in nature, which is a
more graphic way of saying that dS
Gen
and SGen are positive
definite (always greater than zero), or zero in the special case of
reversible processes.
The term
. ( 1 dQ
Sheat transfer = T ;it' or ~ )
which is associated with heat transfer to the system, can be
interpreted as a flux of entropy. The boundary is crossed by heat
and the ratio of this heat flux to temperature can be defined as a
flux of entropy. There are no restrictions on the sign of this
quantity, and we can say that this flux either contributes towards,
or drains away, the system's entropy.
During a reversible process, only this flux can affect the
203
The Second Law of Thermodynamics
entropy of the system. This terminology suggests that we interpret
entropy as a kind of weightless fluid, whose quantity is conserved
(like that of matter) during a reversible process.
During an irreversible process, however, this fluid is not
conserved; it cannot disappear, but rather is created by sources
throughout the system.
While this interpretation should not be taken too literally, it
provides an easy mode of expression and is in the same category
of concepts such as those associated with the phrases "flux of
energy" or "sources of heat." In fluid mechanics, This graphic
language is very effective and there should be no objections to
copying it in thermodynamics.
ENTROPY AND UNAVAILABLE ENERGY
Consider a system consisting of a heat reservoir at in
surroundings (the atmosphere) at T
2
• The surroundings are
equivalent to a second reservoir at To' For an amount of heat, Q,
transferred from the reservJir, the maximum work we could derive
is Q times the thermal efficiency of a Carnot cycle operated
between these two temperatures:
Maximum work we could = Wmax = Q (1 )
Only part of the heat can be turned into work, in
other words only part of the heat energy is available to be used as
work.
Suppose we transferred the same amount of heat from the
reservoir directly to another reservoir at a temperature TI < T
2
.
The maximum work available from the quantity of heat, Q, before
the transfer to the reservoir at TI is
W max, hTo = Q ( 1  ); (Maximum work between T
2
, To)'
The maximum amount of work available after the transfer to
the reservoir at TI is
W
max
, TI,TO = Q (1 (Maximum work between T
1
, To)'
Heat and Thermodynamics 204
There is an amount of energy that could have been converted
to work prior to the irreversible heat transfer process of
magnitude E',

or
E'=To r Q _.2.].
L 11 T2
However, QIT
1
is the entropy gain of the reservoir at and T
1
(
QIT
2
) is the entropy decrease of the reservoir at T
2
. The amount
of energy, E', that could have been converted to work (but now
cannot be) can therefore be written in terms of entropy changes
and the temperature of the surroundings as
E' = TOCMreservoir at Ii + Mreservoir at T
2
)
= To Mirreversible heat transfer process
E = "Lost work," orenergy which isnolonger avialable to rio work.
The situation just described is a special case of an important
principle concerning entropy changes, irreversibility and the loss
of capability to do wod;;:. We thus now develop it in a more general
fashion, considering an arbitrary system undergoing an irreversible
state change, which transfers heat to the surroundings, which can
be assumed to be at constant temperature, To' The change in
internal energy of the system during the state change is I1U= Q
W. The change in entropy of the surroundings is (with Q the heat
transfer to the system)
 Q
Msurroundings   To .
Now consider restoring the system to the initial state by a
reversible process. To do this we need to do wprk, W
rev
' on tI:e
system and extract from the system a quantity of heat, Qrev' (In
"undoing" the free expaI!sion process.) The change in internal
energy is (with the quantities Qrevand W
rev
both regarded, in this
example, as positive for work done by the surroundings and heat
given to the surroundings). 
IlU
rev
= ·Qrev + w..ev·
205 The Second Law of Thermodynamics
In this reversible process, the entropy of the surroundings is
changed by
IlS Qrev
surroundmgs = T·
For the combined changes (the irreversible state change and
the reversible state change back to the initial state), the energy
change is zero because the energy is a function of state,
I:!.U
rev
+ I:!.U = 0 = Q  W + (Qrev + W
rev
)·
Thus,
Qrev  Q = W rev  W.
For the system, the overall entropy change for the combined
process is zero, because the entropy is a function of state,
!':!.Ssystem,combined process = !':!.Sirreversible process + !':!.Sreversible process =0.
The total entropy change is thus only reflected in the entropy
change of the surroundings:
!':!.Stotal = !':!.S surroundings·
The surroundings can be considered a constant temperature
heat reservoir and their entropy change is given by
, A C' _ (Qrev  Q)
l.lI.)total  .
To
We also know that the total entropy change, for system plus
surroundings is,
!':!.Stotal =
[ IlSirreversible process + ;'XS'0 reversible process] system and surroundings.
The total entropy change is associated only with the irreversible
process and is related to the work in the two processes by
l!S _ (w;.ev  W)
total  To .
The quantity W
rev
 W represents the extra work required to
restore the system to the original state. If the process were
reversible, we would nct have needed any extra work to do this.
It represents a quantity of work that is now unavailable because
of the irreversibility. The quantity W
rev
can also be interpreted as
the work that the system would have done if the original pr6cess
Heat and Thermodynamics 206
were reversible. From either of these perspectives we can identify
(W
rev
 W) as the quantity we denoted previously as E',
representing lost work. The lost work in any irreversible process
can therefore be related to the total entropy change (system plus
surroundings) and the temperature of the surroundings by
Lost work = W
rev
 W = TOMtotal.
To summarize the results of the above arguments for
processes where heat can be exchanged with the surroundings at:
• W
rev
 W represents the difference between work we
actually obtained and work that would be done durillg a
reversible state change. It is the extra work that would
be needed to restore the system to its initial state.
• For a reversible process, W
rev
= W; Mtotal = o.
• For an irreversible process, W
rev
> W; Mtotal> O.
• (W
rev
 W) = E' = To Mtotal is tre energy that becomes
unavailable for work during an irreversible process.
EXAMPLES OF LOST WORK IN ENGINEERING
PROCESSES
1. Lost work in Adiabatic Throttling: Entropy and
Stagnation Pressure Changes
<D Q)
I I
I I
 + ( ( / ~ m m p ///r//:...
/;)} 7» / /) 7 'd1n7'"7"n"';77,77rT7
CI Cz
PI P
z
TI Adiabatic throlliing T z
Fig. Adiabatic Throttling
A process we have encountered before is adiabatic throttling
of a gas, by a valve or other device. The velocity is denoted by c.
There is no shaft work and no heat transfer and the flow is steady.
Under these conditions we can use the first law for a control
volume (the Steady Flow Energy Equation) to make a statement
about the conditions upstream and downstream of the valve:
2 2
h
CI C2
1 +=h
2
+=h
t
,
2 2
where hI is the stagnation enthalpy, corresponding to a (possibly
fictitious) state with zero velocity. The stagnation enthalpy is the
207 The Second Law of Thermodynamics
same at stations 1 and 2 if Q = W = 0, even if the flow processes
are not reversible. For a perfect gas with constant specific heats,
h = cpT and hI = cpTr The relation between the static and stagnation
temperatures is:
Tt = 1 + ~ = 1 + ('I  I) = 1 + ('I _1)c
2
T 2pT 2yRT 2a
2
'v'
a
2
Tt =1+(YI)M2
T 2 '
where a is the speed of sound and M is the Mach number, M =
cia. In deriving this result, use has only been made of the first
law, the equation of state, the speed of sound, and the definition
of the Mach number. Nothing has yet been specified about whether
the process of stagnating the fluid is reversible or irreversible.
When we define the stagnation pressure, however, we do it
with respect to isentropic deceleration to the zero velocity state.
For an isentropic process
P
2
=(T
2
)Y/(Yl)
PI 11
The relation between static and stagnation pressures is
 /  ~ '   T . T,
T  /  ~   ~ : T
s
Fig. Static and Stagnation Pressures and Temperatures
The stagnation state is defined by P
t
, T,. In addition,
Sstagnation state' The static and stagnation states are shown in T  s
coordinates.
Stagnation pressure is a key variable in propulsion and power
systems. To see why, we examine the relation between stagnation
pressure, stagnation temperature, and entropy. The form of the
combined first and second law that uses enthalpy is
Heat and Thermodynamics
T
1
Tds = dh  dP.
,A,
I
I
I
P
'B,
I
I I
I B
I
I
A
a" .•
s
Fig. Stagnation and Static States
208
This holds for small changes between lI.ny thermodynamic
states and we can apply it to a situation in which we consider
differences between stagnation states, say one state having
properties (P
t
, Pt)and the other having properties (T
t
+ dT
t
,
P
t
+ dP
t
). The corresponding static states are also indicated.
Because the entropy is the same at static and stagnation conditions,
needs no subscript. Writing in terms of stagnation conditions yields
cpdTr 1 cpdTr R
=dpt.
Tr PtTr Tr
Both sides of the above are perfect differentials and can be
integrated as
= y 1 = ( ) In ( )
For a process with Q = W = 0, the stagnation enthalpy, and
hence the stagnation temperature, is constant. In this situation, the
stagnation pressure is related directly to the entropy as,
!ls
R
209 The Second Law of Thermodynamics
T
!
Fig. Losses reflected in changes in stagnation pressure when
This relation on a T s diagram. We have seen that the entropy
is related to the loss, or irreversibility. The stagnation pressure
plays the role of an indicator of loss if the stagnation temperature
is constant. The utility is that it is the stagnation pressure (and
temperature) which are directly measured, not the entropy. The
throttling process is a representation of flow through inlets,
nozzles, stationary turbomachinery blades, and the use of
stagnation pressure as a measure of loss is a practice that has
widespread application.
Equation can be put in several useful approximate forms.
First, we note that for aerospace applications we are (hopefully!)
concerned with low loss devices, so that the stagnation pressure
change is small compared to the inlet level of stagnation pressure,
= «1.
Expanding the logarithm (using In (1  x) ==  x + .... ),
(
) ( ) L\Pr
In = In 1  '
or
III
R
Another useful form is obtained by dividing hoth sides by
c
2
/2 and taking the limiting of the expression for stagnation
pressure in the limit of low Mach number (M« 1). Doing this,
we find:
Till _
c
2
/ 2 = pc
2
/ 2 .
Heat and Thermodynamics 210
The quantity on the right can be interpreted as the change in
the "Bernoulli constant" for incompressible (low Mach number)
flow. The quantity on the left is a nondimensional entropy change
parameter, with the term T!1s now representing the loss of
mechanical energy associated with the change in stagnation
pressure.
To summarize: For many applications the stagnation
temperature is constant and the change in stagnation pressure is a
direct measure of the entropy increase.
Stagnation pressure is the quantity that is actually measured
so that linking it to entropy (which is not measured) is useful.
We can regard the throttling process as a "free expansion" at
constant temperature Ttl from the initial stagnation pressure to the
final stagnation pressure. We thus know that, for the process, the
work we need to do to bring the gas back to the initial state is
which is the "lost work" per unit mass.
2. Adiabatic Efficiency of a Propulsion System Compo
nent (Turbine)
.4s s
Fig. Schematic of Turbine and Associated Thennodynamic
Representation in hs Coordinates
A schematic of a turbine and the accompanying
thermodynamic. There is a pressure and temperature drop through
the turbine and it produces work. There is no heat transfer so the
expressions that describe the overall shaft work and the shaft work
per unit mass are
lh(hl2  h
ll
) =
(h12  h
ll
) = wshaft.
If the difference in the kinetic energy at inlet and outlet can
be neglected, Equation reduces to
(h2  hI) = w
shaft
·
211
The Second Law of Thermodynamics
The adiabatic efficiency of the turbine is defined as
[
actual work ]
11ad = 'd 1 k(An 0)
1 ea wor Lll = . .
for a gIven pressure ratIo
The performance of the turbine can be represented in an hs
plane (similar to a T s plane for a perfect gas with constant specific
heats). From the figure the adiabatic efficiency is
hI h2 _ hI h
2s
(h
2
h
2s
)
11ad =   .
hI  h
2s
hI  h
2s
The adiabatic efficiency can therefore be written as
11ad = 1  ( ).
The nondimensional term work) represents the
departure from isentropic (reversible) processes and hence a loss.
The quantity is the enthalpy difference for two states along a
constant pressure line. From the combined first and second laws,
for a constant pressure process, small changes in enthalpy are
related to the entropy change by Tds = dh, or approximately,
=
The adiabatic efficiency can thus be approximated as
11ad = 1 T
2
fls = 1 (Lost work).
hI  h
2s
Ideal work
The quantity Tfls represents a useful figure of merit for fluid
machinery inefficiency due to irreversibility.
3. Isothermal Expansion with Friction
I PoT:
/
Friction
Fig. Isothermal Expansion with Friction
In a more general look at the isothermal expansion, we now
Heat and Thermodynamics 212
drop the restriction to frictionless processes work is done to
overcome friction. If the kinetic energy of the piston is negligible,
a balance of forces tells us that
Wsystem on piston = Wdone by friction + Wreceived'
During the expansion, the piston and the walls of the container
will up because of the friction. The heat will be (eventually)
transferred to the atmosphere; all frictional work ends up as heat
transferred to the surrounding atmosphere.
Wfriction = Qfrictiot/'
The amount of heat transferred to the atmosphere due to the
frictional work only is thus,
Qfriction = on piston  w..eceived .
'.r' '.,'
Work produced Work produced
The entropy change of the atmosphere (considered as a heat
reservoir) due to the frictional work is
Q
Work
0
0
The engine operates in a cycle and the entropy change for
the complete cycle is zero (because entropy is a state variable).
Therefore,
M = 0 + Ll
heat
source + M
heat
sink'
, I
Y
ASsurroundings
The total entropy change is
Q Qo
M M +M  +.
total  heat source heat sink   T TO
Suppose we had an ideal reversible engine working between
these same two temperatures, which extracted the same amount
of heat, Q, from the high temperature reservoir, and rejected heat
of magnitude Qo. rev to the low temperature reservoir. The work
done by this reversible engine is
213 The Second Law of Thermodynamics
W
rev
= Q  Qo, rev'
For the reversible engine the total entropy change over a cycle is
= + =_ Q + QO,rev =0.
Mtotal M heat source M heat sink T TO
Combining the expressions for work and for the entropy
changes,
Q
o
= QO'rev + W
rev
 W.
The entropy change for the irreversible cycle can therefore
be written as
!!:.s __ Q + Qo, rev + W
rev
 W
total  T To To
~
=0
The difference in work that the two cycles produce is
proportional to the entropy that is generated during the cycle:
TOMtotai = W
rev
 W.
The second law states that the total entropy generated is
greater than zero for an irreversible process, so that the reversible
work is greater than the actual work of the irreversible cycle.
An "engine effectiveness," Een . e' can be defined as the ratio
of the actual work obtained dividefby the work that would have
. been delivered by a reversible engine operating between the two
temperatures T and To:
TJengine
Eengine = "''
TJreversible engine
W Actual work obtained
==
w;.ev Work that would be delivered by
a reversible cycle between T, To
E. = Wrev  TO!!:'stotal = 1 TO!!:'stotal .
engme W rev W
rev
The departure from a reversible process is directly reflected
in the entropy change and the decrease in engine effectiveness.
Propulsive Power and Entropy Flux: The final example in
this section combines a number of ideas presented in this subject
and in Unified in the develolJment of a relation between entropy
generation and power needed to propel a vehicle.
Heat and Thermodynamics 214
An aerodynamic shape (airfoil) moving through the
atmosphere at a constant velocity. A coordinate system fixed to
the vehicle has been adopted so that we see the airfoil as fixed
and the air far away from the airfoil moving at a velocity co.
Streamlines of the flow have been sketched, a:; has the 'Velocity
distribution at station "0" far upstream and station "d" far
downstream.
The airfoil has a wake, which mixes with the surrounding air
and grows in the downstream direction. The extent of the wake is
also indicated. Because of the lower velocity in the wake the area
between the stream surfaces is larger downstream than upstream .
.de
\
Co II
/
Streamlines (control surface)
Actual wake profile
Fig. Airfoil with Wake and Control Volume for Analysis of Propulsive
power requirement
We use a control volume description and take the control
surface to be defined by the two stream c;urfaces and two planes
at station 0 and station d. This is useful in simplifying the analysis
because there is no flow across the stream surfaces. The area of
the downstream plane control surface is broken into AI' which is
the area outside the wake and A
2
, which is the area occupied by
wake fluid, i.e., fluid that has suffered viscous losses. The control
surface is also taken far enough away from the vehicle so that the
static pressure can be considered uniform. For fluid which is not
in the wake (no viscous forces), the momentum equation is
cdc = iP/p.
Uniform static pressure therefore implies uniform velocity,
so that on Al the velocity is equal to thf" upstream value, co. The
downstream velocity profile is actually continuous, as indicated.
215 The Second Law of Thermodynamics
It is approximated in the analysis as a step change to make the
algebra a bit simpler.
The equation expressing mass conservation for the control
volume is
Po Aoc
o
= Po Ai Co + P02
c
2·
The vertical face of the control surface is far downstream of
the body. By this station, the wake fluid has had much time to
mix and the velocity in the wake is close to the free stream value,
co. We can thus write,
wake velocity = c
2
= (co  1.
(We chose our control surface so the condition « 1
was upheld.)
The integral momentum equation (control volume form of
the momentum equation) can be used to find the drag on the
vehicle:
=  Drag + + P2
A
2
C
i·
There is no pressure contribution in Equation because the
static pressure on the control surface is uniform. Using the form
given for the wake velocity and expanding the terms in the
momentum equation we obtain
==  Drag + + P2A2[ci.  +
The last term in the right hand side of the momentum
equation, is small by virtue of the choice of control
surface and we can neglect it. Doing this and grouping the terms
on the right hand side of Equation in a different manner, we have
co[PoAoco] = cor PoAlco + P2
A
2(cO + {Drag
The terms in the square brackets on hoth sides of this equation
are the continuity equation multiplied by co. They thus sum to
zero leaving the curly bracketed terms as
Drag = PoAoCOLlC.
The wake mass flow is P02c:z = p0i Co  All this flow
has a velocity defect (compared to the free stream) of so that
the defect in flux of momentum (the mass flow in the wake times
the vebcity defect) is, to first or,jer in
Heat and Thermodynamics 216
Momentum defect in wake =  P:02CO = Drag.
The combined first and second law gives us a means of
relating the entropy and velocity:
Tds = dh  dP/p.
The pressure is uniform (dP = 0) at the downstream station.
There is no net shaft work or heat transfer to the wake so that the
mass flux of stagnation enthalpy is constant. We can also
approximate that the condition of constant stagnation enthalpy
holds locally on all streamlines. Applying both of these to the
combined first and second law yields
Tds = dh
t
 cdc.
For the present situation, dh
t
= 0; cdc = so that
Toru
In Equation the urstream temperature is used because
differences between wake quantities and upstream quantities are
small at the downstream control station. The entropy can be related
to the drag as
Drag =
The quantity P:02coru is the entropy flux (mass flux times
the entropy increase per unit mass; in the general case we would
expres<; this by an integral over the locally varying wake velocity
and density). The power needed to propel the vehicle is the product
of drag x flight speed, Drag x co.
From Equation, this can be related to the entropy flux in the
wake to yield a compact expression for the propulsive power
needed in terms of the wake entropy flux:
Propulsive power needed = To (PoA2 coru) = To x Extropy flux
wake.
This amount of work is dissipated per unit time in connection
with sustaining the vehicle motion. Equation is another
demonstration of the relation between lost work and entropy
generation, in this case manifested as power that needs to be
supplied because of dissipation in the wake.
REVERSIBLE AND IRREVERSIBLE PROCESSES
Entropy
• Entropy is a thermudynamic property that measures the
217 The Second Law of Thermodynamics
degree of randomization or disorder at the microscopic
level. The natural state of affairs is for entropy to be
produced by all processes.
• A macroscopic feature which is associated with entropy
production is a loss of ability to do useful work. Energy
is degraded to a less useful form. and it is sometimes
said that there is a decrease in the availability of energy.
• Entropy is an extensive thermodynamic property. In other
words, the entropy of a complex system is the sum of
the entropies of its parts.
• The notion that entropy can be produced, but never
destroyed, is the second law of thermodynamics.
Reversible and Irreversible Processes
Processes can be classed as reversible or irreversible. The
concept of a reversible process is an important one which directly
relates to our ability to recognize, evaluate, and reduce
irreversibilities in practical engineering processes.
Consider an isolated system. The second law says that any
process that would reduce the entropy of the isolated system is
impossible. Suppose a process takes place within the isolated
system in what we shall call the forward direction. If the change
in state of the system is such that the entropy increases for the
forward process, then for the backward process (that is, for the
reverse change in state) the entropy would decrease. The backward
process is therefore impossible, and we therefore say that the
forward process is irreversible.
If a process occurs, however, in which the entropy is
unchanged by the forward process, then it would also be unchanged
by the reverse process. Such a process could go in either direction
without contradicting the second law. Processes of this latter type
are called reversible. The key idea of a reversible process is that
it does not produce any entropy.
Entropy is produced in irreversible processes. All real
processes (with the possible exception of superconducting current
flows) are in some measure irreversible, though many processes
can be analyzed quite adequately by assuming that they are
Heat and Thermodynamics 218
reversible. Some processes that are clearly irreversible include:
mixing of two gases, spontaneous combustion, friction, and the
transfer of energy as heat from a body at high temperature to a
body at low temperature.
Recognition of the irreversibilities in a real process is
especially important in engineering. Irreversibility, or departure
from the ideal condition of reversibility, reflects an increase in
the amount of disorganized energy at the expense of organized
energy. The organized energy (such as that of a raised weight) is
easi ly put to practical use; disorganized energy (such as the random
motions of the molecules in a gas) requires "straightening out"
before it can be used effectively. Further, since we are always
somewhat uncertain about the microscopic state, this straightening
can never be perfect. Consequently the engineer is constantly
striving to reduce irreversibilities in systems, in order to obtain
better performance.
EXAMPLES OF REVERSIBLE AND IRREVERSIBLE
PROCESSES
Processes that are usually idealized as reversible include:
• Frictionless movement
• Restrained compression or expansion
• Energy transfer as heat due to infinitesimal temperature
nonuniforrnity
• Electric current flow through a zero resistance
• Restrained chemical reaction
• Mixing of two samples of the same substance at the same
state.
Processes that are irreversible include:
• Movement with friction
• Unrestrained expansion
• Energy transfer as heat due to large temperature non
uniformities
• Electric current flow through a non zero resistance
Spontaneous chemical reaction
• Mixing of matter of different composition or state.
219 The Second Law of Thermodynamics
REAL CYCLE BEHAVIOUR
We will now improve our estimates of cycle performance by
including the effects of irreversibility. We will use the Brayton
cycle as an example. What are the sources of nonideal
performance and departures from reversibility?
• Losses (entropy production) in the compressor and the
turbine.
• Stagnation pressure decrease in the combustor.
• Heat transfer.
We take into account here only irreversibility in the
compressor and in the turbine. Because of these irreversibilities,
we need more work, Mcornp(the changes in kinetic energy from
inlet to exit of the compressor are neglected), to drive the
compressor than in the ideal situation. We also get less work,
~ h t u r b ' back from the turbine. The consequence, as can be inferred
is that the net work from the engine is less than in the cycle with
ideal components.
,
Fig. Gas Turbine Engine (Brayton) Cycle Showing Effect of Departure
from Ideal Behaviour in Compressor and Turbine
To develop a quantitative description of the effect of these
departures from reversible behaviour, consider a perfect gas with
constant specific heats and neglect kinetic energy at the inlet and
exit of the turbine and compressor. We define the turbine adiabatic
efficiency as
Heat and Thermodynamics 220
actual h h
Wturb 4  S
llturb = ideal = h k'
Wturb 4  "5s
where wactual is specified to be at the same pressure ratio as wideal
turb turb .
There is a similar metric for the compressor, the compressor
adiabatic efficiency:
ideal h
wturb 3s  "0
llcomp = actual = h k'
Wturb 3 ,'0
again for the same pressure ratio. Note that for the turbine the
ratio is the actual work delivered divided by the ideal work,
whereas for the compressor the ratio is the ideal work needed
divided by the actual work required. These are not thermal
efficiencies, but rather measures of the degree to which the
compression and expansion approach the ideal processes.
We now wish to find the net work done in the cycle and the
efficiency. The net work is given either by the difference between
the heat received and rejected or the work ofthe compressor and
turbine, where the convention is that heat received is positive and
heat rejected is negative and work done is positive and work
absorbed is negative.
Y 'v'
{
q  qR
Net work = heat in heat out_
Wturb w
comp
Ch4 hs)C
h
3 h
o
)·
The thermal efficiency is
Net work
llthermal = Heat input
We need to calculate T
3
, Ts.
From the definition of ll
comp
'
With
(13s
/
O)_'1' C13s
IT
o
1
)
T  T. = LO .
3 0 llcomp llcomp
(
P )Yl yl
= isentropic temperature ratio = Y = IT
c
6mp'
ltnlet
221 The Second Law of Thermodynamics
(n1, I]
1j=To +To·
llcomp
Similarly, by the definition
actual work received
1'. . '
ideal work for same
(
YI]
Ts = T4 llturb
T
4 1 .
The thermal efficiency can now be found:
With
and
or
= 1 + QL = 1 _ Ts  To
llthermal Q 'T' 'T"
H ·Q.l3
IT = _1_=IT
comp IT
turb
't
s
= IT g;1 = the isentropic cycle temperature ratio,
_ )]10
T
4
T
o
[_I_('t
s
l)+I]
llcomp
Heat and Thermodynamics 222
There are several nondimensional parameters that appear
in this expression for thermal efficiency. We list these in the
two sections below and show their effects in accompanying.
PARAMETERS REFLECTING THE ABILITY TO DESIGN AND
EXECUTE EFFICIENT COMPONENTS
l1
comp
: compressor adiabatic efficiency
1l
tur
b : turbine adiabatic efficiency
In addition to efficiency, net rate of work is a quantity we
need to examine,
Wnet = wturbine  Wcompressor·
Putting this in a nondimensional form,
Wnet = (·s 1) + 1lturb (1
mCpTo 'y I
work to drive compressor work extracted from flow by turbine
W
net
= (ts _l)[1lturb _1_].
mc pTo • s 1lcomp
Trends in net power and efficiency for parameters typical
of advanced civil engines.
• For any l1
comp
' l1
tur
b * 1 the optimum pressure ratio
Pj for maximum t is not the highest that can be
achieved, as it is for the ideal Brayton cycle. The ideal
analysis is too idealized in this regard. The highest
efficiency also occurs closer to the pressure ratio for
maximum power than in the case of an ideal cycle.
Choosing this as a design criterion will therefore not
lead to the efficiency penalty inferred from ideal cycle
analysis.
• There is a strong sensitivity to the component
efficiencies. for Pi = 1, the cycle efficiency is roughly
I
twothirds of the ideal value.
• The maximum power occurs at a value of (E) or
pressure ratio pjless than that for max
223 The Second Law of Thermodynamics
(E) = LP;
(this trend is captured by tdeal analysis).
• The maximum power and maximum tj are strongly
dependent on the maximum temperature, Pj'
A scale diagram of a Brayton cycle with nonideal
compressor and turbine behaviors, in terms of temperature
entropy (hs) and pressurevolume (Pv) coordinates.
luel
T.I(
pPo
~ ~
• J,1(gK y m3AIg
Fig. Scale Diagram of Nonideal gas Turbine Cycle. Nomenclature
Pressure ratio = I, P2' = 0, Compressor and Turbine Efficiencies P3
REFERENCES
• Schaum's Outline of Thermodynamics for Engineers,
2nd edition (Schaum's Outlines) by Merle Potter and
Ph.D., Craig Somerton.
• Essentials of Thermodynamics (Essentials) by
Research & Education Association, Rea, and Staff
of Research Education Association.
• Statistical mechanics, R. P. Feynman, W. A.
Benjamin.
• A Modern Course in Statistical Physics, L. E. Reichl
• Thermodynamics by J.P. Holman.
9 ____________________________ __
Third Law of Thermodynamics
The Third Law of Thermodynamics is the lesser known of
the three major thermodynamic laws. Together, these laws help
form the foundations of modern science. The laws of
thermodynamics are absolute physical laws  everything in the
observable universe is subject to them. Like time or gravity,
nothing in the universe is exempt from these laws. In its simplest
form, the Third Law of Thermodynamics relates the entropy
(randomness) of matter to its absolute temperature.
The Third Law of Thermodynamics refers to a state known
as "absolute zero." This is the bottom point on the Kelvin
temperature scale. The Kelvin scale is absolute, meaning 0° Kelvin
is mathematically the lowest possible temperature in the universe.
This corresponds to about 273.15° Celsius, or 459.7 Fahrenheit.
In actuality, no object or system can have a temperature of
zero Kelvin, because of the Second Law of Thermodynamics. The
Second Law, in part, implies that heat can never spontaneously
move from a colder body to a hotter body. So, as a system
approaches absolute zero, it will eventually have to draw energy
from whatever systems are nearby. If it draws energy, it can never
obtain absolute zero. So, this state is not physically possible, but
is a mathematical limit of the universe.
In its shortest form, the Third Law of Thermodynamics says:
"The entropy of a pure perfect crystal is zero (0) at zero Kelvin
(0° K)." Entropy is a property of matter and energy discussed by
the Second Law of Thermodynamics. The Third Law of
225 Third Law of Thermodynamics
Thermodynamics means that as the temperature of a system
approaches absolute zero, its entropy approaches a constant (for
pure perfect crystals, this constant is zero). A pure perfect crystal
is one in which every molecule is identical, and the molecular
alignment is perfectly even throughout the substance. For non
pure crystals, or those with lessthan perfect alignment, there will
be some energy associated with the imperfections, so the entropy
cannot become zero.
The Third Law of Thermodynamics can be visualized by
thinking about water. Water in gas form has molecules that can
move around very freely. Water vapour has very high entropy
(randomness). As the gas cools, it becomes liquid. The liquid water
molecules can still move around, but not as freely. They have lost
some entropy. When the water cools further, it becomes solid ice.
1be solid water molecules can no longer move freely, but can only
vibrate within the ice crystals. The entropy is now very low. As
the water is cooled more, closer and closer to absolute zero, the
vibration of the molecules diminishes. If the solid water reached
absolute zero, all molecular motion would stop completely. At
this point, the water would have no entropy (randomness) at all.
Most of the direct use of the Third Law of Thermodynamics
occurs in ultralow temperature chemistry and physics. The
applications of this law have been used to predict the response of
various materials to temperature changes. These relationships have
become core to many science disciplines, even though the Third
Law of Thermodynamics is not used directly nearly as much as
the other two.
MATHEMATICAL NOTATIONS
If we have sufficient heat capacity data (and the data on phase
changes) we could write
rTC
S(T)=S(T=O)=.b ; dT.
(If there is a phase change between 0 K and T we would have to
add the entropy of the phase change.) If C
p
were constant near T
= 0 we would have,
Heat and Thermodynamics
T
SeT) = SeT = 0) +C
p
In,
o
226
which is undefined. experimentally C
p
0 as T
O. For nonmetals C
p
is proportional to T3 at low temperatures.
For metals C
p
is proportional to T3 at low temperatures but shifts
over to being proportional to T at extremely low temperatures.
(The latter happens when the atomic motion "freezes out" and
the heat capacity is due to the motivn of the conduction electrons
in the metal.)
Equation could be used to calculate absolute entropies for
substances if we knew what the entropy is at absolute zero.
Experimentally it appears that the entropy at absolute zero is the
same for all substances. The third law of thermodynamics codifies
this observation and sets
S(T= 0) = 0
for all elements and compounds in their most stable and perfect
crystalline state at absolute zero and one atmosphere pressure. (All
except for helium, which is a liquid at the lowest observable
temperatures at one atmosphere.)
The advantage of this law is that it allows us to use
experimental data to compute the absolute entropy of a substance.
For example, suppose we want to calculate the absolute entropy
of liquid water at 25° C. We would need to know the C
p
of ice
from 0 K to 273.15 K and the f:..p of liquid water from 273.15 K to
298.15 K. We also need the heat of fusion of water at its normal
melting point. With all of this data, which can be obtained partly
from theory and partly from experiment, we find
o 173.15Cp(S) DH
fus
I:98.15Cp(l)
SHo(25°C)=0+ dT,
2 T 273.15 73.15 T
Some substances may undergo several phase changes.
Entropy Changes in Chemical Reactions
We can use the third law entropies to calculate entropy
changes for chemical reactions. For a typical reaction,
aA+bB'!cC+dD.
227 Third Law of Thermodynamics
the entropy change is
tlrS
o
= c S ~ + dS;  a S ~  b S ~ .
Notice two things:
• We did not define or use an entropy offormation, t1. po.
• So element is not zero.
As we have said before, t1.f ° and t1./fo are independent of
each other. They can not be calculated from each other. They must
be calculated from Equation and a comparable equation using heats
of formation.
There is another way to calculate t1.fo,
tlrSo = tlrH
o
 tlrGo .
T
As we have seen before, the t1.p ° and t1./fo can be calculated
from free energies and heats of formation.
As T ~ 0 K , S ~ O.
For the General student, the important point about the third
law is that entropy is an absolute quantity which depends upon
temperature. This is in contrast to t1.H for reactions which have as
a reference the elemental state. Thus, when one looks up the t1.Ho f
of an elements, the answer is O. In contrast, So for an element
(note difference in symbols as well) has a value for temperature
above 0 K. Careful when doing calculations for t1.So of reactions
that you do not use 0 for the So of the elements.
The entropy change with respect to temperature can be
thought of a continuous summation of all the increments of heat
added to the system divided by the temperature at the time of the
addition. Or symbolically:
M = JCdqIT)dT which is approximately SUM of the (t1.q /
T)s
Thus, to calculate a change in S one simply adds up the little
increments of heat added divided by temperature.
The question then is, what if the addition of these increments
start with the temperature at 0 K? The answer is, that at OK the q
Heat and Thermodynamics 228
added is also O. 0 divided by 0 presents a dilemma and the
third law answers this by the following:
For a pure component in the most stable condition, S = 0
at T = 0 K.
This leads to the assumption needed above, that the SO s
for pure components are absolute values and are not referenced
against some arbitrary initial condition like the ~ H ° s are. As
an illustration, see the example thermodynamic table and
notice that the elements do have SO s listed. Check out the
following:
For the pure components (complete chemicals) the SOs are
positive
For ions, which are not complete chemicals but only one
leg of the ionic compound, there are ~ S o listed which can be
either positive or negative. These ions are reference against the
H+ (understood to stand for H30+ ) ion.
REFERENCE
• Course in Thermodynamics . Revised Printing.
Volume II. (Series in Thermal and Fluids Engineering)
by Joseph Kestin.
• Thermodynamics In Materials Science by Robert T.
Dehoff.
• Statistical Mechanics, SK Ma
• Schaum Engineering Thermodynamics (Schaum's
Outlines) by Merle Potter.
• Thermodynamics by J.P. Holman
10 ______________________ __
Entropy
ENTROPY CHANGE IN MIXING OF TWO IDEAL GASES
Consider an insulated rigid container of gas separated into
two halves by a heat conducting partition so the temperature
of the gas in each part is the same. One side contains air, the
other side another gas, say argon, both regarded as ideal gases.
The mass of gas in each side is such that the pressure is also
the same .
. The entropy of this system is the sum of the entropies of
the two parts: turbine adiabatic efficiency. Suppose the
partition is taken away so the gases are free to diffuse
throughout the volume. For an ideal gas, the energy is not a
function of volume, and, for each gas, there is no change in
temperature. (The energy of the overall system is unchanged,
the two gases were at the same temperature initially, so the
final temperature is the same as the initial temperature.) The
entropy change of each gas is thus the same as that for a
reversible isothermal expansion from the initial specific
volume. For a mass of ideal gas, the entropy change is
W. [TJturb ~ 4 1 1
~ = (Ts 1) 0 . The entropy change of the
me pTo 't s TJcomp
system is
11turb * 1
Equation states that there is an entropy increase due to
the increased volume that each gas is able to access.
Examining the mixing process on a molecular level gives
Heat and Thermodynamics 230
additional insight. Suppose we were able to see the gas molecules
in different colors, say the air molecules as white and the argon
molecules as red. After we took the partition away, we would see
white molecules start to move into the red region and, similarly,
red molecules start to come into the white volume. As we watched,
as the gases mixed, there would be more and more of the different
colour molecules in the regions that were initially all white and
all red.
If we moved further away so we could no longer pick out
individual molecules, we would see the growth of pink regions
spreading into the initially red and white areas. In the final state,
we would expect a uniform pink gas to exist throughout the
volume. There might be occasional small regions which were
slightly more red or slightly more white, but these fluctuations
would only last for a time on the order of several molecular
collisions.
In terms of the overall spatial distribution of the molecules,
we would say this final state was more random, more mixed, than
the initial state in which the red and white molecules were confined
to specific regions. Another way to say this is in terms of
"disorder;" there is more disorder in the final state than in the
initial state. One view of entropy is thus that increases in entropy
are connected with increases in randomness or disorder. This link
can be made rigorous and is extremely useful in describing systems
on a microscopic basis. While we do not have scope to examine
this topic in depth, the purpose of is to make plausible the link
between disorder and entropy through a statistical definition of
entropy.
MICROSCOPIC AND MACROSCOPIC DESCRIPTIONS OF
A SYSTEM
The microscopic description of a system is the complete
description of each particle in this system. In the above example,
the microscopic description of the gas would be the list of the
state of each molecule: position and velocity in this problem. It
would require a great deal of data for this description; there are
roughly 10
19
molecules in a cube of air one centimeter on a side
231
Entropy
at room temperature and pressure. The macroscopic description,
which is in terms of a few (two!) properties is thus far more
accessible and useable for engineering applications, although it is
restricted to equilibrium states.
To address the description of entropy on a microscopic level,
we need to state some results concerning microscopic systems.
These results and the and arguments below are taken
almost entirely from the excellent of Engineering Thermodynamics
by Reynolds and Perkins.
For a given macroscopic system, there are many microscopic
states. A key idea from quantum mechanics is that the states of
atoms, molecules, and entire systems are discretely quantized. This
means that a system of particles under certain constraints, like
being in a box of a specified size, or having a fixed total energy,
can exist in a finite number of allowed microscopic states. This
number can be very big, but it is finite. The microstates of the
system keep changing with time from one quantum state to another
as molecules move and collide with one another. The probability
for the system to be in a particular quantum state is defined by its
quantumstate probability Pi' The set of the Pi is called the
distribution of probability. The sum of the probabilities of all the
allowed quantum states must be unity, hence for any time I,
LP, =1
i
When the system reaches equilibrium, the individual
molecules still change from one quantum state to another. In
equilibrium, however, the system state does not change with time;
so the probabilities for the different quantum states are independent
oftime. This distribution is then called the equilibrium distribution,
and the probability P, can be viewed as the fraction oftime a system
spends in the ith quantum state. In what follows, we limit
consideration to equilibrium states.
We can get back to macroscopic quantities from the
microscopic description using the probability distribution. For
instance, the macroscopic energy of the system would be the
weighted average of the successive energies of the system (the
Heat and Thermodynamics 232
energies of the quantum states); the energies are weighted by the
relative time the system spends in the corresponding microstates.
In terms of probabilities, the average energy, (E), is
(E)= LPiEj,
j
where Cj is the energy of a quantum state.
The probability distribution provides information on the
randomness of the equilibrium quantum states suppose the system
can only exist in three states (1, 2 and 3). If the distribution
probability is
PI = 1, P2 = 0 P3 = 0,
the system is in quantum state 1 and there is no randomness. If
we were asked what quantum state the system is in, we would be
able to say it is always in state 1. If the distribution were
PI = 0.3, P2 = 0.2, P3 = 0.5,
or
PI = 0.5, P2 = 0.2, P3 = 0.3,
the randomness would not be zero and would be equal in both
cases. We would be more uncertain about the instantaneous
quantum state than in the first situation.
Maximum randomness corresponds to the case where the
three states are equally probable:
PI = 1/3, P2 = 113, P3 "" 1/3,
In this case, we can only guess the instantaneous state with
33% probability.
STATISTICAL DEFINITION OF ENTROPY
The list of the Pi is a precise description of the randomness
in the system, but the number of quantum states in almost any
industrial system is so high this list is not useable. We thus look
for a single quantity, which is a function of the Pi' that gives an
appropriate measure of the randomness of a system. As shown
below, the entropy provides this measure.
There are several attributes that the desired function should
have. The first is that the average of the function over all of the
microstates should have an extensive behaviour. In other words
233 Entropy
the microscopic description of the entropy of a system C,
composed of parts A and B should be given by
SC=SA+SB
Second is that entropy should increase with randomness and
should be largest for a given energy when all the quantum states
are equiprobable.
The average of the function over all the microstates is defined
by
S=(I)= IpJ(p;),
;
where the function.f{pj) is to be found. Suppose that system A has
nmicrostates and system Bhas mmicrostates. The entropies of
systems A, B, and C, are defined by
;=1
m
SA = IpJ(pj)
j=1
n m n m
Sc = IIpJ(pj) = IpJ(p;)IpJ(pj)
;=1 j=1 ;=1 j=1
In Equations, the term Pij means the probability of a microstate in
which system A is in state i and system B is in state j. For
Equation to hold given the expressions in Equations,
n m
Sc = I pJ(p;)IpJ(Pj)
;=1 j=1
n m
= IpJ(p;) + IPj!(Pj)=SA +SB·
1=1 j=1
The function/must be such that this is true regardless of the values
of the probabilities Pi and Pj" This will occur ifjO = In 0 because
In (a. b) = In (a) + In (b).
To verify this, make this substitution in the expression for Sc
in the first part of Equation (assume the probabilities Pjand Pjare
independent, such that Pij = PRj' and split the log term):
Heat and Thermodynamics 234
n m n m
Sc = IIpiPj In (Pi) + IIpiPj In (p).
/=1 j=1 i=1 j=1
Rearranging the sums, becomes
Sc = f{p/ln (p;)[fpj]} + t{Pj In (Pi)[tP;]}.
1=1 )=1 )=1 )=1
Because
n m
Ipj = IPj =1,
;=1 j=1
the square brackets in the right hand side of Equation can be set
equal to unity, with the result written as
n m
Sc = I P j In (Pi) + I P j In (p j ).
1=1 j=1
This reveals the top line of Equation to be the same as the
bottom line, for any Pi' Pp n, m, provided that./{) is a logarithmic
function. Reynolds and Perkins show that the most generalj{p;)
isf= C In (P), where is an arbitrary constant. Because the Pi are
less than unity, the constant is chosen to be negative to make the
entropy positive.
Based on the above, a statistical definition of entropy can be
given as:
S = k IPi In (p;).
;
The constant k is known as the Boltzmann constant,
J
k = 1.380 x 10
23
K·
The value of is (another wonderful result!) given by
R
k
NAvogadro,
where R is the universal gas constant, 8.3143 J/(molK) and
NAvogadrO is Avogadro's number, 6.02 x 10
23
molecules per mol.
Sometimes k is called the gas constant per molecule. With this
value for k, the statistical definition of entropy is identical with
the macroscopic definition of entropy.
235 Entropy
CONNECTION BETWEEN THE STATISTICAL DEFINITION
OF ENTROPY AND RANDOMNESS
We need now to examine the behaviour of the statistical
definition of entropy as regards randomness. Because a uniform
probability distribution reflects the largest randomness, a system
with allowed states will have the greatest entropy when each state
is equally likely. In this situation, the probabilities become
1
Pi == P == n'
where Ois the total number of microstates. The entropy is thus
S ==
,
== kinO.
Equation states that the larger the number of possible states
the larger the entropy. The behaviour of the entropy stated in
Equation can be summarized as follows:
• S is maximum when 0 is maximum, which means many
permitted quantum states, hence much randomness,
• S is minimum when 0 is minimum. In particular, for
0= 1, there is no randomness and S = o.
These trends are in accord with our qualitative ideas
concerning randomness. Equation is carved on Boltzmann's
tombstone.
We can also examine the additive property of entropy with
respect to probabilities. If we have two systems, A and B, which
are viewed as a combined system, C, the quantum states for the
combined system are the combinations of the quantum states from
A and B. The quantum state where A is in its state x and B is in its
state would have a probability pAx· pBybecause the two
probabilities are independent. The number of probabilities for the
combined system, 0
0
is thus defined by 0c= 0A.OB. The entropy
of the combined system is
Sc = kin (OAOB) = k In 0A + kin 0B = SA + SB
Equation is sometimes taken as the basic definition of entropy,
but it should be remembered that it is only appropriate when each
quantum state is equally likely. Equation is more general and
Heat and Thermodynamics 236
applies equally for equilibrium and nonequilibrium situations.
A simple numerical example shows trends in entropy changes
and randomness for a system which can exist in three states.
Consider the five probability distributions
(i)pl = 1.0,P2 = 0,P3 = 0;
S =  k(1ln (1) + 0 In(O) + 0 In (0» = 0
(ii) PI = 0.8 P2 = 0.2, P3 = 0;
S =  k(O.8 In (0.8) + 0.2 In (0.2) + 0 In (0» = 0.5k
(iii)pl = 0.8p2 = 0.1,P3 = 0.1;
S =  k(0.8In (0.8) + O.lln (0.1) + 0.1 In (0.1» = 0.6k
(iv) PI = 0.5 P2 = 0.3, P3 = 0.2;
S =  k(0.5 In (0.5) + 0.3 In (0.3) + 0.2 In (0.2» = 1.0k
The first distribution has no randomness. For the second,
we know that state 3 is never found. Distributions (iii) and
(iv) have progressively greater uncertainty about the
distribution of states and thus higher randomness. Distribution
(v) has the greatest randomness and uncertainty and also the
largest entropy.
REFERENCES
• Heat and Thermodynamics, M. W. Zemansky
• Thermodynamics (and Introduction to
Thermostatistics), H.B. Callen
• Schaum's Outline of Thermodynamics for Engineers,
2nd edition (Schaum's Outlines) by Merle Potter and
Ph.D., Craig Somerton.
• Introduction to Metallurgical Thermodynamics by
David R. Gaskell.
• Equilibrium Thermodynamics, C. J. Adkins.
11
Enthalpy Generating Heat
There are a wide variety of fuels used for aerospace power
and propulsion. A primary one is jet fuel (octane, essentially
kerosene) which has the chemical formula C
S
H
1S
. Other fuels
we consider are hydrogen (H
2
) and methane (CH
4
).
The chemical process in which a fuel, methane, is burned
consists of (on a very basic level  there are many
intermediate reactions that need to be accounted for when
computations of the combustion process are carried out):
CH
4
+ 202 t CO
2
+ 2H
2
0
~ ~
(Reactants) (Products)
The reactions we describe are carried out in air, which can
be approximated as 21% 02 and 79% N
2
. This composition is
referred to as "theoretical air." There are other components
of air (Argon, which is roughly 1 %), but the results given using
the theoretical air approximation are more than adequate for
our purposes. With this definition, for each mole of 02' 3.76
(or 79/21) moles of N2 are involved:
CH
4
+ 202 + 2(3.76)N
2
7C0
2
+ 2H
2
0 + 7.52N
2
·
Even if the nitrogen is not part of the combustion process, it
leaves the combustion chamber at the same temperature as the other
products, and this change in state (change in enthalpy) needs to be
accounted for in the stt!ady flow energy equation. At the high
temperatures achieved in internal combustion engines (aircraft and
automobile) reaction does occur between the nitrogen and oxygen,
which gives rise to oxides of nitrogen, although we will
Heat and Thermodynamics 238
not consider these reactions. The condition at which the mixture
of fuel and air is such that both completely participate in the
reaction is called stoichiometric. In gas turbines, excess air is often
used so that the temperatures of the gas exiting the combustor is
kept to within desired limits.
FuelAir Ratio
The reaction for aeroengine fuel at stoichiometric conditions is
CSHIS + 12.5 02 + 12.5 (3.76)N
2
~ 8C0
2
+ 9H
2
0 + 47.0 N
2
.
On a molar basis, the ratio offilel to air is [1/(12.5 + 47.0)]=1/
59.5 = 0.0167.
To find the ratio on a mass flow basis, which is the way in
which the aeroengine industry, we need to "weight" the molar
proportions by the molecular weight of the components. The fuel
molecular weight is 114 glmol, the oxygen molecular weight is
32 glmol and the nitrogen molecular weight is (approximately)
28 glmol. The fuel/air ratio on a mass flow basis is thus
Fuelair ratio:
= 1 mol x 114 glmo) = 0.0664
12.5 mol x 32 glmol + 12.5x3.76 mol x 28 glmol
Ifwe used the actual constituents of air we would get 0.0667,
a value about 0.5% different.
Enthalpy of formation
The systems we have worked with until now have been of
fixed chemical composition. Because of this, we could use
thermodynamic properties relative to an arbitrary base, since all
comparisons could be made with respect tc the chosen base. The
specific energy ujCO.Ol 0c) =0.0 for steam. If there are no changes
in composition, and only changes in properties of given substances,
this is adequate. If there are changes in composition, however,
we need to have a reference state so there is consistency for
different substances.
The convention used is that the reference state is a
temperature of 25
c
C (298 K) and a pressure of 0.1 MPa. (These
are roughly room conditions.) At these reference conditions, the
239 Enthalpy Generating Heat
enthalpy of the elements (oxygen, hydrogen, nitrogen, carbon, etc.)
is taken as zero.
The results of a combustion process can be diagrammed. The
reactants enter at standard conditions; the combustion (reaction)
takes place in the volume indicated. Downstream of the reaction
zone there is an appropriate amount of heat transfer with the
surroundings so that the products leave at the standard .;onditions.
For the reaction of carbon and oxygen to produce CO
2
, the heat
that has to be extracted is Qcv=  393,522 kJ/mole: this is heat
that comes out of the control volume.
I kmalcC
•
2S" C.O.I Ml'I
C+0zC02
I
_, I kmoIcC02
2SOC.O.1 MPa
a... 393.522 KJ. bell _I volume
Fig. Constant Pressure Combustion
There is no shaft work done in the control volume and the
first law for the control volume (SFEE) reduces to:
mass flow of enthalpy in + rate of heat addition = mass flow
of enthalpy out.
We can write this statement in the form
+ Qcv = Lmchc·
R P
In Equation the subscripts "R" and "P" on the summations
refer to the reactants (R) and products (P) respectively. The
subscripts on the mass flow rates and enthalpies refer to all of the
components at inlet and at exit.
The relation in terms of mass flows can be written in molar
fOrIn, which is often more convenient for reacting flow problems,
by using the molecular weight, M;, to define the molar mass flow
rate,l1
i
, and molar enthalpy, Ii;, for any individual ith (or eth)
component as
l1i = mj t1vli; mass flow rate in terms of kmoleslsec
Ii; = Mjh
j
; enthaply per kmole.
Heat and Thermodynamics 240
The SFEE is, in these tenns,
Ln;h; + = Liz;iic'
R P
The statements that have been made do not necessarily need
to be viewed in the context of flow processes. Suppose we have
one unit of C and one unit of Q
2
at the initial conditions and we
carry out a constant pressure reaction at ambient pressure, P ambO
If so,
U
fina1
 = Q  W
= Qcv P amb (V
fina1
 Vinitial)'
since Pi = P
j
= P
amb
• Combining terms,
U
final
+ P final V
flllal
 + Pintial Vinitial) = Q
cv
'
or
HfmalHintial = Qcv·
In terms of the numbers of moles and tbe specific enthalpy
this is
Ln;h; + Qcv =
R P
The enthalpy of CO
2
, at 25°C and 0.1 MPa, with reference
to a base where the enthalpy of the elements is zero, is called the
enthalpy of formation and denoted by h;. Values of the heat of
formation for a number of substances are given in Table in
SB&VW.
The enthalpies of the reactants and products for the formation
of CO
2
are:
hoz =hc =0,
For one kmoke: Qcv= =Hp =(hj)C0
2
= 393,522 kJ/
kmole. P
The enthalpy of CO
2
in any other state (T, P) is given by
hT,p= (h;)398K,O.lMPA =
These descriptions can be applied to any compound. For
elements or compounds that exist in more than one state at the
241 Enthalpy Generating Heat
reference conditions (carbon exists as diamond and as graphite),
we also need to specify the state.
Note that there is a minus sign for the heat of formation. The
heat transfer is out of the control volume and is thus negative by
our convention. This means that > heo
2
=  393,522 kJ/
kmole.
First Law Analysis of Reacting Systems
The form of the first law for the control volume is (there is
no shaft work):
Lnj!i; +Qev = Lnchc'
R P
This is given in terms of the moles of the different
constituents, and it reduces to the more familiar form for a single
fluid (say air) with no reactions occurring. We need to specify
one parameter as the basis of the solution; 1 kmole of fuel, 1 kmole
of air, 1 kmole total, etc. We use 1 kmole of fuel as the basic unit
and examine the burning of hydrogen.
2H2 + O
2
2H
2
0
The reactants and the products are both taken to be at 0.1
MPa and 25°C, so the inlet and exit P and T are specified. The
control volume is the combustion chamber. There is no shaft work
done and the SFEE is in the form of Equation. The of
the entering gas is zero for both the hydrogen and the oxygen
(elements have enthalpies defined as zero at the reference state).
If the exit products are in the gaseous state, the exit enthalpy is
therefore related to the enthalpy of formation of the product by:
n
c
, H
2
0h
c
, H
2
0 = n
c
,H
2
0(h; )H
2
0(g)
= 2 x (241,827) kJ =  483,654 kJ; gaseous state at exit.
If the water is in a liquid state at the exit of the process:
n
c
' H
2
0h
c
, H
2
0 = n
c
,H
2
0(h; )H
2
0(1)
= 2 x (285,783) kJ =  571,676 kJ.
There is mort:; heat given up if the products emerge as liquid.
Heat and Thermodynamics 242
The difference between the two values is the enthalpy needed to
tum the liquid into gas at: 25°C: h
fg
= 2442 kJ/kg.
A more complex example is provided by the burning of
methane (natural gas) in oxygen, producing
CH
4
+ 202 + C02 + 2H
2
0(l).
The components in this reaction equation are three ideal gases
(methane, oxygen, and CO
2
) and liquid water. We again specify
that the inlet and exit states are at the reference conditions so that:
= (Ji;)CH
4
=74,873kJ
R
= (Ji;>Co
2
+2(Ji;)H
2
0(I)
p
= 393.522+ 2(285,838) =  965,198 kJ
Qcv =965,198(74,873) = 890,325 kJ
Suppose the substances which comprise the reactants and
the products are not at 25°C and 0.1 MPa. If so, the expression
that connects the reactants and products is
Qcv + Lni(Ji;. + §. lLnc(Ji; + §. l·
R Between and p Between and
reference conditions reference conditions
Equation shows that we must compute the enthalpy
difference !!.Ji between the reference conditions and the given state
if the inlet or exit conditions are not the reference pressure and
temperature.
There are different levels of approximation for the
computation:
• Assume the specific heat is constant over the range at
some average value,
• Use the polynomial expressions in the integral,
• Use tabulated values.
The first is the simplest and the crudest. Combustion
processes often involve changes of a thousand degrees or more
and, the specific heat for some gases can change by a factor of
two or more over this range, although the changes for air are more
243 Enthalpy Generating Heat
modest. This means that, dei,ending on the accuracy desired, one
may need to consider the temperature dependence of the specific
heat in computing !1h.
Ar,He,Ne,Kr,Xe
500 1000 1500 2000 2500 3000 3500
T[k]
Fig. Specific heat as a function of temperature [from SB&VW]
Adiabatic Flame Temperature
F or a combustion process that takes place adiabatically with
no shaft work, the temperature of the products is referred to as
the adiabatic flame temperature.
This is the maximum temperature that can be achieved for
given reactants. Heat transfer, incomplete combustion, and
dissociation all result in lower temperature.
The maximum adiabatic flame temperature for a given fuel
and oxidizer combination occurs with a stoichiometric mixture
(correct proportions such that all fuel and all oxidizer are
consumed).
The amount of excess air can be tailored as part of the design
to control the adiabatic flame temperature. The considerable
distance between present temperatures in a gas turbine engine and
the maximum adiabatic flame temperature at stoichiometric
conditions, based on a compressor exit temperature of (922 K).
Heat and Thermodynamics
T
State i
o
I
I
  ~ I
I 1= Final state
I
I
I
I dh2
GY
f1\ : ~ Constant P
\.:.J dh 1 .....
'2
Constant P I
Percentage
completion
of reaction
I
100%
Fig. Schematic of adiabatic flame temperature
244
An initial view of the concept of adiabatic flame temperature
is provided by examining two reacting gases, at a given pressure,
and asking what the end temperature is. The process is shown
schematically, where temperature is plotted versus the percentage
completion of the reaction. The initial state is i and the final state
is J, with the final state at a higher temperature than the initial
state. The solid line in the figure shows a representation of the
"actual" process.
To see how we would arrive at the final completion state the
dashed lines break the state of reaction change into two parts.
Process (1) is reaction at constant T and P. To carry out such a
process, we would need to extract heat. Suppose the total amount
of heat extracted per unit mass ~ q I' The relation between the
enthalpy changes in Process (1 ) is
h2  hi  qi = (hj )unit mass'
where q J is the "heat of reaction."
For Process (2), we put this amount back into the products to
raise their temperature to the final level. For this process,
h
f
h2 =ql>
or, if we can approximate the specific heat as constant (using some
appropriate average value)
c
p
, avg (T
1
 T
2
) = qI'
245 Enthalpy Generating Heat
For the overall process there is no work done and no heat
exchanged so that the difference in enthalpy between initial and
final states is zero:
I1h\  I1h2 = iVladiabatic = o.
The temperature change during this second process is
therefore given by (approximately)
CTf  T
2
) = ~ = 1 Chj )unit mass I.
C
p
, avg Cp, avg
The value of the adiabatic flame temperature given in
Equation is for 100% completion of the reaction. In reality, as the
temperature increases, the tendency is for the degree of reaction
to be less than 100%. For the combustion of hydrogen and oxygen,
at high temperatures the combustion product (water) dissociates
back into the simpler elemental reactants. The degree of reaction
is thus itself a function of temperature that needs to be computed.
We used this idea in discussing the stoichiometric ramjet,
when we said that the maximum temperature was independent of
flight Mach number and hence of inlet stagnation temperature. It
is also to be emphasized that the idea of a constant (average)
specific heat, c
p
, a v ~ ' is for illustration and not inherently part of
the definition of adiabatic flame temperature.
An example computation of adiabatic flame temperature is
furnished by the combustion of liquid octane at 25°C with 400%
theoretical air. The reaction is
C
S
H
1S
(l) + 12.502 + 12.5(3.76N
2
) + 3[12.502 + 12.5(3.76N
2
)]
~ 8C0
2
+ 9H
2
0 (g) + 37.502 + 188N
2
.
For an adiabatic process
In;(hj +t:.h); = IncChj + tiE )c·
R P At adiabatic
flame temp.:rature
We can again think of the general process in steps:
• Bring reactants to 25°C [the term (1111)] from the initial
temperature, using whatever heat transfer, q1' is needed.
In this example we do not need step (i) because we are
already at the reference temperature.
Heat and Thermodynamics 246
• Reaction at 25°C [the term (hi )reactants +products]. There
will be some heat transfer in this step, qa' out of the
combustor.
• Put back heat qa + qb into the products of combustion.
The resulting temperature is the adiabatic flame
temperature.
In the present case Equation is, explicitly:
(hi )CgHlg(l) = 8(h
l
)C0
2
+ 9( hi )H
2
0 + + 9Ail H
2
0 +
37.5 +
We can examine the terms in the SFEE separately, starting
with the heat of formation terms, and keeping track of units:
by:
o 0 0 0
hf: 8(ll
f
) CO
2
+ 9(h
f
) H
2
0 (h
f
) CgH
lg
(f)
= 8 kmole (393,522 kJ/kmole) + 9 kmole (241,827 3
kJ/kmole)
1 kmole (249,952 kJ/kmole)
 5.075· 10
6
kJ.
The exit state at the adiabatic flame temperature is specified
,, 6
L..JncMc=5.075xI0 kJ.
p
We find the adiabatic flame temperature in three ways:
• an approximate solution using an average value of c
p
'
• a more accurate one using the tabulated evolution of c
p
with temperature,
Approximate Solution Using "Average" Values of
Specific Heat
We can use the values at 500 K as representative. These are:
Gas c
p
(kJ/mole)
CO
2
45
H
2
0 35
02 30
N2 30
Using M
247 Enthalpy Generating Heat
= (C
p
) CO
2
+9 (c
p
) H
2
0 + 37.5
p
(C
p
) 02 + 188 (c
p
)N
2
},
where = T
final
 25°C = T
final
 298 K.
= kJ/K,
p
and using the exit state calculated above, find that
= 682 K => T
final
= 980 K.
Solution for adiabatic flame temperature using
evolutions of specific heats with temperature
Tables give the following evolutions of specific heats with
temperature:
Gas Evolution of C p.JR with T (kJ/kmol)
C0
2
2.401 + (8.735 x 10
3
)T  (6.607 x 10{)T2 +
(2.002 x 10
9
)T3
H
2
0, 4.070  (1.108 x 10
3
)T + (4.152 x 10{)T2
(2.964 x 1O
9
)T3 + (0.156 x 1O
12
)T4
°
2
,3.626  (1.878 x 1O
3
)T+ (7.055 x 10{)T2
 (6.764 x 10
9
)T3 + (2.156 x 10
12
)]'1
N
2
, 3.675  (1.208 x 10
3
)T+ (2.324 x 10{)T2 3
 (0.632 x 10
9
)T3 + (0.226 x 10
12
)]'1
Using
rTf inK
= J.z98 C p (T)dT
and the same equation as above, we obtain
T
f
= 899 K.
Solution for adiabatic flame temperature using
tabulated values for gas enthalpy
  
T= 28,04121,92419,24618,221 kJ/kmole
T= 33,40525,97822,70721,460 kJ/kmole
Heat and Thermodynamics 248
Plugging in the numbers shows the answer is between these
two conditions. Linearly interpolating gives a value of
Tfinal = 962 K.
REFERENCES
• Introductory Statistical Mechanics, R. Bowley and M.
Sanchez
• Thermodynamics In Materials Science by Robert T.
Dehoff.
• The Cluster Expansion, W. J. Mullin
The Language of Science by Sidney B. Cahn.
• Course in Thermodynamics . Revised Printing.
Volume II. (Series in Thermal and Fluids Engineering)
by Joseph Kestin
12 ________________________ _
Isolated Paramagnets
MICROCANONICAL ENSEMBLE
OF ISOLATED PARAMAGNET
The mobile electrons in a semiconductor, carrying
electrical charge under any applied voltage, are the electrons
occupying the energy states of conduction band (E > Ec)' The
counting statistics of conduction band electrons is based on
number of electrons = (number of states) * (probability of
occupancy by an electron).
The number of electron energy states per unit volume over
the energy interval, E  E+dE, is defined as
Number of states = g(E)dE.
Here g(E) is called the density of states (DOS).
Then, an energy state at energy E has a definite probability
to be occupied by an electron given by
Probability of occupancy = f(E).
This probability is the main conclusion of the FermiDirac
statistics and f(E) is called the Fermi distribution function.
Therefore, the number of electrons over the energy
interval, E  E+dE, is found as number of electrons over
E  E + dE = (number of states) * (probability of occupancy)
= g(E)dE * f(E)
Total number of conduction band electrons is found by
integrating this:
n = g(E)f(E)dE
over E = Ec  +infinity.
"
 Heat and Thermodynamics 250
For holes in the valence band (i.e., the unoccupied states in
VB),
number of holes over E  E+dE = (number of states) *
(probability of vacancy)
= g(E)dE * [1f(E)]
And the total number of holes,
p = g(E)[If(E)]dE
over E = infinity  Ev.
ARRANGEMENT OF SUBATOMIC PARTICLES IN AN
ATOM
Rutherford's Scattering Experiment:
• Experimental setup: Positively charged particles (alpha)
were focused at a thin (0.00004 cm) sheet of gold foil.
• Expectation: The alpha particles would scatter as they
were deflected by the gold atoms, producing a pattern
similar to spray from a nozzle.
• Observation 1: Most alpha particles passed straight
through the gold foil.
Conclusion: Volume taken up by atoms is mostly empty
space.
• Observation 2: A few alpha particles bounced back
toward the source.
• Conclusion: Particles must have hit something that was
tiny, dense and electrically charged.
Rutherford named the tiny, dense, positively charged
r ~ ~ i o n at the centre of the atom the nucleus.
• Protons and neutrons are found in the nucleus. Electrons
occupy a large region of space around the nucleus
(electron cloud) and are in motion.
• Atomic number: number of protons. Each element has a
different atomic number.
Elements in the periodic table are listed according to
increasing atomic number.
Mass number: total number of protons and neutrons in
nucleus of an atom
251 Isolated Paramagnets
ARRANGEMENT OF ELECTRONS IN ATOMS
An element's properties are determined largely by the number
of electrons in its atoms and how these electrons are arranged.
The Bohr Model
• Electrons occupy different energy levels in the space
surrounding an atomic nucleus.
• Electrons under normal circumstances maintain the
lowest possible energy level.
(Ground state or unexcited state)
• Electrons can absorb energy and "jump" to a higher
energy level.
(Excited state)
•
•
•
When returning to the ground state, the electron gives
off energy as a particular blend of colours.
Separating this blend of colours produces an element's
line spectrum (i.e. fingerprint).
The energy difference between levels is specific to a
given element, resulting in a specific colour emission:
Element Colour
K
Ca
Na
lavender
orangered
yellow
Ba green
• The significance of line spectra is that energy can be
given off or absorbed only in definite amounts
(quanta).
• These specific amounts of energy relate to differences
between energy levels:
• Electrons occupy the lowest energy level available
until it is full.
• The reactivity of elements is due to the number of
electrons in the outermost energy level (valence
electrons).
Heat and Thermodynamics 252
• The construction of the periodic table indicates the
number of valence electrons for each element.
ELECTROMAGNETIC RADIATION
All types of radiant energy can be described as waves, with a
specific wavelength (A.) and frequency (v) .
• The speed at which the wave is travelling is equal to
the wavelength times the frequency.
AV= C
• Light corresponds to a portion of the electromagnetic
spectrum, and c represents the speed of light, 3.00 10
8
m/s.
• When passed through a prism, white light can be
separated into a continuous spectrum of colours:
ROYGBIV.
• Frequency and wavelength change with the
progression of colours. Red (A.  710
7
In, V  4.3x 10
14
Hertz), Violet (A. 4xl0
7
m, v 7.5xl0
14
Hertz)
• IHertz=1/s=ls
1
• 1 Angstrom (A) = lX10
10
m
• Light can also be described as composed of particles
called photons, with each photon having a particular
amount (quantum) of energy.
• The energy of a photon of light is given by Planck's
equation:
E = hv or E = hell
• Planck's constant = h = 6.626210
34
Js
• Energy is directly proportional to frequency and
inversely proportional to wavelength.
The red colour in many fireworks is due to the emission of
light from strontium salts.
Calculate the frequency of a photon oflight of wavelength 6.50
103 A. Also calculate the energy in kJ for one mole of these photons.
AV = C E = hv
253 Isolated Paramagnets
In the 19
th
century J. R. Rydberg developed an equation based
on observations showing a relationship between the wavelengths
of the lines in the hydrogen line spectrum.
lit.. = R (lIn
l
2
 1In/)
R = Rydberg constant = 1.097 10
7
m
I
n
l
and n
2
are integers such that n
2
>n
l
Niels Bohr further explained this relationship by suggesting
that n
l
and n
2
represent energy levels where electrons can exist in
the hydrogen atom.
• He assumed that these levels corresponded to
quantized amounts of energy, so that electrons could
only exist at these levels and m t l s ~ absorb or emit a
specific amount of energy to move fo a different level.
• Bohr described these energy levels as circular orbits
around the nucleus.
Calculate the wavelength and energy of a photon of light
needed to promote an electron from the 1 st energy level to the 4th
energy level in a hydrogen atom.
Rydberg's equation and Bohr's model are able to explain the
behaviour of an electron in a one electron species (H atom, He+
ion, etc.), but do not explain more complex species.
• A more accurate explanation of how electrons are
arranged and what types of transitions are possibl.,. is
needed.
• Electrons in atoms behave more like waves than
particles.
Heisenberg Uncertainty Prillciple
It is impossible to determine accurately both the momentum
and the position of an electron simultaneously.
Instead, we can describe the probability of finding an electron
within a specific region, using quantum numbers.
• Atomic orbital: a region of space where there is a high
probability of finding an electron.
• Quantum numbers are used to describe electrons in
possible atomic orbitals.
Heat and Thermodynamics 254
Principal quantum number (n) ... describes the main energy
level in which the electron is found
• Possible values: 11 = 1, 2, 3, 4, etc. with each level
existing further out from the nucleus
Subsidiary quantum number (I) ... describes the shape of
atomic orbital; these shapes are referred to as sublevels
• Possible values within a main energy level:
A. = 0,1,2, ... (n  1)
• Energy level n=1 has 1 sublevel (A. =0)
Energy level n = 2 has 2 sublevels (A. =0, 1)
Energy level n = 3 has 3 sublevels (A. =0, 1, 2)
Energy level n = 4 has 4 sublevels (A. =0, 1, 2, 3)
• Sublevel A. = 0 is a "s" sublevel (spherical)
Sublevel A. = 1 is a "p" sublevel (hour glass)
Sublevel A. = 2 is a "d" sublevel
Sublevel A. = 3 is a "f' sublevel
• Relative arrangement of s sublevels:
Magnetic quantum number (rnA.) ... describes the spatial
orientation of an atomic orbital
• Possible values within a sublevel:
rnA. =  A., ... , 0, ... , A.
• s sublevels have 1 possible orientation (rnA. = 0)
p sublevels have 3 possible orientations (rnA. = 1, 0,
1)
d sublevels have 5 possible orientations (rnA. = 2, 1,
0,1,2)
f sublevels have 7 possiblE: orientations (rnA. = 3, 2,
1, 0, 1, 2, 3)
Spin quantum number (ms) .. , describes the spin of
an electron and the orientation of the magnetic field
produced by the spin.
255 Isolated Paramagnets
• Possible values: ms = 1/2, 1/2
Atomic orbitals can accommodate a maximum of two
electrons, each with opposite spin.
• Electrons in the same orbital with opposite spins are
spinpaired, often called paired.
How many orbitals exist and how many electrons can fit in ...
Level I?
Level2?
Level3?
Level4?
Energy
Level Sublevel Orbitals Electrons
01 s 1 2
n=2 s,p 1+3=4 8
n=3 s, p, d 1+3+5=9 18
n=4 s, p, d, f 1+3+5+7=16 32
The Aufbau principle provides a guideline for the order in
which orbitals fill. It is a general guideline, but several exceptions
occur for specific elements.
Orbitals fill based on their relative energy, with orbitals
increasing in energy as n increases and as ').. increases within a
level n. Orbitals within a sublevel are equal in energy (degenerate).
The usual order of energies is as shown below. Remember,
exceptions to this order do occur.
~
~ 4 f
~ d 5 f
Pauli Exclusion Principle: No two electrons in an atom may
have identical sets of four quantum numbers.
Hund's Rule: Electrons must occupy all orbitals of a given
sublevel before electron pairing begins. These unpaired electrons
have parallel spins.
Heat and Thermodynamics 256
ORBITAL NOTATIONS
•
•
Iden
tity
H
He
Li
Be
B
C
N
0
F
Ne
Note electron configurations and orbital notations
mostly follow the Aufbau principle.
Note exceptions to expected order of filling in Cr and
Cu  halffilled and filled sets of equivalent orbitals
have a special stability.
Noble gases are very unreactive and have
configurations (except He)  often oversimplified as
"a full outer shell"
15 25 2p Electron Simplified
configur configuration
ation
1
J, J, J, J,
151 lSI
1'J.
J, J, J, J, 15
2
ls
2
1'J.
J,
1
J, J, ls
2
2s
1
1'J.
J,
tJ.
J, J, ls
2
2s
2
[He]2s2
tJ.
J,
tJ.
J,
tJ,J,.!
lS22s22pl [He]2s22pl
tJ.
J,
1'J.
J,
11J,.!.
ls22s22p2 [He]2s22p2
tJ.
J,
tJ.
J,
111
ls22s22p3 [He]2s22p3
tJ.
J,
tJ.
J,
tJ. 11
ls22s22p4 [He]2s22p4
tJ.
J,
tJ.
J,
tJ.tJ.1.
ls22s22pS
[He]2s22p5
tJ.
J,
tJ.
J,
tJ.tJ. tJ.
ls
2
2s22p6 [He]2s22p6
There is a direct correlation between electron arrangement
and arrangement of elements in the periodic table.
• The main group elements contain elements in which
s and p orbitals are being filled.
•
For the main group elements, the element IS position
in the periodic table can be used to determine the
number of valence electrons the element has.
• The transition and inner transition metals contain
elements in which the highest s level contains 1 or 2
electrons and the d and f orbitals are being filled.
PARAMAGNETISM AND DIAMAGNETISM
•
Substances that contain unpaired electrons are
paramagnetic (weakly attracted into a magnetic field).
257 Isolated Paramagnets
• Substances that have all electrons paired are
diamagnetic (very weakly repelled by a magnetic
field).
• Which of the following would be paramagnetic  Mg,
5, Br, Au, Zn?
TRENDS IN THE PERIODIC TABLE
Chemical Properties
Elements with the same number of valence electrons have
similar chemical properties. (Example: Na and K)
Atomic Radius
Increases as we move down in a group because valence
electrons are located at higher energy levels, further from the
nucleus Decreases as we move from left to right in a period.
• Electrons in inner levels screen/ shield electrons in
outer levels so that they "feel" less of the nucleus'
charge  the effective nuclear charge on these electrons
is less than the actual nuclear charge.
• Note: effective nuclear charge = actual nuclear charge
 number of electrons in inner levels
What effective nuclear charge do the valence electrons in
an aluminum atom "feel"?
In a phosphorous atom?
In a sulphur atom?
• As we move from left to right in a group, the effective
nuclear charge increases.
• Increasing effective nuclear charge pulls electrons in
more tightly (closer to the nucleus) resulting in a
smaller atomic radius.
Onization Energy
First ionization energy  amount of energy required to remove
the most loosely bound electron from an isolated gaseous atom
Heat and Thermodynamics 258
•
•
•
•
•
Ex. Ca(g) + 590 kJ ~ Ca+(g) + e
Second ionization energy  amount of energy required
to remove the second electron
Ex. C a + ( ~ ) + 1154 kJ ~ Ca
2
+(g) + e
Second IOnization energy is always larger than first
ionization energy.
Higher ionization energies (IE) relate to more tightly
bound electrons.
Elements, with low IE lose electrons easily to form
cations; elements with high IE gain electrons easily to
form anions.
IE decreases as we move down in a group  most
loosely bound electron is further from nucleus.
IE increases as we move left to right in a period 
effective nuclear charge is increasing and atomic
radius is decreasing.
1
Periodic Table
Increasing IE
• Exception 1  1
st
p electron is easier to remove than
2
nd
s electron because having a filled s sublevel leads
to extra stability (compare Be to B).
• Exception 2  4th P electron is easier to remove than
yd p electron because having a halffilled p sublevel
leads to extra stability (compare N to 0)
Electron Affinity
The amount of energy absorbed when an electron is added
to an isolated gaseous atom.
• CI(g) + e ~ CI_(g) + 349 kJ
EA = 349 kJ / mol
Atoms which release energy when an electron is added have
negative values for EA  indicating that they easily form anions.
General trend in periodic table: EA becomes more negative as we
go up in a group and to the right in a period.
259 Isolated Paramagnets
i ""00'. T.b'.
More negative EA
Exceptions occur as noted for ionization energy.
Ionic radius
Ions formed from the loss of electrons are smaller than the
neutral atom; ions fonned from the gain of electrons are larger
than the neutral atom.
• Ex. Lt is smaller than Li because it has emptied the
second level.
• F is large: than F because it has an additional electron
in its electron cloud, causing the cloud to expand as
electrons repel each other.
Isoelectronic species have the same number of
electrons.
• Ex. AI
3
+,Mg
2
+, Na+, Ne, F, 0
2
_, N
3
 all have 10
electrons (2 in 1
st
level and 8 in 2
nd
level)
Sizes within an isoelectronic species vary based on
nuclear charge  as nuclear c!1arge increases, the radius
decreases.
Electronegativity
A measure of the tendency of an atom to attract electrons to
itself when it is chemically combined with another atom
• Elements with high electronegativity values tend to
gain electrons (form anions); elements with low
electronegativity values tend to lose electrons (form
cations)
• When two atoms with similar electronegativity values
combine, they are more likely to share electrons.
• Electronegativity values generally increase from left
to right and from bottom to top on the periodic table.
Heat and Thermodynamics 260
i
Periodic Table
""""'
Electonegativity
STIRLING'S APPROXIMATION
The ratio of (1n n!) to (n In n  n) approaches unity as n
increases.
In mathematics, Stirling's approximation (or Stirling's
formula) is an approximation for large factorials. It is named in
honour of James Stirling.
10
5
Inx!
xlnx·x 
1 0.
'
'3 ..L,I
105
10 10 10 10 10
The formula is written as
nil
n! .J27rn.
e"
Roughly, this means that these quantities approximate each
other for all sufficiently large integers n. More precisely, Stirling's
formula says that
261 Isolated Paramagnets
                                    ~  
or
n ,
hm ~ = r;:;2
n ~ o o n I " L.7r .
n "n
DERIVATION
The formula, together with precise estimates of its error, can
be derived as follows. Instead of approximating n!, one considers
the natural logarithm:
1n(n!)=1n1 +1n2+···+1nn.
Then, we can apply the EulerMaclaurin formula by puttingj{x)
= In(x) to find an approximation of the value ofln(n!).
Inn III B(1)k( 1 )
In(n1)!=nInnn+1++ I k J;:l1 +R
2 k=2 k(k1) n
where Bk is Bernoulli number and R is the remainder of the
EulerMaclaurin formula.
We can then take limits on both sides,
lim Inn!nInn+n =1+" k  +lim R.
(
Inn) III B ( l)k
HOO 2 ~ k(k1) HOO
Let the above limit be y and compound the above two formula,
we get the approximation formula in its logarithmic form:
In n! = n +  Inn  n + y + I k  k\ + 0 ;;
(
1) III B (1/ ( 1 )
2 k=2 k(kl) n
where O(j(n)) is BigO notation.
Just take the exponential on both sides, and choose any
positive integer m, say 1. We get the formula with an unknown
term ey:
The unknown term eY can be found by taking the limit on
both sides as n tends to infinity and using Wallis' product. One
can approximate the value of eY by .J27r . Therefore, we get
Stirling's formula:
Heat and Thermodynamics 262
The formula may also be obtained by repeated !ntegration by
parts, and the leading term can be found through the method of
steepest descent. The general formula (without the n1/2 term) may
be quickly obtained by approximating the sum
N
In N!= LInn
I
with an integral:
N N
L Inn ~ I In n dn = N In N  N + 1.
11=1
SPEED OF CONVERGENCE AND ERROR ESTIMATES
More precisely,
with
1 1
<A <
12n+1 n 12n
Stirling's formula is in fact the first approximation to the
following se.ies (now called the Stirling series):
n! = ~ 2 1 r n ( : J
(
1 + _1_ + _1=
12n 288n
2
139
51840n
3
571 )
2488320n
4
+ ... .
As n ~ 00 , the error in the truncated series is asymptotically
equal to the first omitted term. This is an example of an asymptotic
expansion.
The asymptotic expansion of the logarithm is also called
Stirling's series:
263
1
Inn! = nInn  n +  In (27rn )
2
Isolated Faramagnets
1 1 1 1
++  +
12n 360n
3
1260n
5
1680n
7
.,.
In this case, it is known that the error in truncating the series
is always ofthe same sign and at most the same magnitude as the
first omitted term.
STIRLING'S FORMULA FOR THE GAMMA FUNCTION
Stirling's formula may also be applied to the Gamma function
i(z + 1) = I1(z) = z!
defined for all complex numbers other than nonpositive
integers. If iRe z) > 0 then
t
Ini(Z)=(X.!.)Inzz+ In27r +2 r arctan; dt.
2 2 exp(x7rt)1
Repeated integration by parts gives the asymptotic expansion
Ini(z) =(X.!.)Inzz+ In27r + f B
2n
2,,\
2 2 ,,=\ 2n(2n 1)z
where Bn is the nth Bernoulli number. The formula is valid
for z large enough in absolute value when larg zl < 7r  & , where
E is positive, with an error term of O(z_m
1I2
) when the first m
terms are used. The corresponding approximation may now be
written:
A CONVERGENT VERSION OF STIRLING'S FORMULA
Thomas Bayes showed, that Stirling's formula did not give a
convergent series.
Obtaining a convergent version of Stirling's formula entails
evaluating
Heat and Thennodynamics 264
t
2 arctan  ( 1 ) 1
r z dt =In r(z) z Inz+zIn(27i).
exp(2m) 1 2 2
One way to do this is by means of a convergent series of
inverted rising exponentials. If, Zii = z(z + 1) ... (z + n 1), then
t
2 arctan  co
r z d L c
n
exp(2m)1 t= n=! (z+1y
where
Cn = : ! xn ( x  dx
From this we obtain a version of Stirling's series
In r(z)=(z.!..)Inzz+ In27i + 1
2 2 12(z+1)
1 59
+ +
12(z + 1)(z + 2) 360(z + 1)(z + 2)(z + 3)
29
+ + ...
90( z + 1)( z + 2)( z + 3)( z + 4 )
which converges when 9l(Z) > 0 ..
A VERSION SUITABLE FOR CALCULATORS
The approximation
(z . 1 1)Z
  zsmh+ ,
z e z 81Oz
6
or equivalently,
2 Inr(z) In(27i)  In z
+z(2Inz + In(zSinh.!..+1_
6
)2J,
z 810z
can be obtained by rearranging Stirling's extended formula
and observing a coincidence between the resultant power series
and the Taylor series expansion of the hyperbolic sine function.
265 Isolated Paramagnets
This approximation is good to more than 8 decimal digits for z
with a real part greater than 8. Robert H. Windschitl suggested it
in 2002 for computing the Gamma function with fair accuracy on
calculators with limited programme or register memory.
Gergq>Nemes proposed in 2007 an approximation which gives
the same number of exact digits as the Windschitl approximation
but is much simpler:
Jl
lOz )
or equivalently,
Inrcz)  Inz) + Z[In[z + 1 1 J 1].
12z
10z
The formula was first discovered by Abraham de Moivre in
the form
n!' [constant ].n"+1I2
e
,,.
Stirling's contribution consisted of showing that the constant
is ..j2; . The more precise versions are due to Jacques Binet.
The "firstorder" version of Stirling's approximation, n! nn,
was used by Max Planck in his 1901 article on the black body
radiation formula. It linked Planck's concept of energy elements
to the black body radiation formula for very large numbers of
energy elements and oscillators. The approximation was often used
in quantum theory, for example by Debye and de Broglie. Einstein
and Bose took a different approach. For very large n, the graph of
the probability expression Planck obtained using the "first order"
Stirling's formula, plotted in a logarithmic coordinate system, is
almost parallel to the line obtained direct from the idea of separated
light quanta.
Heat and Thermodynamics
266
However, the system entropy calculated by using the "first
order" approximation is different and the ratio gets strongly
nonlinear for small n. One can only speculate that a similar total
effect on entropy could be obtained by introducing the uncertainty
principle and the photon spin as well as other quantities which
were unknown at the time when the old quantum theory was
created. Unfortunately, the experimental verification of the link
between the "first order" Stirling's approximation and modern
physical theories is still missing.
SUBSYSTEM AND TEMPERATURE
OF ISOLATED PARAMAGNET
BETA AND THE TEMPERATURE
A negative temperature coefficient (NTC) thermistor is a two
terminal solid state electronic component that exhibits a large,
predictable change in resistance corresponding to changes in
absolute body temperature. This change in body t.:mperature of
the thermistor can be brought about either externally via a change
in ambient temperature or internally by heat resulting from current
passing through the device or by a combination of these effects.
NTC thermistors are manufactured using metallic oxides of
manganese, nickel, cobalt, copper, iron and other metals. They
are fabricated using a mixture of two or more metallic oxides and
a binder material and are then p r e ~ s e d into the desired
configuration.
The resulting material is then sintered at elevated
temperatures. By varying the types of oxides, the sintering time
and temperature as well as the atmosphere, a wide variety of curves
and resistance values can be manufactured.
Thermistor Terminology
Thermistors exhibit a large negative change in resistance with
respect to temperature, on the order of 3%/C to 6%/IC at 25IC.
This relationship between resistanre and temperature follows an
approximately exponentialtype curve. A few parameters will help
to describe the curve and how it changes over temperature.
267
NTC Thermistor

Isolated Paramagnets
Sft.PTC

50 25 +150
Temperature("C)
Fig. Resistance vs Temperature Graph
Resistance at 2S'IC (R
2S
)
The most common temperature used to measure the thermistor
resistance and the one temperature that is most often used to
reference the resistance value of the thermistor is 25IC. ForNTC
thermistors, this value can vary from less than 100 to greater than
IMeg.
The value at 25IC is normally measured in a temperature
controlled bath where very low power is used to measure the
resistance value. When a resistance value for a thermistor is
mentioned, it is the value at 25IC that is usually being used.
Temperature Coefficient of Resistance (a)
One way to describe the curve of an NTC thermistor is to
measure the slope of the resistance versus temperature (RlT) curve
at one temperature. By definition, the coefficient of resistance is
given by:
1 * dR
a= 
R dT
where:
• T = Temperature in OC or K
• R = Resistance at Temp T
The temperature coefficient is expressed in ohms/ohmsfIC
or more commonly %fIC.
The steepest portion of the NTC curve is at colder
temperatures. Depending upon the type of NTC material, the
Heat and Thennodynamics 268
temperature coefficient at 40'IC can be as high as 8%!IC. The
flattest portion of the curve occurs at higher temperatures where,
at temperatures of 300'1C, a can be less than I %!IC.
The temperature coefficient is one method that can be used
to compare the relative steepness ofNTC curves. It is important
that the temperature coefficient be compared at the same
temperature because, as was noted previously, a varies widely over
the opt:rating temperature range.
Resistance Ratio (Slope)
The resistance ratio, or slope, for thermistors is defined as
the ratio of resistance at one temperature to the resistance at a
second higher temperature. The resistance ratio is one method of
describing the NTC curve. It is sometime used to compare the
relative steepness of two curves. There is no industry standard
for the two temperatures that are used to calculate the ratio,
although some common temperature ranges are:
R@O°C R@25°C R@25°C
R@50°C R@50°C R@85°C
• The value obtained by taking the resistance ratio at different
temperatures will vary greatly depending upon the temperatures
used.
Therefore, resistance ratios cannot be used to compare
thermistor curves unless the same temperature ranges are used.
For ATP Curve "Z", the following ratios are obtained:
Beta Value (p)
R@O°C 3.265 = 9.07
R@50°C 0.3601
R@25°C 1.000 = 2.78
R@50°C 0.3601
R@25°C 1.000 = 9.34
R@85°C 0.1071
A simple approximation for the reh:tionship between the
resistance and temperature for a NTC thermistor is to use an
269 Isolated Paramagnets
exponential approximation between the two. This approximation
is based on simple curve fitting to experimental data and uses two
points on a curve to determine the value of. The equation relating
resistance to temperature using is:
R = A e ( ~ f f )
Where:
R = thermistor resistance at temp T
A = constant of equation
[3 = Beta, the material constant
T = Thermistor temperature (K)
To calculate Beta for any given temperature range, the
following formula applies:
p =(T..k*I; J1n!i
T2 T.. R2
[3 can be used to compare the relative steepness of NTC
thermistor curves. However, as with resistance ratios, the value
of [3 will vary depending upon the temperatures used to calculate
the value, although not to the extent that resistance ratio does.
For example, to calculate [3 for the temperature range of OlC to
50'IC for ATP curve "Z":
T1 = O'IC + 273.15IC = 273.15K
T2 = 50"IC + 273.15IC = 323.15K
R
J
= 3.265
~ = 0.3601
This value of [3 would be referenced as [3O"IC/50lC. Using
other temperatures to calculate b for curve "Z" would yield the
following results:
~ 25ICI501C = 3936K
~ 25IC/85IC = 3976K
As we can see, it is important to know what temperatures
were used to calculatp. the value of [3 before it is used to compare
thermistor curves. b can be used to calculate the resistance of the
curve at other temperatures within the range that b was calculated
once the constant A is determined. However, the accuracy of this
equation is only approximately ±OSIC over a 50"IC span.
Heat and Thermodynamics 270
SteinhartHart Thermistor Equation
The SteinhartHart equation is an emperically derived
polynomial formula which best represents the resistance versus
temperature relationship ofNTC thermistors. The SteinhartHart
equation is the best method used to describe the RvT relationship
and is accurate over a much wider range of temperature than is.
To solve for temperature when resistance is known, yields the
following form of the equation:
liT = a + b(LnR) + c(LnR)3
Where:
T = temperature in Kelvins (K = 'IC + 273.15)
a, band c are equation constants
R = resistance in n at temp T
To solve for resistance when the temperature is known, the
form of the equation is:
Where:
[
I
x x
3
'l'0lhl X x
3
'l'Olh'J
R = e "2+4+27 + 1"24+27
1
1
x = aliT
C
b
If/=
C
The a, band c constants can be calculated for either a
thermistor material or for individual values of thermistors within
a material type. To solve for the constants, three sets of data must
be used. Normally, for a temperature range, values at the low end,
middle and high end are used to calculate the constants. This will
ensure the best fit for the equation over the range. Using the
SteinhartHart equation allows for an accuracy as good as
±o.oonc over a IOO'IC temperature span.
THERMISTOR TOLERANCE AND TEMPERATURE
ACCURACY
There are two factors to consider when discussing thermistors
and their ability to measure temperature. The first is resistance
tolerance and this is defined as the amount of resistance that any
part will vary from its nominal value. The tolerance on the
resistance at any temperature is the sum of:
271 Isolated Paramagnets
• The closest tolerance at any specified temperature
• The additional tolerance due to deviation from the
nominal curve for the material
In any application where the thermistor is to be used to
measure temperature it is more appropriate to discuss the
temperature accuracy for the device. The accuracy can be
calculated if the resistance tolerance and ex are known.
There are two generally accepted methods of describing the
tolerance or accuracy of a thermistor. The first is point matched.
This describes a thermistor that has its tightest resistance tolerance
at one temperature, the reference temperature, which is normally
25IC. At temperatures below and above the reference temperature
the resistance tolerance will become larger due to the uncertainty
in the material curve. The other type of thermistor tolerance is
known as curve matched or interchangeable. These thermistors
are normally defined to have a certain accuracy over a range,
typically ±O.2'IC from OlC to 70'IC.
A simple equation is used to describe the relationship between
resistance tolerance and temperature accuracy. When one is known
the other can be calculated.
ResTol
Accy = or ResTol=Accyea
a
For example, for ATP part number Al 004Z2, the resistance
tolerance is ±2% @ 25IC. Looking at the data for curve "Z" shows
that the a at 25IC is 4.4 %!IC. Therefore, the accuracy at 25'IC
can be calculated to be (±2% / 4.4%!IC) = ±0.45IC.
Similarly, for ATP part number AI004ZC3, the temperature
accuracy is expressed as ±O.2'IC from OlC to 70'IC. To calculate
the resistance tolerance at 25IC divide the temperature accuracy
at the temperature by the a at that temperature. For 25IC, the
resistance tolerance would be (±O.2'IC * 4.4%!IC) = ±O.88%.
In the data section for NTC thermistors, A TP also provides
the curve deviation for parts that are point matched at 25IC. Using
this information and the value of, allows for the temperature
accuracy to be calculated at any temperature. For example for
curve "Z" at 50lC for A TP part number A I 004Z2, the resistance
Heat and Thermodynamics 272
tolerance at 2S'IC is ±2%. The deviation due to the curve
uncertainty is listed as ±1.2%. Therefore, the total resistance
tolerance would be:
(±2%) + (±1.2%) = ± 3.2% @ SO'IC
The at SCJIe for this material is listed as 3.8%!IC. Therefore,
to calculate the temperature accuracy at SOlC for Al004Z2:
(±3.2%) / (3.8%!IC) = ±O.84'IC
The a at SCJIC for this material is listed as 3.8%!IC.
NTC Thermistor Selfheated Parameters
Selfheating occurs in a thermistor when current passing
through the device is such that the internal heat generated is
sufficient to raise the thermistor body temperature above that of
its environment.
For temperature sensing applications, it is not desirable to
selfheat the thermistor to any extent. Other NTC thermistor
applications utilize the self heated characteristics inherent to the
parts. The ability of a thermistor to dissipate power is a function
of the size of the part, its geometry, lead material and size, method
of mounting and any other factor that would contribute to the
ability of the part to dissipate heat.
Dissipation Factor (t5)
The dissipation factor, 8, defines the relationship between
the applied wattage and the thermistor self heating in ternlS of
temperature rise. This relationship is defined as follows:
where:
o = ~
/).T
P = power dissipated in watts
~ T = the rise in temperature (lC )
The dissipation factor (8) is expressed in units ofmW!IC. A
particular value of 8 will con'espond to the amount of power
necessary to raise the body temperature of the thermistor by nco
Because the dissipation factor, 8, is dependent upon a number of
factors, the values listed in the data sheets are for reference only.
273 Isolated Paramagnets
Time Constant (r)
The thermal time constant for a thermistor is defined as the
time required for a thermistor to change 63.2% of the difference
between the initial temperature of the thermistor and that of its
surroundings when no power is being dissipated by the thermistor.
The value of defines a response time for the thermistor when it
has been subjected to a step change in temperature.
A thermistor that has been in an ambient temperature of 25IC
for a period of time long enough for it to reach equilibrium, is
then moved to an environment where the temperature is 75IC.
The thermistor will not immediately indicate a resistance
corresponding to the new temperature but rather will exponentially
approach the new resistance value. For measurement will
correspond to 63.2% of the temperature span, i.e.
T
t
= 0.632 (7025) = 31.6 + 25 = 56.6IC
Therefore the temperature that the part must reach is 56.6IC.
The resistance of the part at that temperature can be calculated
using the SteinhartHart equation or an approximation can be used.
For example for A TP part number Al 004ZC3, using the equation,
the value at 56.6IC should be 2814
0
, Therefore, to find the value
for, t, we would monitor the res!stance value of the part using a
multimeter or similar instrument.
The part should start at 25IC where the resistmce should be
10,000
0
, The time that the part takes to reach 2814
0
once the
part is moved to the new temperature o05IC will correspond the
value of 't and will have the units of seconds. The factors that
affect t are similar to those that affect 8 and include the mass of
the thermistor, mounting, environment and other factors.
NEGATIVE TEMPERATURE
In physics, certain systems can achieve negative temperatures;
that is, their thermodynamic temperature can be of a negative
quantity. Negative temperatures can be expressed as negative
numbers on the Kelvin scale. Temperatures that are expressed as
negative numbers on the familiar Celsius or Fahrenheit scales are
simply colder than the zero points of those scales. By contrast, a
system with a truly negative temperature is not colder than absolute
Heat and Thermodynamics 274
zero; in fact, temperatures colder than absolute zero are impossible.
Rather, a system with a negative temperature is hotter than the same
system with an infinite temperature.
Heat and Molecular Energy Distribution
Negative temperatures can only exist in a system where there
are a limited number of energy states. As the temperature is increased
on such a system, particles move into higher and higher energy
states, and as the temperature becomes infinite, the number of
particles in the lower energy states and in the higher energy states
becomes equal. (This is a consequence of the definition of
temperature in statistical mechanics for systems with limited states.)
By injecting energy into these systems in the right fashion, it
is possible to create a system in which there are more particles in
the higher energy states than in the lower ones. This situation can
be characterised as having a negative temperature. A substance
with a negative temperature is not colder than absolute zero, but
rather it is hotter than infinite temperature. As Kittel and Kroemer
put it, "The temperature scale from cold to hot runs +0 K, ... , +300
K, ... , +00 K, «) K, ... , 300 K, ... , 0 K."
Generally, temperature as it is felt is defined by the kinetic
energy of atoms (heat). Since there is no upper bound on
momentum of an atom there is no upper bound to the number of
energy states available if enough energy is added, and no way
to get to a negative temperature. However, temperature is more
generally defined by statistical mechanics than just kinetic
energy.
TEMPERATURE AND DISORDER
The distribution of energy among the various translational,
vibrational, rotational, electronic, and nuclear modes of a system
determines the macroscopic temperature. In a "normal" system,
thermal energy is constantly being exchanged between the various
modes.
However, for some cases it is possible to isolate one or more
of the modes. In practice the isolated modes still exchange energy
with the other modes" but the time scale of this exchange is much
275 Isolated Paramagnets
slower than for the exchanges within the isolated mode. One
example is the case of nuclear spins in a strong external magnetic
field. In this case, energy flows fairly rapidly among the spin
states of interacting atoms, but energy transfer between the
nuclear spins and other modes is relatively slow. Since the energy
flow is predominantly within the spin s y ~ t e m , it makes sense to
think of a spin temperature that is distinct from the temperature
due to other modes.
A definition of temperature can be based on the relationship:
T = dqrev
ds
The relationship suggests that a positive temperature
corresponds to the condition where entropy, S, increases as thermal
energy, qrev' is added to the system. This is the "normal" condition
in the macroscopic world and is always the case for the
translational, vibrational, rotational, and nonspin related electronic
and nuclear modes. The reason for this is that there are an infinite
number of these types of modes and adding more heat to the system
increases the number of modes that are energetically accessible,
and thus the entropy.
Nuclear Spins
In the case of electronic and nuclear spin systems there are
only a finite number of modes available, often just two,
corresponding to spin up and spin down. In the absence of a
magnetic field, these spin states are degenerate, meaning that they
correspond to the same energy. When an external magnetic field
is applied, the energy levels are split, since those spin states that
are aligned with the magnetic field will have a different energy
than those that are antiparallel to it.
In the absence of a magnetic field, one would expect such a two
spin system to have roughly halfthe atoms in the spinup state and
half in the spindown state, since this maximizes entropy. Upon
application of a magne:ic field, some of the atoms will tend to align
so as to minimize the energy of the system, thus slightly more atoms
should be in the lowerenergy state (for the purposes of this example
Heat and Thermodynamics 276
we'll assume the spindown state is the lowerenergy state). It is
possible to add energy to the spin system using radio frequency (RF)
techniques. This causes atoms to flip from spindown to spinup.
Since we started with over half the atoms in the spindown
state, initially this drives the system towards a 50/50 mixture, so
the entropy is increasing, corresponding to a positive temperature.
However, at some point more than half of the spins are in the
spinup position. In this case, adding additional energy reduces
the entropy since it moves the system further from a 50/50 mixture.
This reduction in entropy with the addition of energy corresponds
to a negative temperature.
Semiconductor Lasers
This phenomenon can also be observed in many lasing
systems, wherein a large fraction of the system's atoms (for
chemical and gas lasers) or electrons (in semiconductor lasers)
are in excited states. This is referred to as a population inversion.
The Hamiltonian for a single mode of a luminescent radiation
field at frequency v is
H=(hv,u)a.
The density operator in the grand canonical ensemble is
exp(f3H)
 Trexp(f3H)·
For the system to have a ground state, the trace to converge,
and the density operator to be generally meaningful, must be
positive semidefinite. So if hv < J! and H is negative semidefinite,
then must itself be negative, implying a negative temperature ..
Negative Temperature Coefficient
A negative temperature coefficient (NTC) occurs when the
thermal conductivity of a material rises with increasing
temperature, typically in a defined temperature range. For most
materials, the thermal conductivity will decrease with increasing
temperature.
Materials with a negative temperature coefficient have been
used in floor heating since 1971. The negative temperature
277 Isolated Paramagnets
coefficient avoids excessive local heating beneath carpets, bean
bag chairs, mattresses etc., which can damage wooden floors, and
may infrequently cause fires.
Most ceramics exhibit NTC behaviour, which is governed
by an Arrhenius equation over a wide range of temperatures: R =
A exp (BIT) where R = resistance A, B = constants T = absolute
temperature (K) The constant B is related to the energies required
to form and move the charge carriers responsible for electrical
conduction  hence, as the value of B decreases, the material
becomes insulating. Practical and commercial NTC resistors aim
to combine modest resistance with a value ofB that provides good
sensitivity to temperature.
Such is the importance of the B constant value, that it is
possible to characterize NTC thermistors using the B parameter
equation: R = rooeB/T where roo = RO eB/TO RO = resistance at
temperature TO Therefore, many materials that produce acceptable
values of B include materials that have been alloyed or possess
variable cation valence states and thus contain a high natural defect
centre concentration. The ·.ralue of B strongly depends on the
energy required to dissociate the charge carriers that are used for
the electrical conduction from these defect centres.
NTC thermistors are generally manufactured from pressed
die chip of semiconducting material  often a sintered ceramic
oxide  and are based on a conduction model. A semi conductor is
intermediate between an insulator and a conductor, and behaves
as an insulator as low temperatures and becomes more conducting
as temperature increases.
One of the main reasons that semiconductors are so useful
for thermistors is that their electrical properties can be controlled
and enhanced by 'doping' or alloying with impurities  either
elements or compounds.
A common commercially available NTC thermistor material
is MnjO 4 which can be doped with varying amounts ofNiO. Since
the N
j
+ cation has less positive charges than the Mn
3
+ cation so to
maintain charge neutrality a M ~ + is converted to a Mn4+ cation for
each of the substituted Ni
2
+ cations.
Heat and Thermodynamics 278
The electrical conduction is therefore increase by an electron
hopping mechanism between the M ~ + and Mn4+ ions on equivalent
sites in the crystal lattice. It is also possible to dope the Mn
3
0
4
with
other combinations of impurities such as CoO and CuO. Due to these
properties of semiconductors, as the t(;;mperature increases, the
energy ofthe electrons increases due to the increased thermal energy
available and therefore enables them to be promoted to the
conduction band. This results in a greater proportion of electrons
being able to move around and carry charge  the more electrons that
are mobile and can carry charge, the more current a material can
conduct and therefore the resistivity has decreased  hence the NTC
thermistors exhibit a decrease in resistivity with increasing
temperature. This phenomenon is also described by the change in
the temperature coefficient of resistance: ex = (l/R) dR/dT ex = BI
T 3' It is therefore clear thatthe temperature coefficient of resistance
is inversely proportion to the temperature, and decreases when the
temperature. increases.
Negative Temperature Coefficient of Reactivity
In a nuclear reactor, temperature changes can introduce
reaclivity changes. This property is called the "temperature
coefficient of reactivity." In watercooled nuclear reactors, the
predominant reactivity changes are brought about by changl:s in
the temperature of the coolant water. In this case the temperature
coefficient is negative, which means that an increase in coolant
temperature causes a decrease in reactivity, and viceversa. A
reactor with a negative temperature coefficient of reactivity is
therefore inherently selfcontrolling and safe.
NEGATIVE TEMPERATURE MEAN
Under certain conditions, a closed system can be described
by a negative temperature, and, surprisingly, be hotter than the
same system at any positive temperature.
Temperature
To get things started, we need a clear definition of
279 Isolated Paramagnets
"temperature." Actually various kinds of "temperature" appear in
the literature of physics (e.g., kinetic temperature, colour
temperature). The relevant one here is the one from
thermodynamics, in some sense the most fundamental.
Our intuitive notion is that two systems in thermal contact
should exchange no heat, on average, if and only if they are at the
same temperature. Let's call the two systems S 1 and S2. The
combined system, treating S I and S2 together, can be S3. The
important question, consideration of which will lead us LO a useful
quantitative definition of temperature, is "How will the energy of
S3 be distributed between S 1 and S2?"
With a total energy E, S has many possible internal states
(microstates). The atoms ofS3 can share the total energy in many
ways. Let's say there are N different states. Each state corresponds
to a particular division of the total energy in the two subsystems
S 1 and S2. Many microstates can correspond to the same division,
El in SI and E2 in S2.
A simple counting argument tells us that only one particular
division of the energy, will occur with any significant prouability.
It's the one with the overwhelmingly largest number of microstates
for the total system S3. That number, N(El,E2) isjust the product
of the number of states allowed in each subsystem, N(El,E2) =
Nl(EI)*N2(E2), and, since EI + E2 = E, N(El,E2) reaches a
maximum when N 1 *N2 is stationary with respect to variations of
EI and E2 subject to the total energy constraint.
For convenience, physicists prefer to frame the question in
terms of the logarithm of the number of microstates N, and call
this the entropy, S.
We can easily see from the above analysis that two systems are
in equilibrium with one another when (dS/dE)l = (dS/dE)2' i.e., the
rate of change of entropy, S, per unit change in energy, E, must be
the same for both systems. Otherwise, energy will tend to flew from
one subsystem to another as S3 bounces randomly from one
microstate to another, the total energy E3 being constant, as the
combined system mov';s towards a state of maximal total entropy.
Heat and Thermodynamics 280
We define the temperature, T, by liT == dS/dE, so thatthe equilibrium
condition becomes the very simple T 1 = T 2'
This statistical mechanical definition of temperature does in
fact correspond to our intuitive notion of temperature for most
systems. So long as dS/dE is always positive, T is always positive.
For common situations, like a collection of free particles, or
particles in a harmonic oscillator potential, adding energy always
increases the number of available microstates, increasingly faster
with increasing total energy.
So temperature increases with increasing energy, from z ~ r o ,
asymptotically approaching positive infinity as the energy
increases.
Negative Temperature
Not all systems have the property that the entropy increases
monotonically with energy. In some cases, as energy is added to
the system, the number of available microstates, or configurations,
actually decreases for some range of energies. Imagine an ideal
"spinsystem", a set ofN atoms with spin 112 on a onedimensional
WIre.
The atoms are not free to move from their positions on the
wire. The only degree of freedom allowed to them is spinflip:
the spin of a given atom can point up or down.
The total energy of the system, iIl"a magnetic field of strength
B, pointing down, is (N+  N)*uB, where u is the magnetic
moment of each atom and if and N are the number of atoms
with spin up and down respectively. Notice that with this
definition, E is zero when half of the spins are up and half are
down. It is negative when the majority are down and positive when
the majority are up.
The lowest possible energy state, all the spins pointing down,
gives the system a total energy of NuB, and temperature of
absolute zero. There is only one configuration of the system at
this energy, i.e., all the spins must point down. The entropy is the
log of the number of microstates, so ill this case is log( 1) = O. If
we now add a quantum of energy, size uB, to the system, one spin
281 Isolated Paramagnets
is allowed to flip up. There are N possibilities, so the entropy is
10g(N). Ifwe add another quantum of energy, there are a total of
N(N  1)/2 allowable configurations with two spins up. The
entropy is increasing quickly, and the temperature is rising as well.
However, for this system, the entropy does not go on increasing
forever. There is a maximum energy, +NuB, with all spins up. At
this maximal energy, there is again only one microstate, and the
entropy is again zero. Ifwe remove one quantum of energy from
the system, we allow one spin down. At this energy there are N
available microstates. The entropy goes on increasing as the energy
is lowered. In fact the maximal entropy occurs for total energy
zero, i.e., half of the spins up, half down.
So we have created a system where, as we add more and more
energy, temperature starts off positive, approaches positive infinity
as maximum entropy is approached, with half of all spins up. After
that, the temperature becomes negative infinite, coming down in
magnitude toward zero, but always negative, as the energy
increases toward maximum. When the system has negative
temperature, it is hotter than when it is has positive temperature.
If we take two copies of the system, one with positive and one
with negative temperature, and put them in thermal contact, heat
will flow from the negativetemperature system into the positive
temperature system.
Atoms always have other degrees of freedom in addition to
spin, usually making the total energy of the system unbounded
upward due to the translational degrees of freedom that the atom
has. Thus, only certain degrees of freedom of a particle can have
negative temperature.
It makes sense to define the "spintemperature" of a collection
of atoms, so long as one condition is met: the coupling between
the atomic spins and the other degrees of freedom is sufficiently
weak, and the coupling between atomic spins sufficiently strong,
that the timescale for energy to flow from the spins into other
degrees of freedom is very large compared to the timescale for
thermalization of the spins among themselves. Then it makes sense
to talk about the temperature of the spins separately from the
Heat and Thermodynamics 282
temperature of the atoms as a whole. This condition can easily be
met for the case of nuclear spins in a strong external magnetic
field.
Nuclear and electron spin systems can be promoted to
negative temperatures by suitable radio frequency techniques.
Various experiments in the calorimetry of negative temperatures,
as well as applications of negative temperature systems as RF
amplifiers, etc., and the rderences therein.
IS A NEGATIVE KELVIN TEMPERATURE POSSIBLE?
Thermodynamics is older than the atomistic view of matter,
hence thermodynamic quantities such as temperature are not
defined atomistically. The definition of temperature allows
negative absolute temperatures. But do such temperature have any
empirical meaning? While this might be questionable, it is certainly
interesting to discuss it because it helps understand the concept
of temperature. As follows, a simplified statistical concept of
temperature is discussed and used to explain the state of matter in
lasers as well as the technique to attain very low temperature
(adiabatic demagnetization).
The most often given answer to this question is something
like "no, because at zero K, molecules are not moving anymore
and we cannot have less than zero motion."
This answer, while not completely wrong, ignores that
temperature is not defined as motion of molecules. It is, for certain
systems, equal to the mean kinetic energy of molecules, but this
is an equality, not a definition. Temperature is usually taken as
simple, because we all can feel it. But have we ever tought of
explaining it to an alien who does not feel it? It would be very
difficult. Entropy, for instance, is much simpler, yet seems
difficult, probably because we cannot feel it. What is correct in
the abovecited answer is t h ~ t negative Kelvin temperature cannot
be achieved by cooling; moreover, not even zero K can be achieved
by cooling, as we probably know. Let's have a closer look at that
equality between temperature and mean kinetic energy of
molecules, and see what we can get out of this.
283 Isolated Paramagnets
Statistical Model
In a gas made of tiny hard billard balls temperature is
proportional to mean kinetic energy of the particles. But certainly,
nobody expects all molecules to have the same speed. The image
(Maxwellian distribution) shows the distribution of molecular
speeds for three different temperatures.
speed
Maxwellian distribution of particle speeds
The Maxwellian distribution of molecular speeds for three
different temperatures.
Eyen at. low temperature, there is a small fraction of molecules
having high speed. This fraction increases with temperature, while
the fracition of molecules with low speed becomes smaller but
does not vanish.
Obviously, the distribution of molecular speeds depends on
temperature. Conversely, temperature is determined by the ratio
of the number of molecules at high speed to the nUr.1ber of
molecules at low speed. A model can help us understand this
relationship.
To keep things simple, a system is assumed that can have but
two levels of energy, E(hi) and E(lo): the particles either have
energy or they have not.
When the system is heated, energy is transferred to it; the
particles must somehow accomodate this energy. In this model,
this can only happen if some change from a low to a high energy
state.
o
Heat and Thermodynamics 284
What is the number of particles that will be on the ith energy
level? The answer is given by the Boltzmann distribution:
N(i) = C*exp (E(i)/kT),
where
C a constant (at a given temperature)
N(i) the number of particles with energy E(i)
E(i) is the energy portion, according to our simplifying
assumption it is either nought or it is something
k the Boltzmann constant
T absolute temperature
For only two levels of energy the ratio of the population of
these levels is:
N(hi)/N(lo) = exp (DeltaE/kT)
where
" DeltaE = E(hi)E(lo)
Solving this equation for T
 DeltaE/k
T = In [N(hi)/N(lo)]
HEATING AND COOLING
If heat is added, more and more particles change from the
low energy level to the high energy level (note that the levels
themselves are unchanged); the number of particle with high
energy, N(hi), grows and N(lo) decreases so the logarithm becomes
less negative and temperature rises. The energy of the whole
ensemble rises because now there are more particles on the high
energy level. Try calculating the temperature for the system shown
in picture (two level model), but one particle changed his place
from low to high level.
On the other hand, if energy is withdrawn from a body, E(lo),
the low energy level, is populated at the cost of E(hi). The value
of the logarithlil becomes more and more negative
l
lim Mlk J e
N(hi) >() N(hl') =
N(IO) In['
N(lo)J
285
Isolated Paramagnets
and temperature goes towards zero. Also, from the expression can
be concluded that it must be difficult to reach absolute zero, as a
diagram of the logarithm versus the ratio shows.
INFINITE TEMPERATURE
System At infitine Temperature
At equally populated levels, temperature, but not the energy,
of a system is infinite
If both levels are equally populated, N(hi) = N(lo) and the
logarithm vanishes, so that
lim
N(hi)+N(lo)
/illlk
In[N(hi)]
N(lo)
=00
The value of the temperature becomes infinite (note that
DeltaE does not change). Since number of particles are always
finite, only an finite amount of energy is needed to get infinite
temperature in this model. Infinite temperature cannot be reached
anyway by heating, although not because of the energy needed,
but because heat flows from high temperature to low temperature.
To heat a body, a hotter body is required.
NEGATIVE ABSOLUTE TEMPERATURE
System at Negative Absolute Temperature
If more particles are at the upper level than at the lower one,
absolute temperature of a system is negative
As soon as the high energy level is populated more that the
low energy one, we have negative absolute temperature. Can such
a state be realised?
Yes, it can, but not by cooling. The formula, as well as the
picture, show that a state of matter to which negative absolute
temperature can be attributed has more energy than the states at
usual temperatures, because more particles are at high energy level
than at low energy level.
Heat and Thermodynamics 286
Thus one has to add energy to get negative absolute
temperature. It has been emphasized that such states cannot be
reached by adding heat to a body.
Systems at Negative Absolute Temperature
Nevertheless, both systems at infinite temperature and at
negative absolute temperature can be prepared. Let us look first
at negative temperature. In most lasers atoms are excited
electronically to a high energy level. Prior to laser light emission
of the whole system, more atoms have to be excited than are not,
and a negative absolute temperature can be ascribed to the system.
Note that, as expected, atoms are not excited by heating.
Systems at Infinite Temperature
Systems at infinite temperature are used to attain the lowest
temperatures possible. The technique is that of adiabatic
demagnetization. To get a rough idea of the subject, let us look at
magnetism due to electron spin. Each electron can be seen as a
tiny magnet, except that it can have only two orientations in an
external magnetic field, namely parallel to the field and antiparallel
to it. Without a field, these "electron magnets" are randomly
oriented. Energy of both states is equal, so it is equally probable
to find each orientation. If an external field is applied, the energy
of the parallel state is lowered and energy of the antiparallel state
goes up.
This phenomenon can be used to cool samples of suitable
materials (specific magnetic properties are required). A sample is
cooled down to the temperature ofliquid helium. Still submerged
in liquid helium, a magnetic field is applied to it. At the very first
moment, the number of atoms in the parallel equals that in the
antiparalle! state. But these states are no more energetically
equivalent in the presence of an external magnetic field.
Our formula says that if two states differ in energy but are
equally populated, then the temperature is infinite. This is an
example for the previously stated assertion that one does not need
infinite energy to get infinite temperature. In fact, the energy of
287 Isolated Paramagnets
the sample does not rise, on the contrary! Because it is at infinite
temperature, the system will now lose energy as anti parallel states
change to parallel. The energy is transferred as heat from the
sample to the helium bath. Its temperature changes from infinity
to that of the helium bath.
Now the sample is insulated from the helium bath and the
external magnetic field is reduced to zero. The energy that was
transferred to the helium bath cannot go back to the sample. Hence
in this step, while the populations of the antiparallel and the
parallel states are gradually equalized, the sample cools down.
This is how some of the lowest available temperatures are attained.
SYSTEMS WITH IV''JRE THAN TWO ENERGY LEVELS
Usual systems have more than two excited states and hence
more than two energy levels. Can these temperatures be attributed
to such systems, too?
Looking at the limits of this two level model may help to
elucidate further the concept of temperature. First, each level must
be populated enough to avoid random fluctuations of particle
number. Keep in mind that the systems are dynamic, particles
exchanging energy continually. So the model fails when there are
only a few particles on each level.
The above given Boltzmann relation holds true for multi Ip.vel
systems, of course. Now we can clarify what it means when it is
said that a system must be in thermal equilibrium:
A system is in thermal equilibrium if particle number on each
energy level follows the Boltzmann distribution.
Random fluctuations cause deviations from this distribution,
but the larger the fluctuation, the less it is probable, so most of
the time the system will be close to that distribution.
For systems with an infinite number of states infinite
temperature would also mean infinite energy. Now the relation
Ekin = 3/ kT
2
At equally populated levels, temperature, but not the energy,
of a system is infinite
Heat and Thermodynamics 288
If both levels are equally populated, N(hi) = N(lo) and
the logarithm vanishes, so that
lim
Mlk
In[N(hi)]
N(lo)
=00
shows that, in contradiction to our conclusions above,
infinite temperature means infinite energy. In fact, the number
of translational states is very large, near infinite. For a system
with a Volume of about 1 cm
3
there are more translational
states than molecules.
Translational states thus cannot be described by the above
model. Free particles that store energy in their translational
motion cannot have negative Kelvin temperature.
If we put negative temperature into the Boltzmann
formula, the function value goes up exponetially. Each energy
ievel must be populated more than its iower neighbour. Of
course it is not possible to keep populating levels like this. It
follows that in system that have inversely populated states,
these states cannot be in thermal equilibrium with all other
states of the same system. Negative absolute temperature is
not an equilibrium quantity.
REFERENCES
• A Guide to Physics: Thermodynamics, Statistical
Physics, and Quantum Mechanics by Gerald D.
Mahan, Boris E. Nadgorny, and Max Dresden.
• DK Science Encyclopedia (Revised Edition) by Susan
McKeever and Manyn Foote.
• Statistical Physics, L. D. Landau and E. M. Lifshitz
• Statistical Mechanics, SK Ma
• Course in Thermodynamics . Revised Printing.
Volume II. (Series in Thermal and Fluids Engineering)
by Joseph Kestin.
13 ______________________ __
Power Cycles with TwoPhase
Media
BEHAVIOUR OF TWOPHASE SYSTEMS
The definition of a phase, as given by SB&VW, is "a quantity
of matter that is homogeneous throughout." Common examples
of systems that contain more than one phase are a liquid and its
vapour and a glass of ice water. A system which has three phases
is a container with ice, water, and water vapour. We wish to find
the relations between phases and the relations that describe the
change of phase (from solid to liquid, or from liquid to vapour)
of a pure substance, including the work done and the heat transfer.
To start we consider a system consisting of a liquid and its vapour
in equilibrium, which are enclosed in a container under a moveable
piston. The system is maintained at constant temperature through
contact with a heat reservoir at temperature, so there can be heat
transfer to or from the system.
Liquid vapor
liquid water
Liquid vapor
Fig. Twophase System in Contact with Constant
Temperature Heat Reservoir
Heat and Thermodynamics 290
emperature
Fig. Relation for a Liquidvapour System
For a pure substance, there is a onetoone correspondence
between the temperature at which vaporization occurs and the
pressure. These values are called the saturation pressure and
saturation temperature. This means there is an additional constraint
for a liquidvapour mixture, in addition to the equation of state.
The consequence is that we only need to specify one variable to
determine the state of the system. Ifwe specify Tthen P is set. In
summary, for two phases in equilibrium, P = peT). Ifboth phases
are present, any quasistatic process at constant T is also at constant
P. Let us examine the pressurevolume behaviour of a liquid
vapour system at constant temperature. For a singlephase ideal
gas we know that the curve would be Pv. For the twophase system
the curve looks quite different.
D
"
J
! . ..........
Vapor
.... :!'""__A
: ..... Liquid salLnliocl cum: B   .. __ /.: curve
\'oIume. V
Fig. Pv Diagram for Twophase System Showing Isotherms
291 Power Cycles with TwoPhase Media
Several featuros{}fthefigme should be noted. First, there is
a region in which liquid and vapour can coexist, bounded by the
liquid saturation curve on the left and the vapour saturation curve
on the right. This is roughly domeshaped and is thus often referred
to as the "vapour dome." Outside of this regime, the equilibrium
state will be a single phase.
The regions of the diagram in which the system will be in
the liquid and vapour phases respectively are indicated. Second
is the steepness of the isotherms in the liquid phase, due to the
small compressibility of most liquids.
Third, the behaviour of isotherms at temperatures below the
"critical point" in the region to the right of the vapour dome
approach those of an ideal gas as the pressure decreases, and the
ideal gas relation is a good approximation in this region.
The behaviour shown is found for all the isotherms that go
through the vapour dome. At a high enough temperature,
specifically at a temperature corresponding to the pressure at the
peak of the vapour dome, there is no transition from liquid to
vapour and the fluid goes continu0usiy from a liquidlike behaviour
to a gastype behaviour.
This behaviour is unfamiliar, mainly because the temperatures
and pressures are not ones that we typically experience; for water
the critical temperature is 374°C and the associated critical
pressure is 220 atmospheres.
There is a distinct nomenclature used for systems with more
than one phase. In this, the terms "vapour" and "gas" seem to be
used interchangeably. In the zone where both liquid and vapour
exist, there are two bounding situations.
When the last trace of vapour condenses, the state becomes
saturated liquid. When the last trace of liquid evaporates the state
becomes saturated vapour (or dry vapour). If we put heat into a
saturated vapour it is referred to as superheated vapour. Nitrogen
at room temperature and pressure (at one atmosphere the
vaporization temperature of nitrogen is 77 K) is a superheated
vapour.
Heat and 1hermodynamics
MIlA
B
1 UP,
0.1 MPa
Saturatedliquid tine
line
Volume
292
D
Fig. Constant Pressure Curves in Tv Coordinates Showing Vapour Dome
Lines of constant pressure in temperaturevolume coordinates.
Inside the vapour dome the constant pressure lines are also lines
of constant temperature. It is useful to describe the situations
encountered as we decrease the pressure or equivalently increase
the specific volume, starting from a high pressure, low specific
volume state.
The behaviour in this region is liquidlike with very little
compressibility. As the pressure is decreased, the volume changes
little until the boundary of the vapour dome is reached. Once this
occurs, however, the pressure is fixed because the temperature is
constant. As the piston is withdrawn, the specific volume increases
through more liquid evaporating and more vapour being produced.
During this process, since the expansion is isothermal (we specified
that it was), heat is transferred to the system.
The specific volume will increase at constant pressure until
the right hand boundary of the vapour dome is reached. At this
point, all the liquid will have been transformed into vapour and
the system again behaves as a singlephase fluid. For water at
temperatures near room temperature, the behaviour would be
essentially that of a perfect gas in this region. To the right of the
vapour dome, as mentioned above, the behaviour is qualitatively
like that of a perfect gas.
293 Power Cycles with TwoPhase Media
Critical Point
M' Saturatedvapor Line
State 01 vapot
in mixture
State 01 vapo r
in Mixture
Liquid + gas
I I
''! v ",
Gas (vapor)
,.
Fig. Specific Volumes at Constant Temperature and States within the
Vapour Dome in a Liquidvapour System
We define notation to be used in what follows. The states IJ
and c denote the conditions at which all the fluid is in the liquid
state and the gaseous state respectively.
The specific volumes corresponding to these states are
v/= specific volume of liquid phase,.
v $ = specific volume of gas phase.
For condihons corresponding to specific volumes between
these two values, i.e_, for state b, the system would exist with part
of the mass in a liquid state and part of the mass in a gaseous
(vapour) state. The average specific volume for this condition is
v = average specific volumeof twophase system
We can relate the average specific volume to the specific
volumes for liquid and vapour and the mass that exists in the two
phases as follows. The total mass of the system is given by
total mass = m = liquid mass + vapour mass = m
f
+ m
g
_
The volume of the system is
Volume of liquid = V
f
= mtf
Volume of liquid = Vg = mgvg
Total volume = V = nlJ'f+ mgv
g
.
The average specific volume, v, is the ratio of the total
volume to the total mass of the system
Heat and Thermodynamics 294
_ mivi +mgvg
v = = average specific volume.
IrII +mg
The fraction of the total mass in the vapour phase is called
quality, and denoted by X:
m
X = m : m = quanlity of a liquidvapour system
I g
In terms of the quality and specific volumes, the average
specific volume can be expressed as v = Xv g + (1  X) vI
ab = v  Vj a
c
= Vg  vI
In reference to Figure,
ab v vI
= = X = quality.
ac Vg vI
Fig. Liquid Vapour Equilibrium in a Twophase Medium
WORK AND HEAT TRANSFER WITH TWOPHASE MEDIA
We examine the work and heat transfer in quasis!atic
processes with twophase systems. For definiteness, consider the
system to be a liquidvapour mixture in a container whose volume
can be varied through movement of a piston. The system is kept
at constant temperature through contact with a heat reservoir at
temperature T.
The pressure is thus also constant, but the volume, V, can
change. For a fixed mass, the volume is proportional to the specific
volume so that point in Figure must move to the left or the right
as V changes. This implies that the amount of mass in each of the
two phases, and hence the quality, also changes because mass is
295 Power Cycles with TwoPhase Media
transferred from one phase to the other. We wish to find the heat
and work transfer associated with the change in mass in each phase.
The change in volume can be related to the changes in mass in
the two phases as,
dV= vgdm
g
+ vlm
f
The system mass is constant (m = m
f
+ mg = constant) so that
for any changes
dm = 0 = dm
f
+ dmg.
We can define the quantity
dm
fg
= dmg =  dm
f
= mass transferred from liquid to vapour.
In terms of dmfg the volume change of the system is
dV= (Vg  vf) dm
fg
.
The work done is given by
dW= PdV= P(v
g
 vf) dm
fg
·
The change in internal energy, !l.U, can be found as follows.
The internal energy of the system can be expressed in terms of
the mass in each phase and the specific internal energy (internal
energy per unit mass, u) of the phase as,
dU= ulm
f
+ ugdm
g
= (u
g
 u
f
) dm
fg
.
Note that the specific internal energy of the twophase system
can be expressed in a similar way as the specific volume in terms
of the quality and the specific internal e"nergy of each phase:
u=Xu
g
+ (IX) u
f
Writing the first law for this process:
dQ=dU+dW
=(u
g
uf)dmfg +P(Vg vf)dmfg
= [(u
g
+Pvg)(uf +Pvf)]dmfg
= (h
g
 h
f
)dm jg"
The heat needed for the transfer of mass is proportional to
the difference in specific enthalpy between vapour and liquid. The
pressure and temperature are constant, so that the specific internal
energy and the specific enthalpy for the liquid phase and the gas
phase are also constant. For a finite change in' mass from liquid to
vapour, mfg' therefore, the quantity of heat needed is
Heat and Thermodynamics 296
Q = (h
g
 h
f
).= Ml (enthalpy change)
The heat needed per unit mass, q, for transformation between
the two phases is
q:JL:(h
g
hf):hfg'
mfg
The notationm h
fg
refers to the specific enthalpy change between
the liquid state and the vapour state. The expression for the amount
of heat needed, q, is a particular case of the general result that in
any reversible process at constant pressure, the heat flowing into,
or out of, the system is equal to the enthalpy change. Heat is
absorbed if the change is from solid to liquid (heat of fusion),
liquid to vapour (heat of vaporization), or solid to vapour (heat of
sublimation).
A numerical example is furnished by the vaporization of water
at 100°C:
• How much heat is needed per unit mass of fluid
vaporized?
• How much work is done per unit mass of fluid
vaporized? .
• What is the change in internal energy per unit mass of
fluid vaporized?
In addressing these questions, we make use of the fact that
problems involving heat and work exchanges in twophase media
are important enough that the values of the specific thermodynamic
properties that characterize these transformations have been
computed for many different working fluids. From these, for
water:
• At 100°C, the vapour pressure is 0.1013 MPa.
• The specific enthalpy of the vapour, h , is 2676 kJ/kg
and the specific enthalpy of the liquid, ~ f is 419 kJ/kg.
• The difference in enthalpy between liquid and vapour,
h
fg
, occurs often enough so that it is tabulated also. This
is 2257 kJ/kg.
• The specific volume of the vapour is 1.6729 m
3
/kgand
the specific volume of the liquid is 0.001044 m
3
/kg.
The heat input to the system is the change in enthalpy between
297
Power Cycles with TwoPhase Media
liquid and vapour, h
f
¥, and is equal to 2.257 x 106 J/kg.
The work done 1S P( v g  vf)which has a value of
P(v
g
 vf) = 0.1013 x 10
6
Pa x [1.629 m
3
/kg]
= 0.169 x 10
6
J/kg.
The change in internal energy per unit mass (u
fg
) can be found
from /).U = q  w or from the tabulated values as 2.088
x
10
6
J/kg.
This is much larger than the work done. Most of the heat input is
used to change the internal energy rather than appearing as work.
THE CARNOT CYCLE AS A TWOPHASE POWER CYCLE
TA"frb
:: ~ ~ ~   ~ ~ ~ _ . " • c
tI. ,e d
. .
. .,
'/ 'I
[cycle In Pv coordinates]
[cycle In Ts coordinates] [cycle in hs coordinates]
Fig. Carnot cycle with twophase medium
A Carnot cycle that uses a twophase fluid as the working
medium. Figure gives the cycle in Pv coordinates, Figure in Ts
coordinates, and Figure in hs coordinates. The boundary of the
region in which there is liquid and vapour both present (the vapour
dome) is also indicated. Note that the form of the cycle is different
in the Ts and hs representation; it is only for a perfect gas with
constant specific heats that cycles in the two coordinate
representations have the same shapes.
The processes in the cycle are as follows:
• Start at state a with saturated liquid (all of mass in liquid
condition). Carry out a reversible isothermal expansion
to b(a ~ b) until all the liquid is vaporized. During this
process a quantity of heat qH per unit mass is received
from the heat source at temperature T
2
•
• Reversible adiabatic (i.e., isentropic) expansion (b ~ c)
lowers the temperature to T\. Generally state will be in
the region where there is both liquid and vapour.
• Isothermal compression (c ~ d) at to T\ state d. During
Heat and Thermodynamics 298
this compression, heat qL per unit mass is rejected to
the source at T
I
.
• Reversible adiabatic (i.e., isentropic) compression
(d a) in which the vapour condenses to liquid and
the state returns to a.
In the Ts diagram the heat received, qH, is abe! and the heat
rejected, qL, is dee! The net work is represented by abed. The
thermal efficiency is given by
11 = w
net
= Area abed = 1 11 .
qH Area abef T2
In the gs diagram, the isentropic processes are vertical lines
as in the Ts diagram. The isotherms in the former, however, are
not horizontal as they are in the latter. To see their shape we note
that for these twophase processes the isotherms are also lines of
constant pressure (isobars), since P = pel). The combined first
and second law is
dp
Tds=dh·
p
For a constant pressure reversible process, dqrev = Tds = dh.
The slope of a constant pressure line in hs coordinates is thus,
(
Oh) = T = constant; slope of constant pressure line for two
os p
phase medium.
The heat received and rejected per unit mass is given in tenns
of the ..," the different states as
qH=hbha
qL = h
d
 hc' (In accord with our convention this is less than
zero.)
The thermal efficiency is
_ w
net
_ qH +qL _ (hb ha)+(h
d
hc)
11  ,
qH qH (hb  h
a
)
or, in terms of the work done during the isentropic compression
and expansion processes, whieh correspond to the shaft work done
on the fluid and received by the fluid,
(hb hc)+(h
a
h
d
)
11= (hbha) ,
299 Power Cycles with TwoPhase Media
Carnot Steam Cycle
• Heat source temperature = 300°C
• Heat sink temperature = 20°C
What is the (i) thermal efficiency and (ii) ratio of turbine work
to compression (pump) work if
• All processes are reversible?
• The turbine and the pump have adiabatic efficiencies of
0.8?
Neglect the changes in kinetic energy at inlet and outlet of
the turbine and pump.
• For the reversible cycle,
T,
llthennal = llCamot = 1  T ~
=1 293K =0.489.
573K
• To find the work in the pump (compression process) or
in the turbine, we need to find the enthalpy changes
between states b and c, t1.h
bc
' and the change between a
and d, t1.h
ad
. To obtain these the approach is to use the
fact that S = constant during the expansion to find the
quality at state and then, knowing the quality, calculate
the enthalpy as h = Xhg + (1  X) hI We know the
conditions at state b, wnere the fluid is all vapour, i.e.,
we know T
b
, h
b
, sb:
hb = hvapor (300°C) = hg (300°C) = 2749 kJ/kg
sb = svapor (300°C) = Sg (300°C) = 5.7045 kJ/kgK.
S b = S c III the isentropic expansion process.
• We now need to find the quality at state c, Xc. Using the
definition of quality, and noting that Sc = X ~ + (1 
Xc)sp we obtain, g
X _ scsf(Tc) _scsf(T
c
)
• c  .
S 8 (Tc)  Sf (Tc ) S fg (Tc )
• The quantity S c is the massweighted entropy at state c,
which is at temperature Tc.
Heat and Thermodynamics
300
• The quantity sJJc)is the entropy of the liquid at
temperature T
c
'
• The quantity sjT) is the entropy of the gas (vapour) at
temperature T
c
'
• The quantity t1s
fg
(Tc) = at Tc'
We know:
Sc = sb = 5.7045 kJ/kgK,
Sfg = 8.3706 kJ/kgK,
The quality at state c is thus,
X = 5.7045  0.2966 = 0.646.
c 8.3706
The enthalpy at state is,
hc = XChg + (1  Xc) hfat Tc·
Substituting the values,
hc = 0.646 x 2538.1 kJ/kg + 0.354 x 83.96 kJ/kg
= 1669.4 kJ/kg.
The turbine work/unit mass is the difference between the
enthalpy at state b and state c,
hb  hc = Wturbine = 2749  1669.4 = 1079.6 kJ/kg.
We can apply a similaT process to find the conditions at state d:
Sd s/(T
d
) Sc s/(T
d
)
Xd = "
sg(Td)s/(T
d
) s/g(T
d
)
We have given that Tc = T
d
. Also sd = sa = sf at 300°C. The
quality at state d is
X = 3.253  0.2966 = 0.353 < X .
d 8.3706 c
The enthalpy at state d is
hd =Xjzg + (IX
d
)h
f
= 0.353 x 2538.1 kJ/kg + 0.647 x 83.96
kJ/kg
= 950.8 kJ/kg.
The work of (pump work) is !1had = hahd.
Substituting the numerical values,
!1had = 1344950.8 = 393.3 kJ/kg.
The ratio of turbine work to compression work (pump work) is
301 Power Cycles with TwoPhase Media
Wturbine
=2.75.
wcompression
We can check the efficiency by computing the ratio of net
work (w
net
= Wturbine  wcompression) to the heat input (T crjg)' Doing
this gives, not surprisingly, the same value as the Carnot equation.
• For a cycle with adiabatic efficiencies of pump and
turbine both equal to 0.8 (nonideal components), the
efficiency and work ratio can be found as follows.
We can find the turbine work using the definition of turbine and
compressor adiabatic efficiencies. The relation between the
enthalpy changes is
w
turbine
= hb  he' = l'lturbine (hb  he) = actual turbine work received.
Substituting the numerical values, the turbine work per unit mass
is 863.7 kJ/k.
For the compression process, we use the definition of
compressor (or pump) adiabatic efficiency:
W . = h ' h = (ha  hd )
compressIOn a d l'lcompression
= actual work to achieve given pressure difference
= 491.6 kJ/kg.
The value of the enthalpy at state is a' 1442.4 kJ/kg. The thermal
efficiency is given by
W
net
wturbine  wcompression
= =
heat input heat input
= (hb he,)(h
a
, h
d
)
(hb h
a
,)
Substituting the numerical values, we obtain for the thermal
efficiency with nonideal components, l'lthermal = 0.285
A question arises as to whether the Carnot cycle can be
practically applied for power generation. The heat absorbed and
the heat rejected both take place at constant temperature and
pressure within the twophase region. These can be closely
approximated by a boiler for the heat addition process and a
condenser for the heat rejection. Further, an efficient turbine can
Heat and Thermodynamics 302
produce a reasonable approach to reversible adiabatic expansion,
because the steam is expanded with only small losses. The
difficulty occurs in the compression part of the cycle.
If compression is carried out slowly, there is equilibrium
between the liquid and the vapour, but the rate of power generation
may be lower than desired and there can be appreciable heat
transfer to the surroundings. Rapid compression will result in the
two phases coming to very different temperatures (the liquid
temperature rises very little during the compression whereas the
vapour phase temperature changes considerably). Equilibrium
between the two phases cannot be maintained and the
approximation of reversibility is not reasonable.
Another circumstance is that in a Carnot cycle all the heat is
added at the same temperature. For high efficiency we need to do
this at a higher temperature than the critical point, so that the heat
addition no longer takes place in the twophase region. Isothermal
heat addition under this circumstance is difficult to accomplish.
Also, if the heat source and the cycle are considered together, the
products of combustion which provide the heat can be cooled only
to the highest temperature of the cycle.
The source will thus be at varying temperature while the
system requires constant temperature heat addition, so there will
be irreversible heat transfer. In summary, the practical application
of the Carnot cycle is limited because of the inefficient
compression process, the low work per cycle, the upper limit on
temperature for operation in the twophase flow regime, and the
irreversibility in the heat transfer from the heat source. We examine
the Rankine cycle, which is much more compatible with the
characteristics of twophase media and available machinery for
carrying out the processes.
THE CLAUSIUSCLAPEYRON EQUATION
Until now we have only considered ideal gases and we would
like to show that the properties u, h, s, etc. are true state variables
and that the I st and 2
nd
laws of thermodynamics hold. when the
working medium is not an ideal gas (i.e. a twophase medium).
An elegant way to do this is to consider a Carnot cycle for a two
303 Power Cycles with TwoPhase Media
phase medium. To state the fact that all Camot engines operated
between two given temperatures have the same efficiency is one
way of stating the 2
nd
law of thermodynamics. The working fluid
need not be an ideal gas and may be a twophase medium changing
phases.
The idea is to run a Camot engine between temperatures T
and T  dT for a twophase medium and to let it undergo a change
in phase. We can then derive an important relation known as the
ClausiusClapeyron equation, which gives the slope of the vapour
pressure curve. We could then measure the vapour pressure curve
for various substances and compare the measured slope to the
ClausiusClapeyron equation. This can then be viewed as an
experimental proof of the general validity of the 1 st and 2
nd
laws
ofthermodynamics!
T p
T
T • efT
v,
Fig. Carnot Cycle Devised to Test the Validity
of the Laws of Thermodynamics
v, v
Consider the infinitesimal Camot cycle abed shown in Figure.
Heat is absorbed between states a and b. To vaporize an arbitrary
amount of mass, , the amount of heat
Q=mh
must be supplied to the system. 'if;om the 1 st and 2
nd
laws of
thermodynamics the thermal efficiency for a Camot cycle can be
written as
W QQR TTR
11= Q = Q =T·
Hence, for the infinitesimal cycle considered above,
dW T(TdT) dT
= =
Q
T T
Heat and Thermodynamics 304
The work along be and da nearly cancel such that the net
work is the difference between the work along ab and cd, and dW
can be viewed as the area enclosed by the rectangle abed:
dW= pm (Vg  Vj)  (P  d
p
) m (Vg  Vj)
= m(vg  vf) d
p
.
Substituting Equations we get
m( v g  v J )dp dT
 . . . ! ! .     = ~  =
mh
Jg
T
Rearranging terms yields the ClausiusClapeyron equation,
which defines the slope of the vapour pressure curve:
dp = hJg
dT T(vgvJ)
The beauty is that we have found a general relation between
experimentally measurable quantities from first principles (1 st and
2
nd
laws of thermodynamics).
In order to plot the ClausiusClapeyron relation and to
compare it against experimentally measured vapour pressure
curves, we need to integrate Equation. To do so, the heat of
vaporization and the specific volumes must be known functions
oftemperature. This is an important problem in physical chemistry
but we shall not pursue it further here except to mention that if
• Variations in heat of vaporization can be neglected,
• The vapour phase is assumed to be an ideal gas, and
• The specific volume of the liquid is small compared to
that or the vapour phase,
i?T
hr. ~ const, v
f
« v ~  ,
Jg g P
the integration can be readily carried out. Making these
approximations, the ClausiusClapeyron equation becomes
dp hfgP dp h
Jg
dT
 ~   ~  ~  
dT T2R P R T
2
·
Carrying out tp,e integration, the resulting expression is
h
Jg
1
lnp = +lnC.
R T .
305 Power Cycles with TwoPhase Media
Note that the vapour pressure curves are straight lines if In p
is plotted versus liT and that the slope of the curves is hj!R,
directly related to the heat of vaporization.
RANKINE POWER CYCLES
Boiler
a
e
W,
Cooling
Water
Fig. Rankine Power Cycle with Twophase Working Fluid
A schematic of the components of a Rankine cycle is shown
in Figure. The cycle is shown on Pv, Ts, and hs coordinates in
Figure. The processes in the Rankine cycle are as follows:
• d ~ e: Cold liquid at initial temperature Tl is pressurized
reversibly to a high pressure by a pump. In this process,
the volume changes slightly.
• e ) a: Reversible constant pressure heating in a boiler
to temperature T
2
.
• a ~ b: Heat added at constant temperature T2 (constant
pressure), with transition of liquid to vapour.
• b ~ c: Isentropic expansion through a turbine. The
quality decreases from unity at point b to Xc < 1.
• c ~ d: Liquidvapour mixture condensed at temperature
Tl by extracting heat.
[Pv coordinates)
[Ts coordinates] [hs coordinates)
Fig. Rankine Cycle Diagram.
Heat and Thermodynamics 306
In the Rankine cycle, the mean temperature at which heat is
supplied is less than the maximum temperature, T
2
, so that the
efficiency is less than that of a Carnot cycle working between the
same maximum and minimum temperatures. The heat absorption
takes place at constant pressure over eab, but only the part ab is
isothermal. The heat rejected occurs over cd; this is at both
constant temperature and pressure.
To examine the efficiency of the Rankine cycle, we define a
mean effective temperature, T m' in terms of the heat exchanged
and the entropy differences:
qH = T
m2
/).s2·
The thermal efficiency of the cycle is
T
m2
(sb sJTml(sc sd)
TJ thermal = =::"':""::""c::'!''""'
Tm2 (sb sc)
The compression and expansion processes are isentropic, so
the entropy differences are related by
sb  Sc = Sc  sd·
The thermal efficiency can be written in terms of the mean
effective temperatures as
1
Tml
TJthermal =  .
Tm2
For the Rankine cycle, Tml ~ Tl Tm2 < T
2
. From this equation
we see not only the reason that the cycle efficiency is less than
that of a Carnot cycle, but the direction to move in terms of cycle
design (increased T
m2
) if we wish to increase the efficiency.
There are several features that should be noted about
Figure and the Rankine cycle in general:
• The Ts and the hs diagrams are not similar in shape,
as they were with the perfect gas with constant specific
heats. The slope of a constant pressure reversible heat
addition line is,
( ~ ; ) p =T.
In the twophase region, constant pressure means also constant
temperature, so the slope of the constant pressure heat addition
line is constant and the line is straight.
307 Power Cycles with TwoPhase Media
• The effect of irreversibilities is represented by the dashed
line from b to e'. Irreversible behaviour during the
expansion results in a value of entropy sc' at the end
state of the e' expansion that is higher than sc. The
enthalpy at the end of the expansion (the turbine exit) is
thus higher for the irreversible process than for the
reversible process, and, as seen for the Brayton cycle,
the turbine work is thus lower in the irreversible case.
• The Rankine cycle is less efficient than the Camot cycle
for given maximum and minimum temperatures, but, as
said earlier, it is more effective as a practical power
production device.
EFFECT OF DESIGN PARAMETERS ON RANKINE CYCLES
The basic Rankine cycle can be enhanced through processes
such as superheating and reheat. Diagrams for a Rankiue cycle
with superheating are given in Figure. The heat addition is
continued past the point of vapour saturation, in other words the
vapour is heated so that its temperature is higher than the saturation
temperature associated with P
a
(= Ph = Pc = P d)· This does several
things. First, it increases the mean temperature at which heat is
added, T m2' thus increasing the efficiency of the cycle.
Second is that the quality of the twophase mixture during
the expansion is higher with superheating, so that there is less
moisture content in the mixture as it flows through the turbine.
This is an advantage in terms of decreasing the mechanical
deterioration of the blading.
/'
7,
7'··A··············
4
7t .•.•.••.
c.
7, •••• •
I ~ . r
4
L.._____ •
[p . v coordinates] [T . $ coordinates] [h .$ coordinates]
Fig. Rankine Cycle with Superheating
The heat exchanges in the superheated cycle are:
• Along abed, which is a constant pressure (isobaric)
process: q2 = hd = h
a
·
Heat and Thermodynamics 308
• Along e/ ql = h
f
 he' « 0).
The thermal efficiency of the ideal Rankine cycle with
superheating is
hd h
a
(he hi)
YJthennal = I h
Id  a
This can be expressed explicitly in terms of turbine work and
compression (pump) work as
hd he (h
a
hi)
YJthennal = hd  ha
Compared to the basic cycle, superheating has increased the
turbine work, increased the mean temperature at which heat is
received, T
m2
, and increased the cycle efficiency.
T
Isothermal
T, r.d
'_'I = Carnot
b d
ap; Rankirrg
Fig. Comparison of Rankine Cycle with Superheating and Carnot Cycle
Entropy (s)
Fig. Rankine Cycle with Reheat
309 Power Cycles with TwoPhase Media
A comparison of the Carnot cycle and the Rankine cycle with
superheating is given in Figure. The maximum and minimum
temperatures are the same, but the average temperature at which
heat is absorbed is lower for the Rankine cycle. To alleviate the
problem of having moisture in the turbine, one can heat again after
an initial expansion in a turbine, which gives a schematic of a
Rankine cycle for space power application. This process is known
as reheat.
The main practical advantage of reheat (and of superheating)
is the decrease in moisture content in the turbine because most of
the heat addition in the cycle occurs in the vaporization part of
the heat addition process.
T
g'g
b
s
Fig. Effect of Exit Pressure on Rankine Cycle Efficiency
We can also examine the effect of variations in design
parameters on the Rankine cycle. Consider first the changes in
cycle output due to a decrease in exit pressure. In terms of the
cycle, the exit pressure would be decreased from P4 to P
4
,. The
original cycle is 1  2  3  4  I, and the modified cycle is l' 
2'3'4'1'.
The consequences are that the cycle work, which is the
integral of Tds around the cycle, is increased. In addition, as drawn,
although the levels of the mean temperature at which the heat is
absorbed and rejected both decrease, the largest change is the mean
temperature of the heat rejection, so that the thermal efficiency
increases.
Heat and Thermodynamics 310
T
Q II' b s
Fig. Effect of Maximum Boiler Pressure on Rankine Cycle Efficiency
Another design parameter is the maximum cycle pressure.
As comparison of two cycles with different maximum pressure
but the same maximum temperature, which is set by material
properties. The average temperature at which the heat is supplied
for the cycle with a higher maximum pressure is increased over
the original cycle, so that the efficiency increases.
COMBINED CYCLES IN GAS TURBINE FOP. POWER
PRODUCTION
The turbine entry temperature in a gas turbine (Brayton) cycle
is considerably higher than the peak steam temperature. Depending
on the compression ratio of the gas turbine, the turbine exhaust
temperature may be high enough to permit efficient generation of
steam using the "waste heat" from the gas turbine. A configuration
such as this is known as a gas turbinesteam combined cycle power
plant.
T
5
3
6 :l c IdealTurbine
....• ~ V Actualv Turbine
. .'
.'" ""fv Sloam Cycle
a·········::',; d'
Elemenlary carnol cycle
S
Fig. Gas Turbinesteam Combined Cycle
311
Combined Cycle
Efficiency
Power Cycles with TwoPhase Media
Heat Exchanger
Fig. Schematic of Combined Cycle Using Gas Turbine
(Brayton Cycle) and Steam Turbine (Rankine Cycle)
The heat input to the combined cycle is the same as that for
the gas turbine, but the work output is larger (by the work of the
Rankine cycle steam turbine). A schematic of the overall heat
engine, which can be thought of as composed of an upper and a
lower heat engine in series. The upper ~ n g i n e is the gas turbine
(Brayton cycle) which expels heat to the lower engine, the steam
turbine (Rankine cycle).
The overall efficiency of the combined cycle can be derived
as follows. We rlenote the heat received by the gas turbine as Qin
and the heat rejected to the atmosphere as Qout" The heat out of
the gas turbine is denoted as Q1. The hot exhaust gases from the
gas turbine pass through a heat exchanger where they are used as
the heat source for the twophase Rankine cycle, so that Q
1
is also
the heat input to the steam cycle. The overall combined cycle
efficiency is
TjCC = W = W
B
+ W
B
Qin Qin
where the subscripts refer to combined cycle (CC), Brayton cycle
(B) and Rankine cycle (R) respectively.
From the first law, the overall efficiency can be expressed in
terms of the heat inputs and heat rejections of the two cycles as
(using the quantity IQd to deltote the magnitude of the heat
transferred):
Heat and Thermodynamics 312
llCC = QinI Q,I +(1 Q,IQout) =[l_Jill]+[l Qout ](1 Q,Ii.
Qin Qin 1 Q, 1 Qm /:.
The first square bracket term on the right hand side is the
Brayton cycle efficiency, 11B' the second is the Rankine cycle
efficiency, 11R, and the term in parentheses is (I11B). The
combined cycle efficiency can thus be written as 11cc = 11B +l1R
l1B11R; Combined cycle efficiency. 
Equation.Jgives insight into why combined cycles are so
successful. Suppose that the gas turbine cycle has an efficiency
of 40%, which is a representative value for current Brayton
cycle gas turbines, and the Rankine cycle has an efficiency of
30%. The combined cycle efficiency would be 58%, which is a
very large increase over either of the two simple cycles. Some
representative efficiencies and power outputs for different
cycles.
Hoat Rato
STU kwh
5,688
6,824
8,530
11,373
17,060
34,120
Thermal
Efficiency
60% Combined Cycle
Diesel Y
Gas Fixed Storm
50% Turbine
t Generators
:::
Nudear Powered
Heavy Industrial Steam plants
Gas Turbines Gas Turbines
Simple Cycle Simple Cydo
20%
10%
o L________ L____ ____ ______ __
o 10 100 1000 MW
Maximum Single Unit Output
Fig. Comparison of efficiency and power output of various power
products
Some Overall Comments on Thermodynamic Cycles
• There are many different power and propUlsion cycles,
and we have only looked at a few of these. Many
other cycles have been devised in the search for ways
to increase efficiency and power in practical devices.
313 Power Cycles with TwoPhase Media
• We can view a given cycle in terms of elementary
Carnot cycles. This shows that the efficiency of any
other cycle operating between two given temperatures
will be less than that of a Carnot cycle.
• If we view the thermal efficiency as
(T
heat
rejected) Average
TJthennal = 1  ,
(T
heat
absorbed ) Average
this means that we should accept heat at a high
temperature and reject it at a low temperature for high
efficiency. This objective must be tempeled by
considerations of practical application.
• The cycle diagrams in Ts and hs coordinates will
only be similar if the working medium is an ideal gas.
For other media (, a twophase mixture) they will look
different.
• Combined cycles make use of the rejected heat from
a "topping" cycle as heat source for a "bottoming"
cycle. The overall efficiency is higher than the
efficiency of either cycle.
REFERENCES
•
•
•
•
•
Heat and Thermodynamics: A Historical Perspective
(Greenwood Guides to Great Ideas in Science) by
Christopher J. T. Lewis
Equilibrium Statistical Physics, M. Plische and B.
Bergersen
A Modern Course in Statistical Physics, L. E. Reichl
Thermodynamics by J.P. Holman.
Statistical mechanics, R. P. Feynman, W. A.
Benjamin.
Bibliography
Statistical Mechanics, K Huang,
• Statistical Physics, L. D. Landau and E. M. Lifshitz
• Modern Thermodynamics, D. Kondepundi and I.
Prigogine
• Statistical SK Ma
Thermodynamics In Materials Science by Robert T.
Dehoff·
• Fundamentals of Statistical and Thermal Physics, F Reif
• Heat and Thermodynamics: A Historical Perspective
(Gree!1wood Guides to Great Ideas in Science) by
Christopher J. T. Lewis.
Statistical mechanics, R. P. Feynman, W A. Benjamin.
Quantum Mechanics. E. Merzbacher
DK Science Encyclopedia (Revised Edition) by Susan
McKeever and Martyn Foote.
• The Cluster Expansion, W 1. Mullin
Noise and Fluctuations, D. K C MacDonald
Introduction to Metallurgical Thermodynamics by David
R. Gaskell.
• An introduction to Statistical Thermodynamics, T. L. Hill
A Guide to Physics: Thermodynamics, Statistical Physics,
and Quantum Mechanics by Gerald D. Mahan. Boris E.
Nadgomy, and Max Dresden.
Equilibrium Statistical Physics, M. Plische and B.
Bergersen
Equilibrium Thermodynamics, C J. Adkins,
Course in Thermodynamics. Revised Printing. Volume
315 Bibliography
II. (Series in Thennal and Fluids Engineering) by Joseph
Kestill.
• Thennodynamics (and Introduction to Thenllostatistics),
H. B. Callen
• Schaum's Outline of Thennodynamics for Engineers, 2nd
edition (Schaum's Outlines) by Merle Potter and Ph.D.,
Craig Somertofl.
Introduction to Thennal Sciences: Thermodynamics Fluid
Dynamics Heat Transfer by Frank W Schmidt, Robert
E. Henderson, and Carl H. Wolgemuth.
• Heat and Thermodynamics, M. W Zemamky
Mixing and Excess Thennodynamic Properties (Physical
sciences data) by Jaime Wisniak and Abraham Tamil'.
• A Modern Course in Statistical Physics, L. E. Rj!ichl
• Schaum Engineering Thermodynamics (Schaum's
Outlines) by Merle Potter.
• Essentials of Thermodynamics (Essentials) by Research
& Education Association, Rea, and Staff of Research
Education Association.
• Thermodynamics by J.P. Holman.
• Introductory Statistical Mechanics, R. Bowley and M.
Sanchez
• Tlte Language of Science by Sidney B. Cahn.
"This page is Intentionally Left Blank"
Heat and Thermodynamics
"This page is Intentionally Left Blank"
Heat ~nd Ther~o~Yn"mics
,
, ,
Hilary. D. Brewster
Oxford Book Company
Jaipur India
I
ISBN: 9789380179087 First Edition 2009
Oxford Book Company
267, IOBScheme, Opp. Narayan Niwas. Gopalpura By Pass Road, .Iaipur3020l8 Phone: 01412594705. Fax: 01412597527 email: oxfordbook@sify.com website: www.oxfordbookcompany.com
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Preface
Heat is basic science that deals with energy and has long been an essential part of Engineering Curricula all over the world. It was developed during the eighteenth and nineteenth century during a time when Temperature and Heat were not well understood yet. Its development was driven by the need for an improved theoretical understanding of Steam Engines invented at the same time. It evolved as a rather formal and elegant theory that proved to be of great importance to Engineers. Thermodynamics is the science of Energy, Heat, Work, Entropy and Spontaneity of processes. It is closely related to Statistical Mechanics from which many Thermodynamic relationships can be derived. While dealing with processes in which systems exchange Matter or Energy, Classical Thermodynamics is not concerned with the rate at which such processes take place, termed Kinetics. The book contains detailed descriptions of Modern Techniques in Thermodynamics. The aim of the book is to make the subject matter broadly accessible to advanced students, whilst at the same time providing a reference text for graduate scholars and research scientists active in the field.
Prabhat Kumar Choudhary
"This page is Intentionally Left Blank" .
Thermal Equilibrium and Zeroth Law 56 76 85 95 116 177 7. The First Law of Thermodynamics 8. The Second Law of Thermodynamics 9. Third Law of ThennodYD11mics 10.Contents Preface v 1. Heat Conduction 4. Introduction 1 21 2. Enthalpy Generating Heat 224 229 237 249 289 314 12. Entropy 11. Specific Heat of Solids 6. Isolated Paramagnets 13. Power Cycles with TwoPhase Media Bibliography . Heat transfer 3. The Behaviour of Gases 5.
"This page is Intentionally Left Blank" .
Heat can only be transferred between objects. Heat can flow spontaneously from an object with a high temperature to an object with a lower temperature. Heat can be transferred between objects by radiation. In thermodynamics. High temperature bodies. only in the direction of the colder body (as per the second law of thermodynamics). which often result in high rates of heat transfer. can be created by chemical reactions (such as burning). in the absence of work. and then. the quantity TdS is used as a representative measure of heat. or mechanical dissipation (such as friction). symbolized by Q. Temperature is used as a measure of the internal energy or enthalpy. is energy transferred from one body or system to another due to a difference in temperature. that is the level of elementary motion giving rise to heat transfer. electromagnetic dissipation (as in electric stoves). heat. conduction and convection. which is the absolute temperature of an object multiplied by the differential quantity of a system's entropy measured at the boundary of the object. nuclear reactions (such as fusion taking place inside the Sun).1 Introduction HEAT In physics. The transfer of heat from one object to another object with an equal or higher temperature can happen only with the aid of a heat pump. or areas within an object. The temperature and phase of a substance subject to heat transfer are determined . with different temperatures (as given by the zeroth law of thermodynamics).
Surroundings r .) Heat Q can flow across the boundary of the system and thus change its internal energy U.. The unit for the rate of heat transfer is the watt (W = J/s). Heat and work are the only two mechanisms by which energy can be transferred to or from a control mass..... :::·.... The term heat is used to describe the flow of energy.. ~:~~~:~ . The adjective hot is used as a relative term to compare the object's temperature to that of the surroundings (or that of the person using the term). A related term is thermal energy.. In the absence of work interactions.... Specific heat is a property. loosely defined as the energy of a body that increases with its temperature. as opposed to a point function (state quantity)... they will exchange internal energy until their temperatures are equalized. Heat flows between systems that are not in thermal equilibrium with each other. the heat that is transferred to an object ends up getting stored in the object in the form of internal energy Specific heat is defined as the amount of energy that has to be transferred to or from one unit of mass or mole of a substance to change its temperature by one degree.'. that is.. Heat transfer is a path function (process quantity). Heat is the transfer of energy caused by the temperature difference. The unit for the amount of energy transferred by heat in the International System of Units SI is the joule (1).. When two bodies of different temperature come into thermal contact. The first law of thermodynamics states that the energy of a closed system is conserved.... energy must be transferred to or from the system. it spontaneously flows from the areas of high temperature to areas of low temperature.. to change the energy of a system.. Therefore. though the British Thermal Unit and the calorie are still occasionally used in the United States. until they reach thermal equilibrium..Heat and Thermodynamics by latent heat and heat capacity. . ..
but only energy. but is more likely to be only used as a descriptive word. Upon changing from one phase to another.3 Introduction which means that it depends on the substance under consideration and its state as specified by its properties. Q < 0 (). Heat transfer rate. whereas cold objects possess little thermal energy.. tend to be preferred and used more often than the term "thermal energy". when burned. Thermal energy then is often mistakenly defined as being synonym for the word heat. a pure substance releases or absorbs heat without its temperature changing. "enthalpy" (heat content). objects that are hot are referred to as being in possession ofa large amount of thermal energy. The amount of heat transfer during a phase change is known as latent heat and depends primarily on the substance and its state. i. when a body absorbs heat from its surroundings. dQ . THERMAL ENERGY Thermal energy is a term often confused with that of heat. "external forces". or heat flow per unit time. NOTATION The total amount of energy transferred through heat transfer is conventionally abbreviated as Q. "internal energy". the words "heat". The tenh "thermal energy" when used in conversation is often not used in a strictly correct sense. Loosely speaking. Q> 0 (+). dt . Fuels. In this point of view. The conventional sign convention is that when a body releases heat into its surroundings. when heat is added to a thermodynamic system its thermal energy increases and when heat is withdrawn its thennal energy decreases. etc. "work". "entropy". In physics and thermodynamics. This. which is difficult to define. which can be defined exactly. is not the case: an object cannot possess heat. without recourse to internal atomic motions and vibrations. however. release much of the energy in the chemical bonds of their molecules.e. is denoted by: Q=.
such that..S = T and thus. as per the second law of thermodynamics. stationary system: Q !J. and thus treated mathematically like other measurable quantities. and is denoted q. . resulting in units of watts per square metre. DEFINITIONS In modern terms. be called equivalent. Scottish physicist James Clerk Maxwell. has the equivalencevalue:" Q T In 1865. he came to define this ratio as entropy symbolized by S. then the generations of the quantity of heat Q from work at the temperature T. without necessitating any other permanent change. Two. it is "something which may be transferred from one body to another".Heat and Thermodynamics 4 It is measured in watts. Maxwell outlined four stipulations on the definition of heat. in his 1871 classic Theory of Heat. ENTROPY In 1854. for a closed. by reduction. Heat flux is defined as rate of heat transfer per unit crosssectional area. can mutually replace one another. the entropy function S facilitates the quantification and measurement of heat flow through a thermodynamic boundary. In short. it can be spoken of as a "measurable quantity". though slightly different notation conventions can be used. One. German physicist Rudolf Clausius defined the second fundamental theorem (the second law of thermodynamics) in the mechanical theory of heat (thermodynamics): "if two transformations which. quantities of heat oQ (an inexact differential) are defined as quantities of TdS (an exact differential): 8Q= TdS In other words. was one of the first to enunciate a modern definition of "heat". heat is concisely defined as energy in transit.
of its molecules or atoms • Heat is the transfer of energy between substances of different temperatures. THERMODYNAMICS INTERNAL ENERGY Heat is related to the internal energy U of the system and work W done by the system by the first law of thermodynamics: tl. e. between a system and its surroundings. When energy in the form of heat is added to a system. initially isolated and in a stable equilibrium.e. caused by a difference in temperature between two objects Heat may be defined as energy in transit from a hightemperature object to a lowertemperature object Heat as an interaction between two closed systems without exchange of work is a pure heat interaction when the two systems.5 Introduction Three.U= Q. are placed in contact. it "can not be treated as a substance". but as kinetic and potential energy of the atoms and molecules making up the system . • The noun heat is defined only during the process of energy transfer by conduction or radiation • Heat is defined as any spontaneous flow of energy from one object to another. heat is never regarded as being stored within a body. i. mechanical work. for it may be transformed into something which is not a substance. it is "one of the forms of energy". The energy exchanged between the two systems is then called heat • Heat is a form of energy possessed by a substance by virtue of the vibrational movement. it exists only as energy in transit from one body to another. kinetic energy. Similar such modern. it is stored not as heat. Lastly.g. succinct definitions of heat are as follows: • In a thermodynamic sense. in thermodynamic terminology.W which means that the energy of the system can change either . Like work.
U + Wboundary = Q . yields the following: !l. neither Q nor Ware . Internal eI). H. In contrast. The internal energy associated with the phase of a system. In more detail.. one of the thennodynrulllc potentials.properties of a system and need not sum to zero over the steps of a cycle. The infinitesimal .r. provided the volume is not cons.1Jhalpy. rotation.Heat and Thermodynamics 6 via work or via heat flows across the boundary of the thermodynamic system. mass transfer. and mternal energy. heat transfer. It is related to the molecular structure and the degree of molecular activity and may be viewed as the sum of kinetic and potential energies of the molecules.Wother This combined 9uanti.k perfonned by a COmpressor fan).return to their initial values upon· completion of each c·ycle in cyclic processes such as that of a l:leat engine. electron translation and spin. but which are recognized at the system boundary as they cross it. and work). which represent gains or losses by a system during a process The sum of sensible and latent forms of internal energy. U are state (uncti<. The internal energy associated with the atomic bonds in a molecule The tremendous amount of energy associated wit)t the strong bonds within the nucleus of the atom itself Those types of energies not stored in the system (e.el..to the first law equation and separating the work tenn into two types.tr~ined. Both e1. allows a control volume of gas to become larger or smaller).g. Returning . "houndary work" and "other" (e. Latent energy Chemical energy Nuclear energy Energy interactions Thermal energy The transfer of heat to an ideal gas at constant pressure increases the internal energy and perfonns boundary work (Le. and vibration. it comprises the following types of energies: Type Sensible energy Composition of Internal Energy (U) The portion of the internal energy of a system associated with kinetic energies (molecular translation. shaft wo.ty ~U + Wbounc/ary is .g. and nuclear spin) of the molecules. State functions .ergy is the sum of all microscopic fonns of energy of a system.lns.t~alpy. H.
oQ.lll) are ne~Jy . or other external parameters.ction between the two types of heat cl. applied m?gnetic field. m . the changes in enthalpy and internal energy can be related to the heat capacity at constant pressure and volume.g. Q. forms an inexact differential for processes involving work. csaccordjng to: Cp = mcs or is dependelLt on the number of mqles and the molar heat capacity. . rh.s (e.e. T is given by: f Q= r: CvdT=flU Removing the volume constraint and allowing the system to expa»d or contract at constant pressure: Q =flU t: PdT =!ill = r: CpdT For inconwressible substances. required to change its temperature from an initial temperature.pe. oQ. HEAT CAPACITY For a simple compressible system such as an ideal gas inside a piston.l.gage. Constrained to have constant volume.g.odence. he1il. but for processes involving transfer of heat it forms an inexact differential.. and specific heat capacity. for adiabatic processes (no heat transfer).and A':llllher of molecules. respectively.es of freedom of the systep1 and not on any ext.corc!i. the ~xpression for work forms an exact differential.7 Introduction expression for heat. for processes involving no change in volume.lpacity disappears.. the distin. To.lp~ci~es are dependent upon the inter.ernal prQpel1<\es ~\lch as volume. forms an exact differential. and triatomic gases (e. to a final temperature.nal ~e:gr. such as solids and liquids. Likewise.ng to: Cp =ncn The lJlolar and specific :heat cl.lperature. It can be represented as the product of mass. the heat. as no work is performed.e specific heats of monatom:ic . Pi/itomic ~ases such as hydrogen display some temperature de. However.constant with tell. Heat capacity is an extensive quantity and as such is dependent on the number of molecules in the system. cn ac.
the L rises slightly. An example is the behaviour of bosons such as helium4. Latent heat is the heat per unit mass necessary to change the state of a given substance. quantum effects become significant. Here. its specific heat will be proportional to the cube of absolute temperature. so that the integral can be written as: Q= fL dm dt.m. The extra heat changes the phase of the water from liquid into water vapour. For such substances. The heat added to change the phase of a substance in this way is saio to be "hidden" and thus it is called latent heat (from the Latin latere meaning "to lie hidden"). as pressure increases. an example of FermiDirac statistics. dt . Note that.L generally does not depend on the amount of mass that changes phase. CHANGES OF PHASE The boiling point of water. a second term is needed to account for the behaviour of the conduction electrons. At temperatures well below the characteristic Debye temperature of a solid lattice.Heat and Thermodynamics 8 carbon dioxide) still more in liquids at sufficiently low temperatures. Mo is the amount of mass initially in the new phas~. at sea level and normal atmospheric pressure a!1d temperature. Sometimes L can be timedependent if pressure and volume are changing with time. or: L=~ 11m and Q= JMo rM Ldm. Also. so the equation can normally be written: Q=L!:l. and M is the amount of mass that ends up in the new phase. For lowtemperature metals. the behaviour of heat capacity with temperature is discontinuous at the BoseEinstein condensation point. will always be at nearly 100°C. no matter how much heat is added. The quantum behaviour of solids is adequately characterized by the Debye model.
and the thermal and electrical conductivities of most metals have about the same ratio. A good electrical conductor. In convection. Electrons also conduct electric current through conductive solids. The "electron fluid" of a conductive metallic solid conducts nearly all of the heat flux through the solid. Commonly an increase in temperature produces a reduction in density. such as copper. transferring some of their energy (heat) to these neighboring atoms. Two types of convection are . but carries less than 1% of the energy. enthalpy transfer occurs by the movement of hot or cold portions of the fluid together with heat transfer by conduction. Thermoelectricity is caused by the relationship between electrons. This is a term used to characterize the combined effects of conduction and fluid flow. displacing the colder more dense liquid which falls. Conduction Conduction is the most significant means of heat transfer in a solid. usually also conducts heat well.9 Introduction HEAT TRANSFER MECHANISMS Heat tends to move from a hightemperature region to a lowtemperature region. hot water from the bottom of the pan rises. In engineering. Hence. Mixing and conduction result eventually in a nearly homogenous density and even temperature. the term convective heat transfer is used to describe the combined effects of conduction and fluid flow and is regarded as a third mechanism of heat transfer. The PeltierSeebeck effect exhibits the propensity of electrons to conduct heat through an electrically conductive solid. heat fluxes and electrical currents. Convection Convection is usually the dominant form of heat transfer in liquids and gases. On a microscopic scale. In insulators the heat flux is carried almost entirely by phonon vibrations. rapidly moving or vibrating atoms and molecules interact with neighboring atoms and molecules. when water is heated on a stove. This heat transfer may occur by the mechanisms of conduction and radiation. Phonon flux is still present. conduction occurs as hot.
Heat and Thermodynamics 10 commonly distinguished. and forced convection. which carries energy away from the surface. in which gravity and buoyancy forces drive the fluid movement. Since the amount of emitted radiation increases with increasing temperature. Wien's displacement law. free convection. thus it is the only means of heat transfer through a vacuum. Thermal radiation is a direct result of the movements of atoms and molecules in a material. approximating the behaviour of a black body at 300 K with spectral peak atfmax' At these lower frequencies. at a temperature of approximately 6000 K. the surface is constantly bombarded by radiation from the surroundings. Since these atoms and molecules are composed of charged particles (protons and electrons). and hence does not occur in microgravity environments. Buoyant convection is due to the effects of gravity. there is a frequency f max at which the power emitted is a maximum. a net transfer of energy from higher temperatures to lower temperatures results. emits radiation principally in the visible portion of the spectrum. The power that a black body emits at various frequencies is described by Planck's law. The earth's surface emits the absorbed radiation. It is this spectral selectivity of the atmosphere that is responsible for the pl:inetary greenhouse effect. At the same time. For any given temperature. The photosphere of the Sun.y form of heat transfer that can occur in the absence of any form of medium. their movements result in the emission of electromagnetic radiation. it is absOl bed and subsequently reemitted by atmospheric gases. and the fact that the frequency of light is inversely proportional to its wavelength in vacuum. mean that the peak frequency j~ax is proportional to the absolute temperature T of the black body. stirrer. The earth's atmosphere is partly transparent to visible light. where a fan. Though some radiation escapes into space. the atmosphere is largely opaque and radiation from the earth's surface is absorbed or scattered by the atmosphere. or other means is used to move the fluid. and the light reaching the earth's surface is absorbed or reflected. resulting in the transfer of energy to the surface. Radiation Radiation is the on. .
Originally invented for use in satellites. from them. However. heat pipes can carry many times as much heat as a similarsized copper rod. and RF hair removal. A portion of the photons emitted by a tungsten light bulb filament at 3000K are in the visible spectrum. Other Heat Transfer Mechanisms • • Latent heat: Transfer of heat through a physical change in the medium such as watertoice or watertosteam involves significant energy and is exploited in many ways: steam engine. houses with their heating systems form dissipative systems. Whenever EM radiation is emitted and then absorbed. which can 'make their interiors uncomfortably cool or cold. but will still transfer heat to the environment.of warmth in a sea of cold and the thermal gradient between the inside and outside is often quite steep.:trum overlapping the blackbody spectra of the Sun and the earth. these will not help a person. heat is transferred. as can be deduced empirically by observing a household incandescent lightbulb. This is why modern insulation techniques are required to reduce heat loss. most of the energy is associated with photons of longer wavelengths. if left unaddressed. the interior of a house must be maintained out of thermal equilibrium with its external surroundings. can cause structural damage to the property. laser cutting. This can lead to problems such as condensation and uncomfortable draughts (drafts) which. HEAT DISSIPATION In cold climates. In such a house. In spite of efforts to insulate such houses to reduce heat losses to their exteriors. they are starting to have applications in personal computers. Heat pipes: Using latent heat and capillary action to move heat. a thermostat is a device capable of starting the heating system when the house's interior falls below a set . domestic residences are oases. In effect. or dissipated.11 Introduction The commOn household lightbulb has a spe<. considerable heat is lost. This principle is used in microwave ovens. For the comfort of its inhabitants. refrigerator etc.
However. bimetallic thermometers and temperature sensitive paint or film thermometers.2°C (O.5°e ±o. the material being measured and your expectations of accuracy. IS TEMPERATURE MEASUREMENT DIFFICULT? The answer depends on the temperature.Heat and Thermodynamics 12 temperature. poor thermal contact. various gas thermometers. TEMPERATURE MEASUREMENT Temperature is the most commonly measured parameter. Generally the accuracy of all sensor types can be greatly improved by individual calibration. pressure based thermometers. The information in this section is oriented towards electronic thermometers those with an electrical output that can be connected to a measuring instrument. Thus the thermostat controls the flow of energy into the house.4°F) great care in needed. a data logger. It is a surprisingly difficult parameter to measure with the precision that one might reasonably expect.]Oe care needed easy care needed very difficult difficult care needed very difficult extremely difficult difficult very difficult difficult very difficult extremely almost difficult impossible don"t almost even try impossible . These include: the glass thermometer. sensor nonlinearities. The table below summarises the difficulty of temperature measurement over a range of temperatures: Accuracy Required Temperature 200°C O°C to 50°C IOOO°C 2000°C ±5°e ±]Oe ±O. To obtain accuracies better than O. drafts. Errors occur due to the presence of temperature gradients. calibration drifts. there is also a wide range of thermometers that can be used for manual temperature measurement. such as: a data acquisition system. that energy eventually being dissipated to the exterior. radiant energy and sensor self heating. yet in many respects it is the least understood. and of stopping that same system when another (higher) set temperature has been achieved. a control system or a chart recorder.
each of these errors can drift with time and temperature cycling. scale and linearity errors. In addition. Acr~=~:~~n8JI Gradient Iron. The following diagram indicates some of the complexity in temperature measurement. Identify exactly what is to be measured and the accuracy needed. This applies to both sheathed and unsheathed sensors.OOloC (l°mC) or even better. using a quality platinum temperature sensor and / or a Type S thermocouple. Understanding the thermal resistances and where they are located is especially useful in identifying potential errors sources.O:~::~:erfluid 1il ::2: 2 Conducbon In w . surface ~ Sensor to sensor 9:nlment ) ~ fi "L:. then consider using the thermopile to avoid the need for closely matched sensors. This is typically done by interpolation (estimation of the values) between two standards. 1~~~~~ ~ Gradient in thickness of material Temperature gradient to environment Thermal Flows To and From a Temperature Sensor Below is a description of temperature measurement error sources and some suggestions on minimising these errors. . SOURCES OF TEMPERATURE MEASUREMENT ERROR In using temperature sensor3 it is helpful to think of where heat flows. such a:.13 Introduction In a laboratory with appropriate standards and equipment.:.. These gradients can be particularly troublesome when measuring the materials with poor thermal conductivity. Hysteresis (where a value depends on the direction from whjch it was approached) can be noticed . When measuring temperature it is important to keep your goals in mind. plastics and even stainless steel. it is possible to measure temperature to O. SENSOR CALIBRATION Sensors calibration errors can be due to offset. Note the presence of thermal gradients in the material being measured. If accurate temperature differences are of prime importance.
a high quality platinum RTD is best. Employing multiple sensors for spatial diversity and averaging the readings is another solution. HEAT CONDUCTION IN SENSOR LEADS All sensors \\lith the exception of noncontact and maybe the fibre optic types require that wires be brought to the sensor. In the case of fluids it important that the fluid be stirred. the defining reference points of the ITS':90 are not practical for routine calibration purposes.Heat and Thermodynamics 14 with some sensors. an excellent heat conductor. An unstirred ice bath (a mixture of ice and water) can have a vertical temperature gradient of several degrees. Other references include iced water bath. Platinum RTD's are considered the most accurate and stable of standard sensors. These wires are usually copper. the system. Sensor interchangeability is often the decisive factor. THERMAL GRADIENTS Thermal gradients are often a major source of measurement error. along with an appropriate indicator. but the effect is usually small with the exception of the bimetallic strip where it may be several degrees. Choosing a practical calibration reference can be an issue. In general. However. gradients can be minimised by insulating the system b~ing measured. most liquids and nonmetallic solids. individually calibrated thermocouples can come close over the same temperature range. The platinum based thermocouples can be just a stable as platinum RTD's and cover a higher temperature range.y. requiring the sensing element to be in better thermal contact with . It refers to the maximum temperature reading error likely to occur in replacing a sensor with another of the same type without recalibrating the system. If stirring is not practical. traditional glass thermometers (especially laboratory grade) and medical thermometers. This is especially true when measuring materials with poor thermal conductivity such as: air. The wires allow heat flow into or out of the sensor lJoQ. For professional purposes. The placement of these wires can have a significant impact on accuracy. to prevent heat transfer :nto or out of.
RADIATION Radian heat can be a major source of error in measuring air temperature. This ensures a higher thermal resistance because of a longer length of wire. To avoid this error the sensor must be shielded from source of radiant energy. (Note: this contradicts good practice for high temperature thermocouple measurement where the reverse rule appliesuse the thickest wire that is practical) • Place the wires in or against the material being measured. The sun is the most obvious source. The best solutions are the following: • Ensure that the sensor's outside surface is highly reflective of infrared radiation (i.15 Introduction the material being measured than would otherwise be needed. There are three solutions. so that they actually assist in transferring the temperature of the material into the sensor Good Wring Poor Wiring Heat Conductance in leads • Attempt to minimise the thermal gradient along the sensor wires by placing the wires at an angle to the gradient. however just about any object that is at a different temperature to the air is a potential source (or sink) of troublesome radiant energy. When measuring the temperature of thermal insulation materials. A sensor in sunlight is almost certain to read significantly higher than the actual air temperature. this can be a major source of error. all of which are good standard practice: • Use as thin wires as is practical for sensor hookup.e.it is painted white or has a bright metal finish) .
the magnitude of the self heating effect is between 0. However.SoC. shield the sensor if possible. the equipment must be allowed time to 'warm up'.g. This power can heat the sensor. Small sensors are generally better. Radiant heat loss can be a source of sensor error when measuring elevated temperature. SENSOR SELFHEATING Thermistors. and different calibrations are required for mediums with different thermal characteristics e.Heat and Thermodynamics 16 Ensure the sensor is thermally 'well connected' to the air by having a good surface areatovolume ratio. causing a high reading. However this is not necessary as simple as that. Typically. and if there is adequate time between readings for cooling • Avoid selfheating sensor typesuse thermocouples. However.1 °C and I. Again. Place the sensor in a vented radiation shield that also has a highly reflective surface on the outside and inside Ensure the sensor has a high surface areatovolume ratio to ensure good thermal 'contact' with the air. The effect depends on the size of the sensing element and the level of power. This is perhaps the easiest solution. befOIe the sensor has time to warm. Use reflective surface finish on the sensor. This is the best solution if the readings can be made quickly. a compromise between selfheating and sensitivity (and signaltonoise ratio) must be made Avoid unnecessarily small sensing elementsthey will selfheat more than larger elements Switch the excitation power off between readings. air and water • Use the lowest possible excitation power. The best solutions are the following: • Calibrate out the selfheating effect. the same rules apply. • . RTDs and semiconductor sensors require the application of an excitation power in order that a reading may be taken. as the measuring device is likely to use a reference junction temperature sensor that is itself prone to selfheating. and ensure a good thermal contact with the medi urn being measured.
17 Introduction THERMAL CONTACT Obviously. care needs to be taken to compensate for the phase (time) delay in the response. thermal contact with the material being measured is important. air) and radiant energy transfers. by minimising material in contact with the sensing element that is not associated with improving thermal contact • Compensate the readings using an inverse matching filter. it is possible to predict the temperature dynamical1y. . but the degree of contact required is dependent on other parasitic thermal connections to the surroundings which are likely to have a significant impad on heat flow. THERMAL TIME CONSTANT When the temperature changes. while others take minutes or even hours. If there is no temperature gradient in the vicinity of the sensor. sometimes. The time taken to reach 63% of the way to the new temperature is referred to as the 'thermal time constant'. the thermal contact of the sensor can be poor and the sensor will still provide accurate readings. If the thermal characteristics of the system are constant and known. Some sensors respond quickly. The best solutions include the following: • Use a more rapidly responding sensor • Improve thermal contact • Reduce the sensors thermal mass. Most sensors have one dominant time constant. it takes time for a sensor to respond.g. direct contact with other material (e. time constants present that can confuse the measurement process. there are minor. Obviously if the temperature is changing more quickly than a sensor is able to track. If this effect is to be exploited. These parasitics include: lead conduction. Sometimes long time constants are useful in providing an averaging effect on a rapidly fluctuating temperature. the measurement wil1 be in error. but longer. However. some in less than a second.
.Heat and Thermodynamics 18 READOUT ERRORS The measuring device connected to the sensor is never perfect. In some industrial processes. linearity and temperature dependent errors. It is recommended that a test be conducted where the temperature of the sensor is held constant. electrical noise can be so intense that noncontact or fibreoptic sensors are the only option. These errors can be reduced by: • Calibration of the readout device against known references Calibration of the total sensor . Use the standard procedures as described in the Measurements Methods section to minimise the impact. Temperature effects on the readout device can be a subtle source of error. but the readout device be placed in an oven or freezer. Prevention is better than cure. transformers and electrical machinery • Install low pass filters into the measuring device • Avoid ground loops.readout system. condensation in the sensor and wiring can collect and become an electrical leakage path. can have calibration. using a reference temperature or against a precision thermometer (glass or RTD+readout). as their performance can be greatly impacted by temperature gradients and the quality of the internal reference junction sensing. ELECTRICAL NOISE OR INTERFERENCE Electrical noise can induce errors in systems with poor noise rejection. These include the following: Use shielded twisted pair cable Keep wiring away from power cables. The measuring device. be it a: meter. This is particularly important for thermocouple readout devices. causing errors. chart recorder. data acquisition board or data logger. CONDENSATION Sometimes in situations where temperatures are frequently cycled through the dew point.
Again. Condensation can be a sourc~ of intermittent errors and may go unrecognized for a long time. SENSOR MECHANICAL STRESS Many temperature sensor elements can respond to mechanical stress. Evaporating condensation can also lead to measurement errors due to evaporative cooling effects . The differences in the thermal coefficients of linear expansion will induce mechanical stress • Use sensor that are less sensitive to stress . Preventative measures include: • Ensure that sensing elements are not subjected to deformation in the way they are mounted • Avoid using adhesives in attaching sensors to the surfaces to be measured. When an air volume is sealed.19 Introduction Preventative measures include the following: Ensure that the sensor and its wiring is sealed. special purpose temperature calibrators .a subtle but real error source. accelerated by sensor excitatio!l power.the thermocouple • Wound (as opposed to film) RTDs can be prone to vibration damage. It also can lead to corrosion. Avoid potting sensor elements in epoxy_ Calibration If funds are available. Semiconductor sensors can be particularly prone to moisture penetrating the metalplastic interface of plastic packages. prevention is better than cure. film type RTD has the appearance of a strain gauge and will behave like one given the opportunity. or using a penetrating oil from both ends. with a mediumviscosity super glue. ultimately leading to complete failure. This can be inhibited by sealing wires at the sensor end. ensure that the air is dry • Moisture can wick along wires by capillary action. Take great care in the seft:ction and mounting of sensors in highvibration environment • Use grease in preference to adhesive to ensure thermal connection.
there are two low cost standards that can be effectively employed to achieve O. These points (O. Robert E.2°C accuracy. ('ahn. these are expensive and not always as accurate as one might expect To calibrate over th~ normal environment range. Boris E. Introduction to Thermal Sciences: Thermodynamics Fluid Dynamics Heat Transfer by Fnn'k W. and Max D~esden. Dehoff. llgemuth. and Quantum Mechanics by Gerald D.O°C and about 37°C) are sufficiently far apart to provide a useful calibration o'ver the 20 oe to +60"C range REFERENCES • A Guide to Physics: Thermodynamics. V. Schmidt. The Language of Science by Sidney B. However. Heat and Thermodynamics: A Historical Perspective (Greenwood Guides to Great Ideas in Science) by Christopher J. These are icewater mix made from distilled water and a standard medical thermometer. Mahan. Henderson. •. Lewis. and Carl H. . Nadgorny. Thermodynamics In Materials Science by Robert T.Heat and Thermodynamics 20 can be purchased. T. Statistical Physics.
2 _________________________________ Heat Transfer CONDUCTIVE HEAT TRANSFER HEAT TRANSFER MODES Heat "flows" to right ( q) Fig. The second heat transfer process is convection. A solid (a block of metal. which is defined a~ lransfer of heat occurring through intervening matter with0ut bulk motion of the matter. This type of heat conduction can occur. is at a higher temperature than the inside surface. The level of the wall temperilture is critical for a turbine blade. which has cooling air next to it. The fluid can he a gas or a liquid: . or heat transfer due to a flowing fluid. The process pictorially. say) has one surface at a high temperature and one at a lower temperature. whIch is exposed to gases from the combustor. The outside surface. through a turbine blade in a jet engine. Conduction Heat Transfer Heat transfer processes are classified into three types. The first is conduction.
the bar geometry and the bar properties. We must first determine how to relate the heat transfer to other properties (either mechanical. is a function of the temperature of the two reservoirs. the heat is moved through bulk transfer of a nonun iform temperature fluid. as said. The answer to this is rooted in experiment. TATBIf is zero. Radiation can be important even in situations in which there is an intervening medium. 12 ..TB. (Are there other factors that should be considered? If so._ _ L _ _. bar geometry.. TA. but it can be motivated by considering heat flow along a "bar" between two heat reservoirs at TA . Radiation is the only method for heat transfer in space. Heat transfer along a bar It also seems reasonable to postulate that Q should depend on the temperature difference TA .. then the heat transfer should also be zero. bar properties] . This can be expressed as Q= 11(TA . bar geometry.. bar properties) . as follows. is if 12 = o.. The third process is radiation or transmission of energy through space without the necessary presence of matter. what?). a familiar example is the heat transfer from a glowing piece of metal or from a fire. or geometrical). Conduction We will start by examining conduction heat transfer.. In convection heat transfer. The temperature dependence can therefore be expressed aSQ= 12 [TA  TB..Heat and Thermodynamics 22 both have applications in aerospace technology.. TB. An argument for the general form of can be made from physical considerations.. Q. Fig. thermal. One requirement. . TA = TB Using a Mac Laurin series expansion. TB • It is plausible that the heat transfer rate.
TB ~ 0. we can say .nits are Watts/ m2 . k is a proportionality factor that is a function of the material and the temperature. It also seems reasonable that if we had two bars of the same area. experience leads us to believe that as L increases Q should get smaller. for the bar.TB ) = kA (TB . The expression in can be written in terms of heat flux as dT If = _k . Finally. we would have twice the heat transfer. In addition.. In the limit for any temperature difference !1T across a length ~ as both L. The derivative evaluated at TA = TB (thermal equilibrium) is a measurable property of the bar.TA) = kA dT . defined as Q= kA (TA iF"Q.TB) > 0. All of these lead to the generalization that.TB ) L In Equation.fiTA TB)= Q=h(O)+ oCT ~T) A B I TATJl=O (TATB) +. so that we can postulate that Q is proportional to the area. Ais the crosssectional area and Lis the length of the bar. dx ...23 f(!:'T) = f(O) + Heat Transfer ~I 0 !:'T + . although the argument is by no means rigorous.TB andf= f2' we find that (for small TA TB). the derivative in Equation has the form Of2 ° I TrTJl=O kA O(TA . c(!:'T) cf~ Ifwe define !1T= TA . we know that Q> ifTA>TB or 8i/8(TA .. TA . We know thatfiO) = 0. L L dx A more useful quantity to work with is the heat transfer per unit area. A The quantity If is called the heat flux and its ".
we can devise a basic description of the process. Onedimensional Heat Conduction For onedimensional heat conduction (temperature depending on one variable only).15 0. L.026 0.40. <Xx + u) ~ . the heat transfer rate in at the left (at x) IS Q(x)=k A dx . U . The proportionality constant k is called the thermal conductivity. Its units are W/mK. ( dT) x' . Some values for familiar materials are given in Table. From Equation.04 Air Engine oil 0. others can be found in the references.2 Cork 0. Thennal conductivity is a welltabulated property for a large number of materials. The first law in control volume form (steady flow energy equation) with no shaft work and no mass flow reduces to the statement that LQ for all surfaces = 0 (no heat transfer on top or bottom )..Heat and Thermodynamics Equation is the onedimensional fonn of Fourier's law of heat conduction. ~. The thermal conductivity is a function of temperature and the values shown in Table are for room temperature.18 0.5 SteadyState OneDimensional Conduction j ~ Q{x) I I I I lnsulalcd (no beat transfer) 1. Table: Thermal conductivity at room temperature for some metals and nonmetals (W/mK)  24 Metals Nonmetals Ag 420 H 2O 0.x Fig.6 Cu 390 Al 200 Fe 70 H2 Steel 50 Brick Wood 0.
If is constant (i.( Q(x) + 1.' now apply this to an example. dx or !(kA:)=O.X . X'" 0 X'" L Fig.. ifthe properties of the bar are independent of temperature). 2 Heat Transfer Through a Plane Slab T'" T. dx x Using the conditions on the overall heat flow and the expressions Q(x) ... WI.. Q(x+dx) =Q(x) + dQI dx+ . this reduces to dx or (USiilg the chain rule) 2 d_(AdT)=o dx ' dx A dx dx Equation or describes the temperature field for quasionedimensional steady state (no time dependence) heat transfer. d T +(ldA)dT =0.) = o.. ..25 The heat transfer rate on the right is Heat Transfer . Temperature Boundary Conditions for a Slab . (x)dx + .e. Taking the limit as dx approaches zero we obtain dQ(x) =0.
T2. This is given by ij = k dT dx = _ k (T2 11) =constant.Heat and Thermodynamics 26 For this configuration. With these expressions for and (he temperature distribution can be written as T(x)=l1 +(T2 ~11 )x. This linear variation in temperature for a situation in which T J > T2 · T . can be integrated immediately to yield dT =a d 2T =0 dx and T=a'C+b. L Thermal Resistance Circuits There is an electrical analogy with conduction heat transfer that can be exploited in problem solving. dx 2 Equation. thus becomes . the area is not a function of x. The analog of Qis current. T J . The condition ItO) = T J implies that b = T J• The condition T2 = T(L) implies that T2 = aL + T J. One such set of boundary conditions can be the specification of the temperatures at both sides of the slab ItO) = T J.TJ)/L. is . such as. Equation is an expression for the temperature field where a and b are constants of integration. For a second order equation. i. we need two boundary conditions to determine and . or a= (T2. T(L) = T2. A. and the analog of the temperature difference.c Fig.e. Equation. Temperature Distribution Through a Slab The heat flux ij is also of interest.
as Adecreases. and TR is the temperature at the right. R/ 1<. the heat transfer rate is given by . the heat transfer resistances are in parallel. Heat Transfer for a Wall with Dissimilar Materials (Parallel Thermal Resistance) Another example is a wall with a dissimilar material such as a bolt in an insulating layer. The physical configuration.nce. If TL is the temperature at the left. the thermal resistance. The resistances are in series and sum to R = RI R 2 . From this perspective the slab is a pure resistance to heat transfer and we can define Q = 'rt T2 R where R = LlkA. and as kdecreases. TL TR TL TR Q= = .: Fig. . The thermal resistance Rincreases as Lincreases. the heat flux is constant with. the heat transfer paths and the thermal resistance circuit. R R( +R2 model c::::> Fig. In this case.27 Heat Transfer voltage differt. In the composite slab. Heat Transfer Across a Composite Slab (Series Thermal Resistance) The concept of a thermal resistance circuit allows ready analysis of problems such as a composite slab (composite planar heat transfer surface).
07 W/m. Heat Transfer Through an Insulated Wall The overall thermal resistance is given by R = RI + R2 + R3 = ~ ~ ~ k A +k A +k A . R RI R2 More complex configurations can also be examined. we obtain ARI = AR3 = ~ = kl 0. . ./ ~ «/ «. ~~r 0. a brick wall with insulation on both sides.lm =0.03 m 0.14m 2 K/W. T.42 m2 K/W AR2=~= k2 O. the total heat flow Qis made up of the heat flow in the two parallel paths. I 1 2 2 3 3 Some representative values for the brick and insulation thermal conductivity are: kbrick = k2 = 0.Heat and Thermodynamics 28 For this situation.~"niT 14 ~ Brid< 0.. q= Q = constant throughout = _1_ _ = 4 A RA 0.T." . given by Q= QI + Q2' with the total resistance 1 1 1 =+. and noting that Al = A2 = A3 = A.98 m K/W =142 W/m 2 .07 W/mK Using these values. =l • t ".7 W/mK 140 K 2 This is a series circuit so .K =0.03111 Fig. 1111 ".7 W/mK kinsulation = kl = k3 = 0. 0.
can be written as .29 1. since Q is constant across the slab. Temperature Distribution Through an Insulated Wall " The temperature is continuous in the wall and the intermediate temperatures can be found from applying the resistance equation across each slab.T. Cylindrical Shell An important case is a cylindrical shell. ~ _ _ control volume Fig. to find T2: q = 11 T2 RIA =142 W/m 2 • This yields T1T2 = 60 K or T2 = 90°C. I 2 4 Heat Transfer 7. the temperature depends only on a single coordinate (r) and Equation.0 TT. As sketched. the larger drop is across the insulating layer even though the brick layer is much thicker. Cylindrical Shell Geometry Notation For a steady axisymmetric configuration. 0 Fig. The same procedure gives T3 = 70°C. a geometry often encountered in situations where fluids are pumped and heat is transferred. such as cylindrical and spherical shells. Steady QuasiOneDimensional Heat Flow in NonPlanar Geometry The quasi onedimensional equation that has been developed can also be applied to nonplanar geometries.
. To do this. dT Q=k21tr. dr Equation is a second order differential equation for T.Heat and Thermodynamics 30 k =~(A(r) dT) = 0. dr dr The steadyflow energy equation (no fluid flow. ~(r dT)=O. Applying T= TI r = rlat gives TI = b. Applying T= T2 at r = r2 yields . yields T = a In (r) + b. These will be taken to be known temperatures TI and T2 at rland r2 respectively. r l. dr The heat transfer rate per unit length is given by . or dQ =0. It is useful to cast this equation in terms of a dimensionless normalized spatial variable so we can deal with quantities of order unity. dr dr or. can be written as dr dT=a r where both sides of Equation are exact differentials. divide through by the inner radius. boundary conditions are needed. (r1) To find the constants of integration a and b. since A = 21tr.{)ut. (r I 1j) Integrating. no work) tells us that ~n = Q. Equation. dT=ad(rlrl). Integrating this equation once gives dT r=a dr ' where a is a constant of integration.
. having an answer that goes to zero at one limit is also useful from the perspective of ensuring the answer makes sense.. consider the case when (r2 . From the series expansion for In (1 + x) we recall that In (l+x) ~x . In(r / rl ) +1. To make the connection.) In(r2 / 'i ) The heat transfer rate. Equation can be put in nondimensional form as ='"' T 1J T2 1J In(r / r. dr Q. 1JT2 comparison with.. When the heat flow rate is written so as to incorporate our definition of thermal resistance. If convenient. In(r2 / rl) The temperature distribution is thus a= T . Q = leA dT = 21tr..+ .(T2 '1') '1' I. is given by 1 = 21t k(1J . it is generally useful to put expressions into nondimensional and normalized form so that we can deal with numbf:rs of order unity (this also helps in checking whether results are consistent). 2 3 x2 x3 .T2) In(r2 / 'i)'i 'i In(r2 / 'i ) per unit length. In(r2 / 'i) As said.+ . 21tk The cylindrical geometry can be viewed as a liqtiting case of the planar slab problem.31 Heat Transfer or T2 1J . « 1.r1)/r.k (T2 1J) Q=R' . reveals the thermal resistance R to be R = In ('i /1j ) .
Heat and Thermodynamics 32 (Look it up.81 Spherical Shell A second example is the spherical shell with specified temperatures T(r l ) = T J and 1(r2 ) = T2 .84 0. L T ~2 ~I _T (rrl) +~I' T = L we obtain which is the same as Equation. the ratio of thickness to inner radius should be less than 0.x + X2 + .r l )« r l . For <10% error. ) and integrate term by term. where the heat transfer can be regarded as taking place in (approximately) a planar slab. try it numerically. and r2 .rl T (r2 lj) With the substitution of r . the thickness to inner radius should be less than 0. gives 1j ) == r 1j 1j 1j ~n(r2) == r2 .2.5 0.95 0.r l x T=1) +(T2 1). consider the expansion In (I + x)/x. Table: Utility of plane slab approximation x 10(1 + x) x 0. Using these expressions in Equation. can thus be written as In(I + r and 1j rl in the limit of (r2 . or use the binomial theorem on the series ( 11x =1.3 0. which is the ratio of heat flux for a cylinder and a plane slab.87 0. The plane slab is thus the limiting case of the cylinder if (r2 .2 0. and for 20% error..) The logarithms in Equation.. To see when this is appropriate.4 0. ..5.r l = x.rl)/R t « 1.1 0.91 0.
(Ij / r2) . normalizing the spatial variable at T=+b.rl Ir2 lrl I r2 In nondimensional form the temperature distribution is thus 1i .= '''1i . so the equation for the temperature fieid is ~(r2 dT)=o. Applying the second boundary condition gives at T(r2) = T2 . Spherical Shell The area is now A(r) = 47tr2 . (r I Ij) where a' and b are constants of integration.33 T.(r 1 / r) b' =11 '7' 1i . Heat Transfer Fig. once yields dT a dr = r 2 ' Integrating again gives T=+b. a'= 1i T2 1.T2 .T 1...+ b.T2 1. (r2 11j) Solving for d and b. As before. dr dr Integrating Equation. we specify the temperatures at r = r l and r = r2 • Use of the first boundary condition gives T(r l ) = TI = d+ b. r a or.
Heat and Thermodynamics 34 CONVECTIVE HEAT TRANSFER The secocnd type of heat transfer to be examined is convection. Outside this layer. In a region of thickness 0. An example is the wall temperature in a turbine blade because turbine temperatures are critical for creep (and thus blade) life. A view of the problem is given which shows a crosssectional view of a turbine blade. Turbine Blade Heat Transfer Configuration y y Velocity distributioa. c (velocity) Fig.binc blade lurbine blade Fig. The conditions near a surface are illustrated schematically. where a key problem is determining the boundary conditions at a surface exposed to a flowing fluid. There are three different types of cooling indicated. (2) convection cooling 3) film cooling (I) jet impinging on insidcof Iu. The heat flux can thus be expressed as . In this case. T. there is a thin "film" of slowly moving fluid through which most of the temperature difference occurs. c . T is roughly uniform (this defines 0'). we need to analyze convective heat transfer.0 at sur&cc T T.. Temperature and Velocity Distributions near a Surface To find the turbine wall temperature. the turbine wall temperature is not known and must be found as part of the solution to the problem. which means we need to examine some features of the fluid motion near a surface. all meant to ensure that the metal is kept at a temperature much lower than that of the combustor exit flow in which the turbine blade operates.
It cannot be emphasized enough that this is a very crude picture. the fluid motion is smooth and laminar. is correct. Outside of this regiun is high mixing. and the heat flux dY l. Very near the wall. and molecular conduction and shear are important. A Equation is often called Newton's Law of Cooling. For many situations of practical interest. structure ofthe wall surface. A  . pressure gradient and Mach number. The difficulty is that the thickness of the layer is not a fluid property. in that close to the wall. . The treatment closely follows that in Eckert and Drake.Too). The units of hare WIm 2K. The convective heat transfer coefficient is defined by q = Q= h(Tw . the dominant mechanisms of shear stress and heat transfer change in nature as one moves away from the wall. _ Q_ k(T. however. at a plane is given by de ~= ='t (where ~ is the dynamic viscosity).v Too) 0' . The boundary layer is a region in which the velocity is lower than the free stream. The general concept. there is a thin layer in which heat is transferred basically by conduction.y q = k ~~ . The shear stress. It depends on velocity (Reynolds number). This quantity has the symbol h and is known as the convective heat transfer coefficient. Generally 0' is not known and needs to be found and it is customary to calculate the heat transfer using kfluiio' . the quantity is still known mainly through experiments. 't.. THE REYNOLDS ANALOGY We describe the physical mechanism for the heat transfer coefficient in a turbulent boundary layer because most aerospace vehicle applications have turbulent boundary layers.35 Heat Transfer q _. The latter is the same expression that was used for a solid. In a turbulent boundary layer.
. " . the same amount crosses aa from the other side.c).I m'c. If T' > T. Momentum and Energy Exchanges in Turbulent Flow With reference to Figure. .C)... the relation between heat flux and shear stress at plane aa is .1).T Fig. In steady flow. Fluid moving up also has momentum m' e and fluid moving down has momentum m' e'. .T' " . . The fluid particles move in random directions and the transfer of momentum and energy is mainly through interchange of fluid particles. Fluid moving up transports heat m'epT. :f): l~. Based on these considerations. This net flux of momentum per unit area and time is a force per unit area or stress. there is a turbulent downwards heat flow if turbulent' given by if turbulent = m' ep (T . . because of the turbulent velocity field. Fluid moving down transports m' cpT downwards.Heat and Thermodynamics 36 ~~ plane Fig. the flow is turbulent. . given by 'turbulent = m'(e' . The net flux of momentum down per unit area and time is therefore m' (e'. Velocity Profile Near a Surface As one moves away from the wall (but still in the boundary layer). that results. m'c. a fluid mass tn' penetrates the plane aa per unit time and unit area.
To get this. we from the wall to the free stream integrate the expression for dT dT=dc. The Prandtl number varies little over a wide range of temperatures: approximately 3% from 3002000 K. p where v is the kinematic viscosity. . T J.lCJk is known as the Prandtl number (Pr). the heat flux towards the wall is q=kdTldy and dividing by the expression for the shear stress._ c (T'T) ' q turbulent = 'tturbulent ep . cp't lq where the relation between heat transfer and shear stress has been taken as the same for both the laminar and the turbulent portions of the boundary layer. kdT Il dc The same relationship is applicable in laminar or turbulent flow if klJl = ep or.71 at room temrerature. For the laminar region. Equation can be integrated from the wall to the freestream (conditions "at 00"): .37 Heat Transfer qturbulent = 'tturbulent ep or (again approximately) e .lC p Illp _v_l k/pc . and a is the thermal diffusivity. The quantity J. We want a relation between the values at the wall (at which T = Twand e = 0) and those in the free stream. For gases. "fier the man who first presented the idea of the boundary layer and was one of the pioneers of modern fluid mechanics. The assumption being made is that the mechanisms of heat and momentum transfer are similar. 't = ~c1dy. yields q='t. (dT) ' de since the locations of planes 11 and 22 are arbitrary. Prandtl numbers are in fact close to unity and for air Pr = 0. expressed slightly differently.a ..
2 Equation provides a useful estimate of h. Carrying out the integration yields c Tw oC]w ""' T = o "wcp where Coo is the velocity and cp is the specific heat.Too)coo h(Too . h as C h ~ Poocpcoo f . 2 The relation between the heat transfer and the skin friction coefficient .~v) Poocp(Tw . known as the Stanton Number.Heat and Thermodynamics 38 r dT= C~ r( ~)dC. or drag. 'The relation between skin friction (shear stress) at the wall and heat transfer is thus C]w _~ PooC p (Tw . and cp are assumed constant.Too) Coo . If we define a nondimensional quantity C]W Poocp(Tw . The quantity i Poocoo 1 "w 2 is known as the skin friction coefficient and is denoted by Cj The skin friction coefficient has been tabulated (or computed) for a large number of situations. The direct relationship between the Stanton Number and the skin friction coefficient is Sf= Cf . C] IV is the heat flux to the wall and is the shear stress at the wall. we can write an expression for the heat transfer coefficient. "w where C] IT. In Equation.Too)coo = h Poocpcoo =St. or C] w' based on knowing the skin friction.Pooc~ .
The total heat transfer." An example of the use of the Reynolds analogy is in analysis of a heat exchanger. qw ~ 'twcp T8 Tw _ C The tluid resistance (drag) is all due to shear forces and is given by 'tw4w =D. where Aw is the tube "wetted" area (perimeter length). with the objective of transferring heat between them. which can be accomplished by increasing the crdsssectional area. i. Qriz2 Poc P cp(TBTw)A 2 2' Equations shows that to decrease the power dissipated. is if w4w' so that . To begin. One type of heat exchanger has an array of tubes with one fluid flowing inside and another fluid flowing outside. it is more appropriate to use an average velocity e and a bulk temperature TB • Thus. we need to examine the flow resistance of a tube. For fully developed flow in a tube. we need to decrease e. Q. The Reynolds analogy is extremely useful in obtaining a first approximation for heat transfer in situations in which the shear stre5s is "known. Dc . =D TB Tw Q cp _ • C The power. Two possible heat exchanger configurations the one on the right will have a iower loss. P. the power scales as c2 or as lIA2. so that Q= cp(TB Tw) P e2 The mass flow rate is given by m= peA.e. to drive the flow through a resistance is given by the product of the drag and the velocity. where is the cross sectional area. For a given mass flow rate and overall heat transfer rate. an approximate relation for the heat transfer is . .39 Heat Transfer is known as the Reynolds analogy between shear stress and heat transfer..
Heat Exchanger Configurations To recap. =2' 'w COMBINED CONDUCTION AND CONVECTION We can now analyze problems in which both conduction and convection occur. starting with a wall cooled by flowing fluid on each side. It is emphasized that it is a useful tool based on a hypothesis about the mechanism of heat transfer and shear stress and not a physical law. The relation is expressed by C Sf =1 2 ' or heat flux to wall convected heat flux or momentum flux to wall convected momentum flux ' tlw Pa:.Tw) paJCaJ The Reynolds analogy can be used to give information about sc.caJcp(TaJ .aling of various effects as well as initial estimates for heaL transfer. there is an approximate relation between skin friction (momentum flux to the wall) and heat transfer called the Reynolds analogy that provides a useful way to estimate heat transfer rates in situations in which the skin friction is known. A description of the convective heat transfer can be given explicitly as Q =ij=h(TwTaJ)' A This could represent a model of a turbine blade with internal cooling. .Heat and Thermodynamics beat exchanger 40 ~ high loss kwerloss Fig.
For a turbine blade in a gas turbine engine. ~A .Twl2) + (Tw2 . We can derine a thermal resistance.J.T I : T2 . Putting them all together to write the known overall temperature drop yields a relation between heat transfer and overall temperature drop.41 Heat Transfer Fig. QA which is the heat transfer per unit area to the fluid. such that Q= where R is given by 1 R L ' 1 AK ~A Equation is the thermal resistance for a solid wall with convection heat transfer on e.WI)' A L Q k The quantity QfA is the same in all of these expressions. Conducting Wall with Convective Heat Transfer The heat transfer in fluid 1 is given by ~ (Twl 1)). (T2 1)) ~ [~I + ~ + .TI ) = . R.TI = (T2 . T2 . as before. cooling is a critical R=++. \\' e have =(T. The heat transfer in fluid 2 is similarly given by Q=h2 (T2 Tw2)' A Across the wall.W 2 T.Tw 1) + (Twi .ach side.
One way to achieve the first of these is to have h2 low.. . Lh . In terms of Figure. the wall temperature can be written as Q T2 1J 1 ~Y2 =T2 . We wish to find Tw2 because this is the highest metal temperature.ce is given by q = Q= h(T. Cylinder in a Flowing Fluid For the cylinder the heat flux at the outer surf~. T = TI at r = r l .r I. the wall temperatures can be expressed in terms of heat transfer coefficients and wall properties as h. =+_2 +1 hi k Equation provides some basic design guidelines. From. This means h/h2 should be large. k should be large (but we may not have much flexibility in choice of material) and L should be small. T2 is the combustor exit (turbine inlet) temperature and TI is the temperature at the compressor exit. we use the latter to simplify the algebra.TrJeJ A atr = r2· The boundary condition at the inner surface could be either a heat flux condition or a temperature specification. A second example of combined conduction and convection is given by a cylinder exposed to a flowing fluid.Ah2 =T2 RAh · 2 Using the expression for the thermal resistance. ~Y2 = T2  T2 1J :> Fig.y . Thus. This is a model for the heat transfer in a pipe of radius r I surrounded by insulation of thickness r2 . The goal is to have a low value of Tw2.Heat and Thermodynamics 42 consideration. The solution for a cylindrical region was given as T(r) =a In(~) + h.
(TI Too is the driving temperature distribution for the pipe.43 Heat Transfer Use of the boundary condition T(r l ) = TI yields b = T 1• At the interface between the cylinder and the fluid. +htn(. Q. 1) Too +In(r21'i) hr2 The heat flow per unit length. in normalized nondimensional form. is given by Q = 21(1) .. " I heart flux inside cylinder surface heat flux to flu id Plugging the form of the temperature distribution in the cylinder into Equation yields a[:. )):h(1i T~) The constant of integration. q= _ _ k dT ~ dr = k. k . r = r2. 1) T In(l"lrl) = k .+ In (r2 Irl) hr2 The units in Equation are W1mso A problem of interest is choosing the thickness of insulation to minimize the heat loss for a fixed temperature difference TI Too between the inside of the pipe and the flowing fluid far away from the pipe. the temperature and the heat flow are continuous.' :h[[atn(. )+~ )T~] .Too )k . is and the expression for the temperature is. The thickness of insulation that gives maximum heat transfer is given by ..) To understand the behaviour of the heat transfer we examine the denominator in Equation as r 2 varies. a.
which shows a schematic of the thermal resistance and the heat transfer. tending to increase the heat transfer. the first with the In (ri r 1) term.. It is generally good practice to use nondimensionaI numbers. The second ofthese is (loosely) associated with the klhrs z term. First.. Casting equations in dimensionless form helps show the generality of application to a broad class of situations (rather than just one set of dimensional parameters). dr2 hrz lj From Equation. Ii Fig. There are thus two competing effects which combine to give a maximumQ at r z = klh. These parameters giv~ information as to the relevant flow regimes of a given solution. . As r 2 increases from a value less than r 2 = klh. Critical Radius of Insulation k DIMENSIONLESS NUMBERS AND ANALYSIS OF RESULTS Phenomena in fluid flow and heat transfer depend on dimensionless parameters.Heat and Thermodynamics 44 !!. the area of the outside surface of the insulation increases. two effects take place. the thickness ofthe insulation increases.. tending to drop the heat transfer because the temperature gradient decreases. the value of r2 for maximum k (rZ)maximum heat transfer Q is thus = . Secondly.. The Mach number and the Reynolds number are two you have already seen.(~+ In(rz J] = o. we can add insulation and increase heat loss. To understand why this occurs. If r 2 is less than this.
45
Heat Transfer
forms of equations, and results presentation whenever possible. The results for heat transfer from the cylinder are already in dimensionless form but we can carry the idea even further. For the cylinder, we had in Equation,
T Ii
Too
In (r / rj )
hr2
Ii = ~ + In (r2 /1j) .
The parameter hr21k or hLlk, where L is a relevant length for the particular problem of interest, is called the Biot number, denoted by Hi. In terms of this parameter, T Ii In (r / rj ) :...= 1 . Too Ii Hi + In (r2 /1j) The size of the Biot number gives a key to the regimes in which different features are dominant. For Bi » I the convection heat transfer process offers little resistance to heat transfer. There is thus only a small L\Toutside (i.e. T(r2) close to Too) compared to the L\T through the solid with a limiting behaviour of T Ii In (r / 1j ) =~~ Too  T In (r2 /1j) as Hi goes to infinity. This is much like the situation with an external temperature specified. For Bi « 1the conduction heat transfer process offers little resistance to heat transfer. The temperature difference in the body (i.e. from rjto r2 ) is small compared to the external temperature difference, T j  Too' In this situation, the limiting case is
T Tj = Bi In Too Ii 1j In this regime there is approximately uniform temperature in the cylinder. The size of the Biot number thus indicates the regimes where the different effects become important.
(!...).
RADIATION HEAT TRANSFER
All bodies radiate energy in the form of photons moving in a random direction, with random phase and frequency. When
Heat and Thermodynamics
46
radiated photons reach another surface, they may either be absorbed, reflected or transmitted. The behaviour of a surface with radiation incident upon it can be described by the following quantities: • a = absorptance  fraction of incident radiation absorbed • p = reflectance  fraction of incident radiation reflected • t = transmittance  fraction of incident radiation transmitted. Figure shows these processes graphically.
~
''\N<i'\,.Radi tion absorbed, a
I....J\MJ\.04. Radiation transmitted, 't
Incident radiation
Radiation reflected. P _VVOil\#1
Fig. Radiation Surface Properties
From energy considerations the three coefficients must sum to unity
a+p+t=l.
Reflective energy may be either diffuse or specular (mirrorlike). Diffuse reflections are independent of the incident radiation angle. For specular reflections, the reflection angle equals the angle of incidence.
IDEAL RADIATORS
An ideal thermal radiator is called a "black body." It has several properties: • It has a = 1, and absorbs all radiation incident on it. • The energy radiated per unit area is Eb = (J]4 where (J is the StefanBoltzmann constant, (J = 5.67 x 108 W/m 2K4. The units of Eb are therefore W/m 2 The energy of a black body, E b, is distributed over a range of wavelengths of radiation. We can define e').. = dEJdA ~ M/!lA, the energy radiated per unit area for a range of wavelengths of width !lA. The behaviour of eA
47
Heat Transfer
... J!
·s .
0
~
e
.: u
~
~
1~~~~~
~nll'a.)' 0.2898 emoK
=
:r 8.~
·S u
.~
;;
]
E
8
3 .!:
1 234 I • 7
~
Fig. Emissive Power of a Black Body at Several Temperatures, Predicted and Observed; (A.T)eA.max = 0.2898 cm K
The distribution of eA varies with temperature. The quantity AT at the condition where eA is a maximum is given by (AneAmax
= 0.2898 cm K. As T increases, the wavelength for maximum
energy emission shifts to shorter values. The frequency of the radiation, j, is given by f = ciA so high energy means short wavelengths and high frequency.
Fig. A Cavity with a Small hole (Approximates a Black Body)
I
Heat and Thermodynamics
Temperature T
48
Cavity
Blackbody
Fig. A Small Black Body Inside a Cavity
A physical real ization of a black body is a cavity with a small hole. There are many reflections and absorptions. Very few entering photons (light rays) will get out. The inside of the cavity has radiation which is homogeneous and isotropic (the same in any direction, uniform everywhere). Suppose we put a small black body inside the cavity. The cavity and the black body are both at the same temperature. The radiant energy absorbed by the black body per second and per m2 is all!, where H is the irradiance, the radiant energy falling on any surface inside the cavity. The radiant energy emitted by the black body is EB . Since aB = 1 for a black body, H= EB . The irradiance within a cavity whose walls are at temperature T is therefore equal to the radiant emittance of a black body at the same temperature and irradiance is a function of temperature only.
KIRCHHOFF'S LAW AND "REAL BODIES"
Real bodies radiate less effectively than black bodies. The measurement of this is the emittance, e, defined by E . E mlttance : e =, Eb where Eis radiation from the real body at T, and Eb is radiation from a black body at T. Values of emittance vary greatly for different materials. They are near unity for rough surfaces such as ceramics or oxidized metals, and roughly 0.02 for polished metals or silvered reflectors. The level of the emittance can be related to the absorptance using the following arguments. Suppose we have a small nonblack body in the cavity. The power absorbed per unit area is equal to
49
Heat Transfer
aH. The power emitted is equal to E. An energy balance gives E= EbE = aH= aEb. Thus E
=U=E.
Eb
Equation, the relation 0.= E, is known as Kirchhoffs Law. It implies that good radiators are good absorbers. It was derived for the case when Tbody = Tsurroundings (cavity) and is not strictly true for all circumstar.ces when the temperature of the body and the cavity are different, but it is true if at.. = a, Et.. = E, so the absorptance and emittance are not functions of A. This situation describes a "gray body." Also, since at.' Et.. are properties of the surface,
at..
= Et...
Surface 2
Radiation Heat Transfer Between Planar Surfaces
Surface: I
Fig. Path of a Photon between Two Gray Surfaces
Consider the two infinite gray surfaces. We suppose that the surfaces are thick enough so that a + p = 1 (no radiation transmitted so = 0). Consider a photon emitted from Surface 1 (remembering that the reflectance p = 1  a): Surface 1 emits E1 Surface 2 absorbs E1 0.2 Surface 2 reflects E1 (1  0.1) Surface 1 absorbs E1 (1  0.2) 0. 1 Surface 1 reflects E1 (1  0.2 )(1  0. 1) Surface 2 absorbs E\ (l  0.2) (1  0. 1) 0. 2 Surface 2 reflects E1 (1  0. 2) (l  0. 1) (1  0.2) Surface 1 absorbs E 1(1  0.2)(1  0. 1)(1  0. 2) 0. 1 The same can be said for a photon emitted from Surface 2: Surface 2 emits E2 Surface 1 absorbs E2o. 1
Heat and Thermodynamics
50
Surface I reflects E2(l  a\) Surface 2 absorbs E 2( 1  a 2)a2 Surface 2 reflects Ei1  a\)(l  a 2 ) We can add up all the energy E\ absorbed in 1 and all the energy E2 absorbed in 2. In doing the bookkeeping, it is helpful to define 13 = (I  a\)(l  a 2). The energy E\ absorbed in I is
E( (la2)a\ + E((1a2)a( (la2)(1 a\) + ....
This is equal to However
1=(113)( =1+13+13 2 + .... 113 We thus observe that the radiation absorbed by surface 1 can be written as
Likewise
E\(Ia\)a2
113 is the radiation generated at 2 and absorbed there as well. Putting th is all together we find that
E2 _(E2(1 a\) a2) = E2a\
113 113 is absorbed by 1. The net heat flux from 1 to 2 is
= E\ _ E\(la2)a\
qnetlto2 113
E2a\
113 l(la( a2 +a,a2)
E\E\(lala2 +ala2)E1a l +E1a la2 E2a l
or
Qnetlto2 al +a2 a1a2
If TI
= T2, we would have Q= 0, so from Equation,
EI = E2 = J(T).
a(
a2
Ela1l4E2 . and E2 El = crT4. Schematic of a Thermos Wall El = E2 = 0. surfaces. 4E . E) = a 1for any gray surface (Kirchhoffs Law).02 (293 K)4) = 69 WI 2 . Therefore. Using Kirchhoffs Law we find.E2 aT2 I qnetlto2 = E) +E2 EIE2 or.02 0.02 for silvered walls. as the final expression for heat transfer between gray. qnet lto 2 = s(lI4 . El crT4 a) =crT4. cr(1I4 Qnetlto2 = El . again. planar.51 Heat Transfer If body 2 is black. ('(.1 = art. .1)7 x 108 W/m2K4)«373 K)4 1 1 +1 0. a 2 = 1.T24) . +1 USE OF A THERMOS BOTTLE TO REDUCE HEAT TRANSFER Silvered Walls Inside oflhennos (hot fluid) OulSidc ofl1lennos (Cold) I '2 Fig. Tl = 100°C = 373 K T2 = 20°C = 293K.T24 ) El E2 1 1 . 1 1 = qnet lto 2 +1 E2 = (5. m. .
.. kl:!T .. the walls are at 100°C. L _ kflT _ (0.047 q=Tsoathlckness 6./ \·olumc ><..~..: Control .Heat and Thermodynamics 52 For the same I:!T. m T would be needed! The thermos is indeed a good insulator. Consider a black thermocouple in a chamber with black walls. . Thermocouples are commonly used to measure temperature.04 W/m. and the convective heat transfer coefficient is h = 15 Wmf2K. what thickness would be needed? ." I Hcal oul (convection) TwoIl Fig.04 WI mK. Effect of Radiation Heat Transfer on Measured Temperature . TEMPERATURE MEASUREMENT ERROR DUE TO RADIATION HEAT TRANSFER metal I mccal2 ~Volla&O Fig. Thermocouple Used to Measure Temperature... .9W/m . Note: The Measured Voltage is Related to the Difference between T) and T2 (the Latter is a known Temperature). What temperature does the thermocouple read? Heal in (radiation) tTie ' . . There can be errors due to heat transfer by radiation. if we had cork insulation with k = 0. ..K)(80 K) .. Suppose the air is at 20°C..
although it would be included for accurate measurements. Radialionshicld 1000<: Fig. The thermocouple thus sees a higher temperature than the air. a given object 1 radiates to object 2. for any two objects in space. The heat balance states that heat convected away is equal to heat radiated into the thermocouple in steady state. We could reduc~ this error by shielding the thermocouple.53 Heat Transfer We use a heat (energy) balance on the control surface. Substituting the numerical values gives (15 Wm2K)Ttc293 K) = (5. (Conduction heat transfer along the thermocouple wires is neglected here.67 x 108 W/m2K4) ((373 K)4_ ~~) from which we find ~c = 51°C = 324 K. Radiation hetween Two Bodies . and to other places as well. Fig. where A is the area of the thermocouple.) The heat balance is hA(~c .~ir ) = sA(T~all  ~~). Shielding a Thermocouple to Reduce Radiation Heat Transfer Error RADIATION HEAT TRANSFER BETWEEN BLACK SURFACES OF ARBITRARY GEOMETRY In general.
Thus Equation is the shape factor reciprocity relation. The net energy interchange from body 1 to body 2 is Ebl A IF I_2 . Fig.Eb2A2F2_1 = 0. so the energy leaving body I is EblA I.Heat and lherrnodynamics 54 Pody2 Body I Fig. we know that Eb is the emissive power of a black body. but also Ebl = E b2 .Eb2A2F2_1 Suppose both surfaces are at the same temperature so there is no net heat exchange. Radiation between Two Arbitrary Surfaces We want a general expression for energy interchange between two surfaces at different temperatures. This is given by the radiation shape factor or view factor. The energy leaving body I and arriving (and being absorbed) at body 2 is EblA IFI_ 2. Radiation Heat Transfer for Concentric Cylinders or Spheres . F i _/ For the situation in figure. The net heat exchange between the two surfaces is A 1F I _2 = QI2· =A 2F2_ 1• g2 =A1Fi2(Ebl Eb2 ) [or A2F2_1(F2_1Eb2)] Concentric cylinders or concentric spheres (SfT' T. If so. F I _2 =fraction of energy leaving I which reaches 2 F2_ 1 = fraction of energy leaving 2 which reaches I F I _2 ' F2 _1 are functions of geometry only For body 1. Ebl A IF I_2 . The energy leaving body 2 and being absorbed at body 1 is Eb2A2F2_1.
G2 =A2F2.Ebl ) =AlFi2 (Fb2 . Gaskell.Eb2 ) =I. Mixing and Excess Thermodynamic Properties (Physical sciences data) by Jaime Wisniak and Abraham Tamir.. that all of the energy emitted G2 =Al (Ebl . 2nd edition (Schaum's Outlines) by Merle Potter and Ph.55 Heat Transfer The net heat transfer from surface I to surface 2 of figure is We know that F I _2 by I gets to 2. Schaum's Outline of Thermodynamics for Engineers.1(Eb2 . Craig Somerton.e.Ebl ) =At (Eb2 . i. Holman. Schaum Engineering Thermodynamics (Schaum's Outlines) by Merle Potter. ..P.Eb2 )· This can be used to find the net heat transfer from 2 to I.D. Thermodynamics by J.Ebl )· REFERENCES • • • • • Introduction to Metallurgical Thermodynamics by David R. Thus G2 =A1Fi2(Ebl .
Examples are: • Electrical heaters where electrical energy is converted resistively into heat. T. Slab with Heat Sources With reference to Figure. a steadystate energy balance yields an equation for the heat flux. Sli(c III. Nuclear power supplies.3 _______________ Heat Conduction TEMPERATURE DISTRIBUTIONS IN THE PRESENCE OF HEAT SOURCES There are a number of situations in which there are sources of heat in the domain of interest...t. • Propellants where chemical energy is the source.. We take the outside walls to be at temperature Tw and we will determine the maximum internal temperature. x t dot beac sour<:eI W a m' . These situations can be analyzed by looking at a model problem of a slab with heat sources (W/ m3) distributed throughout. .... t [InfiniteSimal slice] x x + dx Fig.(q + ~! ax) = o. : q + adx .
5 1. with half the energy due to the sources exiting the slab on each side.(~~l . The boundary conditions imposed are T(O) = T(L) = Tw' Substituting these into Equation gives b = Tw and a = aLl2k. nondimensional fashion gives a form that exhibits in a more useful manner the way in which the different parameters enter the problem: T Tw aL2 I k . The temperature distribution is thus T=_~X2 +~Lx+T . Fig.!. dT a =x+a dx k ' and again to give 2k where and are constants of integration. 2k 2k w T=x +ax+b.. . dx 2 k d 2T a Equation can be integrated once. The equation for the temperature is +=0.57 or Heat Conduction a.2 L .0 I. a 2 Writing in a normalized. dx dq _ There is a change in heat flux with x due to the presence of the heat sources. Temperature Distribution for Slab with Distributed Heat Sources It is symmetric about the midplane at x = Ll2. L2 (:~/: ) X o 0.
the heat flux and temperature are continuous so ' Referring to the temperature distribution of Equation gives for the two terms in Equation.l=h( a. x = 0. can be found by differentiating the temperature distribution and evaluating at x = 0: _kdTI dx x=o =k aL2 != _aL 2k L 2 This is half of the total heat generated within the slab. with the high thermal conductivity allowing increased heat being conducted from the wall through the fin. Typically. so that Tw is not known.Heat and Thermodynamics 58 The heat flux at the side of the slab. We again determine the maximum temperature.= h(T .: +ax+hT. This is left as an exercise for the reader. k dT =k (ax a ) = (ax + ka). although the direction is opposite.) Evaluating Equation at x = 0 and L allows determination cf the two constants a and b. . which cools or heats it. HEAT TRANSFER FROM A FIN Fins are used in a large number of applications to increase the heat transfer from surfaces. dx T+ dT k . the fin material has a high thermal conductivity. At x = 0 and L.T. A related problem would be one in which there were heat flux (rather !han temperature) boundary conditions at x = 0 and x = L. The design of cooling fin~ is encountered in many situations and we thus examine heat transfer in a fin as a way of defining some criteria for design.oo ) at x dx =0 L h(TT. The magnitude of the heat flux is the same at x = L. The fin is exposed to a flowing fluid.
The end of the fin can have a different heat transfer coefficient. The heat transfer per unit area within the fin in the transverse direction is (again in the same approximate terms) ~ k (1. AlP = rl2). With a fin crosssection equal to A and a perimeter P. The regime of interest will be taken to be that for which the Biot number is much less than unity. which we can call hL. there is a much larger capability for heat transfer per unit area across the fin than there is between the . in that the temperature in the fin will be assumed to be a function of only. The approach taken will be quasionedimensional. Bi = h (AIPlk« 1). Heat transfer per unit area out of the fin to the fluid is roughly of magnitude ~ h( Tw . The other parameters of the problem are indicated. where T} is an internal temperature. which is a realistic approximation in practice. if Bi « 1. and it needs some explanation. . In other words. These two quantities must be of the same magnitude.Too). then (T} . The fluid has velocity cooand temperature Too. the characteristic dimension in the transverse direction is AlP (For a circular fin. We assume (using the Reynolds analogy or other approach) that the heat transfer coefficient for the fin is known and has the value h. Geometry of Heat Transfer Fin The fin is of length L. The physical content of this approximation can be seen from the following.59 Heat Conduction T.TOO> per unit area.Tw)/(Tw .(wall) y Fig. This may seem a drastic simplification.. If h(AIP)lk« I. ~v) AlP .
an appropriate model is to say that the temperature within the fin is a function of x only.Heat and Thennodynamics 60 Q +! % · . for a cooling fin. dx In terms of the temperature distribution.. Q = irA. where Pdx is the area for heat transfer to the fluid.Trr). To do this. and use a quasionedimensional approach. : · x+tbc Q Fig. dx. Element of Fin Showing Heat Transfer If there is little variation in temperature across the fin. consider an element. of the fin. T(x): . for a fin of constant area: rjA = Ph(T .Too)dx + (rjA + : dxA ) From Equation we obtain drj A +Ph(TToo)=O. There is also heat transfer around the perimeter on the top. T = T(x). and sides of the fin. but here. in each elemental slice of thickness there is essentially a heat sink of magnitude Pdxh(T . dx2 Ak 00 The quantity of interest is the temperature difference (T . this is a situation similar to that with internal heat sources. There is heat flow of magnitude Qin at the lefthand side and heat flow out of magnitude Qout = Qin + dx at the right hand side.Too)' and we can change variables to put Equation in terms of this quantity using the substitution . dT _ Ph (T T )=0. bottom. + ! : +. From a quasionedimensional point of view. The heat balance for the element in Figure can be written in terms of the heat flux using 1.
It is a second order equation and needs two boundary conditions. (Does this sound plausible? Why or why not?) (T . dx2 00 Ak 00 Equation describes the temperature variation along the fin. d~2 2  .Too)x=O = To .Too' The second boundary conditicn is at the other end of the fin.61 dx 00 dx Equation can therefore be written as Heat Conduction !!.Too). as!1T where the values of!1T range from zero to one. d2 Ph (TT )(TT )=0. d~2 kA == !!. d d~ dId There is one nondimensional parameter in Equation.Too)1 (To. where ~ also ranges over zero to one. We also define ~ = xlL.(T . The first of these is that the temperature at the end of the fin that joins the wall is equal to the wall temperature. The boundary condition at x = L is dx x=L The last step is to work in terms of nondimensional variables to obtain a more compact description.Too )/ =o. The relation between derivatives that is needed to cast the equation in terms of ~ is dx dx d~ L d~ Equation can be written in this dimensionless form as 2 d !1T _(hP L2)!1T = O. We will assume that tht: heat transfer from this end is negligible.(T . In this we define as (T .T ) = dT . which we will call m and define by m 2 L2 = hPL 2 kA The equation for the temperature distribution we have obtained is d !1T _m 2L2!1T =O.
2 llT = cosh mL (1. : .~ cosh ( (li)JgL ) JgL) I The amount of heat removed from the wall due to the fin. The boundary condition at ~ = 0 is LlT(O) = a + b = 1. d Q = kA(T . cosh mL This is the solution to Equation for a fin with no heat transfer at the tip. cosh (mL) = tanh (mL).~) . The boundary condition ~ = 1 at is that the temperature gradient is zero or dllT (L) = mLaemL _ mLbemL = o. which is the quantity of interest.Too) dx x=o or _ dllTI kA(To Too) d~ x=o = mL sin h(mL) = mL tanh (mL).X) cosh X= . can be found by differentiating the temperature and evaluating the derivative at the wall. d~ Solving the two equations given by the boundary conditions for a and b gives an expression for LlT in terms of the hyperbolic cosine or: (eX +e. ~kAhP(To Too) QL .Too cosh ( = ''.:=.Heat and Thermodynamics 62 This second order equation has the solution td =aemL~ + bemL~ . In terms of the actual heat transfer parameters it is written as T Too To .
T. tip (T. the assumption about no heat transfer at the end begins to be inappropriate as gets smaller than 3. Dimcnsionlcu heat flow into the fin. The disks that hold the blades are large and take a long time to come to temperature.xII. Tip Temperature and Heat Flux in a Straight Onedimensional Fin with the Tip Insulated... An example is the heating up of gas turbine compressors as they are brought up to speed during takeoff. Second. First.T.T. Q Dmsionless temperalUI'C . TRANSIENT HEAT TRANSFER All the heat transfer problems we have examined have been steady state. The Temperature Distribution. but there are often circumstances in which the transieni: response to heat transfer is critical. while the casing is thin and in the path of high velocity compressor flow and thus comes to temperature .)I(7"o. so for very short fins the simple expression above would not be a good estimate.) Diml:nsionlcss temperature (T.T.63 Heat Conduction The solution is plotted in Figure.) Dimensionless axial posilion ~ . which is taken from the book by Lienhard. Several features of the solution should be noted. Fig. We will see below how large the error is.)I(T. one does not need fins which have a length such that is much greater than 3.
. The first law applied to the object is (using the fact that for solids cp = Cv = c). L where L is a relevant length scale.Tw)/(Tw.lysis would be appropriate. The ratio of the temperature difference is 11 Tw TwToo ~T' hL If the Biot number is small the ratio of temperature differences described in Equation is also (T1. The approximation made is to view the object as having a spatially uniform temperature that is a function of time only. To address this. k h(Tw Too)~(l1 ~v). This will allow us to see what the relevant nOlldimensional parameters are and. we examine a lumped parameter analysis of an object cooled by a stream.Tw between two locations in the object.Tw) « Tw .Too and neglect the temperature nonuniformity within the object. say half the thickness of the object. Temperature Variation in an Object Cooled by a Flowing Fluid If the heat transfer within the body and from the body to the fluid are of the same magnitude.TrL)« 1. We need to determine when this type of ana. The result is that the case expands away from the blade tips. To introduce the topic as well as to increase familiarity with modeling of heat transfer problems. We want to view the object as a "lump" described by a single parameter. Explicitly. consider the temperature difference TI . sometimes enough to cause serious difficulties with aerodynamic performance. c T Fig. T = T(t). We can thus say (T1 . at least in a qualitative fashion.Heat and Thermodynamics 64 rapidly. how more complex heat transfer objects will behave.
is equal to some known value. this nondimensional quantity is equal to one. a number of physical processes which have (or can be modeled as having) this type of exponentially decaying behaviour. high density. dT Qin =pVc . Equation can be written in terms of a nondimensional temperature difference (T . while high heat transfer coefficient and large area will tend to decrease the time constant. dt where p is the density of the object and is its volume. . as shown schematically in Figure.Too. Equation is an equation you have seep.65 Heat Conduction . (: + ~ = 0) which has the solution x ~ (~ = ) ~c ~ = ) . large volume. + ( =O. 't.pVcdTldt. is in accord with our intuition. The rate of heat transfer to the fluid is Ah(T .: ~: "'=ae = aetir• For the present problem the form is T TCX) hAt/pVc 1'. In terms of heat transferred to the fluid. Qout =. The time dependence of the voltage in the RC circuit when the switch is opened suddenly is given by the equation dt RC There are. At time t = 0.Too)/(Tj . before. ItO). The constant can be seen to be equal to unity to satisfy the initial condition. dt The initial temperature. dE E +=0. so the expression for the time evolution of the temperature is dT Ah(TTCX»)=pVc. The time constant. This is the same form of equation and the same behaviour you have seen for the RC circuit. or experience. which we can canTr Using this. or high specific heat all tend to increase the time constant.TCX»). This form of equation implies that the solution has a heat transfer "time constant" given by 't = pVclhA. in fact. TCX) .
especially for fluid flow problems. one almost always cannot compute the process exactly. Modeling can span an enormous range from the level of our assumption of uniform temperature within the solid object to a complex model for the small scale turbulent eddies in the flow past a compressor blade.Tw):::. we said that Tbody is approximately uniform and Tw :::.(Tc . it is critical to have a clear idea of just what the assumptions really mean.e. to define some plausible behaviour for attributes of the system that will not be computed. i. These are all part of the general approach to modeling of physical systems. One assertion made was that because hLlk« 1 and on the basis of a heat balance. 1 Based on this. h(Tw . one generally needs to model. L we could assume (Tbody interior  Tw) (TwToo) «. The only place where . The main idea is that for engineering systems. as well as the fidelity that we ascribe to the descriptions of actual physical phenomena. Tbody interior.Too). At some level of detail.Heat and Thermodynamics 66 R Fig. Another aspect is that setting erases any geometrical detail of the fin cross section. In carrying out such modeling. k . and we thus look at the statements we have made in this context. Voltage Change in an RC Circuit MODELING COMPLEX PHYSICAL PROCESSES A number of assumptions were made about the processes that we were attempting to describe.
The simplest heat exchanger is one for which the hot and cold fluids move in the same or opposite directions in a concentric tube (or doublepipe) construction. you can see that Equation reduces to the previous result. was that the heat transfer at the far end can be neglected. In the counterflow arrangement of Figure. In the parallelflow arrangement of Figure. where hLLlk is an axial Biot number is given as Equation. and leave at opposite ends. 1 . the fluids enter at opposite ends. Conductive heat transfer through the tube wall. the hot and cold fluids enter at the same end.)) cosh(mL)+(Biaxial/mL)sin h(mL) Q _ BiaxIal / mL + tan h (mL) 1+ Biaxial tan h (mL) mL . flow in the same direction. and • Convective heat transfer from the outer tube wall to the outside fluid. The solution including this effect.Too ToToo and =cosh (mL(l1. If the quantity hLLlk is small. made in the fin problem.67 Heat Conduction P and A enter the problem is in a nondimensional combination. T . flow in opposite directions.Too) HEAT EXCHANGERS The general function of a heat exchanger is to transfer heat from one fluid to another. A third assumption. There are thus three heat transfer operations that need to be described: • Convective heat transfer from fluid to the inner wall of the tube.)) + (Biaxial / m) sin h(mL(I1. Heat exchangers are typically classified according to flow arrangement and type of construction.JkAhP(To . and leave at the same end. The basic component of '1 heat exchanger can be viewed as a tube with one fluid running through it and another fluid flowing by on the outside.
. and temperature variations are primarily in the main flow direction. Crossflow Heat Exchangers Alternatively. hence mixing.() [Parallel flow] [Counter flow] . while one fluid is mixed and the other unmixed in the unfinned exchanger. .!.. To develop the methodology for heat exchanger analysis and design. In contrast. we look at the problem of heat transfer from a fluid inside a tube to another fluid outside.  It ~l~~:~'j T=/1Jl) Fig. The two configurations differ according to whether the fluid moving over the tubes is unmixed or mixed. The fluid is said to be unmixed because the fins prevent motion in a direction (x) that is transverse to the main flow direction (y). both fluids are unmixed in the finned exchanger. in the transverse direction is possible.. In this case the fluid temperature varies with x and y.Heat and Thermodynamics 68 ~ ~~. . as shown by the finned and unfinned tubular heat exchangers of Figure.·/  . for the unfinned tube bundle of Figure. . Since the tube flow is unmixed. Concentric Tubes heat Exchangers ('n~sn('M T=ftr••. the fluids may be in cross flow (perpendicular to each other)..: Tube flow [Finned with both fluids unmixed] [Unfinned with one fluid mixed and the other unmixed] Fig.~: ' . fluid motion.
n.2. Counterflow Heat Exchanger . t Fig.69 Heat Conduction T. the resistance due to convection on the interior.. he 'i~ k 'i h2 We will make use of this in what follows. and include in our expres')ion for heat transfer the bulk temperature of the fluid. TI • It is useful to define an overall heat transfer coefficient ho per unit length as TB) From Equations the overall heat transfer coefficient....J T. Tl Fig.+ r2 In(r2 )+~.. T»~~~~ rJ~~ r :=J llr. rather than the interior wall temperature. TA. ho' is Q= 27tr2 hO (TA  ~=. Geometry for Heat Transfer between Two Fluids We examined this problem before in Section and found that the heat transfer rate per unit length is given by Q= 'ihl 2pk(TA TB ) • ~+~+ln(r2) r2h2 rl Here we have taken into account one additional thermal resistance..
where D is the pipe diameter. Fluid Temperature Distribution Along the Tube with Uniform Wall Temperature The objective is to find the mean temperature of the fluid at x.Heat and Thennodynamics 70 A schematic of a counterflow heat exchanger. we find 1tD2 . x=O x=L tbc T. We wish to know the temperature distribution along the tube and the amQunt of heat transferred. The heat given to the fluid (the change in enthalpy) is given by pumc p dT = mCpdT. the heat flow from the pipe wall in a length dx is ero {J1tl1dx = h1tD(To . T(x). in the case where fluid comes in at x = 0 with temperature T j and leaves at x = L with temperature T 2• The expected distribution for heating and cooling are sketched in Figure. c is the specific heat of the fluid and mis the mass flow rate o{the fluid. Fig. SIMPLIFIED COUNTERFLOW HEAT EXCHANGER To address this we start by considering the general case of axial variation of temperature in a tube with wall at uniform temperature To and a fluid flowing inside the tube. 4 where p is the density of the fluid. T. urn is the mean velocity of the fluid. For heating > 1).T)dt. .+It. . Setting the last two expressions equal and integrating from the start of the pipe.
The exit temperature at x = L is To T2 rirc p To Ii The total heat transfer to the wall all along the pipe is "== e nhDL Q = mC p (1] T2 )· From Equation. 4hx = pumcpD I.7tum cp D· Equation can be written as To T /h =e .71 Heat Conduction . defined as . This is the temperature distribution along the pipe.lnc p .dT 1 To T = 1pumcpD dx. IToT IToT TOT 1 In ( To .T2 ) In (Ii To) T2 To or Q=h7tDL!)'Tu.T ) _ _ 4hx To Ii ..e. 4h 1 Carrying out the integration. '~=_'~=_'d(ToT)=_ln(To_T)I~. To 1] where B_ 4h _ 7thD . mep ~ ( To Ii hrtDL l To T2 The total rate of heat transfer is therefore Q= hnDL(Ii .f' where !)'TLM is the logarithmic mean temperature difference.pumcpD .
q = hoL1T where ho is the overall heat transfer coefficient.c 1 maC pa mb pb Wa Wb where W = mcp' Also. and write an overall heat balance between the two counterflowing streams as Q=maCpa(Tal Ta2)=mbcpb(Tb2 1[.= L11\ ._1____l_]qdA =_(_1 __ )q1CDd:"(. Solving for dTa and dTb. the heat given up by ~tream in length dx is macpadTao (There is a negative sign since Ta decreases). .Tb2 Wa Wb Equation can also be written as .qdA .L1T2 r From a local heat balance. we find = = = dTa = _ .1)' ~ = ) ~~ i 11 = '. The heat taken up by stream b is mbcpadTb.. The local heat balance is maC padTb mbc pbdTb qdA q1CDx.b = qdA . . We will define a logarithmic mean temperature difference for the general counterflow heat exchanger below. macpa macpb 0 d(Ta Tb )=dL1T =_(_. In(Ta2 Tbl)=_ho1CDL(_1 __ ). dT. GENERAL COUNTERFLOW HEAT EXCHANGER We return to our original problem. We can then say dL1T =ho 1CL1 (_1 __ 1 L1T Wa Wb Integrating from x = 0 to x gives )\dx. 1 Tal . (There is a negative sign because Tb decreases as x increases).Heat and Thennodynamics DTLM = 72 T2 In ( In ( The concept of a logarithmic mean temperature difference is useful in the analysis of heat exchangers.
Tb2 ) .(Ta2 . (1 1) Wa .73 Heat Conduction where a.Wb .Tb2 ) or (Ta2 . _1___1_) n Tal Tb2 ( = Wa Wi.Tbl ) In(Tal .~b ) in terms of other (Ta2 Tbl ) . ho7tDL Substituting Equations we obtain a final expression for the total heat transfer for a counterflow heat exchanger: Q= ho7tDL (Tal .Tb2) Ta2 Tbl . Solving for the total heat transfer: Q= (Tal Tb2 )(Ta2 Tbl ). 1 Wa Wb We know that Thus (Tal . (~a ~b) Rearranging allows us to express parameters as I (~a .Tbl ) = Q . =ho 7tDL (_1 __ ).
.Tbl )· We examine three examples.T bl ) eu Wa (Tal .Tal = Tbl . (Tal .~ eu ) = (Tal Ta2 )(1e U ). Ta2 .u Wb or (Tal T b2 {1.. mb c pb 1 rcDLho . Ta2 ..Heat and Thermodynamics 74 EFFICIENCY OF A COUNTERFLOW HEAT EXCHANGER Suppose we know only the two inlet temperatures and we need to find the outlet temperatures..Tal = Tbl .. Tb2 = Tbl Tal' T bl . • > maC pa D T can approach zero at cvld end. We can use this result in to find Tb2 : Tb2 .Tb2 ) = 11 (Tal . + Wa Wb (Tal .(Tal mbcpb maCpa Ta2 ) =..T b2 ) ea.Ta2 ) e.Tal)' where 11 is the efficiency of a counterflow heat exchanger: 11 = 1eu 1.Tb2 ) ea. Solving first for T a2 .T a2 ). Ta2 . or.e Wb Wa u 1eu = : le mbCpa maCpa_u Equation=gives Ta2 in terms of known quantities..Tal + (Tal . From.Tbl = (Tal .Tbl =. We now have two equations. rearranging..Tal + (Tal . Equation and two unknowns... Ta2 and T b2 .11 (Tal mbcpb macpa . Eliminating Q from Equation. [ macpa mbcpb 1) .
11 ~ ~ as [] ® ¥ (Wb < Wa ) a pa Ta2 .Tbl mb c pb Maximum value of ratio Maximum value of ratio • a is negative. R. M. Course in Thermodynamics. Essentials of Thermodynamics (Essentials) by Research & Education Association. • • • • • DK Science Encyclopedia by Susan McKeever and Martyn Foote. Rea. Introductory Statistical Mechanics. Bowley and M. . Bergersen . 11 References < maC pa = 1. Revised Printing.Tb2 maC pa =Tal .Tb) = 0 temperature difference remains uniform. and Staff of Research Education Association. Tal Ta2 Tal Tbl Tb2 . (Series in Thermal and Fluids Engineering) by Joseph Kestin. Volume II.75 Heat Conduction h ~ 1as ho' surface area. Sanchez Equilibrium Statistical Physics.Ta2 mbCpb Maximum value of ratio T al ~ bl = m Cpa a 1 mb Cpb Maximum value of ratio • mb c pb Ta2 Tal = Tal T bl d (Ta . Plische and B.
these only become important when the gas is very close to the temperature at which it become liquid. The tortuous path that led him to this conclusion is described in an earlier lecture. Julius Robert Mayer was the first to appreciate that there is an equivalence between heat and mechanical work. . This heatwork interplay is called thermodynamics. and vice versa.4 ______________________________ The Behaviour of Gases IDEAL GAS MODEL. heating the gas necessarily increased its volume. Mayer realized that in the latter case. we will be analyzing the behaviour of gases in the pressure and temperature range corresponding to heat engines. The key was that they had measured specific heats both at constant volume and at constant pressure. In fact. It ignores interactions between molecules. though. In this lecture. but once he was there. our Programme here is to learn how gases absorb heat and turn it into work. he realized that in fact the numerical equivalencehow many Joules in one calorie in present day terminologycould be figured out easily from the results of some measurements of gas specific heat by French scientists. HEAT. and in this range the Ideal Gas Model is an excellent approximation. WORKAND HERMODYNAMICS The Kinetic Theory picture of a gas (outlined in the previous lecture) is often called the Ideal Gas Model. and tne gas therefore did work in pushing to expand its container. and the finite size of molecules. or under extremely high pressure. Essentially.
• Specific heat at constant pressure. and this total weight. will not change as the piston moves slowly up or down: the gas is at constant pressure. of course. C v (piston glued in place). GAS MOVEABLE PISTON Moveable ~ piston .. no friction). evidently the extra heat needed to raise the temperature of the gas at constant pressure was exactly the work the gas did on its container. so one mole of gasAvogadro's number of 2 moleculeswill have total kinetic energy... Cp (piston free to rise. In fact..77 The Behaviour of Gases Having convinced himself that mechanical work and heat were equivalent. recall the average kinetic energy per molecule is 2kT. The pressure on the gas is just the total weight pressing down divided by the area of the piston.. able to move up and down the cylinder smoothly with negligible friction.. Gas1. we already worked out C v in the Kinetic Theory lecture: at temperature T. let's say one mole: • Specific heat at constant volume. which we'll label internal energy. carrying a fixed weight. . held in by a piston. The simplest way to see what's going on is to imagine the gas in a cylinder. The Gas Specific Heats Cv and Cp Consider now the two specific heats of this same sample of gas.
the total heat energy needed to raise the temperature of one mole by one degree. the gas does work PA. If the area of piston is A. As Mayer realized. Now. then the gas at pressure P exerts force PA.l1h tk = PI1V. PV = RT. is held in a cylinder at constant pressure. CIt's known as Mayer's relationship.NA That the internal energy is RT per mole immediately gives us the specific heat of a mole of gas in a fixed volume. 3 Cv =R 2 t =t RT. Therefore. the total heat energy that must be supplied to raise the temperature of the gas one degree at constant pressure is per molecule plus the energy required to lift the weight. this relationship is true whether or not the molecules have rotational or vibrational internal energy. and R from the two rotational modes of a dumbbell molecule Gust why there is no contribution form rotation about the third axis can only be understood using quantum mechanics). experiment confirms that more heat must be supplied to raise the gas temperature by one degree.) The specific heat of oxygen at constant volume 5 CV (02 ) ="2 R and this is understood as a contribution of R from kinetic energy. the work done by the gas in raising the weight is just RI1T. if the gas. for one mole of gas. The work the gas must do to raise the weight is the force the gas exerts on the piston multiplied by the distance the piston moves. the specific heat at constant pressure. Cp = Cv+R. If on heating through one degree the piston rises a distance 1111. However.Heat and Thermodynamics 78 EmdkT. that being the heat which must be supplied to raise the temperature by one degree. The specific heat of oxygen at constant pressure t . so at constant P PI1V= RI1T. instead of being in a fixed box. In fact.
The two sets of reversible paths are the isotherms and the adiabats. 2 The Behaviour of Gases It's worth having a standard symbol for the ratio of the specific heats: =y. In a heat engine. say. V will trace a hyperbolic path in the (P. We do that by tracing a curve in the (P. the variables P.79 7 Cp (02) = R. V) plane backwards. T. The gas can expand doing work. we must follow the varying state of the gas. Cp Cv Tracking a Gas in the (P. To track what's going on as a gas engine transfers heat to work. Supplying heat to a gas which consequently expands and does mechanical work is the key to the heat engine. V) plane. But if there is a fixed mass of gas. Isothermal be!7m'iour: The gas is kept at constant temperature by allowing heat flow back and forth with a very large object (a "heat reservoir") at temperature T. it is evident that for a fixed mass of gas. There are. From PV = nRT. V. The route it follows will depend on whether or not heat is being supplied (or taken away) at the same time. held at constant T but subject to (slowly) varying pressure. V) plane. heat can enter the gas. however. But just knowing that a gas is expanding and doing work is not enough information to follow its path in the (P. It's important to concentrate on reversible paths. . fixing two of these variables fixes the third from PV= nRT(for n moles). two particular ways a gas can expand reversiblymeaning that a tiny change in the external conditions would be sufficient for the gas to retrace its path in the (P. then leave at a different stage. V) plane. V) Plane: Isotherms and Adiabats An ideal gas in a box has three thermodynamic variables: P. because as Carnot proved they correspond to the most efficient engines. or contract as work is done on it.
As the gas is compressed. it follows a curve in the (P. So all the work done ion compressing the gas has to go into the internal energy E int . its temperature is necessarily rising. in this case no heat gets in or out of the gas through the walls. Since the gas's internal energy is increasing. In the diagram below. PV = nRTI' say is called the isotherm at temperature T1• Here are two examples of isotherms: Adiabatic behaviour: "Adiabatic" means "nothing gets through". This means the adiabats are always steeper than the isotherms. imagine beginning at some point on the blue 273K isotherm on the above graph. V) plane called an adiabat. it will move towards the red curve. taen above it. Adiabatic Compression Cylinder of insulating material: Isotherms PV = RT for One Mole at 273K. but the number of molecules is staying the same. we've added a couple of adiabats to the isotherms: . 373K 18r~ 16 2 0+~~~~~~~~ o 2 3 4 s 6 7 8 __ ~4 9 10 Volume In Ller. and applying pressure so the gas moves to higher pressure and lower volume. To see how an adiabat differs from an isotherm.Heat and Thermodynamics 80 This path.
we take the infinitesimal limit PdV= C~T Divide the lefthand side by PV. Cv Hence Cv (yl) f dV T v= fdT ..... the righthand side by RT to find =Cv V T Recall now that C p = C v + Rand CpiC v = YIt follows that R dV dT R = Cp Cv =yl.. (Compressing the gas of course gives negative I:!. .... rotational energy and vibrational energy (if any). V = CvAT. In adiabatic compression. Mint = CvA T ... This is always true: whether or not the gas is changing volume is irrelevant. all that counts in E int is the sum of the energies of the individual molecules (assuming as we do here that attractive or repulsive forces between molecules are negligible). .. the change in the internal energythe sum of molecular kinetic energy... . V positive Mint..81 The Behaviour of Gases I Cylinder of insularing Material ..... so PI:!. ...T.. .. .. .. • Adiabatic Compression • Equation for an Adiabat What equation for an adiabat corresponds to PV= nRTJ for an isotherm? On raising the gas temperature by I:!.) To find the equation of an adiabat.. all the work done by the external pressure goes into this internal energy.
and the volume of the molecules playa factor under conditions of large gas molecules and small container volumes. Joseph van der Waals studied the behaviour of real gases and made comparisons to the ideal gas law. attractive forces between the molecules that cause liquefaction are not a factor. if a gas is compressed enough the particles will attract and will liquefy. the P. for a diatomic gas. giving PvY = for an adiabat. Therefore at low temperatures or high pressures. However. In reality. small though it may be. it will liquefy. The second is that the gas molecules have no volume. the ideal gas law. These constants are derived to give the best agreement between the observed behaviour and the equation. The equation adds in two constants.Heat and Thermodynamics 82 and integrating In T+ (yl) In V= const. Gas molecules also definitely have a volume. to the ideal gas law. IDEAL GASES Most of the discussions of gases assume that the gases exhibit ideal behaviour. the effect of the attractive forces becomes larger. PV=nRT. a and b. from which the equation of an adiabat is n>rl = const From PV = RT. can be used. % Ys REAL GASES VS. Similarly if the gas is cooled to its boiling point. however. Therefore each gas has its own values for the constants. He derived an equation to account for the differences. V equation for an adiabat can be found by multiplying the lefthand side of this equation by the constant PV/ T. The van der Waals equation is stated as: [ n~a p+ v~2 1 (Vnb)=nRT . if the gas is moving fast enough. Ideal behaviour involves two things: the first is that the gas can be infinitely compressed or infinitely cooled and the gas will not liquefy. where y = for a monatomic gas. With these assumptions.
.04267 0. The a values are small for those gases with small intermolecular attractions. Vllb accounts for volume of the particles.0 L.83 The Behaviour of Gases P + n2a/V2 deals with attractive forces between molecules and how they reduce the ideal pres3ure.0821 La\ ~ )(298 K) rr:o :::: 200L 1.0 L)2 atm . Van der Waals received a Nobel Prize in physics in 1910 for his work in gases and liquids.02661 0.0 L container at 25°C.493 14. Example: One mole of acetylene gas is placed in a 20.Octane Formula He H2 N2 02 CO 2 C ZH2 Cl z a [(L 2 .390 (2~~:)21 20. Below is a table giving the a and b constants for various gases.390 1.05622 0. Gas Helium Hydrogen Nitrogen Oxygen Carbon dioxide Acetylene Chlorine n .(l mo\)(0.05136 0. such as He.Butane n .122G 0.360 3.2368 To illustrate the differences between the two equations. though this is not the only factor for determining b.47 37. the effective size of the container is decreased. as can be seen for octane.592 4. In general the larger molecules have a larger b constant.03913 0.223 atm The pressure using the van der Waals equation is shown to be: p = ( nRT _ \) _ (l n a V nb V2 = ( \ mol)(0.= V nRT (1 mol)(0.2444 1.32 0.03412 0. where the constant b is related to the size of the molecule and since the molecules take up space.390 6.02370 0.215 (20.0821) 2 1 ~)(298 K)]_ ((l mol)2 (4. an example using acetylene and helium gas will be shown.05136 ~ol) = 1. atm}/mole 2J b [Llmole] C4HJO CgH lg 0. The pressure using the Ideal Gas Law is shown to be: P =.03183 0.
Hill Statistical Mechanics. J. Callen. Adkins.13%. REFERENCE • • • • Equilibrium Thermodynamics. W. If the same calcul Isotherms and Adiabats for One Mole 2!' 20 e )15 ·i a. Thermodynamics (and Introduction to Thermostatistics). P.L. ation was done with helium gas. A. . 10 5 0 0 2 4 6 8 10 Volume in liter. Feynman. R. K.66% difference between the two values.Heat and Thermodynamics 84 There is approximately a 0. Benjamin. H. the difference would only be about 0. C. B. Huang. Statistical mechanics. An introduction to Statistical Thermodynamics. T.
5 ______________________________ Specific Heat of Solids Consider a simple solid containing atoms. In effect. Now. Each mode has its own particular oscillation frequency. It is always possible to perform a normal mode analysis of the oscillations. and three conjugate momentum coordinates. Any general oscillation can be written as a linear combination of these normal modes. the total energy of the lattice vibrations takes the particularly simple form E=2L. Each atom is specified ty three independent position coordinates. and Pi the momentum conjugate to this coordinate. Let us only consider small amplitude vibrations.)Pi +wi qi ). the linearized . It is clear that in normal mode coordinates. and its own particular pattern of atomic displacements. but are free to vibrate about their equilibrium positions. In this case. we can find 3N independent modes of oscillation of the solid. atoms in solids cannot translate (unlike those in gases). Let qi be the (appropriately normalized) amplitude of the ith normal mode. i=1 I ~ 2 2 2 where Wi is the (angular) oscillation frequency of the th normal mode. Such vibrations are called lattice vibrations. and can be thought of as sound waves propagating through the crystal lattice. we can expand the potential energy of interaction between the atoms to give an expression which is quadratic in the atomic displacements from their equilibrium positions. In normal mode coordinates.
so we can use the estimate w . Thus. Sound wave frequencies are far lower than the typical vibration frequencies of gaseous molecules. indeed.Jk! m (k is the force constant which measures the strength of interatomic bonds. It follows th8t the molar heat capacity at constant volume is cV=. The strength of interatomic bonds in gaseou~ molecules is similar to those in solids. whereas in the former case the mass involved is that of very many atoms (since lattice vibrations are nonlocalized)..Heat and Thermodynamics 86 lattice vibrations are equivalent to 3N independent harmonic oscillators (of course. This gins a value of 24.d. at room temperature most solids (in particular. and (l/2)kT resides in the potential energy]. In fact. it is likely (and is.~oT 1 (0£\ l =3R for solids. but. make their full classical contribution to the molar specific heat of the solid. the mass involved in the vibration is simply that of the molecule. and is the mass involved in the oscillation) as proof that the typical frequencies of lattice vibrations are very much less than the vibration frequencies of simple molecules.E = nw that the quantum energy levels of lattice vibrations are far more closely spaced than the vibrational energy levels of gaseous molecules. Thus. each normal mode of oscillation has an associated mean energy in kT equilibrium at temperature T[(l/ 2)kT resides in the kinetic energy of the oscillation. metals) have . according to the equipartition theorem. instec. the mean internal energy per mole of the solid is E = 3N k T = 3vRT. If the lattice vibrations behave classically then. each oscillator corresponds to a different normal mode). the case) that lattice vibrations are not frozen out at room temperature. In the latter case. The typical value of wi is the (anguiar) frequency of a sound wave propagating through the lattice. It follows from /)..9 joules/mole/degree.
In fact.4 26. since.9 joules/mole/degree) holds pretty well for metals. that all solids have a molar heat capacities close to 24. Diamond is also a fairly low density substance. This is not surprising.1 Dulong and Petite's law is essentially a high temperature limit. suggesting that the force constant k is large. We can make a crude model of the behaviour . the spacing between the different vibration energy levels (which scales like hW) is sufficiently large in diamond for the vibrational degrees of freedom to be largely frozen out at room temperature. and was used to make some of the first crude estimates of the molecular weights of solids (if we know the molar heat capacity of a substance then we can easily work out how much of it corresponds to one mole.5 25.~k / m ) is high. so its intennolecular bonds must be very strong. From Reif. The heat capacity at constant volume is somewhat less than the constant pressure value. by Equation. but not by much. so the mass involved in lattice vibrations is comparatively small.5 26. diamond is an extremely hard subshnce.4 25. This fact was discovered experimentally by Dulong and Petite at the beginning of the nineteenth century. As is wellknown.4 Aluminium Tin (white) Sulphur (rhombic) Carbon (diamond) c 24. It can be seen that Dulong and Petite's law (i.. The molar heat capacity cannot remain a constant as the temperature approaches absolute zero.4 6. The experimental molar heat capacities cp at constant pressure for various solids. and then dividing the result by Avogadro's number. ~~ ~ ~~ Copper Silver Lead Zinc 24. the law fails badly for diamond. e. Table 4: Values of cp (joules/mole/degree) for some solids at T = 298 0 K. this would imply S ~ 00. and by weighing this amount. Both these facts suggest that the typical lattice vibration frequency of diamond (w . we can obtain an estimate of the molecular weight). However.87 Specific Heat of Solids heat capacities which lie remarkably close to this value. which violates the third law of thermodynamics. because solids are fairly incompressible.4 22.
vkT2 (aE) aT aT ap giving C y = 3NA liw = kT2 l r 1 exp(pliw)liw [exp(pliw) _1]2 J' . in this simple model the specific heat approaches zero exponentially as T ~ o. making use of Einstein's approximation. y' 1 1 ap 1 =. which reduces to cy =3 R=(9 E)2 T exp(9 EIT) [exp(9 E IT)1]2 Here. We can use the quantum mechanical result Equation for a single oscillator to write the mean energy of the solid in the form exp(phw)1 The molar heat capacity is defined cv y l' E =3Nliw +  (12 1 ). after expansion of the exponential functions. This approximation was first employed by Einstein in a paper published in 1907. independent oscillators which. say. the solid acts like a set of 3N . . n "'E the law of Dulong and Petite is recovered for temperatures significantly in excess of the Einstein temperature. 9 T . (aE) =. if the temperature is sufficiently low that T« 9 E then the exponential factors in Equation become very much larger than unity.Heat and Thermodynamics 88 of c y at low temperatures by assuming that all the normal modes oscillate at the same frequency. According to Equation. On the other hand. _liw k is called the Einstein temperature. all vibrate at the same frequency. So. (aE) aT =. and the above expression reduces to cy = 3 R. Thus. giving Cy  E 3 Rexp (9 E IT). If the temperature is sufficiently high that T» 9E then kT» h w. w.
It is plausible that these modes are not particularly sensitive to the discrete nature of the solid: i. There are analogous constraints on kyand kz . The molar heat capacity does not decrease with temperature as rapidly as suggested by Einstein's model because these long wavelength modes are able to make a significant contribution to the heat capacity even at very low temperatures.. In the Debye model. where the wavevector k and the frequency of oscillation satisfy the dispersion relation for sound waves in an isotropic medium: W = kcs' Here.r . for the sake of argument. The reason for this discrepancy is the crude approximation that all normal modes have the same frequency. In fact. The disturbance varies with position vector r and time t like exp [. It follows that in a periodic medium the components of the wavevector are quantized. y. Consider a sound wave propagating through an isotropic continuous medium. liw. those whose wavelengths greatly exceed the interatomic spacing. This approach is reasonable because the only modes which really matter at low temperatures are the long wavelength modes: i. is smaller in the former case). the frequencies of the normal modes of vibration are estimated by treating the solid as an isotropic continuous medium. the specific heats of solids do not approach zero quite as quickly as suggested by Einstein's model when T ~ O. Suppose. and can only take the values .WI]. The experimentally observed low temperature behaviour is more like C v ocT3.e. that the medium is periodic in the X. and zdirection~ with periodicity lengths Lx' Ly and L z' respectively. so the former are much harder to freeze out than the latter (because the spacing between quantum energy levels.e..i.89 Specific Heat of Solids In reality. A more realistic model of lattice vibrations was developed by the Dutch physicist Peter Debye in 1912. In order to maintain periodicity we need ky (x + LX> = kxx + 21tnx' where nx is an integer. long wavelength modes have lower frequencies than short wavelength modes. the fact that it is made up of atoms rather than being continuous. Cs is the speed of sound in the medium.
is ~ "' pd k 3 =(Lx dkx ) (Ly dky ) (Lz dkz ) =~dkxdkydkz' 21t 21t 21t (21t) where V = L~fz is the periodicity volume. the number of allowed values of kx which lie in the range kx to kx + dkx is given by Llnx = Lx dkx . Thus. Thus. n z and are all integers. For given values of and k . The density of modes per unit volume when the magnitude of k lies in the range k to k + dk is given by multiplying the density of modes per unit volume by the "volume" in kspace of the spherical shell lying between radii and k + dk.e. 21t It follows that the number of allowed values of k(i. and d 3k == dkxdkydkz.. the density of modes per unit volume is a constant independent of the magnitude or shape of the periodicity volume. so the allowed values of the components of the wavevector are very closely spaced.Heat and Thermodynamics 90 21t ky =ny . the number of allowed modes) when kx lies in the range kx to kx + dhx' kv lies in the range ~v to ky + dky' and kz lies in the range k z to k~ + dh_. It is assumed that Lx' Ly' and L z are macroscopic lengths. The quantity p is called the density of modes. p dk = 4nk dk k (21t)3 2 =~dk. . 21t2 Consider an isotropic continuous medium of volume V. Ly 21t k z =nz ' Lz where nx' ny. Note that this density is independent of k. and proportional to the periodicity volume.
We know that there are only 3N independent normal modes. in the Debye approximation the density of normal modes takes the form crD(w) = crc(w) for w < wD crD(w) = 0 for w < wD . It follows that we must cut off the density of states above some critical frequency. where the displacement is perpendicular to the direction of propagation.91 Specific Heat of Solids According to the above relation.3 w dw. 21t2 21t 2Cs k V 2 V 2 The factor of 3 comes from the three possible polarizations of sound waves in solids. Here. torsion waves can not propagate in gases because gases have no resistance to deformation without change of volume. where the displacement is parallel to the direction of propagation. otherwise we will have too many modes. The longitudinal mode is very similar to the compressional sound wave in gases. the number of normal modes whose frequencies lie between wand w + dw (which is equivalent to the number of modes whose kvalues lie in the range wlcs to wi C + djc ) is s s crcCw)dw = 3 . Suppose that we are dealing with a solid consisting of N atoms. The Debye approach consists in approximating the actual density of normal modes cr(w) by the density in a continuous medium crc (w). so . but also at higher frequencies where they may differ substantially. w D say. wD is the De bye frequency. Thus. This critical frequency is chosen such that the total number of normal modes is 3N.dk =3 . For every allowed wavenumber (or frequency) there are two independent torsional modes. Of course. Torsion waves are vaguely analogous to electromagnetic waves (these also have two independent polarizations). not only at low frequencies (long wavelengths) where these should be nearly the same. and one longitudinal mode.
and coincide at low frequencies. there is not a particularly strong resemblance between these two curves. we find that . to calculate the mean energy of lattice vibrations in the Debye approximation. It follows that the cutoff of normal modes whose frequencies exceed the Debye frequency is equivalent to a cutoff of normal modes whose wavelengths are less than the interatomic spacing.1  vkT 2 r cr D ()1iW [ exp(l31iw)1iw W [exp(l31iw) If jdw • Substituting in Equation./ith the density predicted by Debye theory. We can use the quantum mechanical expression for the mean energy of a single oscillator. We obtain E = rcrD(W)1iw(~+ 2 exp(l31iw)I 1 )dw. 21t 21t Cs WD =Cs ( 61t 2 ~)1I3 Thus. 3V ('"'D 2 V 3 W dw=23 wD =3N. Not surprisingly. The actual density of normal modes in diamond \. the molar heat capacity takes the form Cv . Sufficient to allow Debye theory to cl)rrectly account for the temperature variation of the specific heat of solids at low temperatures. the areas under both curves are the same. Equation. Nevertheless. Of course.b This implies that . it makes physical sense that such modes should be absent. the Debye frequency depends only on the sound velocity in the solid and the number of atoms per unit volume. both curves exhibit sharp cutoffs at high frequencies. since Debye theory is highly ~dealized. The wavelength corresponding to the Debye frequency is 21tCJ wD ' which is clearly on the order of the interatomic spacing a ~ (V/N)1I3. According to Equation. Furthermore.Heat and Thermodynamics 92 Substituting Equation into the previous formula yields 2.
b exp x 4dx exp x 4dx 4n (expxl)2 x =. y r . now.b eo. so that x2dx =1.b exp x 4dx (expxl)2 x . the asymptotic limit in which T« For large y. we can approximate exp x as 1 + x in the integrand of Equation.93 Specific Heat of Solids giving 3V k ~lIWD cv =2n2v(Cs Ph)3 . and can be looked up in any (large) reference book on integration. if the temperature greatly exceeds the Debye temperature we recover the law of Dulong and Petite that Cv = 3 R. e fD(Y)~~ . Y Thus. According to V=6P2N(~J so the heat capacity reduces to C v= 3 Rfo(!3hwo) = 3 RfD(edT) where the Debye junction is defined JD I" ( _ Y ) =3  l £" exp x X 4dx• (expxl) We have also defined the Debye temperature D as keo = hwo ' Consider the asymptotic limit in which T» eo. in terms of the dimensionless variable x Equation. Consider. the volume can be written = ph w.b (expxl)2 x =15 r 4 The latter integration is standard (if rather obscure). Thus. For small y. in the low temperature limit .
REFERENCES • • • • • Statistical Physics. Landau and E. E.e. aD should be calculable from Equation in terms of the sound speed in the solid and the molar volume. E. Debye temperatures evaluated by this means with temperatures obtained empirically by fitting the law Equation to the low temperature variation of the heat capacity. It can be seen that there is fairly good agreement between the theoretical and empirical Debye temperatures. Merzbacher The Cluster Expansion. Table: Comparison of Debye temperatures (in degrees kelvin) obtained from the low temperature behaviour of the heat capacity with those calculated from the sound speed. although it is sometimes necessary to go to temperatures as low as 0. D. M. thought not perfect. Theoretically. C v varies with temperature like T3. Lifshitz Statistical Mechanics. SolidS D from low temp SD from sound speed 308 NaCI KCl 230 Ag 225 Zn 308 320 246 216 305 The fact that C v goes like 7 3 at low temperatures is quite well verified experimentally.Heat and Thermodynamics 94 This yields C= 12n4 R(~)3 v 5 e D in the limit T« eD:i. Reichl.. L.02 eD to obtain this asymptotic behaviour. W. representation of the behaviour of C v in solids over the entire temperature range. Mullin A Modern Course in Statistical Physics. J. . This suggests that the Debye theory affords a good. L. SK Ma Quantum Mechanics.
consider a dosed system with fixed volume V. Consider next an infinitesimally small change from an . and energy E. and that all the Q(E. N)possible states are equally likely.e. In fact. number of particles N. We define the entropy as S =kB In Q(E. all memory of how the system was initially prepared is lost. In principle. V. This tolerance should be chosen so that for a large system the precise value of 3E does not matter. i. Next. In order to avoid problems associated with the discreteness of the quantum states we take the energy to be specified within a tolerance 3E. our fundamental assumption is that at equilibrium our ignorance in this matter is complete. where g(E) is the density of states. For a large system the states will be very closely spaced. volume. N. V). except for the values of the energy. these are discrete quantum states.6 _______________ Thermal Equilibrium and Zeroth Law STATISTICAL DEFINITION OF THERMODYNAMIC VARIABLES Our starting point is the idea that one can count the number of available states of a system. The number of possible states with energy between E and E + 3E is Q(E) =g(E) 3E. and number of particles. We do not know in which of the allowed states the system finds itself.
We refer to changes in energy associated with bulk motion or transport of matter as work. V. We also distinguish between the random motion of a molecule and bulk (ordered) movement. In principle. The change in the entropy is then dS = as dE + as dV + as dN. Heat is a form of energy associated with random or thermal motion of atoms and molecules. In practice. it should be possible to predict the outcome of the toss using Newton's laws and the initial velocity and position. This type of motion has been described as chaotic. equilibrium state E + dE. A very similar situation occurs when throwing an unbiased die or tossing a coin. N + dN. The difficulty is not just the enormous amount of data required to describe a large number of particles. A more fundamental problem is the fact that after a few collisions the positions and the velocities of the particles become extremely sensitive to the initial conditions. slightly different. After a few collisions it becomes practically impossible to relate the velocity and position of the molecules to the corresponding quantities at an earlier time. The molecules will move in straight trajectories until they collide with other molecules or the walls of the gas container.N to another. An example of the latter is the flight of a solid object such as a pebble thrown in the air. because initial conditions that give rise to radically different outcomes are so close together that the problem of specifying the intial conditions and parameters of the problem with sufficient accuracy becomes severe. the calculation will not be able to predict the behaviour of real coins.Heat and Thermodynamics 96 equilibrium state E. and the the speed of the particles is frequently changing. aE av an The change in energy in this process is given by dE=dQ+dU. In dQ is the heat supplied to the system and dU the work done on the system. Consider a gas of low density. We distinguish between two forms of energy heat and work. The . Each particle is just as likely to move in any direction as in any other. V + dV.
. THE ZEROTH LAW OF THERMODYNAMICS To establish the equivalence of our definitions and the conventional thermodynamic on~s we shall make contact with the zeroth law of thermodynamics.! __ T(8S) 8N EV .! dE +1:. In particular if two subsy~tems are in contact and in equilibrium: TI = T2 ~ thermal equilibrium PI = P2 ~ mechanical equilibrium J. where in equilibrium the forces are balanced. T and J..E It is important to note that our basic assumption is that all allowed states are equally likely.97 Thermal Equilibrium and Zeroth Law internal energy E is a state variable and its differential is exact. The conventional mathematical formulation of the second law on the other hand only becomes an essentially trivial matter of definition. This law has an analogy with mechanics. pressure. T =( 8E N. We want to do this in such a way as to allow us to write dE = TdS .dN + P dV. i. P_T(8S) 8V N .otherwise they would not be useful. the difference in notation: dE.ldN or T T T T We now define the temperature. We must next show that these definitions lead to familiar looking results.!2 T2 ~ chemical equilibrium .PdV + J. On the other hand "heat" and "work" are not state variables and the partition into heat and work depends on the process.!.. dE depends only on the initial and final state and is independent of the process leading to the change. Hence. The second law of thermodynamics now becomes the statement that a closed system will tend to approach a macroscopic state which can be achieved the most possible ways. and chemical potential as dS =~dE + J.!l = J.~ 8S)1 J.e. but dQ and dU We have not yet defined the variables P...
Assume that the densities of state g(E). The total energy will be constant under our assumptions and we assume further that the two subsystems are sufficiently weaklY interacting that E=El +E2.EI )gl (EI ). The most probable partition of energy between the two systems is the one for which the two temperatures are the same. g 1(E). but the number of particles is fixed in each subsystem and the total volume V = VI + V2 is constant. T2 or TI = T2 . The two systems are free to exchange energy. The particle numbers N 1. We write E = El + E 2. the product giEEj)gl(E) will be a sharply peaked function of E I . The density of allowed states for the total system is then 1i . . From the definition of the entropy we note that it is a monotonically increasing function of g and that the product glg2 will be at a maximum when the total entropy SeE. that 1 1 =0. . The most likely value (E I ) of EI is the one for which 8S1 + aS2 aE2 = aEI aE2 aEI o.Heat and Thermodynamics 98 The zeroth law has a fairly straightforward statistical interpretation and this will allow us to begin to establish the equivalence between the statistical definitions and the conventional thermodynamic ones. Consider next two subsystems that are separated by a movable wall. If the subsystems are sufficiently large. Consider two systems that are free to exchange energy but are isolated from the rest of the universe by an ideal insulating surface. where El and E2 are the energies of the subsystems.g2(E) are coarse grained so that 0= g(E)oE 01 = gl (E 1) oE 02 = g2 (E2) oE. N2 and volumes VI' V2 are fixed for each subsystem. Since aE/aE I we find using. E I ) = SI(E I ) + S2(EE I ) is at a maximum. We then have geE) = fdElg2 (E .
consider two systems 1 and 2 which are free to exchange particles and energy. BOLTZMANN FACTOR Consider now a system in contact with a heat bath.ll_P2 1J. PI = P2' Conventionally. We assume that all compatible microstates are equally likely. The argument now being made is quite different.f'i)g21(EEl . We assume that system 2 is much larger than 1. or reservoir. so that El« E = E I + E 2 • Another way of putting this is to say that the heat capacity C 2 of system 2 is very large. Similarly.EI)dEI I JdEIgl (E1)g2(E .T2 or TI = T2.vl)+SiEEl'VV1)=max. ( 8S) EN =P T implies that it is overwhelmingly probable that the system will be near a state for which 1_1. Differentiation using 8S ( 8E )VN I' _  T'~8V 1 .Ell g2 = 8E eXPl kB r . instead the movable wall is guided to its equilibrium by the invisible hand of the law of large numbers.E1) From the definition of entropy 1 S2(E .99 g(E. and we want to find the probability P(EI) that it has energy E I . III = 112.T2'1J. System 1 is the one we are interested in. there are no forces. It is easy to show that the most probable configuration is the one for which TI = T2 .V) = Thermal Equilibrium and Zeroth Law L volume settings JdE1 1(E1.VVi) g The integrand is sharply peaked for large systems and takes on its maximum value when SI(El. one would say that the pressure in the two compartments must be equal at equilibrium because the forces have to be in balance. We have P(El)dE = gl(EI )g2(E .
e~El where we define 13 = lI(kB 1). the partial derivatives are given by 8S2 1 =8E T 82_ _ S2 8E 2 8E T2 8E T 2C Since E1«TC we neglect the last term in giving g2 = const. Instead. requiring that Jp(E)dE=1 Let us define the canonical partition function (a = microstate) Zc = 2:e~E(a) a = fdEg(E)e~E We find that the probability p(a) that a state is in a given microstate p(a)=_l e~E Zc If x( a) is the value of some physical property in microstate ..e.L= ___ =___ const.Heat and Thermodynamics 100 We expand in a Taylor series 8S2 E18 2s2 S2(EE 1)=S2(E)E1 8E +2 8E2 +. all possible microstates of the system are no longer equally likely. We conclude The factor e~EI is the Boltzmann factor. PARTITION FUNCTION AND THE CANONICALDISTRIBUTION The constant in eqnaution can be determined by normalizing the probability distribution i. When a system is in contact with a heat bath at a certain temperature.exp[E1 ] = kBT 811 8T 1 =. With T the temperature of the heat bath and C its heat capacity. the Boltzmann factor acts as a weight factor biasing the distribution towards states with lower energy...
SdT = . N independent variables. or control parameter.1= aF aN In statistical mechanics we define the Helmholtz free energy as A = (E) . The energy E and entropy S will then fluctuate about their mean values and.13E . V. and E(a) the energy of this state then the canonical ensemble average is given by (x) = _I Lx(a)e~E(a) Zc a Equation is a very useful formula. V. V. E and S become dependent variables given by equations of state. N.TdS .101 Thermal Equilibrium and Zeroth Law a. and we will give many examples of its use. V. with E. For a system in contact with a heat bath at a given temperature. We have S=_oF oT p=_oF aT J. The change of variables is handled most efficiently by introducing he Helmholtz free energy. T becomes an independent variable. V.T (S) = (F) We wish to show that for a large system Zc JeEg(E)e. N) We see tilat the Helmholtz free energy is should be considered to be dependent on the control variables T.N) dF = dE .PdV + IJdN = dF (T. HELMHOLTZ FREE ENERGY For an isolated system S = SeE. In thermodynamics it is defined as F=ETS Imagine a reversible process which takes the system from one equilibrium state to another dE= TdSPdV+ ~N=dE(S. N).
T(5) . pressure. V. and occasionally bounces off the walls of the room. E. V. In other words. How can we obtain some information about the statistical properties of the molecules which make up air? Consider a specific molecule: it constantly collides with its immediate neighbour molecules.T (S)] IdE exp{(E BE 2CkB T (E~)2} U sing we find ~27tk BE B T C 2 exp[~(E)T(S)] and from A = .anonical partition function is = f~~ exp{~[E  TS(E.kBT In [ J27tkBT C BE 2 1 The last term in will be small compared to the first two terms for a large system. we know something about its internal energy and specific heat capacity.Heat and Thermodynamics 102 Proof: The r.kBT In Zc = (E) ... BOLTZMANN DISTRIBUTIONS We have gained some understanding of the macroscopic properties of the air around us. The statistical distribution of the molecule over its own particular microstates must be consistent with this macrostate. These interactions "inform" it about the macroscopic state of the air. and volume. For instance. and it is possible to choose the tolerance 8E so that it is identically zero.. N) = minimum. V.T (S) Zc:::: . .2 + . such as its temperature. Almost all the contribution to the integral will come from values of E near E = (E) the value for which ET (S. 2 8E Zc :::: exp[ ~((E) . N) = (5) and 2 Substituting Equation we obtain 1 28 S ETS::::(E)T(s)T(E(E) . We let S(E). N)]} We evaluate this integral using the saddle point method.
Thus.e. so E + E' = 8°) r ' where E' denotes the energy of the reservoir A'.. The energy of A is not known at this stage.103 Thermal Equilibrium and Zeroth Law if we have a large group of such molecules with similar statistical distributions.Er ). since A is in one definite state (i. So. Hence. Pr = C' 0'(8°) . Suppose that the total energy lies in the range 8°) to 8°) + oE. As usual.Er)' The principle of equal a priori probabilities tells us the the probability of occurrence of a particular situation is proportional to the number of accessible microstates. since is assumed to be an isolated system. and the total number of states accessible to A' is 0' (8°) . if system A has an energy Er then the reservoir A' must have an energy close to E = 8°) E. Clearly.. The air acts like a heat reservoir because its energy fluctuations due to any interactions with the molecule are far too small to affect any of its macroscopic parameters. it follows that the total number of states accessible to the combined system is simply Q' (80) . r . Let us determine the probability Pr of finding system A in one particular microstate r of energy Er when it is thermal equilibrium with the heat reservoir A'. This constant can be determined by the normalization condition ~)~. Let 0' (E) be the number of microstates accessible to the reservoir when its energy lies in the range E' to E' + oE. The overall energy A(O) is constant in time. then they must be equivalent to air with the appropriate macroscopic properties. it ought to be possible to calculate the probability distribution of the molecule over its microstates from a knowledge of these macroscopic properties. We can think of the interaction ofa molecule with the air in a classroom as analogous to the interaction of a small system A in thermal contact with a heat reservoir A'. In fact. we assume fairly weak interaction between A and A " so that the energies ofthese two systems are additive.Er) where is a constant of proportionality which is independent of r. state r). only the total energy of the combined system A(O) = A + A'is known. =1.
The parameter C is determined by the normalization condition.Heat and 1bermodynamics 104 where the sum is over all possible states of system A. irrespective of their energy. Now the derivative l 8E' ']°. The higher order terms in Equation ~an be safely neglected. r 81n O Inp" = In C'+lnO'(E(O»)l ~'] Er+···. we know. Let us now make use of the fact that sygtem A is far smaller than system A'. rather than P r itself. and is undoubtably the most famous result in statistical physics. giving P r = C exp (.p. ° Note that we must expand In P. where C is a constant independent of r. The Boltzmann distribution often causes confusion. Hence. so the slowly varying logarithm of Pr can be Taylor expanded abcut E' = E<n). 1 = 8InO is evaluated at the fixed energy E'= E<0) and is. because the latter function varies so rapidly with energy that the radius of convergence of its Taylor series is far too small for the series to be of any practical use. because Er« E<0). which says that all microstates are equally probable.Lr exp(pEr)· exp(PEr) This is known as the Boltzmann probability distribution. It follows that Er «Fj. Equation becomes In Pr = In C' + In fl' (E<0») .f3 E r). which gives r so that the distribution becomes p.o>. _ r. a constant independent of the energy Er of A. People who are used to the principle of equal a priori probabilities. Thus. thus. are understandably . that this derivative is just the temperature parameter f3 = (kT)1 characterizing the heat reservoir A'. In fact.f3 Er ..
The strong increase in the number of accessible microstates of the reservoir with increasing E' gives rise to the strong (i. hence. The Boltzmann distribution gives the probability of finding the small system A in one particular state of energy E r . For a large system. and. If the small system is in a microstate with a comparatively high energy Er then the rest of the system (i. there is no need for any confusion. This gives a sharp maximum of PCE) at some particular value of the energy.e. but still very much smaller than system A'.. Suppose that system A is itself a large system. It follows that when the small system has a high energy then significantly less states than usual are accessible to the reservoir.I3E). However. The principle of equal a priori probabilities applies to the whole system. since each of these states has approximately the same Boltzmann factor this sum can be written peE) = c neE) exp (.e.e. we expect neE) to be a very rapidly increasing function of energy. whereas the Boltzmann distribution only applies to a small part of the system. the configuration is comparatively unlikely. The exponential factor exp (13 Er) is called the Boltzmann factor. the reservoir) has a slightly lower energy E' than usual (since the overall energy is fixed).. The larger system A. The probability peE) that A has an energy in the small range between E and E + oE is just the sum of ail the probabilities of the states which lie in this range. The two results are perfectly consistent. and so the number of microstates accessible to the overall system is reduced. exponential) decrease in the likelihood of a state of the small system with increasing Er. so the probability peE) is the product of a rapidly increasing function of E and another rapidly decreasing function (i.105 Thermal Equilibrium and Zeroth Law surprised when they come across the Boltzmann distribution which says that high energy microstates are markedly less probable then low energy states. where neE) is the number of microstates of A whose energies lie in the appropriate range. the sharper this maximum . The number of accessible microstates of the reservoir is a very strongly increasing function of its energy.. However. the Boltzmann factor).
. and consequently possess an intrinsic magnetic moment 11. PARAMAGNETISM The simplest microscopic system which we can analyze using the Boltzmann distribution is one which has only two possible states (there would clearly be little point in analyzing a system with only one possible state). however. the most probable energy is evaluated by looking for the maximum of In P. Note. so alnP  106 aE giving = alnn _p =0 aE alnn _p ' aE Of course. This is a result which we have seen before. this corresponds to the situation in which the temperature of A is the same as that of the reservoir. Most elements.e. that the Boltzmann distribution is applicable no matter how small system A is. According to quantum mechanics. the magnetic moment of a spin 112 particle can point either parallel or anti parallel to an external magnetic field B. so it is a far more general result than any we have previously obtained. and treat the remaining atoms as a heat bath at temperature. their constituent atoms. that each atom (or molecule) only interacts weakly with its neighbouring atoms. This enables us to focus attention on a single atom. Eventually. and some compounds. We assume. the maximum becomes so sharp that the energy of system A is almost bound to lie at the most probable energy. Our atom can be in one of two possible states: the (+) state . Consider a substance whose constituent particles contain only one unpaired electron. or molecules.Heat and Thermodynamics becomes. As usual. Such particles have spin 112. for the sake of simplicity. possess a permanent magnetic moment due to the presence of one or more unpaired electrons. Let us determine the mean magnetic moment iTB (in the direction of B) of the constituent particles of the substance when its absolute temperature is T. are paramagnetic: i.
.e. the atomic magnetic moment is parallel to the magnetic field.lB' According to the Boltzmann distribution..lB)exp(~J. the most probable state is the state with the lowest energy [i.e.[3E+) = C exp([3 J. the probability of finding the atom in the (+) state is p+ = C exp(.... and the probability that the atomic moment points parallel to the magnetic field is about the same as the probability that it points antiparallel. antiparallel to B)...lB. the mean magnetic moment points in the direction of the magnetic field (i.l B) .l.. In the (+) state.1.. Clearly..l B). The magnetic energy of the atom is E+ = ..lB = J. ... kT This parameter measures the ratio of the typical magnetic energy of the atom to its typical thermal energy.J. the probability of finding the atom in the () state is p _ = C exp(. we expect the mean atomic moment to be small. the atomic magnetic moment is antiparallel to the magnetic field. The magnetic energy of the atom is E_= J.107 Thermal Equilibrium and Zeroth Law in which its spin points up (i.lB = .. if the magnetic energy greatly exceeds the thermal energy then y» 1. and the () state in which its spin points down (i..l • Let us calculate the mean atomic moment iTB' The usual definition of a mean value gives  J.. so that ~ B :: 0 . e.e.lB = p+ + j. It is clear that the critical parameter in a paramagnetic system is Y=~J.l exp(~J. If the thermal energy greatly exceeds the magnetic energy then y« 1. we expect iT B = j.. where C is a constant. and the atomic moment is far more likely to point parallel to the magnetic field than antiparallel..l+ P_(J. In this situation... so thatJ.J.lB) exp(~ J. In this situation.l) P+ + P_ =J.lB' In the () state.. and [3 = (kn... Thus. the atom is more likely to point parallel to the field than antiparallel).[3E> = C exp([3 J. Likewise.l B) + exp( ~ J.l. the (+) state]. so that J.l B).lB= J. parallel to B). On the other hand.
kT» /lB.B IlB . and is given by Mo = NofiB' At high temperatures. y» 1. tanhy==l. where X is a constant of proportionality known as the magnetic susceptibility.'< 1. is proportional to the applied magnetic field. _ exp(y)exp(y) tan h y= .Heat and Thermodynamics This can also be written 108 kT where the hyperbolic tangent is defined . It is clear that the magnetic susceptibility of a spin 112 paramagnetic substance takes the form X=. kT« J1B. because it was Na/l 2 .. kT» JlB' _ 1l2B IlB == kT ' whereas at comparatively low temperatures. y3 It follows that at comparatively high temperatures. and. y <. tan h y==+'" 3 ' whereas for large arguments..r' The fact that X ex: r1is known as Curie's law. iIB == Il· Suppose that the substance contains No atoms (or molecules) per unit volume. The magnetization is defined as the mean magnetic moment per unit volume. the magnetization. exp(y) + exp(y) For small arguments. so we can write Mo=X B. the mean magnetic moment. hence.=Il tan h!J.
109
Thermal Equilibrium and Zeroth Law
discovered experimentally by Pierre Curie at the end of the nineteenth century. At low temperatures, kT « J.!B,
Mo ~NoJl, so the magnetization becomes independent of the applied field. This corresponds to the maximum possible magnetization, where all atomic moments are lined up parallel to the fie)~. The
breakdown of the Mo oc B law at low temperatures (or high magnetic fields) is known as saturation. The above analysis is only valid for paramagnetic substances made up of spin onehalf (J = J/2) atoms or molecules. However, the analysis can eas]y be generalized to take account of substances whose constituent particles possess higher spin (i.e., J > 112). The experimental and theoretical magnetization versus fieldstrength curves for three different substances made up of spin 3/2, spin 5/ 2, and spin 7/2 particles, showing the excellent agreement between the two sets of curves. Note that, in all cases, the magnetization is proportional to the magnetic fieldstrength at small fieldstrengths, but saturates at some constant value as the fieldstrength increases. The previous analysis completely neglects any interaction between the spins of neighbouring atoms or molecules. It turns out that this is a fairly good approximation for paramagnetic substances. However, for ferromagnetic substances, in which the spins of neighbouring atoms interact very strongly, this approximation breaks down completely. Thus, the above analysis does not apply to ferromagnetic substances.
MEAN VALUES
Consider a system in contact with a heat reservoir. The systems in the representative ensemble are distributed over their accessible states in accordance with the Boltzmann distribution. Thus, the probability of occurrence of some state with energy Er is given by
Heat and Thermodynamics
110
The mean energy is written
 L exp( ~ Er )Er E  ~o;r     L r exp( ~ Er) ,
where the sum is taken over all states of the system, irrespective of their energy. Note that
where Z = Lexp(~ Er)
r
It follows that p
E=~ oZ
Z o~
=_ olnZ.
o~
The quantity Z, which is defined as the sum of the Boltzmann factor over all states, irrespective of their energy, is called the partition function. We have just demonstrated that it is fairly easy to work out the mean energy of a system using its partition function. In fact, as we shall discover, it is easy to calculate virtually any piece of statistical information using the partition function. Let us evaluate the variance of the energy. We know that
(/ill)2 = E2 _ E2
Now, according to the Boltzmann distribution,
2
E  L..J r r  Lr~xp(~Er)
"exp(~Er)E
2
However,
111 Hence,
Thermal Equilibrium and Zeroth Law
2" = 21az E
Z
ap2·
We can also write
E2 =~(~ aZ)+_l (az)2 ap Z ap Z2 ap
where use has been made of Equation
2
=_ aE +E2 , ap
(b.E)2 = _ aE = a 1nZ. ap ap2
Thus, the variance of the energy can be worked out from the partition function almost as p.asily as the mean energy. Since, by definition, a variance can never be negative, it follows that
aE / ap ~ 0, or, equivalently, aE / aT ~ O. Hence, the mean energy
of a system governed by the Boltzmann distribution always increases with temperature. Suppose that the system is characterized by a single external parameter x (such as its volume). The generalization to the case where there are several external parameters is obvious. Consider a quasistatic change of the external parameter from x to x + dx. In this process, the energy of the system in state changes by
8Er = aE dx. ax
The macroscopic work dW done by the system due to this parameter change is exp(p Er)( aEr / ax dx) _____________
~===~r~~
L
Lrexp(P Er) In other words, the work done is minus the average change in internal energy of the system, where the average is calculated using the Boltzmann distribution. We can write
~exp(_PE,)a! ~k ![~exp(PE+k:'
Heat and Thermodynamics
112
which gives
dW = __ 1_8Z dx =}_ 81nZ,dx.
PZ ax
P ax
We also have the following general expression for the work done by the system
dW=x dx,
where
x= 8Er
P
ax' ax
is the mean generalized force conjugate to x. It follows that
x=~ 81nZ.
Suppose that the external parameter is the volume, so x = V. It follows that
and
_ 181nZ
P=j3av'
Since the partition function is a function of /3 and V (the energies Er depend on V), it is clear that the above equation relates the mean pressure P to T (via /3 = lIk1) and V. In other words, the above expression is the equation a/state. Hence, we can work out the pressure, and even the equation of state, using the partition function.
PARTITION FUNCTIONS
It is clear that all important macroscopic quantities associated with a system can be expressed in terms cf its partition function Z. Let us investigate how the partition function is related to thermodynamical quantities. Recall that Z is a function of both /3 and x (where x is the single external parameter). Hence, Z = Z(/3, x), and we can write
113
Thermal Equilibrium and Zeroth Law
dlnZ = olnZ dx+ olnZ d~.
ax
o~
Consider a quasistatic change by which x and b change so slowly that the system stays close to equilibrium, and, thus, remains distributed according to the Boltzmann distribution. If follows from Equations that dlnZ =/3dW Ed~. The last term can be rewritten din Z =/3dW  d(E~) + ~dE, giving
d (In Z + ~E) = P(1iW + dE) == 13dQ. The above equation shows that although the heat absorbed
by the system dQ is not an exact differential, it becomes one when multiplied by the temperature parameter 13. This is essentially the second law of thermodynamics. In fact, we know that
dS= dQ. T
Hence, S == k(ln Z + (3E). This expression enables us to calculate the entropy of a system from its partition function. Suppose that we are dealing with a system A(O)consisting of two systems A and A'which only interact weakly with one another. Let each state of A be denoted by an index and have a corresponding energy Er . Likewise, let each state ofA' be denoted by an index and have a corresponding energy E;. A state of the combined systemA(O) is then denoted by two indices r and s. Since A and A' only interact weakly their energies are additive, and the energy of state is
Ers Er+Ex· By definition, the partition function of A(O) takes the form
(0) _ •
Heat and Thermodynamics·
114
Z(O) =
L exp[pE~~)]
r,.s
= Lexp(p[Er
r,s
+ E~])
r,s
Hence,
Z(O) = Z Z',
giving
InZ(O) =lnZ+lnZ',
where Z and Z' are the partition functions of A and A', respectively. It follows from Equations that the mean energies of A (0), A, and A' are related by
E(O) =E+E'.
It also follows from Equations that the respective entropies of these systems are related via
SlO)
=S+S'.
Hence, the partition function tells us that the extensive thermodynamic functions of two weakly interacting systems are simply additive. It is clear that we can perform statistical thermodynamical calculations using the partition function Z instead. of the more direct approach in which we use the density of states n. The former approach is advantageous because the partition function is an unrestricted sum of Boltzmann factors over all accessible states, irrespective of their energy, whereas the density of states is a restricted sum over all states whose energies lie in some narrow range. In general, it is far easier to perform an unrestricted sum than a restricted sum. Thus, it is generally easier to derive statistical thermodynamical results using Z rather than n, although n has a far more direct physical significance than Z.
MacDonald Introduction to Metallurgic. Zemansky Modern Thermodynamics. K. C. D.REFERENCES • • • • • 115 Thermal Equilibrium and Zeroth Law Heat and Thermodynamics. D. . M. R. Introductory Statistical Mechanics.al Thermodynamics by David R. Sanchez. Bowley and M. Prigogine Noise and Fluctuations. W. Kondepundi and I. Gaskell.
7______________________________ The First Law of Thermodynamics Thermodynamics is a science and. The course content can be viewed in terms of a "propulsion chain". The Propulsion Chain . and the relationships between heat and work.. Energy souroe chemical Heat (combustion Mechanical Useful propulsive work (thrust power) nuclear. It can be regarded as a generalization of an enormous body of empirical evidence. + work. and many other phenomena. and refrigerators. where a progression from an energy source to useful propulsive work (thrust power of a jet engine). combustion. from different sources of heat.. but this is not always the case. an engineering tool used to describe processes that involve changes in temperature. It is used to describe the performance of propulsion systems. more importantly. For the most part the heat will be the result of combustion processes. and to describe fluid flow. etc. Fig. transformation of energy. It is extremely general: there are no hypotheses made concerning the structure and type of matter that we deal with. often in the form of kinetic energy or shaft power. process) + ele(:lric power. The focus of thermodynamics in aerospace engineering is on the production of work. power generation systems.
Ifyou need additional information or examples concerning these topics. There are two reasons for this. thermodynamics is concerned with the mathematical modeling of the real world. not a microscopic. we need some precise definitions of the basic concepts. In this section. In order that the mathematical deductions are consistent. a macroscopic. First. and basic electrical theory makes this section the most important to understand if you wish to become proficient at doing electrochemistry problems. a microscopic description of . i.117 The First Law of Thermodynamics FUNDAMENTAL IDEAS OF THERMODYNAMICS As with all sciences. we want "averaged" information. It also permits us to add reduction potentials of two reductions to calculate the potential ofa new. It can tell us whether a given redox reaction is spontaneous and therefore whether it is able to provide useful electrical energy.. The Nernst Equation allows us to calculate the cell potential at any conditions and suggests the construction of concentration cells such as pH meters or other ionselective electrodes. you will get to know and love such formulae as ~Go = nFE O (useful for converting free energy and potentials) and E = £0 . Thermodynamics also describes how to add reduction potentials to determine the cell potential for a galvanic or electrolytic cell. Several of these will be further amplified in the lectures and in other handouts. reduction halfreaction. Thermodynamics provides further insight into electrochemical cells at nonstandard conditions in its derivation of the N ernst Equation. or even theoretical. Thermodynamics plays an important role in our understanding of electrochemical processes. description. Such problems tend to be among the more difficult ones on any exam because they cut across many fields in chemistry and require deep analytical thought and an thorough understanding of electrochemical cells. Combining ideas from thermodynamics. however.e. they are described clearly and indepth. stoichiometry. THE CONTINUUM MODEL Matter may be described at a molecular (or microscopic) level using the techniques of statistical mechanics and kinetic theory.(RT/nF) In Q (the Nernst Equation). For engineering purposes.
. each of which has a position and a velocity. .. The information we have about a continuum represents the microscopic information avera~ed over a volume. Hence the principle of the conservation of mass is automatically satisfied whenever we employ a closed system analysis. This is termed a control volume.' . .. microscopic positions and velocities are generally not useful for determining how macroscopic systems will act or react unless.: Gas.'. Second. Everything outside the boundary is the surroundings.' .'.'. for instance. When working with devices such as engines it is often useful to define the system to be an identifiable volume with flow in and out... This type of system is sometimes termed a control mass. their total effect is integrated.. • _________ • . around which we can draw a boundary. We therefore neglect the fact that real substances are composed of discrete molecules and model matter from the start as a smoothedout continuum. A closed system is a special class of system with boundaries that matter cannot cross. Fluid j.. THE CONCEPT OF A "SYSTEM" A thermodynamic system is a quantity of matter of fixed identity. Piston (Boundary) and Gas (System) . 1 mm3 of air at standard temperature and presscre contains 10 16 molecules. Typical engineering applications involve more than 1020 molecules.'. Work or heat can be transferred across the system boundary. and more importantly. The boundaries may be fixed or moveable. Classical thermodynamics is concerned only with continya.... .Heat and Thermodynamics 118 an engineering device may produce too much information to manage.System Boundary Fig.
.. volume and temperature.: . Intensive properties do not depend on the quantity of matter present.. For fluid systems. . Thus. P2 . Volume is an extensive property. Extensive properties are additive. Temperature and pressure are intensive properties. typical properties are pressure. As an example. the state of an electric battery requires the specification of the amount of electric charge it contains. if the system is divided into a number of subsystems. Sample Control Volume THE CONCEPT OF A "STATE" The thermodynamic state of a system is defined by specifying values of a set of measurable properties sufficient to determine all other properties. Boundary Around Electric Motor (System) s""em_ 1 tn. More complex systems may require the specification of more unusual properties.. _ _ Fig. _ _ . Electrical anergy (work) \. ___ _ Fig. the value of the property for the whole system is equal to the sum of the values for the parts..119 The First Law of Thermodynamics System boundary  . Properties may be extensive or intensive._ .l2 T complex process L L _ _ _ _.
the .T2 Fig Equilibrium A system in thermodynamic equilibrium satisfies: • Mechanical equilibrium (no unbalanced forces). A _ PA Gasal Pressurlt.. It is important to note that properties describe states only when the system is in equilibrium.•· Copper PatIrtIon Overtime. T. P [Mechanical Equilibrium] • 0  [Thermal Equilibrium] I )J ":: 1'. the properties of a system can vary from point to point... If. unchanged values as long as external conditions are unchanged is called an equilibrium state. THE CONCEPT OF "EQUILIBRIUM" The state of a system in which properties have definite. In general. Specific properties are intensive because they do not depend on the mass of the system. . at the end of the process. however. ~o Mass A t t f t Mg P. Chemical equilibrium. The properties of a simple system are uniform throughout. The succession of states through which the system passes defines the path of the process. then it is undergoing a process. Specific volume = VIm = v. THE CONCEPT OF A "PROCESS" If the state of a system changes. • Thermal equilibrium (no temperature differences). We can usually analyze a general system by subdividing it (either conceptually or in practice) into a number of simple systems in each of which the properties are assumed to be uniform.Heat and Thermodynamics 120 Specific properties are extensive properties per unit mass and are denoted by lower case letters.
quasisteady. or isochors on a Tp diagram. which we cannot treat. An extremely useful idealization. the system has undergone a cyclic process or a cycle. or isotherms.121 The First Law of Thermodynamics properties have returned to their original values. so that the process can be viewed as taking place in a series of "quasiequilibrium" states. The figures below demonstrate the use of thermodynamics coordinates to plot isolines. This is generally much shorter than the time scales associated with the bulk properties of the flow (say the time needed for a fluid particle to move some significant fraction of the length of the device of interest).) For this to be true the process must be slow in relation to the time needed for the system to come to equilibrium internally.of 109 seconds. etc. it is a very good approximation to view the thermodynamic processes as consisting of such a succession of equilibrium states. so that. on a pv diagram. which we can chart. the system can pass through nonequilibrium states." it used in a number of contexts such as quasionedimensional. however. They include constant temperature lines. A state only when a system is in equilibrium. unbalanced forces. Note that even if a system has returned to its original state and completed a cycle. the equilibration time is on the orde:. (The term quasi can be taken to mean "as if. If a process involves finite. For a gas at conditions of interest to us. QUASIEQUILIBRIUM PROCESSES We are often interested in charting thermodynamic processes between states on thermodynamic coordinates. is that only "infinitesimal" unbalanced forces exist. a given molecule can undergo roughly 10 10 molecular collisions per second. therefore. or isobars. on a Tv diagram for an ideal gas. constant volume lines. if ten collisions are needed to come to equilibrium. Real substances may have phase changes which we can also plot on thermodynamic coordinates. and constant pressure lines. the state of the surroundings may have changed. Over a large range of parameters. lines along which a property is constant. .
75 1. if we know v and T we know P.r.25 1.25 1. . where v is the volume per unit mass. 1).lIp. P = P (v. 1).5 Specific Volume (m3/kg) Tv diagram Fig. 250 ~2oo 50 0. Thus for a simple compressibie gas like air.0 1. In words. . which is a very good approximation to real gases at conditions that are typically of interest for aerospace applications is Pv =RT.31 kJ/kmolK. v.0 1. which is known as an equation of state. Any of these is equivalent to an equationj{P. or T= T(P. v). where V is the volume per mol of gas and n is the "Universal Gas Constant. or v = v (P.Heat and Thermodynamics 122 300r. etc .5 0." 8.75 1. 1) = 0. The equation of state for an ideal gas.5 200 300 Specific Volume (m3Ikg) 400 500 Temperature (Kelvin) 600 pv diagram pTdiagram ~r77~~~r_~~~ 0. Thermodynamics Coordinates and Isolines for an Ideal Gas EQUATIONS OF STATE It is an experimental fact that two properties are needed to define the state of any pure substance in equilibrium or undergoing a steady or quasisteady process.
R = 0. HEAT Heat is energy transferred due to temperature differences only: • Heat transfer can alter system states. • Two systems which are individually in thermal equilibrium with a third are in thermal equilibrium with each other. ZEROTH LAW OF THERMODYNAMICS With the material so far. which has a different value for different gases due to the different molecular weights. we are now in a position to describe the Zeroth Law. Like the other laws of thermodynamics the Zeroth Law is based on observation. or P=pRT where is RIM. equilibrium (a static or quasistatic process) is necessary for the equations that relate system properties to oneanother to be valid. heat is identified as it comes across system boundaries.287 kJ/kgK. all three systems have the same value of the property called temperature. thermal equilibrium is said to prevail. which are two different modes of energy transfer. For air at room conditions. M: Pv=RT. no further observable changes take place. CHANGING THE STATE OF A SYSTEM WITH HEAT AND WORK Changes in the state of a system are produced by interactions with the environment through heat and work. • Bodies don't "contain" heat. • Adiabatic processes are ones in which no heat is transferred. During these interactions.123 The First Law of Thermodynamics A form of this equation which is more useful in fluid flow problems is obtained if we divide by the molecular weight. • The amount of heat needed to go from one state to another is path dependent. These closely connected ideas of temperature and thermal . We start with two such observations: • If two bodies are in contact through a thermalIyconducting boundary for a sufficiently long time.
Heat and Thermodynamics 124 equilibrium are expressed formally in the "Zeroth Law of Thermodynamics" Zeroth Law: There exists for every thermodynamic system in equilibrium a property called temperature. If work is done on the system (energy added to the system). Consider a simple compressible substance.g. exerting a force on the surroundings via a piston. so in these notes we use either the Kelvin K = 273. electric and magnetic work (e. We can have pushpull work (e.g. an engine) has on its surroundings. surface tension work. an electric motor). the work is negative. Equality of temperature is a necessary and sufficient condition for thermal equilibrium. The Zeroth Law Schematically Heat is a way of changing the energy of a system by virtue of a temperature difference only. The Zeroth Law thus defines a property (temperature) and describes its behaviour. in a pistoncylinder. we focus on the effects that the system (e. etc. a gas (the system).QJ . 3 j [J WORK t 2 (thermometer) lIIen . In defining work.g. Note that this law is true regardless of how we measure the property temperature. lifting a weight). which moves .15 + °C or Rankine scales) The zeroth law is depicted schematically. elastic work. Thus we define work as being positive when the system does work on the surroundings (energy leaves the system). chemical work.0 Fig. Any other means for changing the energy of a system is called work. (Other relationships we work with will typically require an absolute scale.
Use of Px instead of Ps is often inconvenient because it is usually the state of the system that we are interested in. No work is done on the surroundings even though p s changes and the system volume changes. A reversible process can be altered in direction by infinitesimal changes in the external conditions. Px ~ px· Consider Px = Ps ± dp W= CPx dV = (\Ps±dp)dV = (2 PsdV±dpdV. and the work done by the system is the same as the work done on the surroundings Under these conditions. there cannot be any friction. we require a "quasistatic" process. I. WonsuIT. the system and the surroundings will be returned to the original states. we say that the process is "reversible. W= 12 1 PsdV. Therefore. x (A rea x dl) Ar dWon SUIT. = Force on SUIT. dWonSUIT. The external pressure can only be related to the system pressure if Px ~ px· For this to occur. .' is dWon SUIT. when dp is small (the process is quasistatic). x d Volume dWon SUIT. In other words. Why is the pressure Px instead of p/ Consider Px = 0 (vacuum). = Px xdV therefore Won SUIT. = (2 PxdV. The work done on the surroundings. and the process must also be slow enough so that pressure differences due to accelerations are not significant. = Force on SUIT. x dl ea = pressure of SUIT. To reverse the process we need to apply only an infinitesimal dp.125 The First Law of Thermodynamics through some distance." The conditions for reversibility are that: If the process is reversed.
A Closed System (Dashed Box) Against a Piston. 0 (j)~.sdV. dV • 0 Fig.dV . W=m (2 Psdv.Heat and Thermodynamics 126 Remember this result. In the case of a "free expansion. the work done can be represented as the area under a curve in a pressurevolume diagram . which Moves Into the Surroundings fp. We can write the above expression for work done by the system in terms of the specific volume. where is the mass of the system. v. I s~m~I Fa e:temaJ I Px J Area ~dl Fig. For simple compressible substances in reversible processes. not related to the work) because the system is not in equilibrium. Note that if the system volume expands against a force." where Px = 0 (vacuum). . work is done by the system. If the system volume contracts under a force.Q) but fp.. Work During an Irreversible Process '# JP.11l Vi Va Volume [Work is area under curve of P(V)] [Work depends on path] . that we can only relate work done on surroundings to system pressure for quasistatic (or reversible) processes.ps is not related to Px (and thus. work is done on the system.
Vo) = PoVo Along Path b: .Vo) = 2poVo Along Path a: W = Po ( 2Vo . we cannot use • f pdV .V coordinates Key points to note are the following: • Properties only depend on states. Work in P . either the work must be given or it must be found by another method. which shows a system undergoing quasistatic processes for which we can calculate work interactions as fpdV. and not a state variable. Fig. we need to specify the path. therefore work is not a property. Simple processes W = 2po ( 2Vo . Example: Work on Fwo Simple Paths Consider Figure. w~J. p 2Po CD Po b 0 Vo Q) 2Vo V Fig. For irreversible (nonreversible) processes.127 The First Law of Thermodynamics ·1 F~I v W"J. but work is path dependent (depends on the path taken between states). When we say Wl _ 2 ' the work between states 1 ~nd 2.
the path is specified as isothermal. 'R is the Universal gas constant. We write the work as above. a bunsen burner. and • how you would physically know the work is different along each path.v = n'RTln(V2) VI also for T. or in terms of the specific volume and the system mass. = constant. ice. substituting the ideal gas equation of state.:) =mRT In ( :~ ) =mRT In (:~ ). describe • how you would use these to move along either path a or path b above. isothermal expansion of a thermally ideal gas from PI' VI to P2' V2· To find the work we must know the path. Is it specified? Yes.Heat and Thermodynamics 128 Practice Questions Given a piston filled with air. p V Fig. and V is' the total system volume. and a stack of small weights. W = (2 n'RT dV ~V = =n'RT (2 dV 1. where n is the number of moles. Example: Work Done During Expansion of a Gas Consider the quasistatic. Quasistatic. so the work done by the system is W =n'RTln(~) =n'RTln(. p I VI =P2 V2. Isothermal Expansion of an Ideal Gas The equation of state for a thermally ideal gas is pV=n'RT. W .
potential energy." the First Law defines a useful property called "energy. If the system is the water and the resistor combined. A resistor Heating Water • If the water is the system. then the state of the system will be changed by heat transferred from the resistor. CONSERVATION OF ENERGY • FIRST LAW OF THERMODYNAMICS Observation leads to the following two assertions: • There exists for every system a property called energy.129 The First Law of Thermodynamics Work vs. neglect the internal energy. we will neglect the chemical energy. The system energy ~an be considered as a sum of internal energy. . or both: it depends on what crosses the system boundary (and thus. the other. however. Fur most situations in this class. E. Like the Zeroth Law. then the state of the system will be changed by electrical work." The two new terms (compared to what you have seen in physics and dynamics) are the internal energy and the chemical energy. Since this molecular motion . on how we define our system). We will generally not. "temperature. It arises from the random or disorganized motion of molecules in the system. and chemical energy. Heat We can have one. which defined a useful property. Consider a resistor that is heating a volume of water: rv Fig. kinetic energy.
" TI Tl add heat (molecular 1IIOIion) (molecular moUOII) Fig. and W is the work done by the system. !ill =Q. Note that Q and Ware not functions of state. • The change in energy of a system is equal to the difference between the heat added to the system and the work done by the system. E = U (thermal energy) + Ekinctic + Epotenlial +. the internal energy is sometimes called "thermal energy. Recall that for pure substances the entire state of the system is specified if any two properties are specified.w (units are J/kg). Random Motion is the Physical Basis for Internal Energy The internal energy.Heat and Thermodynamics 130 is primarily a function of temperature.W (units are Joules.. Q is the ijeat input to the system. or u = u (p. Thus u = u (p. kinetic energy. 1). • The equation can also be written on a per unit mass basis tle =q . but U. J). We therefore have the striking result that: . depends only on the state of the system. and • tlU=QW or tlu=qw. v). • In many situations the potential energy. or u = u (p. which arises from mclecular motion. does not depend on how the system got to that state. where E is the energy of the system.. and chemical energy of the system are constant or not important. Then !ill = tlU. the First Law describes the behaviour of the new property. • Like the Zeroth Law. is a function ofthe state of the system. u. 1).
• Note that the signs are important: Q is defined to be positive if it is transferred to the system. and negative if heat is transferred from the system to the surroundings.pdv To give an example of where the first law is applied. and negative if work is being done on the system.in one form or another. Pressure Area Heat(Q) Fig. . thus the numerical value we substitute for W will be positive if the system is doing work. The change in energy of the system supplies the connection between the heat added and work done. We heat a gas. because it is well suited to dealing with systems of a fixed mass. it expands against a weight. We will spend most of the course dealing with various applications of the first law . dU =dQ . where the symbol "0" is used to denote that these are not exact differentials but rather are dependent on path.131 The First Law of Thermodynamics I1U is independent of path even though Q and Ware not! Sometimes this difference is emphasized by writing the First Law in differential form. dU =oQoW or du =oqow.pdV or du =oq . some force (pressure times area) is applied over a distance. • For quasistatic processes we can substitute W = psysdV. and work is done. The Change in Energy of a System Relates the Heat Added to the Work Done The form of the first law we have given here is sometimes called the "control mass" form. W is defined to be positive if it is done by the system. thus the numerical value we substitute for Q will be positive if heat is transferred to the system from the surroundings.
(:g) Valve PI' ".Heat and Thermodynamics 132 COROLLARIES OF THE FIRST LAW • Work done in any adiabatic (Q = 0) process is a function of state.. • For a cyclic process heat and work transfers are numerically equal Fig. STEADY. a Generic Throttling Process . Adiabatic flow Through a Valve... any Process that Returns a System to its Original State Leaves its Energy Unchanged. P. We wish to know the relation between properties upstream of the valve... now W can be found as a function of the state change . Since tlUdepends only on the state change.. The change in energy between two states is not path dependent. Fig.". THROTILING OF A GAS The configuration of interest. as tlU=~oW... denoted by"!" and those downstream. setting the heat transfer term equal to zero... . Since Energy is a Function of State Only. _ Fig. V... We can write the first law. denoted by "2". U final = Uinitial therefore tlU=O and Q=W or qOQ=q8W APPLICATIONS OF THE FIRST LAW ADIABATIC.
since we are dealing with a unit mass. as indicated schematically on the right side. The first law for the system is therefore !::. In terms of the specific quantities. the initial and final states of the system have the same value of u + Pv." usually denoted byH. we could replace the fluid external to the system by pistons which exert the same pressure that the external fluid exerts..W.. the enthalpy per unit mass IS h = u + Pv = u + Pip. We define this quantity as the "enthalpy. the initial and final states of the system have the same value of the quantity U + PV. In the final state the gas is downstream of the valve plus just before the valve.u. For the case examined.. .cI~V')_'~'\ _ _ SYSleRI . "~""~~Zl \.U= .:I Fig. In words. The work dene by the ~ystem is W =P2V2 ljVj. however. In terms of the system behaviour. Use of the first law leads to U2 =P2 V2 =U1 +ljVj.133 The First Law of Thermodynamics \\ ®Isystem E?a {Z). H=U+PV. we can defHle the system (choosing the appropriate system is often a critical element in effective problem solving) as a unit mass of gas in the following two states. with changes in potential energy and kinetic energy assumed to be negligible. The process is adiabatic. 7 PlslOns )1 ~':..I»l"'y Initial Slale " ' " pislons _ _. Equivalence of Actual System and Piston Model To analyze this situation. Initially the gas is upstream of the valve andjust through the valve.
. We call this total energy the enthalpy. the work required to make a place for itself is p V.VI) + W. .VI) + P(V2 ... from a surrounding atmosphere. This is so with any object or system. this time for an unsteady flow...VI) since PI =P2 = p.~ that goc:s I \ inco the lank) } " ". We can write the first law in terms of the states before· and after the expansion as Q = (V2 . ____ .. is the transient process of filling a tank. initially evacuated. QUASISTATIC EXPANSION OF A GAS Consider a quasistatic process of constant pressure expansion. Po.(VI + pVI ) =H2 HI TRANSIENT FILLING OF A TANK Another example of a flow process. Yo Fig. Thus the total energy of a body is its internal energy plus the extra energy it is credited with by having a volume Vat pressure p.~ .. H. " " . System \\ : (all the ga. By grouping terms we can write the heat input in terms of the enthalpy change of the system: Q = (V2 + pV2 ) . you have to remember that the object had to push the surroundings out of the way to make room for itself. " "'>( Po ' .T. With pressure P on the object. The force of one atmosphere !lressure on one square meter is equivalent to the force of a mass of about 10 tons. ViICuum . A Transient Problemfilling of a Tank from the Atmosphere . and writing the work in terms of system properties. and this work may not be negligible..Heat and Thermodynamics 134 It is a function of the state ofthe system. The utility and physical significance of enthalpy will become clearer as we work with more flow problems. . Hhas units of Joules.. When you evaluate the energy of an object of volume V.. which is at a pressure Po and a temperature To . and has units of Joules per kilogram. =(V2 .
h =CpT. and the final state has the system completely inside the tank. U =cvT.u. so /). . so the first law again takes the form /). as is the change in potential energy. Work is done on the system. of magnitude Po Vo. Vo where m is the mass of the system)..W. The initial state has the system completely outside the tank. The inflow stops when the pressure inside is equal to the pressure outside.U= Po Vo· In terms of quantities per unit mass (/).135 The First Law of Thermodynamics At a given time. To =yTo. Cv C The final temperature is thus roughly 200°F hotter than the outside air! It may be helpful to recap what we used to solve this problem. The kinetic energy initially and in the final state is negligible. cvTflnal = C pTo. The tank is insulated. flu = mvo' =Urinal ufinaI = Uj Uj = Po Vo· The final value of the internal energy is + Po Vo =hj =110. There were basically four steps: • Definition of the system • Use of the first law • Equating the work to a "PdV" term • Assuming the fluid to be a perfect gas with constant specific heats. For a perfect gas with constant specific heats. Tfinal =2. What is the final temperature of the gas in the tank? This time we take the system to be all the gas that enters the tank.U = . the valve at the tank inlet is opened and the outside air rushes in. so there is no heat transfer to the atmosphere.U = m/). where Vo is the initial volume of the system.
we obtain dH = oQ . the path. Two useful processes are constant pressure and constant volume. can be differentiated (applying the chain rule to the p V term) to produce dH=dU+pdV+ Vdp Substituting the dU above for the dU in the First Law. or cp and cv per unit mass.PE) dU = oQ . Since heat is path dependent. Because the combination appears so frequently.e. where C is a constant that depends on the substance. it is not only defined but also tabulated as a function of temperature and pressure for a number of working fluids. so we will consider these each in turn. no ME or ME) The definition of er. is that the quantity h = u + Pv occurs naturally in problems of fluid flow. to find C. We will call the specific heat at constant pressure Cp. however. i.pdV (true for any quasistatic process.0W (true forany process. we must specify the process. In general Q=CtlT. neglecting ME and f:. We can determine the constant for any substance if we know how much heat is transferred. H=U+pV..oW + pdV + Vdp (valid for any process) or dH = oQ + Vdp (valid for any quasistatic process) THE RELATION BETWEEN TEMPERATURE CHANGE AND HEAT How much does a given amount of heat transfer change the temperature of a substance? It depends on the substance. THE FIRST LAW IN TERMS OF ENTHALPY We start with the first law in differential form and substitute pdV for dW by assuming a quasistatic or reversible process: dU = oQ .thalpy.Heat and Thermodynamics 136 A message that can be taken from both ofthese examples (as well as from a large number of other more complex situations. . and that at constant volume Cv.
du= 8qpdv. dv = O. We can therefore use our definition of specific heat from Equation to define the specific heat for a constant volume process. v) or u = u (p. Equating Equation with dv canceled in each. Consider the form u = u (T. with dW = pdv. "specific heat at constant volume. to think of cn in terms of its definition as a certain partial derivative. however. 8q=(:. v) u = u (p. then the state of the system is fully specified. Cv =(:. vvhich is a thermodynamic property. In other words we can write u = u (T. . Now if we write the First Law for a quasistatic process.)p' In the derivation of cv' we considered only a constant volume process.1 dT. and use the chain rule to write how changes with respect to T and v: du =(00) dT +(au)T dv.137 The First Law of Thermodynamics • The Specific Heat at Constant Volume Remember that if we specify any two properties of the system. 1)." It is more useful. the second term is zero since there is no change in volume. aT av v For a constant volume process. we can perform a similar derivation to the one above and show that c p =(:. and consider a constant pressure process. hence the name. p). v). any energy increase is due only to energy transfer as heat. l· • The Specific Heat at Constant Pressure If we write h = h (T. and rearranging (:l ~(:~l· In this case. we see that again the second term is zero if the· process is also constant volume.
but it can be shown that this is a . Start by listing what information you need to solve this problem. and have been experimentally determined as a function of the thermodynamic state for an enormous number of simple compressible substances.Heat and Thermodynamics 138 rather than as a quantity related to heat transfer in a special process. The names "specific heat at constant volume" and "specific heat at constant pressure" are therefore unfortunate misnomers. and the limits of model validity mUSt always be kept in mind. constant pressure. aT Practice Questions Throw an object from the top tier of the lecture hall to the front of the room. v v or cp =(aH) aT andC P v =(au) . One of the other important features of an ideal gas is that its internal energy depends only upon its temperature. that describing a substance as an ideal gas constitutes a model of the actual physical situation. In fact. the derivatives above are defined at any point in any quasistatic process whether that process is constant volume. (For now. SPECIFIC HEATS OF AN IDEAL GAS The equation of state for an ideal gas is PV=NRT where N is the number of moles of gas in the volume V. Ideal gas behaviour furnishes an extremely good approximation to the behaviour of real gases for a wide variety of aerospace applications. C and c are thermodynamic properties of a substance. They are extremely important values. however. It should be remembered. or neither. and by v p definition depend only the state. this can be regarded as another aspect nfthe model of actual systems that the ideal gas represents. To recap: c P ah \ =1 ( aT) p and C v =( aT au) . Estimate how much the temperature of the room has changed as a result.
dh =( fJh) dT + ( fJl/r dp.) Therefore. there are wide ranges over which specific heats d~ not vary greatly with respect to temperature. using the ideal gas equation of state. U2 . u + Pv is also. Furthermore. If so dh=cpdT. it is often assumed that cy and cp are constant. Like the internal energy. If we are interested in finIte changes of internal energy or enthalpy. (If u is a function of T. U2 UI =cv (T2 11). we integrate. fJT y JP )T and dh = cp (1)dT.) Since u depends only Oil T. These equations are useful in calculating internal energy or enthalpy differences. L\ul_2 = rT2 1ft cy(T)dT and r L\hl _2 = Jr cp(T)dT T2 t Over small temperature changes (DT :::0 200).hI = CP (T2 11). It is thus often useful to treat them as constant. but it should be remembered that they hold only if the specific heats are constant. In the above equation we have indicated that Cv can depend on T. the enthalpy is also only dependent on T for an ideal gas. or du = cv (1)dT. then.139 The First Law of Thermodynamics consequence of the form of the equation of state. We can relate the specific .
oq=du+dW. the expression takes the form CpCv=R.. • All ideal gases: • The specific heat at constant volume (cv for a unit mass or Cv for one kmol) is a function of T only. oq =dhvdp. and assuming an ideal gas. Equating the two first law expressions above. and assume a quasistatic process so that we can also write it in terms of enthalpy. a kilogram. For one kmol ofgas. • A relation that connects the specific heats cp ' cv' and the gas constant is CpCv=R.Heat and Thermodynamics 140 heats of an ideal gas to its gas constant as follows.g. e. cp and Cv woulci be the specific heats for one kilogram of gas and R is as defined above. and give some values for specific types of ideal gases. We write the first law in terms of internal energy. Combining terms. • . d(pv) cp cv =R An expression that will appear often is the ratio of specific heats. (c p cv ) dT = d(pv) cp cv = dT' Since pv = RT. The specific heat at constant pressure (cp for a unit mass or Cp for one kmol) is a function of T only. which we will define as y=. Cv cp Below we summarize the important results for all ideal gases.vdp =cvdT + pdv. we obtain C pdT . For a unit mass of gas. where the units depend on the mass considered.
have values of g closer to . y = c/cv (or CpiC v). • Monatomic gases. • cp (or Cp ) is nearly constant at ordinary temperatures.4]. The general trend is that heavy molecular weight gases (i. • Socalled permanent diatomic gases. It decreases with temperature above this.e. • y is constant over a wide temperature range and is very nearly equal to 5/3 [y = 1. and increases slowly at higher temperatures. and most metallic vapors: • Cv (or C v) is constant over a wide temperature range and is very nearly equal to (3/2)R[or (3/2)R. ocing approximately (7/2) R[(7/2)R. being approximately (5/2)R [(5/2)R. for one kmol]. for one kmol]. such as CO2' NH3 . • y is constant over a temperature range of roughly to and is very nearly equal to 7/5[y = 1. • cp (or Cp) is constant over a wide temperature range and is very nearly equal to (5/2)R[or (5/2)R. • Polyatomic gases and gases that are chemically active. for one kmol]. and to avoid confusion we use the stated terminology. Air. cp = const and C v = const. 02' N2. is a function of T only and is greater than unity • An ideal gas with specific heats independent of temperature. Ne. • The specific heat ratio. In some textbooks perfect gases are sometimes also referred to as ideal gases. Cv and cp ' and g vary with the temperature. more complex gas molecules than those listed in 2 or 3). for one kmol].67]. the variation being different for each gas. and increases slowly at higher temperatures. and CO: • Cv (or C v) is nearly constant at ordinary temperatures. NO. Ar. CH4.141 The First Law of Thermodynamics where Cp and C v have been used to de note the specific heats for one kmol of gas and R is the universal gas constant. such as He. To make this distinction the terminology "a perfect gas with constant specific heats" is used throughout the notes. is referred to as a perfect gas.. Monatomic gases and diatomic gases at ordinary temperatures are considered perfect gases. namely H2. and Freons: The specific heats.
(P2 vi) !(PI v{) = 1. specifically the dependence of the energy and enthalpy on temperature only. du+ pdv=O Also. Rewriting equations. Combining the above two equations we obtain ypdv=vdp or ydv!v =dp! p. and Wor = pdv. In summary.ypdv cvdT = vdp. which. In general. u and h depend on pressure as well as on temperature. In this respect. with Q = 0 du = cvdT. the ideal gas is a very special model. using the definition of enthalpy.2 are typical of Freons which have molecular weights of over one hundred. Values of g below 1. The underlined terms are zero for an adiabatic process. for substances other than ideal gases. the specific heats are thermodynamic properties and can be used even if the processes are not constant pressure or constant volume. The simple relations between changes in energy (or enthalpy) and temperature are a consequence of the behaviour of an ideal gas. dh = du + pdv + vdp. are closer to unity than monatomic gases.Heat and Thermodynamics 142 unity than diatomic gases. For an ideal gas undergoing a reversible. or . ycvdT = . and are not true for more complex substances. or equivalently. the relation between pressure and volume is thus: pvY = constant. and the above relations will not all apply. Equation can be integrated between states 1 an? 2 to give 'I! n(v2!vl) = In (P2! PI). adiabatic process. REVERSIBLE ADIABATIC PROCESSES FOR AN IDEAL GAS From the first law.
m out dt . a specific quantity of matter. the control volume form of the system laws is of great importance. in propulsion and power problems.L yl and T2 =( ~ )Y_I v2 11 ) 11 We will use the above equations to relate pressure and temperature to one another for quasistatic adiabatic processes (for instance. We can substitute for p or v in the above result using the ideal gas law. This requires us to use the control volume form of the thermodynamic laws. We may also be interested in the rates of heat and work into and out of a system.= min . a rocket motor or a jet engine through which mass is flowing at a certain rate. this type of process is our idealization of what happens in compressors and turbines). Rather than focus on a particle of mass which moves through the engine. More often.. For a single flow coming in and a single flow coming out this is dmcv . to also show that P2 PI = constant x = ( T2 . Control Volume and System for Flow Through a Propulsion Device CONSERVATION OF MASS For the control volume shown. or carry out the derivation slightly differently. developed below. For this reason. it is more convenient to focus on the volume occupied by the engine. Fig. . we are interested in what happens in a fixed volume. 9~€J Syslemat/. the rate of change of mass inside the volume is given by the difference between the mass flow rate in and the mass flow rate out. CONTROL VOLUME FORM OF THE SYSTEM LAWS The thermodynamic laws (as well as Newton's laws) are for a system. Syslem at lime I. ..143 p The First Law of Thermodynamics pY.
V.) .Heat and Thermodynamics 144 If the mass inside the control volume changes with time it is because some mass is added or some is taken out.) .V. dt .). which carries energy with 'it. The physical idea is that any rate of change of energy in the control volume must be caused by the rates of energy flow into or out of the volume. The desired form of the equation will be (rate of change of energy in cv) = (rate of heat added to C.. dt W= To derive the first law as a rate equation for a control volume we proceed as with the mass conservation equation. A Control Volume used to Track Mass Flows CONSERVATION OF ENERGY The first law of thermodynamics equation: Chfl be written as a rate de . therefore iii.V. dId! = 0.(rate of energy flow out C. . J:!o (OW) rate of total work done by the system.(rate of work done) + (rate of energy flow into C. + control volume Fig. In the special case of a steady flow. J:!o (OQ) rate of total heat transfer to the system . . . =Q=W dt ' where Q= . The heat transfer and the work are already included and the only other contribution must be associated with the mass flow in and out.
Schematic Diagrams Illustrating Terms in the Energy Equation for a Simple and a more General Control Volume The fluid that enters or leaves has an amount of energy per unit mass given by e=u+c 2 !2+gz. the work done on the surroundings by the flow at the exit station is dWflow = pvdmc ' .. __ o0 Q ... The rate of flow work at exit is given by the product of the pressure times the exit area times the rate at which the external flow is "pushed back. doing work on it. I ~~_~_~_~~_~_~_~_~_~_~~J~ __ . In addition. where c is the fluid velocity relative to some coordinate system. however.. is equal to the volume per unit . Put another way. ..." The latter. and receives work from the surrounding air. in a time dt. whenever fluid enters or leaves a control volume there is a work term associated with the entry or exit. and we have neglected chemical energy. The present derivation is essentially an application of the ideas presented there.. i Fig..145 The First Law of Thermodynamics [Simple] [More General] t ·/ 'IJi 'lot . . Flow exiting at station "e" must push back the surrounding fluid.nass times the rate of mass flow. Flow entering the volume at station "i" is pushed on by..
+ gz) where L includes the sign associated with the energy flow.It = 'Q'cv  JYshaft . the first law for a control volume will be most often used as: dEev . Thus. shear work. In writing the control volume form of the equation we have assumed only one entering and one leaving stream. to make the enthalpy appear: Total energy associated with mass flow: e+ pv =U +c2 /2+ gz+ [iv =h+c 2 /2 + gz. . NOTE: this is consistent with M£ = Q . U. dt Applying this to Equation produces a form of the "Steady Flow Energy Equation" (SFEE). if work or heat are extracted from the system then the sign is negative. + mi (h + 2" + gzi ). d =0 and mi =me =m. pv. in e and the specific flow work term. but this could be generalized to any number of inlet and exit streams. etc. . Ifheat is added or work is done on the system then the sign is positive. where W is the work done by the system on the environment.).W. (he + 2" + gZe ). In the special case of a steadystate flow. shaft work. We can then combine the specific internal energy term.haft +LWshcar + LWpiston + Lm (h+ c.. the first law can then be written as: W =PeVeme flow ~ LEcv = LOcv +LW shaft + LW shcar + LW piston + LW flow + Lm( u+ e. c. + gz)Cl • For most of the applications in this course. Hence.me c~ "i Note how our use of enthalpy has simplified the rate of work term. there will be no shear work and no piston work.Heat and Thermodynamics 146 The net rate of flow work is Pivjmi · Including all possible energy flows (heat. the first law can be written as: !LE = Lfkv + Lri. . piston work. thus work is flowing out of the system.
cf 1 which has units of Joules per second per kilogram. Streamlines and a Stagnation Region. ~:~Stagnation ~  __ ~r~mJine   I Fig. we will neglect the gz telms unless explicitly stated. a Control Volume can be Drawn between the Dashed Streamlines and Points 1 and 2 The streamlines are stationary in space. We could also divide by the mass flow to produce qcvwcv+ m . STAGNATION TEMPERATURE AND STAGNATION ENTHALPY iJ3r'""ii3. + c1 + gz}( hi + ct + gz. I (1.(h c+2+gzC)~''i+2+gZi' c. so there is no external work done on the fluid as it flows. If there is also no heat transferred to the flow (adiabatic). For problems of interest in aerospace applications the velocities are high and the term that is associated with changes in the elevation is small.. .ll which has units of Joules per second.147 The First Law of Thermodynamics Q" w~ +m[(h. . then the steady flow energy equation becomes The quantity that is conserved is defined as the stagnation temperature. From now on.
via a steady r. via a steady. the stagnation temperature is constant. I.)1 and define the relationship between stagnation pressure and static pressure as ~ =(1+ y~1 M2)1. The stagnation temperature and stagnation pressure are the conditions the fluid would reach if it were brought to zero speed relative to some reference frame. It is also convenient to define the stagnation enthalpy.I2 =ht2  htl · Note that for a quasistatic adiabatic process 11 T2 = (!!L)Y. quasistatic process with no external work. adiabatic flow with no external work.Heat and Thermodynamics 148 or T 2 where M = cia is the Mach number. FRAME DEPENDENCE OF STAGNATION QUANTITIES An area of common confusion is the frame dependence of stagnation quantities. The stagnation temperature is the temperature that the fluid would reach if it were brought to zero speed by a steady adiabatic process with no external work./yRT 2 . where. = 1+ Y1 M2 using a = .I P2 yI so we can write i =(. Note that for any steady. the stagnation pressure is the pressure that the fluid would reach if it were brought to zero speed. adiabatic. which allows us to write the Steady Flow Energy Equation in a simpler form as ql2  ht =cpT+ c 2 ws .I .
Example For the case shown below. 2cp c2 where c is the vehicle speed." but in fluid mechanics and thermodynamics static is used to label the thermodynamic properties of the gas (p. . T. is. the skin temperature is much hotter than the atmospheric temperature. a jet engine is sitting motionless on the ground prior to takeoff. which is at temperature. The confusion comes about because T is usually referred to as the static temperature. Air is entrained into the engine hy the compressor. adiabatic.). Consider a high speed reentry vehicle traveling through the still atmosphere. The atmospheric temperature. reversible process with no external work (for stagnation pressure). The inlet can be assumed to be frictionless and 'adiebatic. T. Depending on the speed of the reference frame the stagnation quantities will take on different values. the stagnation temperature is the same as the static temperature. The stagnation temperature of the air in the vehicle frame is 1'. and these are not frame dependent. Tt. etc. looking at the still atmosphere from the vehicle frame we see a stagnation temperature hotter than the atmospheric (static) temperature. =T+. is not frame dependent. The temperature the skin reaches (to first approximation) is the stagnation temperature and depends on the speed of the vehicle. Thus in our reentry vehicle example. Let's place our reference frame on the vehicle and stagnate a fluid particle on the nose of the vehicle (carrying it along with the vehicle and thus essentially giving it kinetic energy). If we look at the same still atmosphere from a stationary frame. Since reentry vehicles travel fast. T.149 The First Law of Thermodynamics adiabatic process with no external work (for stagnation temperature) or a steady. In common language this has a similar meaning as "stagnation. but thestagnation temperature.
. M=O. or equal to T atm ? The stagnation temperature of the atmosphere. is equal to T atm since it is moving the same speed as the reference frame (the motionless airplane). Note the prominent role of enthalpy. A Stationary Gas Turbine Drawing Air in from the Atmosphere Considering the state of the gas within the inlet. ~ § 0~§ r+~~~~ Inlet cP Exhaust jet. T ratm . and working in the reference frame of the motionless airplane: • Is Ttl greater than. as state (1). and neglecting chemical and potential energies. Thus Ttl = Tt'atm = T atm • Is 1'1 greater than.W = m(hIc shaft hti ). or equal to Tatm~' If Ttl = T t' atm then TI < T atm since the flow is moving at station 1 and therefore some of the total energy is composed of kinetic energy (at the expense of internal energy. by the same argument as 1. Steady Flow Energy Equation in Terms of Stagnation Enthalpy The form of the "Steady Flow Energy Equation" (SFEE) that we will most commonly use is Equation written in terms of stagnation quantities. • Is PI greater than. prior to passage into the compressor.Heat and Thermodynamics Atrrosphere: 150 ~I T"tm P"lm =0 +. Fig. less than. by the same argument as 2. The steady flow energy equation tells us that ifthere is nc heat or shaft work (the case for our adiabatic inlet) the stagnation enthalpy (and thus stagnation temperature for constant Cp) remains unchanged. less than. or equal to P atm? Equal. thus lowering TI ) • Is P tl greater than. less than.8 u . less than... or equal to P atm? Less than. The steady flow energy equation finds much use in the analysis of power and propulsion devices and other fluid machinery. Steady Flow Energy Equation: Qcv .
A Control Volume Approach to the Tank Filling Problem The control volume form of the first law is therefore dU =m. In this problem the shaft work is zero. and potential energy changes are neglected. dt Combining we have dU =dm h dt dt" Integrating from the initial time to the final time (the incoming enthalpy is constant) and using U = mu gives the result l'flnal = hi =ho as before. r' m (mass flow) 1 control 1 volume 1 I I control surface 1 1 I 1 _____  Fig. Flow Through a Rocket Nozzle A liquid hipropellant rocket consists of a thrust chamber and nozzle and some means for forcing the liquid propellants into the chamber where they react..hi • dt The equation of mass conservation is dm .151 The First Law of Thermodynamics EXAMPLE APPLICATIONS OF THE STEADY FLOW ENERGY EQUATION Tank Filling Using what we have just learned we can attack the tank filling problem solved from an alternate point of view using the control volume form of the first law. . kinetic energy changes. =m·. In addition there is no exit mass flow. converting chemical energy to thermal energy. and the heat transfer.
and we assume that the flow is adiabatic. in the chamber. We define our control volume as going between location c. Flow Through a Rocket Nozzle Once the rocket is operating we can assume that all of the flow processes are steady. Also. at the exit. hiSh pressure low \'1:locIlY gas Fig. though in general this is a poor approximation.ic pressure.hte . adiabatic expansion then so Te and Pc' the conditions in the combustion chamber. If we assume quasistatic. for now we will assume that the gas behaves as a perfect gas with constant specific heats. and p e is the external sta. There is no external work. and location . so it is appropriate to use the steady flow energy equation. .Heat and Thermodynamics fuel 152 ~xidi7A:r + f> ~~~ I chamber C:C y~ \ ~ ___ hot.Ws ec =.hte which becomes hte = hte or Therefore Ce =~2cp(Te Te). are set by propellants. and then write the First Law as qcc .
We define our control volume to encompass the compression system. We wish to find the total shaft work required to drive the compression system.000 Ibs ofthrust at takeoff. so we write the First Law (steady flow energy equation) as: Ws = m(ht2 htl )· For this problem we must consider two streams. with the shaft cutting through the back side of the control volume.153 The First Law of Thermodynamics Power to Drive a Gas Turbine Compressor The engine is designed to produce about 84. .. and the core stream.4 1t c = total pressure ratio across the fan + cinoressir : : 45 mf =610kg/s moore = 120 kg/s 1inlct = 300 K. The fan and low pressure compressor are driven by the low pressure turbine. The high pressure compressor is driven by the high pressure turbine. Heat transfer from the gas streams is negligible. c: 1°  . from the front of the fan to the back of the fan and high pressure compressor../. • AlII ·"fM1ilUST 'IAn : ''''''SI Fig. The engine is a twospool design. The Pratt and Whitney 4084 (drawing courtesy of Pratt and Whitney) 1tf = total pressure ratio across the fan . the fan stream. :::: 1.
along with estimates of c ' we obtain P W". APPLICATION OF FIRST LAW . = m[f. If a car engine has ~ 110 Hp = 8. The question we will pose is how efficient can this conversion be in the two cases..1 fan T. core = 600 K core Substituting these values into the expression for the first law above. The first of these represents the conversion of work into heat.2 ) = 11: 7. ) ( II J' = yl 1.91 Megawatts negative sign implies work done on the fluid Note that 1 Hp = 745 watts.. concerns the conversion of heat into work. WORK AND EFFICIENCY As preparation for our discussion of cycles (and as a foreshadowing of the second law). SOME PROPERTIES OF ENGINEERING CYCLES.7. we examine two types of processes that concern interactions between heat and work.7.c = m[cpf.110 automobile engines..2 x 104 wa!ts.1 :::::> f.2 =11:c6re =3.7.hl.c We obtain the temperature change by assuming that the compression process is quasistatic and adiabatic.f + mcM/.. then the power needed to drive compressor is equivalent to 1... fan = 30 K . All of this power is generated by the low pressure and high pressure turbines.Heat and Thennodynamics 154 w.. which is much more useful.f + mc cpf.7.s = 610 kg/s x 30 K x 1008 J/kgK + 120 kg/s x 600 K x 1008 J/kgK =91xl06J/s = .0 => f. The second.... ~~(~f then ( 7. .
however. (High temperatures can be reached if the velocities of pulling are high. The final example is the passage of a current through a resistance. Ifwe measured the temperature of the block and the surface we would find that it was higher than when we started. All the examples in Figure have 100% conversion of work into heat. One way to do this is to ask whether we can construct a way that the process could result in the raising of a weight in a gravitational field. this is the basis of inertia welding. The fluid and the paddle wheels wilI be found to be hotter than when we started. This is a case of electrical work being converted to heat. it is removed. we need to have some basis for judging whether work is done in a given process. Is this true for the conversion of heat into work? To answer the last question.155 The First Law of Thermodynamics i +~R Block on rough surface Viscous liquid L~ Resistive heating Fig. Friction resists the pulling. The second example concerns the stirring of a viscous liquid. There is work associated with the torque exerted on the shaft turning through an angle. Examples of the Conversion of Work into Heat The first is the pulling of a block on a rough horizontal surface by a force which moves through some distance. .) The work done to move the block has been converted totally to heat. If so. the fluid comes to rest and there is (again) no change in kinetic or potential energy from the initial state. After the force has moved through the distance. can say "Work has been done. The block then has no kinetic energy and the same potential energy it had when the force started to act. When the stirring stops. indeed it models operation of an electrical heater. but this is a rigorous test for the existence of work." It may sometimes be difficult to make the link between a complicated thermodynamic process and the simple raising of a weight. w(:. This 100% conversion could go on without limit as long as work were supplied.
the piston does work on some external device. W Fig. Work during a~ isothermal expansion = NRTln( V2) .Heat and Thermodynamics 156 One example of a process in which heat is converted to work is the isothermal (constant temperature) expansion of an ideal gas. ~VJ The lowest pressure to which we can expand and still receive work from the system is atmospheric pressure. As the gas expands. Because flU = 0. the internal energy is a function of temperature only. The equation of state for an ideal gas is P=NRTIV. Isothermal Expansion The work exerted by the system is given by where 1 and 2 denote the two states at the beginning and end of the process. heat must be supplied. so that PI /P 2 = Vi VI' The w0fk can be written in terms of the pressures at the beginning and end as . with Nthe number of moles of the gas contained in the chamber. To keep the temperature constant during the expansion. the first law takes the form Q = W. PoT t E f PdV Palm Work received. Using the equation of state. The system is the gas inside the chamber. For an ideal gas. so that if the temperature is constant for some process the internal energy change is zero. This is a process that has 100% conversion of heat into work. the expression for work can be written as Work during an isothermal expansion = NRT f dV / V = NRT In (~ ) For an isothermal process. we . P V = constant. Below this.
QR' The thermal efficiency of the cycle is the ratio of the work done to the heat absorbed. The cycle returns to its initial state. including the Carnot cycle and the Brayton (or Joule) cycle. There is thus a bound on the amount of work that can be obtained in the isothermal expansion. so the overall energy change. we need a series of processes where the system does not progress through a oneway transition from an initial state to a different final state. or rather the fuel that generates the heat. note that all heat engines can be represented generally as a transfer of heat from a .U. To do this." Here what we get is work and what we pay for is heat. the thermal efficiency is l'\= thermal efficlency = Q Q Q Work done = A R = 1. Heat absorbed QA QA The thermal efficiency can only be 100% (complete conversion of heat into work) if QR = 0.) In terms of the heat absorbed and rejected. !:J. we would like a source of continuous power. GENERALIZED REPRESENTATION OF THERMODYNAMIC CYCLES Before we examine individual heat engines. is zero. a basic question is what is the maximum thermal efficiency for any arbitrary cycle? We examine this for several cases.K. which is a model for the power cycle in a jet engine. What is looked for is in fact a thermodynamic cycle for the system.. . however. We define several quantities for a cycle: • QA is the heat absorbed by the system. (Efficiencies are often usefully portrayed as "What you get" versus "What you pay for. For a power or propulsion system. • QR is the heat rejected by the system. The net work done by the system is related to the magnitudes of the heat absorbed and the heat rejected by W = Net work = QA . • Wi s the net work done by the system. but rather cycles back to the initial state.157 The First Law of Thermodynamics would have to do work on the system to pull the piston out further. in other words a device that would give power or propulsion as long as fuel was added to it. we cannot continue indefinitely.
. the ideal gas. • p titta Reservoir Insulating slalld Rcscnoir v Fig. but the concepts can be shown using a familiar working fluid. which does work on the surroundings. There are two adiabatic reversible legs and two isothermal reversible legs.Heat and Thermodynamics 158 high temperature reservoir to a device. The system can be regarded as a chamber enclosed by a piston and filled with this ideal gas . a low temperature reservoir.. followed by a rejection of heat from that device to . It is brought . We can construct a Carnot cycle with many different systems._~W Fig. Camot Cycle Thermodynamic Diagram on Left and Schematic of the Different Stages in the Cycle for a System Composed of an Ideal Gas on the Right The four processes in the Carnot cycle are: • The system is at temperature T2 at state a. A generalized heat engine THE CARNOT CYCLE It has four processes.
In other words. T2 [In (Vb IVa)] The path from states b to c and from a to dare ?oth adiabatic . the heat reservoir is a constant temperature source (or receiver) of heat. rejecting heat QI in the process. During this expansion the temperature decreases to T I . It is then compressed to state d. there is a sign convention implied. Qbe = 0) At state the system is brought in contact with a heat reservoir at temperature TI . The heat exchanged during this part of the cycle. In this example. which is just a liquid or solid mass of large enough extent such that its temperature does not change appreciably when some amount of heat is transferred to the system. The system then undergoes an isothermal expansion from a to b. Web =NRTj [In (Vd IVe)]=[ln(VcIVd)]. The quantities Ql' Q2 on the other hand are defined with reference to heat received by the system. The heat exchange Qda = O.159 The First Law of Thermodynamics in contact with a heat reservoir. the system is thermally insulated (removed from contact with the heat reservoir) and then let expand to c. the system is compressed adiabatically back to the initial state a. QA Q2 In this equation.) The efficiency can now be written in terms ofthe volumes at the different states as QJ = 11 = I + Tj [In (Vd IVc)]. (QI is negative. The quantities QA' QR as defined are the magnitudes of the heat absorbed and rejected. • Finally. The heat absorbed and rejected by the system takes place during isothermal processes and we already know what their values are: Q2 = Wab = }TRT2 [In (Vb IVa)]. the former is negative and the latter is positive.QR =1+ QJ . with heat absorbed Q2· • At state b. The thermal efficiency of the cycle is given by the definition 11 =1.
T2 V~I = TI Vrl.. the heats received and rejected are related to the temperatures of the isothermal parts of the cycle by QI + Q2 =0. we have TJIYI = constant.. there is now net work into the system and ._ /sYIIeIn 1'.ejected is zero. but we can also run it in reverse.) 1 2' V._+ W(neI~) I QJ Fig. Along the curve da.T2 .. 1\ T2 Second. T2 Vr l = T/ V~I . therefore. If so. Using the ideal gas equation of state.. Along curve bc . The efficiency can be 100% only if the temperature at which the heat is . The heat and work transfers to and from the system. For a reversible adiabatic process we know that PVY = constant. Thus. b Vc Vb Comparing the expression for thermal efficiency equations show two consequences. Vd (V c )"rI _(T /1\) (Va )YI. the efficiency of a Camot cycle is given compactly by 11 = 1..Heat and Thermodynamics 160 and reversible. means that . (T'J.. First. 1\ . Vd Va ..= . Camot cycle efficiency. Work and Heat Transfers in a Camot Cycle between Two Heat Reservoirs REFRIGERATORS AND HEAT PUMPS The Camot cycle has been used for power.whIch IT.
The coefficient of performance is thus given in terms of the absolute temperatures as . The result is that work is done on the system. The Camot cycles that have been drawn are based on ideal gas behaviour. and "what we get" is the amount of heat extracted. 12 11 1J This can be much larger than unity. For different working media. . We will see an example when twophase situations. since the cycle is reversible..161 The First Law of Thermodynamics net heat out of the system. heat is extracted from a low temperature source and rejected to a high temperature source. w QI (QI +Q2) 01 V 0. Operation of a Camot refrigerator For a Camot cycle we know the ratios of heat in to heat out when the cycle is run forward and. defined as Coefficient of performance = QI = . Coefficlency of performance = ~. "What we pay for" is the work. . The words "low" and "high" are relative and the low temperature source might be a crowded classroom on a hot day. these ratios are the same when the cycle is run in reverse. they will look different. with the heat extractioll being used to cool the room. The former of these is negative according to our convention and the latter is positive. however. A metric for devices of this type is the coefficient of performance. In this mode of operation the cycle works as a refrigerator or heat pump. "Fig. There will be a quantity of heat Q2 rejected at the higher temperature and a quantity of heat Q) absorbed at the lower temperature.
First the refrigerant passes through a small turbine or through an expansion valve. Schematic of a Domestic Refrigerator Starting in the upper right hand corner of the diagram. REFRIGERATOR HARDWARE Typically the thermodynamic system in a refrigerator analysis will be a working fluid. This lowers the internal energy of the inside and raises the internal energy of the refrigerant. that circulates around a loop. work is done by the refrigerant so its internal energy is lowered to a point where the temperature of the refrigerant is lower than that of the air in the refrigerator.Heat and Thermodynamics 162 What is the same whatever the medium is the efficiency for all Carnot cycles operating between the same two temperatures. Then a pump or compressor is used to do work on the refrigerant. adding additional energy to it and thus further rai3ing its internal . A heat exchanger is used to transfer energy from the inside of the refrigerator to the cold refrigerant. The internal energy (and temperature) of the refrigerant is alternately raised and lowered by the devices in the loop. as shown by the two arrows in the heat exchangers. The working fluid is colder than the refrigerator air at one point and hotter than the surroundings at another point. we describe the process in more detail. Thus heat will flow in the appropriate direction. Electrical Energy In Fig. In these devices. a refrigerant.
• Exhaust stroke. . thus effectively adding heat through converting chemical energy into thermal energy. the internal energy of the refrigerant is reduced and the internal energy of the surroundings is increased.163 The First Law of Thermodynamics energy. repeating the cycle. piston pushes remaining combustion products out of chamber (I + 5). b) compress it. The internal energy of the refrigerant is raised to a point where its temperature is hotter than the temperature of the surroundings. The refrigerant is then passed through a heat exchanger (often coils at the back of the refrigerator) so that energy is transferred from the refrigerant to the surroundings. Intake stroke. • Compression stroke. gasoline vapour and air drawn into engine (5+ 1). p. Electrical energy is used to drive the pump or compressor. • Valve exhaust: valve opens. The refrigerant then continues on to the turbine or expansion valve. Model: heat absorbed from a series of reservoirs at temperatures T2 to T3 . • Combustion (spark). essentially constant volume (2 + 3). As a result. These engines a) ingest a mixture offuel and air. We model the processes as all acting on a fixed mass of air contained in a pistoncylinder arrangement. c) cause it to react. • (4 + I) Model: rejection of heat to series of reservoirs at temperatures T4 to TI . d) expand the combustion products. Power stroke: expansion (3 + 4). and then e) eject the combustion products and replace them with a new charge of fuel and air. It is at this point where the internal energy of the contents of the refrigerator and the energy used to drive the compressor or pump are transferred to the surroundings. gas escapes. Tincrease (l+2). short time. THE INTERNAL COMBUSTION ENGINE (OTTO CYCLE) The Otto cycle is a set of processes used by spark ignition internal combustion engines (2stroke or 4stroke cycles).
Sketch of an Actual Otto Cycle t ~ t (0 EFFICIENCY OF AN IDEAL OTTO CYCLE (9 0 Fig. Piston and Valves in a Fourstroke Internal Combustion Engine The starting point is the general expression for the thermal efficiency of a cycle: . V Fig.Heat and Thennodynamics 3 164 p V2 =vJ Not VI = V. The ideal Otto Cycle p Exhaust valve opens V Fig.
T2 .165 The First Law of Thermodynamics "= work heat input = QH + QL =1+ QL QH QH .I 2 2 13.1J .IV. roughly at constant volume. so QL is negative. T. is that heat exchange is positive if heat is flowing into the system or engine. The convention..=1_ T4 . 'Y. T3 T2 We can simplify the above expression using the fact that the processes from 1 to 2 and from 3 to 4 are isentropic: T v.U41 =Cv (1J T4 )· Substituting the expressions for the heat absorbed and rejected in the expression for thermal efficiency yields . The heat absorbed occurs during combustion when the spark occurs. the efficiency of all ideal Otto cycle .~) IS: T4 1J _(V2 VI The quantity V1iV2 = r is called the compression ratio.yI .I 3 2 ' v. In terms of compression ratio.T 4 I y.IYI = T V. as previously. The heat absorbed can be related to the temperature change from state 2 to state 3 as: QH =Q23 = D.U23 = (W23 = 0) ~CvdT=Cv(T3T2)' The heat rejected is given by (for a perfect gas with constant specific heats) QL =Q4 1 =D.
r y. i.60 70 I: ~~~2~'~+6~8~I~O~12~1~'~16· Fig.Heat and Thermodynamics 166 . • mfuel is the fuel mass flow rate.cpTj W _ mfucl Mrucl [1 1] . increases. Ideal Otto Cycle Thermal Efficiency J: The ideal Otto cycle efficiency is shown as a function of the compression ratio. r. ENGINE WORK. because it means a smaller engine for the same power. evaluated at stoichiometric conditions are: R:: mfucl m 1 15 ..e.1 • The quantities in this equation. RATE OF WORK PER UNIT ENTHALPY FLUX The nondimensional ratio of work done (the power) to the enthalpy flux through the engine is given by __ P_o_w_e_r_ = ~ = Enthalpy flux mcpTj (22i'otto There is often a desire to increase this quantity. the chemical energy liberated per unit mass of fuel. If T2 is too high.. The nondimensional power is mcpTj . the mixture will ignite without a spark (at the wrong location in the cycle). l'Jotto increases. but so does T2. The heat input is given by where • L1h fucI is the heat of reaction. As the compression ratio..
T4) C P (T3 . and there is ignition without a spark. the engine can actually have higher efficiency than an Otto cycle when both are operated at compression ratios that might be achieved in practice. yT2(T31T2 I) This cycle can operate with a higher compression ratio than the Otto cycle because only air is compressed and there is no risk of autoignition of the fuel. The ideal Diesel cycle The thermal efficiency is given by: TiD lese  I .T2 ) Ii (T4 / Ii I) . Fig.:Cv (Ii.167 The First Law of Thermodynamics ~hrucl cpIi ~ 103 x 288' 4xl07 so DIESEL CYCLE The Diesel cycle is a compression ignition (rather than spark ignition) engine. Fuel is sprayed into the cylinder at P2 (high pressure) when the compression is complete. Although for a given compression ratio the Otto cycle has higher efficiency.1+ QH = 1_ QL 1+ "''_. . because the Diesel engine can be operated to higher compression ratio. p +~~~v Vz v.2.
a Cool the air at constant pressure back to its initial condition. or to turn a generator for electrical power generation. a closed cycle. alongside a sketch of an engine: • a . in space power generation. We will typically represent these components schematically. quasistatic (or reversible) compression in the inlet and compressor. where the working fluid enters and then exits the device. with which we • Take some work out of the air and use it to drive the compressor.c Constant pressure fuel combustion (idealized as constant pressure heat addition). quasistatic (or reversible) expansion in the turbine and exhaust nozzle. This is the way ajet propulsion cycle works. and • Take the remaining work out and use it to accelerate fluid for jet propulsion. • c . which recirculates the working fluid. real Brayton cycles take one of two forms. The cycle consists of four processes. The alternative.d Adiabatic. "open" cycle. . • b . Closed cycles are used. Compressor "lUrbine H_!ejection 10 atmosphere Fig. Sketch of the Jet Engine Components and Corresponding Thermodynamic States The components of a Brayton cycle device for jet propulsion.Heat and Thermodynamics 168 BRAYTON CYCLE The Brayton cycle (or Joule cycle) represents the operation of a gas turbine engine. In practice.b Adiabatic. • d .
u is zero because is a function of state. For a constant pressure. Tracing the path shown around the cycle from abcd and back to a. ·3 w . and the thermal efficiency of the cycle.. quasistatic process the heat exchange per unit mass is . Here !J. the heat absorbed. Thermodynamic model of gas turbine engine cycle for power generation [Open cycle operation] elL [Closed cycle operation] Fig. '_ _. We thus need to evaluate the heat transferred in processes bc and da..w. Options for operating Brayton cycle gas turbine engines WORK AND EFFICIENCY The objective now is to find the work done.. 4 Q EquiYllenl heat II'IIISrer IlCDDSWIl paalR I Fig.uabcda = 0 = q2 + ql .169 The First Law of Thermodynamics 2· .. !J. and any cycle returns the system to its starting state. the first law gives (writing the equation in terms of a unit mass). The net work done is therefore w = q2 + ql' where q l' q2 are defined as heat received by the system (ql is negative)...
Ta (Td ITa 1) .Td )].)(Td Ta) Net work per unit mass = ql + q2 = cpr (Tc  TJ= Heat in ='c p (Tc . The thermal efficiency of the Brayton cycle can now be expressed in terms of the temperatures: Net work cp[(Tc T. or [dq]constant P =dh. We know that points a and d are on a constant pressure process as are points band c. ql =ha hd =cp (Ta Td)· The net work per unit mass is given by Tb ) + (Ta .Ta) = 1. and Pa = Pd. TblTa = TR. In terms of compressor temperature ratio. and using the relation for an adiabatic reversible process we can write the efficiency in terms . so Pd = Pa => (Td )Y/(YI) ~ Pb Tc Therefore T jTc = T/Tb' or.T.T . Pb = Pc. we need to examine the relationships between the different temperatures. b compressor eXIt The temperature ratio across the compressor.Heat and Thermodynamics 170 dh =cpdT = dq. Ta Tatmospheric Ideal Bratyton cycle efficiency: l1B = 1. finally. Equation yields an expression for the thermal efficiency of a Brayton cycle: =(Ta )Y/(YI) T" TjTa = T jTb. We can see this by writing the first law in terms of enthalpy or by remembering the definition of cpo The heat exchange can be expressed in terms of enthalpy differences between the relevant states. = 1. (Tc . The other two legs of the cycle are adiabatic and reversible. Treating the working fluid as a perfect gas with constant specific heats. for the heat addition from the combustor. Using this relation in the expression for thermal efficiency. similarly.T ) b _1 _ (Ta . q2 = hc  hb =C p (Tc  Tb )· The heat rejected is..Tb ) Tb(Tc 1Tb 1) To proceed further.
171
The First Law of Thermodynamics
of the compressor (and cycle) pressure ratio, which is th;:: parameter commonly used: 1
l1B =
1 TR = 1 PR(yl)/y'
!
0.7 . . . . .                 , 0.6 .!II 0.5
i
0.4
&0.1
iii 0.3 ~ 0.2
10
20
30
40
50
Compressor Pressure Ratio
Fig. Trend of Brayton Cycle Thermal Efficiency with Compressor Pressure Ratio
Equation says that for a high cycle efficiency, the pressure ratio of the cycle should be increased. The history of aircraft engine pressure ratio versus entry into service, and it can be seen that there has been a large increase in cycle pressure ratio. The thermodynamic concepts apply to the behaviour of real aerospace devices!
GAS TURBINE TECHNOLOGY AND THERMODYNAMICS
The turbine entry temperature, Te , is fixed by materials technology and cost. (If the temperature is too high, the blades fail.) The relation between the gas temperature coming into the turbine blades and the blade melting temperature.
Cy~lc with T.  T,
p
Cydc with lower T•
... ... v

_T = T_
=r.
Fig. Efficiency and Work of Two Brayton Cycle Engines
Heat and Thermodynamics
172
The problem is posed which shows two Brayton cycles. For maximum efficiency we would like TR as high as possible. This means that the compressor exit temperature approaches the turbine entry temperature. The net work will be less than the heat received; as Tb ~ Tc the heat received approaches zero and so does the net work. The net work in the cycle can also be expressed as pdv , evaluated in traversing the cycle. This is the area enclosed by the curves, which is seen to approach zero as Tb ~ Tc' The conclusion from either of these arguments is that a cycle designed for maximum thermal efficiency is not very useful in that the work (power) we get out of it is zero. A more useful criterion is that of maximum work per unit mass (maximum power per unit mass flow). This leads to compact propulsion devices. The work per unit mass is given by: Work/unit mass =cp[(Tc Tb)(Td Ta )], where Tc is the maximum turbine inlet temperature (a design constraint) and Ta is atmospheric temperature. The design variable is the compressor exit temperature, Tb, and to find the maximum as this is varied, we differentiate the expression for work with respect to:
dWork = Cp[dTc 1 dTd + dTa ]. dTb dTb d1b dTb
f
The first and the fourth terms on the right hand side of the above equation are both zero (the turbine entry temperature is fixed, as is the atmospheric temperature). The maximum work occurs where the derivative of work with respect to Tb is zero:
dWork =0=1 dTd . dTb dTb
To use Equation, we need to relate Td and Tb . We know that
173
The First Law of Thermodynamics
Hence,
dTd TaTe dTb=Tl'
Plugging this expression for the derivative into Equation gives the compressor exit temperature for maximum work as Tb = ~TaTe . In terms of temperature ratio,
Tb Compre!lsor temperature ratio for maximum work: T
a
= T'
a
i
e
The condition for maximum work in a Brayton cycle is different than that for maximum efficiency. The role of the temperature ratio can be seen if we examine the work per unit mass which is delivered at this condition: Work/unit mass
r;;:;;r = CP [ Te  "TaTe 
TaTe + Ta . r;;:;;r "TaTe
1
Ratioing all temperatures to the engine inlet temperature, Work/unit mass = CpTa [  2i + 1 . Te e Ta Ta
1
To find the power the engine can produce, we need to multiply the work per unit mass by the mass flow rate:
. Power = mCpTa [Te Ta
ideal Brayton cycle.
rr; . 2Vr: + 1l.,Maximum power for an
J J
(The units are   k K = = Watts.) K s gs The trend of work output vs. compressor pressure ratio, for different temperature ratios TR = TjTa'
kg
Heat and Thermodynamics
Brayton Cycle Work
3~~
174
25
I ~
t. i
2
1
1.5
!
,
I
r•• __ ••••••
1/  
•••••• TR" 4 ···TR=S
TR=6
1/
TR=r
........... .... .. ......... .
..
05
I / '
O~~+~r~
o
10
20
30
40
50
Compres5Of Plessure Ratio
Fig. Trend of Cycle work with Compressor Pressure Ratio, for Different Temperature Ratios Pen Core Drive
Fig. Aeroengine Core Power
The expression for power of an ideal cycle compared with data from actual jet engines. The gas turbine engine layout including the core (compressor, burner, and turbine). The core power for a number of different engines as a function of the turbine rotor entry temperature. The equation in the figure for horsepower (HP) is the same as that which we just derived, except for the conversion factors. The analysis not only shows the qualitative trend very well but captures much of the quantitative behaviour too. A final comment on Brayton cycles concerns the
175
The First Law of Thermodynamics
value of the thermal efficiency. The Brayton cycle thermal efficiency contains the ratio of the compressor exit temperature to atmospheric temperature, so that the ratio is not based on the highest temperature in the cycle, as the Camot efficiency is. For a given maximum cycle temperature, the Brayton cycle is therefore less efficient than a Camot cycle.
Brayton Cycle for Jet Propulsion: The Ideal Ramjet
A schematic of a ramjet is given in Figure.
Station Numbers
t"
If"
Fig. Ideal Ramjet
In the ramjet there are "no moving parts." The processes that occur in this propulsion device are: • 0 + 3 : Isentropic diffusion and compression, with a decrease in Mach number, Mo + M3 « 1. • 3 + 4 : Constant pressure combustion. • 4 + 5 : Isentropic expansion through the nozzle. The ramjet thermodynamic cycle efficiency can be written in terms offlight Mach number, Mo, as follows:
llBrayton
=1 
To Tcompressor exit
=1 _
To T3
=1 _
~o
To
and
=~o 1+ yI 2
To
MJ'
2
_
yl 2 MO
2
so
llBrayton 
y 1
I+MO 2
Heat and Thennodynamics
176
REFERENCES
• • • • •
A Guide to Physics: Thermodynamics, Statistical Physics, and Quantum Mechanics by Gerald D. Mahan, Boris E. Nadgomy, and Max Dresden. Mixing and Excess Thermodynamic Properties (Physical sciences data) by Jaime Wisniak and Abraham Tamir. Statistical mechanics, R.P. Feynman, W. A. Benjamin. The Language of Science by Sidney B. Cahn. Statistical Mechanics, K. Huang,
. we address the steps that we would have to take to reverse. TI'  ~ P" T. Expansion Against a Piston .8 _______ The Second Law of Thermodynamics DIFFERENCE BETWEEN FREE EXPANSION OF A GAS AND REVERSIBLE ISOTHERMAL EXPANSION The difference between reversible and irreversible processes is brought out through examination of the isothermal expansion of an ideal gas...? s ~ P.. The question to be asked is what is the difference between the "free expansion" of a gas and the isothermal expansion against a piston? To answer this.. ~ Gas IGas  P TIP T .. T.. in other words. The total volume (VI plus the evacuated volume) is V2• At a given time a hole is opened in the partition and the gas rushes through to fill the rest of the enclosure. Initially all the gas is in the volume designated as VI with the rest of the insulated enclosure a vacuum. Gas Pt' T.' Fig. . we mean the unrestrained expansion of a gas into a volume. Fig. (ill m. to undo the process. By free expansion. Free Expansion GaS p.
. and we can apply the arguments to the case of a reversible isothermal compression... We have evaluated the work in a reversible isothermal expansion. To restore the original state.. The enclosure is insulated so there is no heat exchange.e. with Psystem ~ Pextemal' If so the work that we need to do is W = 12 PdV. T = TI Q = W = 0. A schematic of the compression process.Psystem ~ II  Pexternal =Psystem + dp ~ return to initial condition Fig. .Heat and Thermodynamics 178 During the expansion there is no work exchanged with the surroundings because there is no motion of the boundaries. The first law tells us therefore that the internal energy is constant (IlU = 0).. to go back to the original volume at the same temperature (V2 ~ VI at constant T= T\) we cali compress the gas isothermally (using work from an external agency).. V = V2.. the internal energy is a function of temperature only so that the temperature of the gas before the free expansion and after the expansion has been completed is the same. . in terms of ~eat and work exchanged.. For an ideal gas.... this amount of heat must also be rejected from :the gas to the surroundings if the temperature of the gas is to remain constant. V = VI' T = TI After: State 2. Returning the Free Expansion to its Initial Condition From the first law. i. so there is no change in the surroundings. The work done on the system to go from state "2" to state" 1" is W= Work done on system = NRT\ In (~). We can do this in a quasiequilibrium manner. Characterizing the before and after states: • Before: State 1.
. W.ttLr . The surroundings received an amount of heat. The net effect is the same as if we let a weight fall and pull a block along a rough surface.. The sum of all of these events is that we have converted an amount of work.. • The surroundings (us!) did work on the system of magnitude W... 100% conversion of work into heat The results of the free expansion can be contrasted against a process of isothermal expansion against a pressure which is slightly different than that of the system.P.. Q. with Wand Q numerically equal in Joules.T L Work roceived. /Weight Fig.179 The Second Law of Thermodynamics Q(beaI out) Fig. Work and Heat Transfer in Reversible Isothermal Expansion . Work and Heat Exchange in the Reversible Isothermal Compression Process At the end of the combined process (free expansion plus reversible compression): The system has been returned to its initial state (no change in system state). Q. IV Q Q Fig. There is 100% conversion of work into heat. I. which is equal to W. into an amount of heat.
For the reversible expansion. for enabling identification of areas in which inefficiencies occur. Similarly the heat put into the system by us (the surroundings) during the expansion process has the same magnitude as the heat received by us during the compression process. That is another meaning of the word "reversible. numerically equal to W. • The surroundings have given up heat.Heat and Thermodynamics 180 During the expansion. is quite different for the reversible expansion than for the free expansion. the work we need to do on the system to compress it has the same magnitude as the work we received during the expansion process. We now wish to restore the system to its initial state. therefore: • The surroundings have received work W. and in giving . so have the surroundings. There is no trace of the overall process on either the system or the surroundings. The result is that when the system has been restored back to its initial state. work is done on the surroundings of magnitude W = JPdV. At the end of the isothermal expansion. As evaluated in Equation. just as we did in the free expansion. just as in the free expansion. which you saw in Unified. Q. the magnitude of the work done by the system is W = NRTJ In (V2IV1)." FEATURES OF REVERSIBLE PROCESSES Reversible processes are idealizations or models of real processes. however. To do this we need to do wo~k on the system and extract heat from the system. we could raise a weight during the expansion and then allow it to be lowered during the compression process. the work and heat exchange are the same as those for the compression process examined just above. where P can be taken as the system pressure. In fact. One familiar and widely used example is Bernoulli's equation. The overall result when we have restored the system to the initial state. because we are doing a transition between the same states along the same path. Indeed. They are extremely useful for defining limits to system or device behaviour.
the system is allowed to double in volume. the volume has increased by a factor of four. Let us consider processes that do work. An important feature of a reversible process is that. depending on the process. so that the pressure inside the cylinder is always in equilibrium with the weight on top of the piston. The gas is contained by a thermally insulated massless piston with a stack of many small weights on top of it. it represents the maximum work that can be extracted in going from one state to another. Initially the system is in mechanical and thermal equilibrium. Suppose we have a thermally insulated cylinder that holds an ideal gas. Half of the weight is removed from the piston instantaneously. .181 The Second Law of Thermodynamics targets for design. or the minimum work that is needed to create the state change. so that we can show that the reversible one produces the maximum work of all possible processes between two states. Air Fig. and then the remaining half of the weight is instantaneously removed from the piston and the gas is allowed to expand until its volume is again doubled. • Each small weight is removed from the piston one at a time. When the last weight is removed. A piston with weights on top Let us consider the following three processes: All of the weights are removed from the piston instantaneously and the gas expands until its volume is increased by a factor of four (a free expansion).
... .. Q.. This means that the following effects must be absent or negligible: • Friction: If Pextemal "/:. Fig. " ". The work done on a system in a reversible process is the minimum work we need to do to achieve that state change. Heat Transfer Across a Finite Temperature Difference Suppose we have heat transfer from a high temperature to a lower temperature. Getting the Most Work Out ofa System Requires that the Work be Extracted Reversibly " Maximum work (proportional to the area under these curves) is obtained for the quasistatic expansion. A process must be quasistatic (quasiequilibrium) to be reversible. Q1 Q.. Fig. Psystem we would have to do net work to bring the system from one volume to another and return it to the initial condition • Free (unrestrained) expansion.... To reiterate: The work done by a system during a reversible process is the maximum work we can get. How do we restore the situation to the initial conditions? One thought would be to run a Carnot refrigerator to get an amount of heat. We could do this but the . • Heat transfer through a finite temperature difference. from the lower temperature reservoir to the higher temperature reservoir.. .Heat and Thermodynamics 182 ..
183
The Second Law of Thermodynamics
surroundings, again us, would need to provide some amount of work (which we could find using our analysis of the Carnot refrigerator). The net (and only) result at the end of the combined process would be a conversion of an amount of work into heat. For reversible heat transfer from a heat reservoir to a system, the temperatures of the system and the reservoir must be Theat reservoir = Tsystem ± dT. In other words the difference between the temperatures of the two entities involved in the heat transfer process can only differ by an infinitesimal amount, dT. While all natural processes are irreversible to some extent, it cannot be emphasized too strongly that there are a number of engineering situations where the effect of irreversibility can be neglected and the reversible process furnishes an excellent approximation to reality. The second law, which is the next topic we address, allows us to make a quantitative statement concerning the irreversibility of a given physical process.
THE SECOND LAW OF THERMODYNAMICS STATEMENTS OF THE LAWS OF THERMODYNAMICS
As a further aid in familiarization with the second law of thermodynamics and the idea of entropy, we draw an analogy with statements made previously concerning quantities that are closer to experience. In particular, we wish to present once more the Zeroth and First Laws of thermodynamics and use the same framework for the Second Law. In this socalled "axiomatic formulation," the parallels between the Zeroth, First and Second Laws will be made explicit.
Zeroth Law
Zeroth Law: There exists for every thermodynamic system in equilibrium a property called temperature. Equality of temperature is a necessary and sufficient condition for thermal equilibrium. The Zeroth law thus defines a property (temperature) and describes its behaviour.
Heat and Thermodynamics
184
First Law
Observations also show that for any system there is a property called the energy. The First Law asserts that one must associate such a property with every system. First Law: There exists for every thermodynamic system a property called the energy. The change of energy of a system is equal to the mechanical work done on the system in an adiabatic process. In a nonadiabatic process, the change in energy is equal to the heat added to the system minus the mechanical work done by the system. On the basis of experimental results, therefore, one is led to assert the existence of two new properties, the temperature and internal energy, which do not arise in ordinary mechanics. In a similar way, a further remarkable relationship between heat and temperature will be established, and a new property, the entropy, defined. Although this is a much less familiar property, it is to be stressed that the general approach is quite like that used to establish the Zeroth and First Laws. A general principle and a property associated with any system are extracted from experimental results. Viewed in this way, the entropy should appear no more mystical than the internal energy. The increase of entropy in a naturally occurring process is no less real than the conservation of energy.
Second Law
Although all natural processes must take place in accordance with the First Law, the principle of conservation of energy is, by itself, inadequate for an unambiguous description of the behaviour of a system. Specifically, there is no mention of the familiar observation that every natural process has in some sense a preferred direction of action. The flow of heat occurs naturally from hotter to colder bodies, in the absence of other influences, but the reverse flow certainly is not in violation of the First Law. So far as that law is concerned, the initial and final states are symmetrical in a very important respect. The Second Law is essentially different from the First Law;
185
The Second Law of Thermodynamics
the two principles are independent and cannot in any sense be deduced from one another. Thus, the concept of energy is not sufficient, and a new property must appear. This property can be developed, and the Second Law introduced, in much the same way as the Zeroth and First Laws were presented. By examination of certain observational results, one attempts to extract from experience a law which is supposed to be general; it is elevated to the position of a fundamental axiom to be proved or disproved by subsequent experiments. Within the structure of classical thermodynamics, there is no proof more fundamental than observations. A statement which can be adopted as the Second Law of thermodynamics is: Second Law: There exists for every thermodynamic system in equilibrium an extensive scalar property called the entropy, S, such that in an infinitesimal reversible change of state of the system, dS = dQIT, where T is the absolute temperature and dQ is the amount of heat ;·eceived by the system. The entropy of a thermally insulated system cannot decrease and is constant if and only if all processes are reversible. As with the Zeroth and First Laws, the existence of a new property is asserted and its behaviour is described.
REVERSIBLE PROCESSES
In the course of this development, the idea of a completely reversible process is central, and we can recall the definition, "a process is called completely reversible if, after the process has occurred, both the system and its surroundings can be wholly restored by any means to their respective initial states". Especially, it is to be noted that the definition does not, in this form, specify that the reverse path must be identical with the forward path. If the initial states can be restored by any means whatever, the process is by definition completely reversible. If the paths are identical, then one usually calls the process (of the system) reversible, or one may say that the state of the system follows a reversible path. In this path between two equilibrium states:
Heat and Thennodynamics
186
• The system passes through the path followed by the equilibrium states only. • The system will take the reversed path by a simple reversal of the work done and heat added. Reversible processes are idealizations not actually encountered. However, they are clearly useful idealizations. For a process to be completely reversible, it is necessary that it be quasistatic and that there be no dissipative influences such as friction and diffusion. The precise (necessary and sufficient) condition to be satisfied if a process is to be reversible is the second part of the Second Law. The criterion as to whether a process is completely reversible must be based on the initial and final states. In the form presented above, the Second Law furnishes a relation between the properties defining the two states, and thereby shows whether a natural process connecting the states is possible.
COMBINED FIRST AND SECOND LAW EXPRESSIONS
The first law, written in a form that is always true:
dU=dQdW. For reversible processes only, work or heat may be rewritten as dW=PdV, dQ=TdS, Substitution leads to other forms of the first law true for reversIble processes only: dU = dQ  PdV, substituted for a reversible dQ. dQ = TdS  dW, substituted for a reversible dQ.
(If the substance has other work modes, e.g., stress, strain,
dU =dQPdV XdY,
where X is a pressurelike quantity, and Y is a volumelike quantity.) Substituting for both dWand dQ in terms of state variables, dU = TdS  PdV Always true.
187
The Second Law of Thermodynamics
The above is always true because it is a relation between properties and is now independent of process. In terms of specific quantities: dU = TdS  PdV Combined first and second law (a) or Gibbs equation (a). The combined first and second law expressions are often more usefully written in terms of the enthalpy, or specific enthalpy, h=u+Pv,
dh = du + Pdv + vdP = Tds  Pdv + Pdv + vdP, using in the first law. dh =Tds + vdP. Or, since v = lip, dh =Tds + dP P Combined first and second law (b) or Gibbs
equation (b). In terms of enthalpy (rather than specific enthalpy) the relation is dH= TdS+ VdP.
ENTROPY CHANGES IN AN IDEAL GAS
Many aerospace applications involve flow of gases (e.g., air) and we thus examine the entropy relations for ideal gas behaviour. The starting point is form (a) of the combined first and second law, du = Tds  Pdv. For an ideal gas, du = cvdT. Thus
dT P Tds = cvdT+ Pdv or ds =cv+dv,
T
T
Using the equation of state for an ideal gas (Pv = RD, we can write the entropy change as an expression with only exact differentials:
ds=c dT +Rdv. v T v
We can think of Equation as relating the fractional change in temperature to the fractional change of volume, with scale factors
Heat and Thermodynamics
C
188
v and R; if the volume increases without a proportionate decrease in temperature (as in the case of an adiabatic free expansion), then increases. Integrating Equation between two states "1" and "2":
dT dv . 1 T 1 V For a perfect gas with constant specific heats
I1s =s2 sl =
2 1
cv+R
[2
I1s =S2
 SI
=Cl'
In[ ~ )+ Rln[ :~ )
In nondimensional form (using R/cv = (y  1»
~ = In[
i)
+ (y  1) In(
:~ ). Entropy change of a perfect gas.
2
J'
Equation is in terms of specific quantities. For N moles of gas,
I1s =N[ln[T
Cv
Ii
+(Y_I)ln[V
Vi )
21].
This expression gives entropy change in terms of temperature and volume. We can develop an alternative form in terms of pressure and volume. which allows us to examine an assumption we have used. The ideal gas equation of state can be written as In P + In v = In R + In T. Taking differentials of both sides yields dP dv dT  +  = .
.P
v
T
Using the above equation in Equation, and making use of the relations cp = C v + R; cJcv = y, we find
dS=cv[dP + dV]+RdV, P v v
or
ds dP dv =+y. Cv P v Integrating between two states 1 and 2
I1s =
Cv
r2 In(P2)+ y In[V2) = Inl P(V2 )Y]. Ii VI Ii VI
Heat Transfer From/to a Heat Reservoir • Heat transfer between two heat reservoirs The entropy change of the two reservoirs in Figure is the sum of the entropy change of each. It was stated that this expression applied to a reversible. a heat reservoir. adiabatic process. process. Through use of the second law. and to the concept of a reversible adiabatic process. i.e.) ITH i f QII QII Fig. For the specific situation in which fls = 0. From the definition of entropy (dS = dQrejT). ~vr Equation describes a general process. !hl=Q T' where Q is the heat into the reservoir (defined here as positive if heat flows into the reservoir.. A heat reservoir is a constant temperature heat source or sink. there is no heat transfer across a finite temperature difference and the heat exchange is reversible. CALCULATION OF ENTROPY CHANGE IN SOME BASIC PROCESSES • Heat transfer from. a deeper meaning to the expression.189 The Second Law of Thermodynamics Using both sides of Equation as exponents we obtain v P2 i = [PvY ]? =e tls1cv . the entropy is constant: we recover the expression PvY = constant. or isentropic. the total entropy change is . or to. If the high temperature reservoir is at TH and the low temperature reservoir is at TL . Because the temperature is uniform. in that both are characteristics of a constant entropy.
QITH' The entropy change of the device is zero. • Possibility of obtaining work from ~ single heat reservoir We can regard the process proposed in Figure as the absorption of heat. because we are considering a complete cycle (return to initial state) and entropy is a function of state. Mtotal <0. The surroundings receive work only so the entropy change of the surroundings is zero. Heat Transfer between Two Reservoirs The second law says that the entropy change must be equal to or greater than zero. Work from a single hel't reservoir The total entropy change in the proposed process is thus less than zero. The entropy change of the reservoir is /l.. and the surroundings. rejecting no heat.Heat and Thennodynamics Cl Til 190 . The total entropy change is the sum of the change in the reservoir. by a device or system. _I Device (block of copper) no wort no c:han&e in stale TL Fig. The total entropy change is ilStotal = Mreservoir + Mdevice + Msurroundings =I QITH + = 0 + 0 Q ~ T"I Fig. the system or device. and producing work. Q. The second law thus tells us that we cannot . This corresponds to the statement that heat must flow from the higher temperature source to the lower temperature source. which is not possible.f\ = .. operating in a cycle.
. The process by which the two bricks come to the same temperature is not a reversible one. . . Mcold brick = (M C:T = Cln( ~ ) The entropy change of the two bricks is Mbriok =+(~~ )+In(~ )]=cm(~~Jo The process is not reversible.. as depicted. • Difference between the free expansion and the reversible isothermal expansion of an ideal gas The essential difference between the free expansion in an insulated enclosure and the reversible isothermal expansion of an ideal gas can also be captured clearly in terms of entropy changes. so we need to devise a reversible path. it means without any other changes occurring.TL+ dT. For a state change flOm initial volume and temperature VITI' to . For the cold brick. To do this imagine a large number of heat reservoirs at varying temperatures spanning the range TH . This quantity is less than zero. The "only" is important. • Entropy changes in the "hot brick problem" [Temperature equalization of two bricks] [Reservoirs used In reversible state transformation] G 0_~ C!iiJ TH·4T GJ DLl TL+4T Fig.dT. The heat exchange at any of these steps is dQ = CdT. The "Hot Brick" Problem We can examine in a more quantitative manner the changes that occurred when we put the two bricks together. the entropy change is: M hot brick = rTM CdT =Cln(TM ). The bricks are put in contact with them sequentially to raise the temperature of one and lower the temperature of the other in a reversible manner. JrH T TH where C is the heat capacity of the brick (Jlkg). For the high temperature brick.191 The Second Law of Thermodynamics get work from a single reservoir only.
There is no change in the entropy ofthe surroundings because there is no interaction between the system and the surroundings. heat is . M tota1 = Msystem + Msurroundings = NR In (~) > o. the entropy change IS M= t dS= td~ + tP~V.Heat and Thermodynamics 192 final volume and (the same) temperature V2T 1. The total entropy change is therefore. For the free expansion: Msystem = NR In (~ ). This is the entropy change that occurs for the free expansion as well as for the isothermal reversible expansion processesentropy changes are state changes and the two system final and end states are the same for both processes. Msurrundings = o. however. making use of the equation of state and the fact that dU = 6for an isothermal process. M=NRln(~ ). There is a direct connection between the work needed to restore the system to the original state and the entropy change: Msystem W = NRT In( ~) = T M 2. • • > 12 dQ I T = 0. For the reversible isothermal expansion: The entropy is a state variable so the entropy change of the system is the same as before. There are several points to note from this result: • Mtotal > 0 so the process is not reversible.1• The TM quantity has a physical meaning as "lost work" in the sense of work which we lost the opportunity to utilize. the equality between M and dQIT is only for a reversible process. or. In this case.
T = O. is equal to the heat received by the system: Qsurroundings = Qsystem = W. the ratio of the magnitudes of the heat absorbed and rejected in a Carnot cycle has the same value for all systems. To see this.193 The Second Law of Thermodynamics transferred to the system from the surroundings (Qsurroundings < 0) S'. For any two temperatures T 1. APPLICATIONS OF THE SECOND LAW THE THERMODYNAMIC TEMPERATURE SCALE The considerations of Carnot cycles in this section have not mentioned the working medium. Arrangement of Heat Engines to Demonstrate the Thermodynamic Temperature Scale . There is a high temperature heat reservoir at Tl and a low temperature heat reservoir at T3 .. More specifically. T2. however. which has three reversible cycles. Vi The total change in entropy (system plus surroundings) is therefore M tota1 Q Q = Msystem + Msurroundings =T . TJ Fig. Earlier we derived the Carnot efficiency with an ideal gas as a medium and the temperature definition used in the ideal gas equation was not essential to the thermodynamic arguments. They are thus not limited to an ideal gas and hold for Carnot cycles with any medium.. '_ _ _ _ _ _ _. M surroundmgs = Qsurroundings = _ W = _ NR T T In (V2 ). The reversible process has zero total change in entropy. The heat transferred from the surroundings. we can define a thermodynamic temperature scale that is independent of the working medium..) thatMsurroundings = Qsurrounding/T < O.
V..Heat and Thermodynamics 194 We choose the cycles so Q! is the same for A and C. the thermodynamic temperature scale and the ideal gas scale are equivalent. Also Q3 is the same for Band C. We could choose any function that is monotonic. QH But QI = QIQ2 Q3 Q2Q3 = !(1\. H =. The maximum temperature is often the .1)~· 2 y Hence ~ F(1\. f(1) f(T ) f(TL ) In general. rather than P. terms of temperature (or enthalpy) and entropy. Q3 I' 3 Y:) = f(Tj) . The temperature defined in this manner is the same as that for the ideal gas. The ratio of the heat exchanged is therefore f1L = F(r. For a Carnot cycle 11 = 1+ QL Also = F(TL' TH ). S. and similarly F{T2 .T ) x F(T2.T3 ) Not a fuction of T2 Cannot be a function of T2 We thus conclude that F(T!. QII'QL = TIi'TL." is only a function of temperature. and one choice is the simplest: j(1) = T. T3 ) = j(T2 )Ij(T3 ). QL QH so that the ratio of the heat exchanged is a function of the temperature. This is the thermodynamic scale oftemperature. REPRESENTATION OF THERMODYNAMIC PROCESSES IN COORDINATES It is often useful to plot the thermodynamic state transitions and the cycles ir. T2) has the formj{T!)!f(T2 ).T.
so that plotting in terms of these variables provides insight into the process. The other two legs are reversible and adiabatic. hence isentropic (dS= dQrejT= 0). and therefore vertical in Ts coordinates. in which it is a rectangle.b T Adiabatic s Fig.) We can integrate this last expression around the closed path traced out by the cycle: cjdU = cjTdS cjdW. the area enclosed by the closed contour in the . which is represented by the term . ISOIhermaI ar_~_.plane. The heat rejected (from c to d) has magnitude IQL= TL MI. This area represents the difference between the heat The work done by the cycle.195 The Second Law of Thermodynamics constraint on the process and the enthalpy changes show the work done or heat received directly. A Carnot cycle is shown below in these coordinates.. However dU is an exact differential and its integral around a closed contour is zero: 0= cjTdS cjdW.. with two horizontal. The work done by the cycle can be fmmd using the first law for a reversible process: dU=4QdW =TdSdW (This form isonly true for a reversible process. constant temperature legs. is equal to cjTdS. 1dW . the heat added is Heat added: QH= QH = lTdS=TH(SbSa)=THM. Camot Cycle in Coordinates If the cycle is traversed clockwise..
The slope of the constant pressure legs in the hs plane is (8hI8s)p= T. BRAYTON CYCLE IN COORDINATES The Brayton cycle has two reversible adiabatic (i. This has advantages because changes in enthalpy directly show the work of the compressor and turbine and the heat added and rejected. . all of the arguments carry over to the specific entropy. and the relation between dh and dT. constant pressure heat exchange legs.. The quantity desired is the derivative of temperature. Finally. We can also plot the Brayton cycle in an hs plane. .s plane. p On constant pressure curves dP = 0 and dh = Tds. isentropic) legs and two reversible. this is T Cp The derivative is the slope of the constant pressure legs of the Brayton cycle on a Ts plane. Finding the work done through evaluation of is an alternative to computation of the work in a reversible cycle from gPdV. The former are vertical. For an ideal gas. and pressure: dP dh=Tds+. entropy.s plane is the same as in a T . T. which relates changes in enthalpy. with a scale factor of cp between the two. so the shape of the cycle in an h . but we need to define the shape of the latter. although we have carried out the discussion in terms of the entropy. From the combined first and second law. s.e. S.Heat and Thennodynamics 196 absorbed CC}TdS at the high temperature) and the heat rejected (gTdS at the low temperature). at constant pressure: (8T/8s)p. changes in specific enthalpy are related to changes in temperature by dh = cpdT. with respectto entropy. For a given ideal gas (specific cp ) the slope is positive and increases as T. This suggests that a place to start is with the combined first and second law. the work of the reversible cycle per unit mass is given by gTds.
.. The temperature ratios ~ 1iow. As we will see when we examine twophase cycles. T . Thigh. All of the elementary Camot cycles therefore have the same pressure ratio: P(Thigh ) =:. 1 11 . however..IThigh.197 The Second Law of Thermodynamics Note that the similarity in the shapes of the cycles in Ts and hs planes is true for ideal gases only.. P(1(ow) = PR = constant (the same for all cycles). ( 1(ow. Ideal Brayton Cycle as Composed of Many Elementary Carnot Cycles Plotting the cycle in Ts coordinates also allows another way to address the evaluation of the Brayton cycle efficiency which gives insight into the relations between Camot cycle efficiency and efficiency of other ...). the shapes look quite different in these two planes when the medium is not an ideal gas. We can break up the Brayton cycle into many small Camot cycles. _____________________ 3 T s Fig. where the indicated lower temperature is the heat rejection temperature for that elementary cycle and the higher temperature is the heat absorption temperature for that cycle. PR. are related by: PR(yl)/y = TR. The "ith" Camot cycle has an efficiency of C .. we know that pressure ratio. From the isentropic relatio\s for an ideal gas.::ycles.. and temperature ratio. The upper and lower curves of the Brayton cycle. have constant pressure. TR. j)of any elementary cycle "i" are 'therefore the same and each of the elementary cycles has .
Arbitrary Cycle Operating between Tmin .:s "'III Fig. Consider the cycle. We know that the temperature ratio of the first elementary cycle is the ratio of compressor exit temperature to engine entry (atmospheric for an aircraft engine) temperature. l'lBrayton =1  linlet Tcompressor T aE. TiTo. the efficiency of the overall Brayton cycle (which is composed of the elementary cycles) must also have this value. Thus. Tmax A benefit of this view of efficiency is that it allows us J way to comment on the efficiency of any thermodynamic cycle. We only need to find the temperature ratio across anyone of the cycles to find what the efficiency is.s) diagram. We can break it up into small Carnot cycles and evaluate the efficiency of each. we can reexamine the net work using an enthalpyentropy (h . which operates between some maximum and minimum temperatures. It can be seen that the efficiency of any of the small cycles drawn will be less than the efficiency of a Carnot cycle between Tmax and Tmin' This graphical argument shows that the efficiency of any other thermodynamic cycle operating between these maximum and minimum temperatures has an efficiency less than that of a Carnot cycle. If the efficiency of all the elementary cycles has this value. Now that we have defined entropy. The net mechanical work of the cycle is given by: Net mechanical work/unit mas') = Wturbine .Heat and Thermodynamics 198 the same thermal efficiency. as previously.wcompressor' . NET WORK PER UNIT MASS FLOW IN A BRAYTON CYCLE We found the net work of a Brayton cycle in terms of heat transfer.
If there is heat Q absorbed by the reservoir at temperature T.1) The turbine work is greater than the work needed to drive the compressor. heat dQrev will be transferred between the system and one of the reservoirs which is at T.199 where. the entropy change of the system is dSsyMem = d~ev . across the compressor and turbine is related to the enthalpy changes: TR _ 1 = llhcomp =ILl~IJrb I hs flo The net work is thus net work = llhcomp Ll~rb =llhcomp ~ • (~ . AND "LOST WORK" Consider a system in contact with a heat reservoir during a reversible process. the temperature ratio. by the first law. IRREVERSIBILITY. as is evident on the (h . If dQrev is absorbed by the system.s) diagram. To analyze these. The entropy change of the reservoir is . During any infinitesimal portion. the change in entropy of the reservoir is I1S = QT. ENTROPY CHANGES. reversible processes are accompanied by heat exchanges that occur at different temperatures. we can visualize a sequence of heat reservoirs at different temperatures so that during any infinitesimal portion of the cycle there will not be any heat transferred over a finite temperature difference. In general. TR. The Second Law of Thermodynamics wcompressor = Mo3 = llhcomp Wturbine = llh45 = llhwrb If kinetic energy changes across the compressor and turbine are neglected.
the system receives heat dQ and does work dW. The change in internal energy . which takes t!le system between the same specified states as in the reversible process with and denoting the irreversihle and reversible processes. In the irreversible process. The entropy change associated with the state change is d'S = dQactual + 1 [dWrev T T  d Wactual ] . no change occurs in the total entropy produced. Ifthe process is not reversible. This is also true if there is a quantity of heat rej ected by the system.first law). For the reversible process dU= TdS . Irreversible and Reversible State Changes We now carry out the same type of analysis for an irreversible process.e..dW (Always true . The total entropy change of system plus surroundings is dStotal =dSsystem + dSreservoir = O. for the irreversible process is dU = dQ . we obtain less work than in a reversible process. Equating the changes in internal energy in the above two expressions yields ~ dQactual. .dWactual = TdS . The conclusion is that for a reversible process. YfB AU Fig.Heat and Thermodynamics 200 dSreservOir = d~ev . the change in internal energy is the same. dWactual < dWrev ' so that for the irreversible process. the entropy of the system plus the entropy of the surroundings: Mtotal = O. i.dWrev ' The subscript "actual" refers to the actual process (which is irreversible).dWrev ' Because the state change is the same in the two processes (we specified that it was).
dWactual represents work we could have obtained. = (dQactual + dWiost ) _ dQactual' T T T dStotal = dWiost > 0 T _. . so the only way to decrease the entropy of a system is through heat transfer. To apply the second law we consider the total entropy change (system plus surroundings). but did not. It is referred to as lost work and denoted by Wiost. dS reser voir  (. The change in entropy for any process that leads to a transformation between an initial state "a" and a final state "b" is therefore tlS = Sb Sa ~ rdQ~tual. The equality is only applicable for a reversible process. The total entropy change is d Stotal = dSsystem T dS surroundings . dS = dQactual + dWiost . If the surroundings are a reservoir at temperature T. The equality only applies to a reversible process. The difference dWrev . The quantity (dWlos!T) is the entropy generated due to irreversibility. The lost work (dWlos t in Equation) is always greater than zero.dS surroundin~s : ) dQactual T .201 The Second Law of Thermodynamics dS > dQactual . with which the system exchanges heat. T T The content of Equation is that the entropy of a system can be altered in two ways: (i) through heat exchange and (ii) through irreversibilities. where dQactual is the heat exchanged in the actual process. In terms of this quantity we can write. T There is no equality between the entropy change dS and the quantity dQIT for an irreversible process.
During a reversible process.Heat and Thermodynamics 202 Yet another way to state the distinction we are making is dSsystem = dSfrom heat transfer + dSgenerated due to irreversible processes = dSheat transfer + dSGen · The lost work is also called dissipation and noted dcf> Using this notation. is affected by two factors: the flow of heat Q and the appearance of additional entropy. ( = T . The term . dt = S = Sheat transfer + SGen . The boundary is crossed by heat and the ratio of this heat flux to temperature can be defined as a flux of entropy. The second law asserts that sinks of entropy are impossible in nature. S. the infinitesimal entropy change of the system becomes: dcD dS. Sheat transfer dS . only this flux can affect the . which is a more graphic way of saying that dSGen and SGen are positive definite (always greater than zero). or drains away. can be interpreted as a flux of entropy.it' 1 dQ or ~) which is associated with heat transfer to the system. due to irreversibility. one can say that the system develops sources which create entropy during an irreversible process. the system's entropy. There are no restrictions on the sign of this quantity. denoted by dSGen . Equation can also be written as a rate equation. Thus. Either of Equations can be interpreted to mean that the entropy of the system. This additional entropy is zero when the process is reversible and always positive when the process is irreversible. and we can say that this flux either contributes towards. . or zero in the special case of reversible processes.ystem = dSheat transfer + T or TdSsystem = dQ + dcD. .
TI. however. To)' The maximum amount of work available after the transfer to the reservoir at TI is Wmax. Q. While this interpretation should not be taken too literally. in other words only part of the heat energy is available to be used as work. During an irreversible process. ENTROPY AND UNAVAILABLE ENERGY Consider a system consisting of a heat reservoir at in surroundings (the atmosphere) at T2 • The surroundings are equivalent to a second reservoir at To' For an amount of heat.~~ ) Only part of the heat transf~rred can be turned into work. (Maximum work between T1. This graphic language is very effective and there should be no objections to copying it in thermodynamics. whose quantity is conserved (like that of matter) during a reversible process.TO = Q (1. transferred from the reservJir. To)' . This terminology suggests that we interpret entropy as a kind of weightless fluid.203 The Second Law of Thermodynamics entropy of the system. before the transfer to the reservoir at TI is Wmax. The maximum work available from the quantity of heat.~). (Maximum work between T2. this fluid is not conserved." In fluid mechanics. it cannot disappear. Q. the maximum work we could derive is Q times the thermal efficiency of a Carnot cycle operated between these two temperatures: Maximum work we could = Wmax = Q (1. Suppose we transferred the same amount of heat from the reservoir directly to another reservoir at a temperature TI < T2 . but rather is created by sources throughout the system. it provides an easy mode of expression and is in the same category of concepts such as those associated with the phrases "flux of energy" or "sources of heat. hTo = Q ( 1 ~ ).
 .ev· .To . which can be assumed to be at constant temperature. L T2 However. Q Now consider restoring the system to the initial state by a reversible process.2.) The change in internal energy is (with the quantities Qrevand W both regarded." orenergy which isnolonger avialable to rio work. The change in entropy of the surroundings is (with Q the heat transfer to the system) Msurroundings .Heat and Thermodynamics 204 There is an amount of energy that could have been converted to work prior to the irreversible heat transfer process of magnitude E'.]. considering an arbitrary system undergoing an irreversible state change. The situation just described is a special case of an important principle concerning entropy changes. W ' on tI:e rev system and extract from the system a quantity of heat. Qrev' (In "undoing" the free expaI!sion process. IlUrev = ·Qrev + w. The amount of energy. To do this we need to do wprk. in this rev example. E'. We thus now develop it in a more general fashion... QIT1 is the entropy gain of the reservoir at and T 1(QIT2 ) is the entropy decrease of the reservoir at T2 . E'~Q[l(£)(l~ )]~Q[~ ~]. that could have been converted to work (but now cannot be) can therefore be written in terms of entropy changes and the temperature of the surroundings as E' = TOCMreservoir at Ii + Mreservoir at T2 ) or E'=To Q r11 _. as positive for work done by the surroundings and heat given to the surroundings). which transfers heat to the surroundings. irreversibility and the loss of capability to do wod. =To Mirreversible heat transfer process E = "Lost work. To' The change in internal energy of the system during the state change is I1U= QW.:.
because the entropy is a function of state.Ssurroundings· _ To We also know that the total entropy change.Ssystem.Sreversible process =0.Q) . the energy change is zero because the energy is a function of state.'XS'0 reversible process] system and surroundings. for system plus surroundings is.Stotal = [ IlSirreversible process + .205 The Second Law of Thermodynamics In this reversible process.W. The quantity W can also be interpreted as rev the work that the system would have done if the original pr6cess . !':!. we would nct have needed any extra work to do this. I:!..Sirreversible process + !':!.lI.ev . The total entropy change is associated only with the irreversible process and is related to the work in the two processes by l!S _ (w. the overall entropy change for the combined process is zero.W) total  To .combined process = !':!. Qrev . It represents a quantity of work that is now unavailable because of the irreversibility.U = 0 = Q .W + (Qrev + W )· rev Thus. A C' = !':!. If the process were reversible. For the system. the entropy of the surroundings is changed by IlS surroundmgs =T· Qrev For the combined changes (the irreversible state change and the reversible state change back to the initial state).Stotal The surroundings can be considered a constant temperature heat reservoir and their entropy change is given by .)total  (Qrev . l.W represents the extra work required to rev restore the system to the original state.Q = Wrev .Urev + I:!. The total entropy change is thus only reflected in the entropy change of the surroundings: !':!. !':!. The quantity W .
W = TOMtotal. corresponding to a (possibly fictitious) state with zero velocity. • For a reversible process. EXAMPLES OF LOST WORK IN ENGINEERING PROCESSES 1.W represents the difference between work we rev actually obtained and work that would be done durillg a reversible state change.W) = E' = To Mtotal is tre energy that becomes unavailable for work during an irreversible process. It is the extra work that would be needed to restore the system to its initial state. representing lost work. Under these conditions we can use the first law for a control volume (the Steady Flow Energy Equation) to make a statement about the conditions upstream and downstream of the valve: h1 +=h2 +=ht . Adiabatic Throttling A process we have encountered before is adiabatic throttling of a gas. The velocity is denoted by c. W = W. 2 2 CI 2 C2 2 where hI is the stagnation enthalpy. by a valve or other device. For an irreversible process.. To summarize the results of the above arguments for processes where heat can be exchanged with the surroundings at: • W . Lost work in Adiabatic Throttling: Entropy and Stagnation Pressure Changes <D I I Q) +((/~mmp /. rev • • (Wrev . From either of these perspectives we can identify (Wrev .W) as the quantity we denoted previously as E'. Pz Tz I I PI TI Adiabatic throlliing Fig.Heat and Thermodynamics 206 were reversible.77. The lost work in any irreversible process can therefore be related to the total entropy change (system plus surroundings) and the temperature of the surroundings by Lost work = Wrev . The stagnation enthalpy is the .. Mtotal = o. There is no shaft work and no heat transfer and the flow is steady. Mtotal> O. Wrev > W.)} 7» / /) 7 'd1n7'"7"n"'.77rT7 CI Cz ///r//:.
h = cpT and hI = cpTr The relation between the static and stagnation temperatures is: Tt = 1 + ~ = 1 + ('I . For a perfect gas with constant specific heats. use has only been made of the first law. When we define the stagnation pressure.. T.I) = 1 + ('I _1)c T 2pT 2yRT 2a 2 'v' 2 a2 Tt =1+(YI)M2 T 2 ' where a is the speed of sound and M is the Mach number. even if the flow processes are not reversible. To see why.T . Fig. In addition. the speed of sound. however. In deriving this result. T. Stagnation pressure is a key variable in propulsion and power systems. M = cia. stagnation temperature. and the definition of the Mach number. Nothing has yet been specified about whether the process of stagnating the fluid is reversible or irreversible. we examine the relation between stagnation pressure.207 The Second Law of Thermodynamics same at stations 1 and 2 if Q = W = 0. we do it with respect to isentropic deceleration to the zero velocity state. For an isentropic process P=(T 2 2 )Y/(Yl) PI 11 The relation between static and stagnation pressures is T/~~:T s /~'. Sstagnation state' The static and stagnation states are shown in T . and entropy. The form of the combined first and second law that uses enthalpy is .. the equation of state.s coordinates. Static and Stagnation Pressures and Temperatures The stagnation state is defined by P t .
the stagnation pressure is related directly to the entropy as. !ls R =In(~2). I .ny thermodynamic states and we can apply it to a situation in which we consider differences between stagnation states. Because the entropy is the same at static and stagnation conditions.dP. The corresponding static states are also indicated.Heat and Thermodynamics 208 1 Tds = dh . Stagnation and Static States This holds for small changes between lI. the stagnation enthalpy. Tr PtTr Tr ~ Both sides of the above are perfect differentials and can be integrated as ds=d~ cpdTr 1 ~ = y ~ 1 ( ~~ ) In (~~ )= For a process with Q = W = 0. is constant. In this situation.• s Fig. P 'B. P t + dP t). say one state having properties (P t .A. and hence the stagnation temperature. needs no subscript. T I I I I I I A I I B ~ a". Pt)and the other having properties (Tt + dTt. ~I . Writing in terms of stagnation conditions yields cpdTr R =dpt.
and the use of stagnation pressure as a measure of loss is a practice that has widespread application.x) == . stationary turbomachinery blades. not the entropy.209 The Second Law of Thermodynamics T ! Fig. so that the stagnation pressure change is small compared to the inlet level of stagnation pressure.. In ( ~l ~2 ) = In ( 1. ~ = (~l ~2) «1. Losses reflected in changes in stagnation pressure when This relation on a Ts diagram. The utility is that it is the stagnation pressure (and temperature) which are directly measured. ). First.. The throttling process is a representation of flow through inlets.~ ) ~ ~l ~. We have seen that the entropy is related to the loss. Equation can be put in several useful approximate forms. Doing this. or irreversibility. ~l ~l Expanding the logarithm (using In (1 . we find: Till _ ~ c 2 / 2 = pc 2 / 2 . nozzles..x + . . The stagnation pressure plays the role of an indicator of loss if the stagnation temperature is constant. L\Pr ' ~l or III R ~ ~l Another useful form is obtained by dividing hoth sides by 2/2 and taking the limiting form~ of the expression for stagnation c pressure in the limit of low Mach number (M« 1). we note that for aerospace applications we are (hopefully!) concerned with low loss devices.
hll ) = wshaft. The quantity on the left is a nondimensional entropy change parameter.4s s Fig.hI) = w shaft· . for the process. Stagnation pressure is the quantity that is actually measured so that linking it to entropy (which is not measured) is useful. with the term T!1s now representing the loss of mechanical energy associated with the change in stagnation pressure. There is no heat transfer so the expressions that describe the overall shaft work and the shaft work per unit mass are lh(hl2 . We can regard the throttling process as a "free expansion" at constant temperature Ttl from the initial stagnation pressure to the final stagnation pressure. There is a pressure and temperature drop through the turbine and it produces work. If the difference in the kinetic energy at inlet and outlet can be neglected. the work we need to do to bring the gas back to the initial state is T~. Adiabatic Efficiency of a Propulsion System Component (Turbine) m~wodc ~ . Schematic of Turbine and Associated Thennodynamic Representation in hs Coordinates A schematic of a turbine and the accompanying thermodynamic. Equation reduces to (h2 .Heat and Thermodynamics 210 The quantity on the right can be interpreted as the change in the "Bernoulli constant" for incompressible (low Mach number) flow. 2. We thus know that. which is the "lost work" per unit mass. To summarize: For many applications the stagnation temperature is constant and the change in stagnation pressure is a direct measure of the entropy increase.hll ) = ~haft (h12 .
h2s hI h2 _ hI h2s (h2 h2s ) . The adiabatic efficiency can thus be approximated as 11ad =1 T2fls hI . or approximately.h2s The adiabatic efficiency can therefore be written as 11ad = 1.hI .. small changes in enthalpy are related to the entropy change by Tds = dh. we now . hI .211 The Second Law of Thermodynamics The adiabatic efficiency of the turbine is defined as actual work ] 11ad = [ 1 ea1 work(An = 0) 'd Lll .. for a gIven pressure ratIo The performance of the turbine can be represented in an hs plane (similar to a T.h2s =1. From the figure the adiabatic efficiency is 11ad = . Isothermal Expansion with Friction I PoT: ~ / Friction ~ Fig. Ideal work The quantity Tfls represents a useful figure of merit for fluid machinery inefficiency due to irreversibility.(Lost work). 3. From the combined first and second laws. The nondimensional term (~h/Ideal work) represents the departure from isentropic (reversible) processes and hence a loss. T2~s = ~h. . for a constant pressure process. Isothermal Expansion with Friction In a more general look at the isothermal expansion.. The quantity ~h is the enthalpy difference for two states along a constant pressure line.( Idea~:ork ).s plane for a perfect gas with constant specific heats).
. The amount of heat transferred to the atmosphere due to the frictional work only is thus. Q.' Work produced The entropy change of the atmosphere (considered as a heat reservoir) due to the frictional work is Q Work 00 The engine operates in a cycle and the entropy change for the complete cycle is zero (because entropy is a state variable). a balance of forces tells us that Wsystem on piston = Wdone by friction + Wreceived' During the expansion. rev to the low temperature reservoir.Heat and Thermodynamics 212 drop the restriction to frictionless processes work is done to overcome friction. T TO Q Qo Suppose we had an ideal reversible engine working between these same two temperatures.. which extracted the same amount of heat. and rejected heat of magnitude Qo. I Y ASsurroundings The total entropy change is M total Mheat source +Mheat sink   +.. all frictional work ends up as heat transferred to the surrounding atmosphere. If the kinetic energy of the piston is negligible.. The work done by this reversible engine is . M = 0 + Ll heat source + M heat sink' . Therefore.' piston .eceived .Work produced '. The heat will be (eventually) transferred to the atmosphere. Wfriction = Qfrictiot/' w. from the high temperature reservoir.r. the piston and the walls of the container will h~at up because of the friction. Qfriction ='~ystemon .
213 The Second Law of Thermodynamics W = Q . T TO Combining the expressions for work and for the entropy changes. Propulsive Power and Entropy Flux: The final example in this section combines a number of ideas presented in this subject and in Unified in the develolJment of a relation between entropy generation and power needed to propel a vehicle.." Een . been delivered by a reversible engine operating between the two temperatures T and To: Eengine = "''TJreversible engine TJengine W Actual work obtained ==w.W. To E.Qo. rev' rev For the reversible engine the total entropy change over a cycle is Mtotal = + M heat source M heat sink =_ Q + QO. engme = Wrev . The second law states that the total entropy generated is greater than zero for an irreversible process.ev Work that would be delivered by a reversible cycle between T.W. rev + Wrev  W total  T =0 To To ~ The difference in work that the two cycles produce is proportional to the entropy that is generated during the cycle: TOMtotai = Wrev .TO!!:'stotal W rev =1. . so that the reversible work is greater than the actual work of the irreversible cycle. e' can be defined as the ratio of the actual work obtained dividefby the work that would have . W rev The departure from a reversible process is directly reflected in the entropy change and the decrease in engine effectiveness. rev The entropy change for the irreversible cycle can therefore be written as !!:. Qo = QO'rev + W .TO!!:'stotal . An "engine effectiveness.s __ Q + Qo.rev =0.
This is useful in simplifying the analysis because there is no flow across the stream surfaces. The airfoil has a wake. Streamlines of the flow have been sketched. which is the area occupied by wake fluid. co. The downstream velocity profile is actually continuous. has the 'Velocity distribution at station "0" far upstream and station "d" far downstream. Airfoil with Wake and Control Volume for Analysis of Propulsive power requirement We use a control volume description and take the control surface to be defined by the two stream c.. A coordinate system fixed to the vehicle has been adopted so that we see the airfoil as fixed and the air far away from the airfoil moving at a velocity co. . . which mixes with the surrounding air and grows in the downstream direction. the momentum equation is cdc = iP/p. For fluid which is not in the wake (no viscous forces). The extent of the wake is also indicated. The area of the downstream plane control surface is broken into AI' which is the area outside the wake and A 2.e. Because of the lower velocity in the wake the area between the stream surfaces is larger downstream than upstream . fluid that has suffered viscous losses.Heat and Thermodynamics 214 An aerodynamic shape (airfoil) moving through the atmosphere at a constant velocity. so that on Al the velocity is equal to thf" upstream value. as indicated. a:. i.urfaces and two planes at station 0 and station d. Uniform static pressure therefore implies uniform velocity. The control surface is also taken far enough away from the vehicle so that the static pressure can be considered uniform.de Co \ II Streamlines (control surface) / Actual wake profile Fig.
p0i~cf.~c).jer in ~c. co.215 The Second Law of Thermodynamics It is approximated in the analysis as a step change to make the algebra a bit simpler. so that the defect in flux of momentum (the mass flow in the wake times the vebcity defect) is.Drag + PoAlc~ + P2 A2Ci· There is no pressure contribution in Equation because the static pressure on the control surface is uniform. We can thus write. All this flow has a velocity defect (compared to the free stream) of ~c.~c). Doing this and grouping the terms on the right hand side of Equation in a different manner. The terms in the square brackets on hoth sides of this equation are the continuity equation multiplied by co.2co~c + (~c)2]. wake velocity = c2 = (co . the wake fluid has had much time to mix and the velocity in the wake is close to the free stream value. (We chose our control surface so the condition ~c/co « 1 was upheld. is small by virtue of the choice of control surface and we can neglect it. The last term in the right hand side of the momentum equation. The wake mass flow is P02c:z = p0iCo .Drag + PoAlc~ + P2A2[ci.p2A2cO~c}. . The equation expressing mass conservation for the control volume is Po Aoco = Po Ai Co + P02 c2· The vertical face of the control surface is far downstream of the body. . ~c/co« 1. we have co[PoAoco] =cor PoAlco + P2 A2(cO ~c)] + {Drag. Using the form given for the wake velocity and expanding the terms in the momentum equation we obtain PoAoc~ == . By this station. to first or.) The integral momentum equation (control volume form of the momentum equation) can be used to find the drag on the vehicle: PoAoc~ = . They thus sum to zero leaving the curly bracketed terms as Drag = PoAoCOLlC.
in the general case we would expres<. From Equation.cdc. In Equation the urstream temperature is used because differences between wake quantities and upstream quantities are small at the downstream control station. cdc = co~c. this by an integral over the locally varying wake velocity and density). There is no net shaft work or heat transfer to the wake so that the mass flux of stagnation enthalpy is constant.Heat and Thermodynamics 216 Momentum defect in wake = . The quantity P:02coru is the entropy flux (mass flux times the entropy increase per unit mass. REVERSIBLE AND IRREVERSIBLE PROCESSES Entropy • Entropy is a thermudynamic property that measures the . dh t = 0. For the present situation. The combined first and second law gives us a means of relating the entropy and velocity: Tds = dh . This amount of work is dissipated per unit time in connection with sustaining the vehicle motion. so that Toru =c~c. in this case manifested as power that needs to be supplied because of dissipation in the wake.P:02CO ~c = Drag. The entropy can be related to the drag as Drag = p:02To~s. The power needed to propel the vehicle is the product of drag x flight speed. Equation is another demonstration of the relation between lost work and entropy generation. The pressure is uniform (dP = 0) at the downstream station. this can be related to the entropy flux in the wake to yield a compact expression for the propulsive power needed in terms of the wake entropy flux: Propulsive power needed = To (PoA2 coru) = To x Extropy flux wake. We can also approximate that the condition of constant stagnation enthalpy holds locally on all streamlines.dP/p. Drag x co. Applying both of these to the combined first and second law yields Tds = dh t .
and it is sometimes said that there is a decrease in the availability of energy. The backward process is therefore impossible. In other words. Entropy is produced in irreversible processes.217 The Second Law of Thermodynamics • • • degree of randomization or disorder at the microscopic level. All real processes (with the possible exception of superconducting current flows) are in some measure irreversible. If the change in state of the system is such that the entropy increases for the forward process. The second law says that any process that would reduce the entropy of the isolated system is impossible. Reversible and Irreversible Processes Processes can be classed as reversible or irreversible. in which the entropy is unchanged by the forward process. but never destroyed. If a process occurs. however. The natural state of affairs is for entropy to be produced by all processes. and reduce irreversibilities in practical engineering processes. and we therefore say that the forward process is irreversible. The notion that entropy can be produced. for the reverse change in state) the entropy would decrease. Consider an isolated system. Such a process could go in either direction without contradicting the second law. though many processes can be analyzed quite adequately by assuming that they are . Entropy is an extensive thermodynamic property. Processes of this latter type are called reversible. Energy is degraded to a less useful form. The key idea of a reversible process is that it does not produce any entropy. then it would also be unchanged by the reverse process. evaluate. The concept of a reversible process is an important one which directly relates to our ability to recognize. then for the backward process (that is. A macroscopic feature which is associated with entropy production is a loss of ability to do useful work. Suppose a process takes place within the isolated system in what we shall call the forward direction. is the second law of thermodynamics. the entropy of a complex system is the sum of the entropies of its parts.
EXAMPLES OF REVERSIBLE AND IRREVERSIBLE PROCESSES Processes that are usually idealized as reversible include: • Frictionless movement • Restrained compression or expansion • Energy transfer as heat due to infinitesimal temperature nonuniforrnity • Electric current flow through a zero resistance • Restrained chemical reaction • Mixing of two samples of the same substance at the same state. Irreversibility. . Further. since we are always somewhat uncertain about the microscopic state. or departure from the ideal condition of reversibility. The organized energy (such as that of a raised weight) is easi ly put to practical use. Some processes that are clearly irreversible include: mixing of two gases. friction. reflects an increase in the amount of disorganized energy at the expense of organized energy. and the transfer of energy as heat from a body at high temperature to a body at low temperature. Processes that are irreversible include: • Movement with friction • Unrestrained expansion • Energy transfer as heat due to large temperature non uniformities • Electric current flow through a non zero resistance Spontaneous chemical reaction • Mixing of matter of different composition or state. Consequently the engineer is constantly striving to reduce irreversibilities in systems. this straightening can never be perfect. Recognition of the irreversibilities in a real process is especially important in engineering. disorganized energy (such as the random motions of the molecules in a gas) requires "straightening out" before it can be used effectively. spontaneous combustion.Heat and Thermodynamics 218 reversible. in order to obtain better performance.
• Heat transfer.219 The Second Law of Thermodynamics REAL CYCLE BEHAVIOUR We will now improve our estimates of cycle performance by including the effects of irreversibility. Because of these irreversibilities. Fig. . We take into account here only irreversibility in the compressor and in the turbine. we need more work. The consequence. What are the sources of nonideal performance and departures from reversibility? • Losses (entropy production) in the compressor and the turbine. Mcornp(the changes in kinetic energy from inlet to exit of the compressor are neglected). Gas Turbine Engine (Brayton) Cycle Showing Effect of Departure from Ideal Behaviour in Compressor and Turbine To develop a quantitative description of the effect of these departures from reversible behaviour. as can be inferred is that the net work from the engine is less than in the cycle with ideal components. • Stagnation pressure decrease in the combustor. consider a perfect gas with constant specific heats and neglect kinetic energy at the inlet and exit of the turbine and compressor. We also get less work. We define the turbine adiabatic efficiency as . to drive the compressor than in the ideal situation. ~hturb' back from the turbine. We will use the Brayton cycle as an example.
turb turb There is a similar metric for the compressor. where the convention is that heat received is positive and heat rejected is negative and work done is positive and work absorbed is negative..Heat and Thermodynamics actual Wturb ideal Wturb 220 h 4 =h  h llturb = S 4 . but rather measures of the degree to which the compression and expansion approach the ideal processes. The net work is given either by the difference between the heat received and rejected or the work ofthe compressor and turbine.~ "0 k' 3 ./O)_'1' C13s ITo. the compressor adiabatic efficiency: llcomp = ideal wturb actual Wturb h 3s =h z. = LO . 3 0 llcomp llcomp With = isentropic temperature ratio = ( ~ ltnlet P )Yl Y =IT c6mp' yl .'0 again for the same pressure ratio. From the definition of ll comp ' (13s. whereas for the compressor the ratio is the ideal work needed divided by the actual work required.T. Note that for the turbine the ratio is the actual work delivered divided by the ideal work.1) T . These are not thermal efficiencies. Ts. We now wish to find the net work done in the cycle and the efficiency."5s k' where wactual is specified to be at the same pressure ratio as wideal . q Net work = Y 'v' qR =Ch4~)Chsho) Ch4 hs)Ch3 h o)· { heat in heat out_ Wturb wcomp The thermal efficiency is llthermal = Net work Heat input We need to calculate T3 .
1 = the isentropic cycle temperature ratio. ' ideal work for same ~ ~nlet Ts = T4 llturb T4 (1.ITt~rb llthermal YI] . QH = 1_ Ts . by the definition ~rb= actual work received 1'.221 The Second Law of Thermodynamics (n1. .T To[_I_('t s l)+I] 4 _ T4[1~"b(lt )]10 llcomp or . ~ennall. I] 1j=To llcomp +To· Similarly.l3 'T' 'T" The thermal efficiency can now be found: = 1+ QL With IT comp = _1_=IT IT turb and 't s = IT g.To ·Q.
• There is a strong sensitivity to the component * • efficiencies. 1lcomp mcpTo Trends in net power and efficiency for parameters typical of advanced civil engines. Choosing this as a design criterion will therefore not lead to the efficiency penalty inferred from ideal cycle analysis.Wcompressor· Putting this in a nondimensional form. The maximum power occurs at a value of (E) or pressure ratio pjless than that for max . for ~ Pi =1. • For any l1 comp ' l1 turb 1 the optimum pressure ratio Pj for maximum t is not the highest that can be achieved. Wnet = mCpTo work to drive compressor ~ 1lc~mp (·s 1) + 1lturb ~: . PARAMETERS REFLECTING THE ABILITY TO DESIGN AND EXECUTE EFFICIENT COMPONENTS l1 comp : compressor adiabatic efficiency 1l turb : turbine adiabatic efficiency In addition to efficiency.~) (1I ' y work extracted from flow by turbine Wnet =(ts _l)[1lturb •s ~ _1_]. We list these in the two sections below and show their effects in accompanying.Heat and Thermodynamics 222 There are several nondimensional parameters that appear in this expression for thermal efficiency. net rate of work is a quantity we need to examine. the cycle efficiency is roughly I twothirds of the ideal value. Wnet = wturbine . as it is for the ideal Brayton cycle. The highest efficiency also occurs closer to the pressure ratio for maximum power than in the case of an ideal cycle. The ideal analysis is too idealized in this regard.
Essentials of Thermodynamics (Essentials) by Research & Education Association. Benjamin. • luel T. 2nd edition (Schaum's Outlines) by Merle Potter and Ph. P. Scale Diagram of Nonideal gas Turbine Cycle. Feynman. Nomenclature Pressure ratio I. W. Compressor and Turbine Efficiencies P3 = REFERENCES • • • • • Schaum's Outline of Thermodynamics for Engineers. A. R. and Staff of Research Education Association. Statistical mechanics.P.1(gK m3AIg Fig. Holman.D.223 The Second Law of Thermodynamics (E) = LP. The maximum power and maximum tj are strongly dependent on the maximum temperature. L. in terms of temperatureentropy (hs) and pressurevolume (Pv) coordinates. A Modern Course in Statistical Physics. (this trend is captured by tdeal analysis).. Reichl Thermodynamics by J.I( pPo ~~ y • J. P2' = 0. Pj' A scale diagram of a Brayton cycle with nonideal compressor and turbine behaviors. E. Rea. Craig Somerton. .
this state is not physically possible. So. Like time or gravity. the Third Law of Thermodynamics says: "The entropy of a pure perfect crystal is zero (0) at zero Kelvin (0° K). The Second Law." This is the bottom point on the Kelvin temperature scale. The Kelvin scale is absolute. but is a mathematical limit of the universe. these laws help form the foundations of modern science. the Third Law of Thermodynamics relates the entropy (randomness) of matter to its absolute temperature.15° Celsius. in part. meaning 0° Kelvin is mathematically the lowest possible temperature in the universe. Together. The Third Law of Thermodynamics refers to a state known as "absolute zero. or 459.7 Fahrenheit. it can never obtain absolute zero. no object or system can have a temperature of zero Kelvin. The Third Law of . In its shortest form. If it draws energy.9 ______________________________ Third Law of Thermodynamics The Third Law of Thermodynamics is the lesser known of the three major thermodynamic laws. In actuality. In its simplest form. nothing in the universe is exempt from these laws.everything in the observable universe is subject to them." Entropy is a property of matter and energy discussed by the Second Law of Thermodynamics. implies that heat can never spontaneously move from a colder body to a hotter body. it will eventually have to draw energy from whatever systems are nearby. The laws of thermodynamics are absolute physical laws . as a system approaches absolute zero. So. because of the Second Law of Thermodynamics. This corresponds to about 273.
225 Third Law of Thermodynamics Thermodynamics means that as the temperature of a system approaches absolute zero. there will be some energy associated with the imperfections. its entropy approaches a constant (for pure perfect crystals.) If Cp were constant near T = 0 we would have. MATHEMATICAL NOTATIONS If we have sufficient heat capacity data (and the data on phase changes) we could write rTC S(T)=S(T=O)=. The entropy is now very low. They have lost some entropy. closer and closer to absolute zero. A pure perfect crystal is one in which every molecule is identical. Water in gas form has molecules that can move around very freely. dT. but can only vibrate within the ice crystals. the water would have no entropy (randomness) at all. it becomes solid ice. As the water is cooled more. or those with lessthan perfect alignment. At this point. (If there is a phase change between 0 K and T we would have to add the entropy of the phase change.b . so the entropy cannot become zero. all molecular motion would stop completely. The applications of this law have been used to predict the response of various materials to temperature changes. it becomes liquid. the vibration of the molecules diminishes. this constant is zero). Most of the direct use of the Third Law of Thermodynamics occurs in ultralow temperature chemistry and physics. If the solid water reached absolute zero. and the molecular alignment is perfectly even throughout the substance. These relationships have become core to many science disciplines. For nonpure crystals. Water vapour has very high entropy (randomness). When the water cools further. but not as freely. The Third Law of Thermodynamics can be visualized by thinking about water. . even though the Third Law of Thermodynamics is not used directly nearly as much as the other two. 1be solid water molecules can no longer move freely. As the gas cools. The liquid water molecules can still move around.
which can be obtained partly from theory and partly from experiment.15 K and the f:. . With all of this data.15 K to 298. suppose we want to calculate the absolute entropy of liquid water at 25° C. For metals Cp is proportional to T3 at low temperatures but shifts over to being proportional to T at extremely low temperatures.15Cp(l) Entropy Changes in Chemical Reactions We can use the third law entropies to calculate entropy changes for chemical reactions.Heat and Thermodynamics 226 T SeT) = SeT =0) +Cp In. Experimentally it appears that the entropy at absolute zero is the same for all substances.15 73. For example. We also need the heat of fusion of water at its normal melting point. 2 SHo(25°C)=0+ o 173.15 T Some substances may undergo several phase changes.p of liquid water from 273. o which is undefined.) The advantage of this law is that it allows us to use experimental data to compute the absolute entropy of a substance.) Equation could be used to calculate absolute entropies for substances if we knew what the entropy is at absolute zero. aA+bB'!cC+dD. We would need to know the Cp of ice from 0 K to 273. For nonmetals Cp is proportional to T3 at low temperatures. T 273. The third law of thermodynamics codifies this observation and sets S(T= 0) = 0 for all elements and compounds in their most stable and perfect crystalline state at absolute zero and one atmosphere pressure.15 K.. experimentally Cp ~ 0 as T ~ O. (The latter happens when the atomic motion "freezes out" and the heat capacity is due to the motivn of the conduction electrons in the metal. (All except for helium.15Cp(S) ~T++ DHfus I:98. Fortuna~ely. For a typical reaction. which is a liquid at the lowest observable temperatures at one atmosphere. we find dT.
The entropy change with respect to temperature can be thought of a continuous summation of all the increments of heat added to the system divided by the temperature at the time of the addition. t1.f ° and t1./fo are independent of each other. o.Ho f of an elements. They can not be calculated from each other. when one looks up the t1. The question then is.tlrGo . S ~ O. Or symbolically: M = JCdqIT)dT which is approximately SUM of the (t1. Thus. the answer is O. what if the addition of these increments start with the temperature at 0 K? The answer is.p ° and t1. the important point about the third law is that entropy is an absolute quantity which depends upon temperature. p As T ~ 0 K . They must be calculated from Equation and a comparable equation using heats of formation.227 the entropy change is Third Law of Thermodynamics tlrS o = cS~ + dS.fo. T As we have seen before.aS~ . . For the General student. • Soelement is not zero.bS~. to calculate a change in S one simply adds up the little increments of heat added divided by temperature. t1./fo can be calculated from free energies and heats of formation. So for an element (note difference in symbols as well) has a value for temperature above 0 K. o tlrSo = tlrH .So of reactions that you do not use 0 for the So of the elements. that at OK the q . As we have said before. This is in contrast to t1. In contrast.q / T)s Thus. Notice two things: • We did not define or use an entropy offormation. the t1.H for reactions which have as a reference the elemental state. There is another way to calculate t1. Careful when doing calculations for t1.
REFERENCE • • • • • Course in Thermodynamics . These ions are reference against the H+ (understood to stand for H30+ ) ion. S =0 at T = 0 K. Statistical Mechanics. (Series in Thermal and Fluids Engineering) by Joseph Kestin. This leads to the assumption needed above. see the example thermodynamic table and notice that the elements do have SO s listed. Volume II.Heat and Thermodynamics 228 added is also O. Dehoff. which are not complete chemicals but only one leg of the ionic compound. that the SO s for pure components are absolute values and are not referenced against some arbitrary initial condition like the ~H ° s are. Thermodynamics by J. 0 divided by 0 presents a dilemma and the third law answers this by the following: For a pure component in the most stable condition. Holman . Revised Printing.P. SK Ma Schaum Engineering Thermodynamics (Schaum's Outlines) by Merle Potter. Check out the following: For the pure components (complete chemicals) the SOs are positive For ions. Thermodynamics In Materials Science by Robert T. As an illustration. there are ~So listed which can be either positive or negative.
say argon. [TJturb 't s ~4 0 . Examining the mixing process on a molecular level gives . For an ideal gas.) The entropy change of each gas is thus the same as that for a reversible isothermal expansion from the initial specific volume. (The energy of the overall system is unchanged. the two gases were at the same temperature initially. the entropy change is ~ = (Ts 1) W. the other side another gas. so the final temperature is the same as the initial temperature.10 ________________________ Entropy ENTROPY CHANGE IN MIXING OF TWO IDEAL GASES Consider an insulated rigid container of gas separated into two halves by a heat conducting partition so the temperature of the gas in each part is the same. 1 1The entropy change of the me pTo system is TJcomp 11turb * 1 Equation states that there is an entropy increase due to the increased volume that each gas is able to access. . both regarded as ideal gases. One side contains air. The mass of gas in each side is such that the pressure is also the same. The entropy of this system is the sum of the entropies of the two parts: turbine adiabatic efficiency. For a mass of ideal gas. Suppose the partition is taken away so the gases are free to diffuse throughout the volume. there is no change in temperature. the energy is not a function of volume. and. for each gas.
It would require a great deal of data for this description. In the final state. as the gases mixed. there are roughly 10 19 molecules in a cube of air one centimeter on a side . red molecules start to come into the white volume. Suppose we were able to see the gas molecules in different colors. This link can be made rigorous and is extremely useful in describing systems on a microscopic basis. say the air molecules as white and the argon molecules as red. we would see the growth of pink regions spreading into the initially red and white areas. than the initial state in which the red and white molecules were confined to specific regions. we would say this final state was more random. MICROSCOPIC AND MACROSCOPIC DESCRIPTIONS OF A SYSTEM The microscopic description of a system is the complete description of each particle in this system. similarly. In terms of the overall spatial distribution of the molecules. After we took the partition away. we would expect a uniform pink gas to exist throughout the volume. One view of entropy is thus that increases in entropy are connected with increases in randomness or disorder. the microscopic description of the gas would be the list of the state of each molecule: position and velocity in this problem. Another way to say this is in terms of "disorder. the purpose of is to make plausible the link between disorder and entropy through a statistical definition of entropy.Heat and Thermodynamics 230 additional insight. If we moved further away so we could no longer pick out individual molecules." there is more disorder in the final state than in the initial state. While we do not have scope to examine this topic in depth. there would be more and more of the different colour molecules in the regions that were initially all white and all red. There might be occasional small regions which were slightly more red or slightly more white. but these fluctuations would only last for a time on the order of several molecular collisions. we would see white molecules start to move into the red region and. In the above example. more mixed. As we watched.
and entire systems are discretely quantized. For a given macroscopic system. The microstates of the system keep changing with time from one quantum state to another as molecules move and collide with one another. the individual molecules still change from one quantum state to another. This means that a system of particles under certain constraints. This number can be very big. or having a fixed total energy. and the probability P. In equilibrium. like being in a box of a specified size. the system state does not change with time. although it is restricted to equilibrium states. LP. These results and the comput~tions and arguments below are taken almost entirely from the excellent of Engineering Thermodynamics by Reynolds and Perkins. A key idea from quantum mechanics is that the states of atoms. there are many microscopic states. To address the description of entropy on a microscopic level. The sum of the probabilities of all the allowed quantum states must be unity. hence for any time I. molecules. For instance. The macroscopic description. which is in terms of a few (two!) properties is thus far more accessible and useable for engineering applications. we need to state some results concerning microscopic systems. can exist in a finite number of allowed microscopic states. however. so the probabilities for the different quantum states are independent oftime. The probability for the system to be in a particular quantum state is defined by its quantumstate probability Pi' The set of the Pi is called the distribution of probability. In what follows. =1 i When the system reaches equilibrium.231 Entropy at room temperature and pressure. This distribution is then called the equilibrium distribution. the macroscopic energy of the system would be the weighted average of the successive energies of the system (the . We can get back to macroscopic quantities from the microscopic description using the probability distribution. but it is finite. can be viewed as the fraction oftime a system spends in the ith quantum state. we limit consideration to equilibrium states.
P3 = 0. we would be able to say it is always in state 1. The probability distribution provides information on the randomness of the equilibrium quantum states suppose the system can only exist in three states (1. the entropy provides this measure. P2 = 0. If the distribution were PI = 0. STATISTICAL DEFINITION OF ENTROPY The list of the Pi is a precise description of the randomness in the system. If we were asked what quantum state the system is in. P2 = 0. We would be more uncertain about the instantaneous quantum state than in the first situation. P3 = 0. P2 = 113.3. we can only guess the instantaneous state with 33% probability. (E). In terms of probabilities. The first is that the average of the function over all of the microstates should have an extensive behaviour. the average energy. We thus look for a single quantity. is (E)= LPiEj. In other words . but the number of quantum states in almost any industrial system is so high this list is not useable. In this case.5. 2 and 3). Maximum randomness corresponds to the case where the three states are equally probable: PI = 1/3. There are several attributes that the desired function should have. or PI = 0. the randomness would not be zero and would be equal in both cases.5.3. which is a function of the Pi' that gives an appropriate measure of the randomness of a system. j where Cj is the energy of a quantum state. the energies are weighted by the relative time the system spends in the corresponding microstates. the system is in quantum state 1 and there is no randomness.2. P3 "" 1/3.Heat and Thermodynamics 232 energies of the quantum states). As shown below.2. If the distribution probability is PI = 1. P2 = 0 P3 = 0.
=1 m SA = IpJ(pj) j=1 n m n m Sc = IIpJ(pj) = IpJ(p. To verify this. For Equation to hold given the expressions in Equations. and C. such that Pij = PRj' and split the log term): . Sc = I n m pJ(p. composed of parts A and B should be given by SC=SA+SB Second is that entropy should increase with randomness and should be largest for a given energy when all the quantum states are equiprobable. are defined by .=1 j=1 .)IpJ(pj) . make this substitution in the expression for Sc in the first part of Equation (assume the probabilities Pjand Pjare independent.f{pj) is to be found. b) = In (a) + In (b).) + IPj!(Pj)=SA +SB· 1=1 j=1 The function/must be such that this is true regardless of the values of the probabilities Pi and Pj" This will occur ifjO = In 0 because In (a.233 Entropy the microscopic description of the entropy of a system C. .=1 j=1 n m = IpJ(p.).=1 j=1 In Equations. where the function. the term Pij means the probability of a microstate in which system A is in state i and system B is in state j. The entropies of systems A. B. The average of the function over all the microstates is defined by S=(I)= IpJ(p. Suppose that system A has nmicrostates and system Bhas mmicrostates.)IpJ(Pj) .
Because the Pi are less than unity. a statistical definition of entropy can be given as: = Sc I n P j In (Pi) + I m S = k IPi In (p. Sometimes k is called the gas constant per molecule. 1=1 )=1 )=1 )=1 Because n m Ipj = IPj =1. .).02 x 10 molecules per mol. where is an arbitrary constant. The constant k is known as the Boltzmann constant.) isf= C In (P). With this value for k. for any Pi' Pp n. with the result written as Pj In (p j ). Based on the above. /=1 j=1 Rearranging the sums.3143 J/(molK) and 23 NAvogadrO is Avogadro's number. m. . 6. . Reynolds and Perkins show that the most generalj{p.)[fpj]} +t{Pj In (Pi)[tP. where R is the universal gas constant.380 x 1023 K· J The value of is (another wonderful result!) given by R kNAvogadro. the statistical definition of entropy is identical with the macroscopic definition of entropy. the constant is chosen to be negative to make the entropy positive./{) is a logarithmic function. k = 1. 8. becomes j=1 Sc = f{p/ln (p.=1 j=1 the square brackets in the right hand side of Equation can be set equal to unity. provided that.Heat and Thermodynamics n m n m i=1 234 Sc = IIpiPj In (Pi) +IIpiPj In (p). 1=1 j=1 This reveals the top line of Equation to be the same as the bottom line.]}.
the probabilities become 1 Pi == P == n' where Ois the total number of microstates. If we have two systems.~ In(~) ==kn[~ In(~)] == kln(~) == kinO. In this situation. a system with allowed states will have the greatest entropy when each state is equally likely.235 Entropy CONNECTION BETWEEN THE STATISTICAL DEFINITION OF ENTROPY AND RANDOMNESS We need now to examine the behaviour of the statistical definition of entropy as regards randomness. In particular. which means many permitted quantum states. The entropy is thus S ==. Equation is carved on Boltzmann's tombstone. Equation states that the larger the number of possible states the larger the entropy. Because a uniform probability distribution reflects the largest randomness.k~. 0 0 is thus defined by 0c= 0A. These trends are in accord with our qualitative ideas concerning randomness. the quantum states for the combined system are the combinations of the quantum states from A and B. A and B. which are viewed as a combined system. The behaviour of the entropy stated in Equation can be summarized as follows: • S is maximum when 0 is maximum. The entropy of the combined system is Sc = kin (OAOB) = k In 0A + kin 0B = SA + SB Equation is sometimes taken as the basic definition of entropy. C. but it should be remembered that it is only appropriate when each quantum state is equally likely. The quantum state where A is in its state x and B is in its state would have a probability pAx· pBybecause the two probabilities are independent. • S is minimum when 0 is minimum. there is no randomness and S = o. for 0= 1. Equation is more general and . We can also examine the additive property of entropy with respect to probabilities. The number of probabilities for the combined system. hence much randomness.OB.
8In (0.B.8) + O.D.k(O. Equilibrium Thermodynamics. REFERENCES • • • • • Heat and Thermodynamics. Distributions (iii) and (iv) have progressively greater uncertainty about the distribution of states and thus higher randomness.2 In (0.0.3) + 0. Introduction to Metallurgical Thermodynamics by David R.1. Distribution (v) has the greatest randomness and uncertainty and also the largest entropy.1. Consider the five probability distributions (i)pl 1.lln (0. H.1 In (0.P2 = 0.5 P2 = 0. P3 = 0. S = .8 P2 = 0.1» = 0. Zemansky Thermodynamics (and Introduction to Thermostatistics).2 In (0. M.8p2 = 0.P3 = 0.2.k(0. 2nd edition (Schaum's Outlines) by Merle Potter and Ph. A simple numerical example shows trends in entropy changes and randomness for a system which can exist in three states.Heat and Thermodynamics 236 applies equally for equilibrium and nonequilibrium situations.3 In (0.8 In (0.5 In (0.6k (iv) PI = 0.1) + 0. P3 = 0.3. For the second.P3 = 0. C. . S =.0k = = = S=3k[~ln(~)J The first distribution has no randomness.2) + 0 In (0» =0.2..8) + 0. Adkins.k(0.2» = 1. S k(1ln (1) + 0 In(O) + 0 In (0» 0 (ii) PI = 0. Gaskell. W.5k (iii)pl = 0. Craig Somerton. we know that state 3 is never found.5) + 0. J. S =. Callen Schaum's Outline of Thermodynamics for Engineers.
With this definition.52N2· Even if the nitrogen is not part of the combustion process. methane. The chemical process in which a fuel. and this change in state (change in enthalpy) needs to be accounted for in the stt!ady flow energy equation. This composition is referred to as "theoretical air. A primary one is jet fuel (octane.76)N2 7C0 2 + 2H20 + 7. but the results given using the theoretical air approximation are more than adequate for our purposes. is burned consists of (on a very basic level .76 (or 79/21) moles of N2 are involved: CH4 + 202 + 2(3. for each mole of 02' 3. essentially kerosene) which has the chemical formula CSH 1S .11 Enthalpy Generating Heat There are a wide variety of fuels used for aerospace power and propulsion. which is roughly 1%).there are many intermediate reactions that need to be accounted for when computations of the combustion process are carried out): CH4 + 202 t CO2 + 2H20 ~~ (Reactants) (Products) The reactions we describe are carried out in air. it leaves the combustion chamber at the same temperature as the other products. which can be approximated as 21% 02 and 79% N 2." There are other components of air (Argon. although we will .. At the high temperatures achieved in internal combustion engines (aircraft and automobile) reaction does occur between the nitrogen and oxygen. Other fuels we consider are hydrogen (H 2) and methane (CH4). which gives rise to oxides of nitrogen.
0167.5 mol x 1 mol x 114 glmo) 32 glmol + 12.0664 x 28 glmol Ifwe used the actual constituents of air we would get 0. In gas turbines. a value about 0. The convention used is that the reference state is a temperature of 25 c C (298 K) and a pressure of 0.Heat and Thermodynamics 238 not consider these reactions.5 = 0. The fuel/air ratio on a mass flow basis is thus Fuelair ratio: = 12. we need to have a reference state so there is consistency for different substances.5x3. the oxygen molecular weight is 32 glmol and the nitrogen molecular weight is (approximately) 28 glmol. the .Ol 0c) =0. which is the way in which the aeroengine industry.5 + 47. the ratio offilel to air is [1/(12. The condition at which the mixture of fuel and air is such that both completely participate in the reaction is called stoichiometric. (These are roughly room conditions. To find the ratio on a mass flow basis.0 N 2 . Because of this. FuelAir Ratio The reaction for aeroengine fuel at stoichiometric conditions is CSHIS + 12.5 (3. and only changes in properties of given substances. The fuel molecular weight is 114 glmol. however. The specific energy ujCO. If there are no changes in composition. this is adequate. since all comparisons could be made with respect tc the chosen base.0 for steam.) At these reference conditions. excess air is often used so that the temperatures of the gas exiting the combustor is kept to within desired limits. If there are changes in composition.76 mol =0.76)N2 ~ 8C02 + 9H2 0 + 47. Enthalpy of formation The systems we have worked with until now have been of fixed chemical composition.1 MPa.0667. we could use thermodynamic properties relative to an arbitrary base.5 02 + 12.5% different. we need to "weight" the molar proportions by the molecular weight of the components.0)]=1/ 59. On a molar basis.
the heat that has to be extracted is Qcv= . C+0zC02 I kmalcC • .522 kJ/mole: this is heat that comes out of the control volume.. mass flow rate in terms of kmoleslsec Ii.) is taken as zero. hydrogen.. which is often more convenient for reacting flow problems. The subscripts on the mass flow rates and enthalpies refer to all of the components at inlet and at exit. = Mjh j. carbon. Downstream of the reaction zone there is an appropriate amount of heat transfer with the surroundings so that the products leave at the standard . the combustion (reaction) takes place in the volume indicated. The reactants enter at standard conditions. ._ . M.I Ml'I a.393. by using the molecular weight. For the reaction of carbon and oxygen to produce CO2. bell is~!of _ I volume Fig.. to define the molar mass flow rate. enthaply per kmole. etc.O.onditions.522 KJ.l1i . nitrogen.239 Enthalpy Generating Heat enthalpy of the elements (oxygen.393. I kmoIcC02 2SOC. and molar enthalpy..O. Ii.. Constant Pressure Combustion I There is no shaft work done in the control volume and the first law for the control volume (SFEE) reduces to: mass flow of enthalpy in + rate of heat addition = mass flow of enthalpy out. for any individual ith (or eth) component as l1i =mj t1vli... We can write this statement in the form Lmi~ + Qcv R = Lmchc· P In Equation the subscripts "R" and "P" on the summations refer to the reactants (R) and products (P) respectively. The relation in terms of mass flows can be written in molar fOrIn. The results of a combustion process can be diagrammed.1 MPa 2S" C.
The enthalpy of CO2 in any other state (T.1 MPa. These descriptions can be applied to any compound. Ln. PambO If so.Vinitial)' since Pi = Pj =Pamb • Combining terms.)398K. is called the enthalpy of formation and denoted by Values of the heat of formation for a number of substances are given in Table in SB&VW.Heat and Thermodynamics 240 The SFEE is. + ~v = Liz.iic' R P The statements that have been made do not necessarily need to be viewed in the context of flow processes. + Qcv = Ln)i~. Suppose we have one unit of C and one unit of Q2 at the initial conditions and we carry out a constant pressure reaction at ambient pressure. hoz =hc =0. in these tenns. at 25°C and 0.lMPa~T.p. R P The enthalpy of CO2 .393.h.Pamb (Vfina1 .W = Qcv.h.522 kJ/ P kmole.p= (h.lMPA = (Llh)298K..O. with reference to a base where the enthalpy of the elements is zero. Ufina1 . The enthalpies of the reactants and products for the formation of CO2 are: h. For elements or compounds that exist in more than one state at the .(~ntial + Pintial Vinitial) = Qcv' or HfmalHintial = Qcv· In terms of the numbers of moles and tbe specific enthalpy this is Ln. For one kmoke: Qcv= Lnc~ =Hp =(hj)C02 =. Ufinal + Pfinal Vflllal . P) is given by hT.O.~nitial = Q .
783) kJ = . +Qev = Lnchc' R P This is given in terms of the moles of the different constituents. First Law Analysis of Reacting Systems The form of the first law for the control volume is (there is no shaft work): Lnj!i. )H20(1) = 2 x (285. If the water is in a liquid state at the exit of the process: nc' H20hc. heat given up if the products emerge as liquid.522 kJ/ kmole. If the exit products are in the gaseous state.H20(h. we also need to specify the state. This means that ~lements > heo2 = . and it reduces to the more familiar form for a single fluid (say air) with no reactions occurring. 1 kmole total. 1 kmole of fuel. H20hc.654 kJ.1 MPa and 25°C. The ~nthalpy of the entering gas is zero for both the hydrogen and the oxygen (elements have enthalpies defined as zero at the reference state). The control volume is the combustion chamber. There is mort:.676 kJ.393. so the inlet and exit P and T are specified.827) kJ = . 1 kmole of air. the exit enthalpy is therefore related to the enthalpy of formation of the product by: nc. We need to specify one parameter as the basis of the solution.483. The heat transfer is out of the control volume and is thus negative by our convention. 2H2 + O2 ~ 2H20 The reactants and the products are both taken to be at 0. H 20 = nc.571. Note that there is a minus sign for the heat of formation.H20(h. We use 1 kmole of fuel as the basic unit and examine the burning of hydrogen.241 Enthalpy Generating Heat reference conditions (carbon exists as diamond and as graphite). . )H20(g) = 2 x (241. There is no shaft work done and the SFEE is in the form of Equation. H 20 = nc. etc. gaseous state at exit.
oxygen. and CO2) and liquid water.522+ 2(285. lLnc(Ji. • Use tabulated values.325 kJ Suppose the substances which comprise the reactants and the products are not at 25°C and 0. • Use the polynomial expressions in the integral.198 kJ Qcv =965.1 MPa. the specific heat for some gases can change by a factor of two or more over this range. Combustion processes often involve changes of a thousand degrees or more and..~ and reference conditions §.965. although the changes for air are more .>Co +2(Ji.873kJ R Ln)i~ = p (Ji. If so. The components in this reaction equation are three ideal gases (methane. + R Between T.Heat and Thermodynamics 242 The difference between the two values is the enthalpy needed to tum the liquid into gas at: 25°C: hfg = 2442 kJ/kg. The first is the simplest and the crudest. producing CH4 + 202 + C02 + 2H20(l).~ and reference conditions §.198(74. There are different levels of approximation for the computation: • Assume the specific heat is constant over the range at some average value.)H 0(I) 2 2 = 393.838) = . We again specify that the inlet and exit states are at the reference conditions so that: Ln)i~ = (Ji. the expression that connects the reactants and products is Qcv + Lni(Ji. l· Equation shows that we must compute the enthalpy difference !!.)CH4 =74. + p Between 11. A more complex example is provided by the burning of methane (natural gas) in oxygen.Ji between the reference conditions and the given state if the inlet or exit conditions are not the reference pressure and temperature..873) = 890.
the temperature of the products is referred to as the adiabatic flame temperature. Ar. and dissociation all result in lower temperature. incomplete combustion. This means that. one may need to consider the temperature dependence of the specific heat in computing !1h. Heat transfer.He. dei.243 Enthalpy Generating Heat modest.Xe 500 1000 1500 2000 2500 3000 3500 T[k] Fig. The maximum adiabatic flame temperature for a given fuel and oxidizer combination occurs with a stoichiometric mixture (correct proportions such that all fuel and all oxidizer are consumed). . This is the maximum temperature that can be achieved for given reactants.Ne. The considerable distance between present temperatures in a gas turbine engine and the maximum adiabatic flame temperature at stoichiometric conditions. based on a compressor exit temperature of (922 K).Kr.ending on the accuracy desired. Specific heat as a function of temperature [from SB&VW] Adiabatic Flame Temperature F or a combustion process that takes place adiabatically with no shaft work. The amount of excess air can be tailored as part of the design to control the adiabatic flame temperature.
J dh 1 GY: ~ . Schematic of adiabatic flame temperature An initial view of the concept of adiabatic flame temperature is provided by examining two reacting gases. we put this amount back into the products to raise their temperature to the final level..I I Constant P '2 Constant P o Percentage completion of reaction 100% Fig.. we would need to extract heat. if we can approximate the specific heat as constant (using some appropriate average value) c p. with the final state at a higher temperature than the initial state. and asking what the end temperature is. The initial state is i and the final state is J.:. Suppose the total amount of heat extracted per unit mass ~q I' The relation between the enthalpy changes in Process (1 ) is h2 .hi . To carry out such a process. at a given pressure.. where temperature is plotted versus the percentage completion of the reaction. avg (T1 . Process (1) is reaction at constant T and P. The solid line in the figure shows a representation of the "actual" process. The process is shown schematically.qi = (hj )unit mass' where q J is the "heat of reaction.T2) = qI' ." For Process (2). To see how we would arrive at the final completion state the dashed lines break the state of reaction change into two parts.Heat and Thermodynamics I I ~I 244 T I 1= Final state I I I I dh2 f1\ State i \. hf h2 =ql> or. For this process..
76N2)] ~ 8C02 + 9H20 (g) + 37. Chj Cp.76N2) + 3[12. as the temperature increases.245 Enthalpy Generating Heat For the overall process there is no work done and no heat exchanged so that the difference in enthalpy between initial and final states is zero: I1h\ .h).502 + 12. The reaction is C SH 1S(l) + 12. avg The value of the adiabatic flame temperature given in Equation is for 100% completion of the reaction. cp. An example computation of adiabatic flame temperature is furnished by the combustion of liquid octane at 25°C with 400% theoretical air.502 + 12. In reality. at high temperatures the combustion product (water) dissociates back into the simpler elemental reactants.:rature We can again think of the general process in steps: • Bring reactants to 25°C [the term (1111)] from the initial temperature. In this example we do not need step (i) because we are already at the reference temperature. avg Cp. For an adiabatic process In.5(3.T2 ) = ~ = 1 )unit mass I. . using whatever heat transfer. It is also to be emphasized that the idea of a constant (average) specific heat.(hj +t:. q1' is needed.I1h2 = iVladiabatic = o. av~' is for illustration and not inherently part of the definition of adiabatic flame temperature. We used this idea in discussing the stoichiometric ramjet.502 + 188N2. when we said that the maximum temperature was independent of flight Mach number and hence of inlet stagnation temperature. the tendency is for the degree of reaction to be less than 100%. The temperature change during this second process is therefore given by (approximately) CTf .5(3. = IncChj + R P tiE At adiabatic )c· flame temp. For the combustion of hydrogen and oxygen. The degree of reaction is thus itself a function of temperature that needs to be computed.
These are: Gas cp (kJ/mole) CO2 45 H 20 35 02 30 N2 30 Using M =cp.. and keeping track of units: hf: 8(llf ) CO2 + 9(hf ) H 20.JncMc=5. There will be some heat transfer in this step.952 kJ/kmole) .5. qa' out of the combustor. 6 We find the adiabatic flame temperature in three ways: • an approximate solution using an average value of cp ' • a more accurate one using the tabulated evolution of cp with temperature.827 3 kJ/kmole) 1 kmole (249. The exit state at the adiabatic flame temperature is specified o 0 0 0 l by: . starting with the heat of formation terms.Heat and Thermodynamics 246 Reaction at 25°C [the term (hi )reactants +products]. The resulting temperature is the adiabatic flame temperature. Approximate Solution Using "Average" Values of Specific Heat We can use the values at 500 K as representative.. In the present case Equation is.p L.075xI0 kJ.522 kJ/kmole) + 9 kmole (241. • Put back heat qa + qb into the products of combustion.075· 106 kJ.5 ~h02 + 188~hN2}' We can examine the terms in the SFEE separately.(hf ) CgHlg (f) = 8 kmole (393. explicitly: • (hi )CgHlg(l) = 8(h )C02 + 9( hi )H20 + {~ilC02 + 9Ail H 20 + 37. .avg~T.
25°C = Tfinal .070 .324 x 10{)T2 3 N 2.156 x 1O.40525.92419.(1.460 kJ/kmole .(1. we obtain T = 899 K.208 x 10.626 . find that ~T = 682 K => Tfinal = 980 K.z98 Cp (T)dT and the same equation as above. f Solution for adiabatic flame temperature using tabulated values for gas enthalpy ~hC02 ~hH20 ~h~ ~hN2 T= 28.226 x 1012)]'1 Using ° ~h rTf inK = J.108 x 103 )T + (4.5 p (C p ) 02 + 188 (c p )N2 }.(1.401 + (8.70721.675 .735 x 103 )T .04121.055 x 10{)T2 2.(0.964 x 1O9 )T3 + (0. 3.152 x 10{)T2(2.JR with T (kJ/kmol) C02 2.632 x 109 )T3 + (0.878 x 1O. Lnc~h = 744~T kJ/K. p and using the exit state calculated above. 4.002 x 109)T3 H 20.(6.(6.24618.3.221 kJ/kmole T= 33.156 x 1012 )]'1 3 )T+ (2.764 x 109 )T3 + (2. Solution for adiabatic flame temperature using evolutions of specific heats with temperature Tables give the following evolutions of specific heats with temperature: Gas Evolution of C p. where ~T = Tfinal .247 Enthalpy Generating Heat Lnc~hc = ~T{8 (C p ) CO2 +9 (c p ) H 2 0 + 37.97822.12)T4 3 )T+ (7.607 x 10{)T2 + (2.298 K.
Bowley and M. J. Sanchez Thermodynamics In Materials Science by Robert T. Revised Printing. (Series in Thermal and Fluids Engineering) by Joseph Kestin . Linearly interpolating gives a value of Tfinal = 962 K. Dehoff.Heat and Thermodynamics 248 Plugging in the numbers shows the answer is between these two conditions. Mullin The Language of Science by Sidney B. Cahn. W. REFERENCES • • • • Introductory Statistical Mechanics. The Cluster Expansion. Course in Thermodynamics . Volume II. R.
Then. = . E . Therefore. The number of electron energy states per unit volume over the energy interval. carrying electrical charge under any applied voltage. an energy state at energy E has a definite probability to be occupied by an electron given by Probability of occupancy =f(E). E .+infinity.E+dE. the number of electrons over the energy interval. is found as number of electrons over E . are the electrons occupying the energy states of conduction band (E > Ec)' The counting statistics of conduction band electrons is based on number of electrons = (number of states) * (probability of occupancy by an electron). is defined as Number of states = g(E)dE.E+dE.E + dE =(number of states) * (probability of occupancy) g(E)dE * f(E) Total number of conduction band electrons is found by integrating this: n = g(E)f(E)dE over E = Ec . This probability is the main conclusion of the FermiDirac statistics and f(E) is called the Fermi distribution function. Here g(E) is called the density of states (DOS).12 _________________________ Isolated Paramagnets MICROCANONICAL ENSEMBLE OF ISOLATED PARAMAGNET The mobile electrons in a semiconductor.
.e. Mass number: total number of protons and neutrons in nucleus of an atom " . Electrons occupy a large region of space around the nucleus (electron cloud) and are in motion.00004 cm) sheet of gold foil. Observation 2: A few alpha particles bounced back toward the source. p = g(E)[If(E)]dE over E = infinity . Conclusion: Particles must have hit something that was tiny. Each element has a different atomic number. dense. Observation 1: Most alpha particles passed straight through the gold foil. positively charged r~~ion at the centre of the atom the nucleus. producing a pattern similar to spray from a nozzle.Ev. Rutherford named the tiny. Expectation: The alpha particles would scatter as they were deflected by the gold atoms. ARRANGEMENT OF SUBATOMIC PARTICLES IN AN ATOM Rutherford's Scattering Experiment: • • • • • • • Experimental setup: Positively charged particles (alpha) were focused at a thin (0.. Atomic number: number of protons.Heat and Thermodynamics 250 For holes in the valence band (i. number of holes over E . Conclusion: Volume taken up by atoms is mostly empty space. Elements in the periodic table are listed according to increasing atomic number. Protons and neutrons are found in the nucleus. dense and electrically charged. the unoccupied states in VB).E+dE = (number of states) * (probability of vacancy) = g(E)dE * [1f(E)] And the total number of holes.
• Separating this blend of colours produces an element's line spectrum (i.251 Isolated Paramagnets ARRANGEMENT OF ELECTRONS IN ATOMS An element's properties are determined largely by the number of electrons in its atoms and how these electrons are arranged. • The energy difference between levels is specific to a given element. (Excited state) • When returning to the ground state. fingerprint). • The reactivity of elements is due to the number of electrons in the outermost energy level (valence electrons). • Electrons under normal circumstances maintain the lowest possible energy level. The Bohr Model Electrons occupy different energy levels in the space surrounding an atomic nucleus. the electron gives off energy as a particular blend of colours.e. . (Ground state or unexcited state) • Electrons can absorb energy and "jump" to a higher energy level. • These specific amounts of energy relate to differences between energy levels: • Electrons occupy the lowest energy level available until it is full. resulting in a specific colour emission: Element Colour • K Ca Na Ba lavender orangered yellow green • The significance of line spectra is that energy can be given off or absorbed only in definite amounts (quanta).
7107 In. Also calculate the energy in kJ for one mole of these photons.62621034 Js • Energy is directly proportional to frequency and inversely proportional to wavelength. • When passed through a prism.Heat and Thermodynamics 252 • The construction of the periodic table indicates the number of valence electrons for each element.4. AV= C • Light corresponds to a portion of the electromagnetic spectrum.3x 1014 Hertz). • Frequency and wavelength change with the progression of colours.. 3.7. • The speed at which the wave is travelling is equal to the wavelength times the frequency. AV = C E = hv • • • . white light can be separated into a continuous spectrum of colours: ROYGBIV. Red (A. • The energy of a photon of light is given by Planck's equation: E = hv or E = hell • Planck's constant = h = 6. with a specific wavelength (A. v.) and frequency (v) .4xl07 m. V . The red colour in many fireworks is due to the emission of light from strontium salts. ELECTROMAGNETIC RADIATION All types of radiant energy can be described as waves. with each photon having a particular amount (quantum) of energy. . Calculate the frequency of a photon oflight of wavelength 6.50 103 A. and c represents the speed of light.5xl014 Hertz) IHertz=1/s=ls1 1 Angstrom (A) = lX1010 m Light can also be described as composed of particles called photons. Violet (A.00 108 m/s.
• A more accurate explanation of how electrons are arranged and what types of transitions are possibl. using quantum numbers. • He assumed that these levels corresponded to quantized amounts of energy. etc. Rydberg's equation and Bohr's model are able to explain the behaviour of an electron in a one electron species (H atom. we can describe the probability of finding an electron within a specific region.). lit. Instead. • Quantum numbers are used to describe electrons in possible atomic orbitals. • Atomic orbital: a region of space where there is a high probability of finding an electron. Calculate the wavelength and energy of a photon of light needed to promote an electron from the 1st energy level to the 4th energy level in a hydrogen atom.I n l and n2 are integers such that n2>n l Niels Bohr further explained this relationship by suggesting that n l and n2 represent energy levels where electrons can exist in the hydrogen atom. He+ ion. R. is needed. but do not explain more complex species. Rydberg developed an equation based on observations showing a relationship between the wavelengths of the lines in the hydrogen line spectrum. = R (lIn l 2 . .097 107 m..253 Isolated Paramagnets In the 19th century J. • Electrons in atoms behave more like waves than particles.. so that electrons could only exist at these levels and mtls~ absorb or emit a specific amount of energy to move fo a different level. Heisenberg Uncertainty Prillciple It is impossible to determine accurately both the momentum and the position of an electron simultaneously. • Bohr described these energy levels as circular orbits around the nucleus.1In/) R = Rydberg constant = 1..
= 3.. = 2 is a "d" sublevel Sublevel A.. 2.. = 3 is a "f' sublevel • Relative arrangement of s sublevels: Magnetic quantum number (rnA.1. 1. 0. 1.. 1. 3) • Sublevel A. = 2.. 2. . 2) Energy level n = 4 has 4 sublevels (A. • s sublevels have 1 possible orientation (rnA. 3) Spin quantum number (ms) .. = 0 is a "s" sublevel (spherical) Sublevel A. . =0) Energy level n = 2 has 2 sublevels (A.) . =0.1.. 3. 4. describes the spin of an electron and the orientation of the magnetic field produced by the spin.. 2.1) • Energy level n=1 has 1 sublevel (A. = . (n .. 0. . 1) d sublevels have 5 possible orientations (rnA. describes the shape of atomic orbital.1... . etc. describes the spatial orientation of an atomic orbital • Possible values within a sublevel: rnA..Heat and Thermodynamics 254 Principal quantum number (n) . . = 0. =0. 0. with each level existing further out from the nucleus Subsidiary quantum number (I) . 0. 2. describes the main energy level in which the electron is found • Possible values: 11 = 1. = 1 is a "p" sublevel (hour glass) Sublevel A.. = 1.A.2. A. . these shapes are referred to as sublevels • Possible values within a main energy level: A. 1. 1) Energy level n = 3 has 3 sublevels (A. . =0. = 0) p sublevels have 3 possible orientations (rnA..2) f sublevels have 7 possiblE: orientations (rnA.
These unpaired electrons have parallel spins. exceptions to this order do occur. 1/2 Atomic orbitals can accommodate a maximum of two electrons. Remember.p s. p. often called paired. • Electrons in the same orbital with opposite spins are spinpaired. It is a general guideline.. Level I? Level2? Level3? Level4? Energy Level Sublevel Orbitals Electrons 2 01 n=2 n=3 n=4 s s. increases within a level n. p.. Orbitals fill based on their relative energy.. . Orbitals within a sublevel are equal in energy (degenerate). but several exceptions occur for specific elements. with orbitals increasing in energy as n increases and as '). f 1 1+3=4 1+3+5=9 1+3+5+7=16 8 18 32 The Aufbau principle provides a guideline for the order in which orbitals fill. ~d5f ~ ~4f Pauli Exclusion Principle: No two electrons in an atom may have identical sets of four quantum numbers. d s.255 Isolated Paramagnets • Possible values: ms = 1/2. The usual order of energies is as shown below. How many orbitals exist and how many electrons can fit in . d. Hund's Rule: Electrons must occupy all orbitals of a given sublevel before electron pairing begins. each with opposite spin.
J. tJ. J. 111 tJ.J. • The transition and inner transition metals contain elements in which the highest s level contains 1 or 2 electrons and the d and f orbitals are being filled. J. [He]2s2 [He]2s22pl [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p6 There is a direct correlation between electron arrangement and arrangement of elements in the periodic table. J. J.tJ. tJ. tJ.tJ. 1'J. Note exceptions to expected order of filling in Cr and Cu . J. J. Noble gases are very unreactive and have ns~p6 configurations (except He) . 11 tJ. J. J. J. For the main group elements. tJ.. tJ. PARAMAGNETISM AND DIAMAGNETISM • Substances that contain unpaired electrons are paramagnetic (weakly attracted into a magnetic field). J. tJ. tJ. J. J. J. J. the element IS position • in the periodic table can be used to determine the number of valence electrons the element has. J. J. J. J.configuration ation 151 lSI 152 ls 22s1 ls 22s2 lS22s22pl ls22s22p2 ls22s22p3 ls22s22p4 ls22s22pS ls22s22p6 ls2 [He]~1 • • Identity H He Li Be B C N 0 F Ne 1 1'J. • The main group elements contain elements in which ~he s and p orbitals are being filled.Heat and Thermodynamics 256 ORBITAL NOTATIONS Note electron configurations and orbital notations mostly follow the Aufbau principle. J. tJ.1. tJ.. tJ. 1'J. tJ. 1 tJ.halffilled and filled sets of equivalent orbitals have a special stability.!. tJ. J.often oversimplified as "a full outer shell" 15 25 2p Simplified Electron configur. J. J. J. . J. tJ. tJ.! 11J. 1'J. J.
further from the nucleus Decreases as we move from left to right in a period. Zn? TRENDS IN THE PERIODIC TABLE Chemical Properties Elements with the same number of valence electrons have similar chemical properties. Which of the following would be paramagnetic . 5. • Increasing effective nuclear charge pulls electrons in more tightly (closer to the nucleus) resulting in a smaller atomic radius.the effective nuclear charge on these electrons is less than the actual nuclear charge.257 Isolated Paramagnets • • Substances that have all electrons paired are diamagnetic (very weakly repelled by a magnetic field).number of electrons in inner levels What effective nuclear charge do the valence electrons in an aluminum atom "feel"? In a phosphorous atom? In a sulphur atom? • As we move from left to right in a group. Au. • Electrons in inner levels screen/ shield electrons in outer levels so that they "feel" less of the nucleus' charge . • Note: effective nuclear charge = actual nuclear charge . (Example: Na and K) Atomic Radius Increases as we move down in a group because valence electrons are located at higher energy levels.amount of energy required to remove the most loosely bound electron from an isolated gaseous atom .Mg. Onization Energy First ionization energy . the effective nuclear charge increases. Br.
General trend in periodic table: EA becomes more negative as we go up in a group and to the right in a period. • CI(g) + e.1st p electron is easier to remove than 2nd s electron because having a filled s sublevel leads to extra stability (compare Be to B). • • • 1 Electron Affinity Periodic Table Increasing IE • Exception 1 .~ CI_(g) + 349 kJ EA = 349 kJ / mol Atoms which release energy when an electron is added have negative values for EA . . elements with high IE gain electrons easily to form anions. IE increases as we move left to right in a period effective nuclear charge is increasing and atomic radius is decreasing. • Exception 2 .4th P electron is easier to remove than yd p electron because having a halffilled p sublevel leads to extra stability (compare N to 0) The amount of energy absorbed when an electron is added to an isolated gaseous atom.Heat and Thermodynamics 258 • Ex.amount of energy required to remove the second electron Ex. Ca+(~) + 1154 kJ ~ Ca2+(g) + eSecond IOnization energy is always larger than first ionization energy. Higher ionization energies (IE) relate to more tightly bound electrons.indicating that they easily form anions. Ca(g) + 590 kJ ~ Ca+(g) + e• Second ionization energy .most loosely bound electron is further from nucleus. with low IE lose electrons easily to form cations. Elements. IE decreases as we move down in a group .
F. More negative EA Exceptions occur as noted for ionization energy. Na+. • Ex. Lt is smaller than Li because it has emptied the second level. . ions fonned from the gain of electrons are larger than the neutral atom. T. Ions formed from the loss of electrons are smaller than the neutral atom. N 3. elements with low electronegativity values tend to lose electrons (form cations) • When two atoms with similar electronegativity values combine.Mg2+. the radius decreases. causing the cloud to expand as electrons repel each other.all have 10 electrons (2 in 1st level and 8 in 2nd level) Sizes within an isoelectronic species vary based on nuclear charge . 0 2_. • Electronegativity values generally increase from left to right and from bottom to top on the periodic table.as nuclear c!1arge increases.259 Isolated Paramagnets i Ionic radius ""00'. Electronegativity A measure of the tendency of an atom to attract electrons to itself when it is chemically combined with another atom • Elements with high electronegativity values tend to gain electrons (form anions). AI 3 +.than F because it has an additional electron in its electron cloud. Ne. they are more likely to share electrons. • F.is large:.b'. Ex. • Isoelectronic species have the same number of electrons.
1~rr~r~r~r~ Inx!xlnx·x .':.L. Stirling's formula says that nil . e" Roughly.. this means that these quantities approximate each other for all sufficiently large integers n. More precisely.Heat and Thermodynamics 260 i 10 5 Periodic Table """"' Electonegativity STIRLING'S APPROXIMATION The ratio of (1n n!) to (n In n . It is named in honour of James Stirling.I 105 10 10 10 10 10 The formula is written as n! ~ .J27rn. Stirling's approximation (or Stirling's formula) is an approximation for large factorials. In mathematics. ' ~Ol.n) approaches unity as n increases. 10.I:2'3.
=1+" Bk (. HOO ( lim Inn) Inn!nInn+n. n "n n I " r. We get the formula with an unknown term ey: The unknown term eY can be found by taking the limit on both sides as n tends to infinity and using Wallis' product. can be derived as follows. Instead of approximating n!. Just take the exponential on both sides. Therefore.Inn . Inn B(1)k( 1 ) In(n1)!=nInnn+1++ k J. 2 ~ k(k1) HOO III Let the above limit be y and compound the above two formula. we can apply the EulerMaclaurin formula by puttingj{x) = In(x) to find an approximation of the value ofln(n!).n + y + .2 L.:l1 +R 2 k=2 k(k1) n III I where Bk is Bernoulli number and R is the remainder of the EulerMaclaurin formula.:. Then. say 1.J27r . DERIVATION The formula.l)k +lim R.. one considers the natural logarithm: 1n(n!)=1n1 +1n2+···+1nn. we get Stirling's formula: .261 ~ Isolated Paramagnets or hm n~oo ~= n . One can approximate the value of eY by .) 1 In n! = ( n + .k\ 2 k=2 k(kl) n III I where O(j(n)) is BigO notation. we get the approximation formula in its logarithmic form: 1) Bk(1/ + 0 ( .. and choose any positive integer m. together with precise estimates of its error. We can then take limits on both sides.7r .
and the leading term can be found through the method of steepest descent. . 571 ) As n ~ 00 .N + 1.. with 1 1 <A <12n+1 n 12n Stirling's formula is in fact the first approximation to the following se.Heat and Thermodynamics 262 The formula may also be obtained by repeated !ntegration by parts. N SPEED OF CONVERGENCE AND ERROR ESTIMATES More precisely. The asymptotic expansion of the logarithm is also called Stirling's series: . the error in the truncated series is asymptotically equal to the first omitted term.ies (now called the Stirling series): n! = ~21rn ( : J 139 1+ _1_ + _1=2 ( 51840n 3 12n 288n 2488320n 4 + . This is an example of an asymptotic expansion.. The general formula (without the n1/2 term) may be quickly obtained by approximating the sum N In N!= LInn I with an integral: L Inn ~ 11=1 N I In n dn = N In N .
=\ 2n(2n 1)z where Bn is the nth Bernoulli number. Obtaining a convergent version of Stirling's formula entails evaluating . The corresponding approximation may now be written: A CONVERGENT VERSION OF STIRLING'S FORMULA Thomas Bayes showed.. The formula is valid for z large enough in absolute value when larg 1I2 f zl < 7r  & ..\ 2 2 .!. In this case. If iRe z) > 0 then 2 2 Ini(Z)=(X. dt. where E is positive.263 Isolated Faramagnets 1 Inn! = nInn . it is known that the error in truncating the series is always ofthe same sign and at most the same magnitude as the first omitted term.n + . exp(x7rt)1 Repeated integration by parts gives the asymptotic expansion Ini(z) =(X.!. STIRLING'S FORMULA FOR THE GAMMA FUNCTION Stirling's formula may also be applied to the Gamma function i(z + 1) =I1(z) = z! defined for all complex numbers other than nonpositive integers..In (27rn ) 2 ++ 3 1 12n 1 360n 1 1 + 5 1260n 1680n 7 . that Stirling's formula did not give a convergent series..)Inzz+ In27r + B2n 2.)Inzz+ In27r +2 r t arctan. with an error term of O(z_m) when the first m terms are used.
1 1)Z zsmh+. Zii = z(z + 1) .Heat and Thennodynamics 264 r t z dt =In r(z). If.z. .Inz+zIn(27i)... The approximation r(z)~ + 29 + .. then r where 2 arctan  t exp(2m)1 z d L c t= (z+1y n n=! co Cn =: ! xn ( x ... (z + n 1).!.In z +z(2Inz + In(zSinh. exp(2m) 1 2 2 2 arctan  ( 1) 1 One way to do this is by means of a convergent series of inverted rising exponentials. z 81Oz 6 or equivalently.~) dx From this we obtain a version of Stirling's series In r(z)=(z.!. 2 Inr(z) In(27i) .)Inzz+ In27i + 1 12(z+1) 2 2 1 59 + +12(z + 1)(z + 2) 360(z + 1)(z + 2)(z + 3) 90( z + 1)( z + 2)( z + 3)( z + 4 ) which converges when 9l(Z) > 0 . A VERSION SUITABLE FOR CALCULATORS ~27i (z z ~ e .+1_ z 810z 6 )2J.... can be obtained by rearranging Stirling's extended formula and observing a coincidence between the resultant power series and the Taylor series expansion of the hyperbolic sine function.
[constant ].. plotted in a logarithmic coordinate system. .Inz) + Z[In[z + 1 1 12z10z J1].265 Isolated Paramagnets This approximation is good to more than 8 decimal digits for z with a real part greater than 8. was used by Max Planck in his 1901 article on the black body radiation formula. Robert H...j2. Gergq>Nemes proposed in 2007 an approximation which gives the same number of exact digits as the Windschitl approximation but is much simpler: rcz)~~[. The more precise versions are due to Jacques Binet. for example by Debye and de Broglie. The approximation was often used in quantum theory. The formula was first discovered by Abraham de Moivre in the form n!'. Inrcz) ~ ~(In(27l') . the graph of the probability expression Planck obtained using the "first order" Stirling's formula.[z+ 12Z~_1 Jl lOz ) or equivalently. Stirling's contribution consisted of showing that the constant is . For very large n. Einstein and Bose took a different approach. The "firstorder" version of Stirling's approximation. Windschitl suggested it in 2002 for computing the Gamma function with fair accuracy on calculators with limited programme or register memory. . is almost parallel to the line obtained direct from the idea of separated light quanta. It linked Planck's concept of energy elements to the black body radiation formula for very large numbers of energy elements and oscillators. n! ~ nn.n"+1I2 e.
This change in body t. on the order of 3%/C to 6%/IC at 25IC. predictable change in resistance corresponding to changes in absolute body temperature. Unfortunately. nickel. A few parameters will help to describe the curve and how it changes over temperature. a wide variety of curves and resistance values can be manufactured. NTC thermistors are manufactured using metallic oxides of manganese. the system entropy calculated by using the "first order" approximation is different and the ratio gets strongly nonlinear for small n. iron and other metals. The resulting material is then sintered at elevated temperatures. They are fabricated using a mixture of two or more metallic oxides and a binder material and are then pre~sed into the desired configuration. By varying the types of oxides. the experimental verification of the link between the "first order" Stirling's approximation and modern physical theories is still missing.:mperature of the thermistor can be brought about either externally via a change in ambient temperature or internally by heat resulting from current passing through the device or by a combination of these effects. Thermistor Terminology Thermistors exhibit a large negative change in resistance with respect to temperature. the sintering time and temperature as well as the atmosphere. This relationship between resistanre and temperature follows an approximately exponentialtype curve. . One can only speculate that a similar total effect on entropy could be obtained by introducing the uncertainty principle and the photon spin as well as other quantities which were unknown at the time when the old quantum theory was created. cobalt. SUBSYSTEM AND TEMPERATURE OF ISOLATED PARAMAGNET BETA AND THE TEMPERATURE A negative temperature coefficient (NTC) thermistor is a two terminal solid state electronic component that exhibits a large. copper.Heat and Thermodynamics 266 However.
The value at 25IC is normally measured in a temperature controlled bath where very low power is used to measure the resistance value. the . Resistance vs Temperature Graph Resistance at 2S'IC (R2S ) The most common temperature used to measure the thermistor resistance and the one temperature that is most often used to reference the resistance value of the thermistor is 25IC. Depending upon the type of NTC material.267 Isolated Paramagnets NTC Thermistor 50 25 Sft. this value can vary from less than 100 to greater than IMeg. When a resistance value for a thermistor is mentioned.*dR where: • T = Temperature in OC or K • R = Resistance at Temp T R dT The temperature coefficient is expressed in ohms/ohmsfIC or more commonly %fIC. The steepest portion of the NTC curve is at colder temperatures. By definition. the coefficient of resistance is given by: 1 a=. it is the value at 25IC that is usually being used.PTC +150 Temperature("C) Fig. ForNTC thermistors. Temperature Coefficient of Resistance (a) One way to describe the curve of an NTC thermistor is to measure the slope of the resistance versus temperature (RlT) curve at one temperature.
Heat and Thennodynamics 268 temperature coefficient at 40'IC can be as high as 8%!IC.78 = 9.265 R@50°C 0.07 = 2. or slope.000 R@85°C 0. as was noted previously. Therefore. It is important that the temperature coefficient be compared at the same temperature because. It is sometime used to compare the relative steepness of two curves. The flattest portion of the curve occurs at higher temperatures where. The resistance ratio is one method of describing the NTC curve.1071 Beta Value (p) = 9. resistance ratios cannot be used to compare thermistor curves unless the same temperature ranges are used. There is no industry standard for the two temperatures that are used to calculate the ratio. Resistance Ratio (Slope) The resistance ratio. at temperatures of 300'1C. a can be less than I %!IC. for thermistors is defined as the ratio of resistance at one temperature to the resistance at a second higher temperature. although some common temperature ranges are: R@O°C R@25°C R@25°C R@50°C R@50°C R@85°C • The value obtained by taking the resistance ratio at different temperatures will vary greatly depending upon the temperatures used.3601 R@25°C 1.3601 R@25°C 1. the following ratios are obtained: R@O°C 3. For ATP Curve "Z". The temperature coefficient is one method that can be used to compare the relative steepness ofNTC curves.34 A simple approximation for the reh:tionship between the resistance and temperature for a NTC thermistor is to use an . a varies widely over the opt:rating temperature range.000 R@50°C 0.
However. . The equation relating resistance to temperature using is: R = Ae(~ff) Where: R = thermistor resistance at temp T A = constant of equation [3 = Beta. to calculate [3 for the temperature range of OlC to 50'IC for ATP curve "Z": T1 = O'IC + 273. the following formula applies: p =(T. b can be used to calculate the resistance of the curve at other temperatures within the range that b was calculated once the constant A is determined.15IC = 273..15K R J = 3.. For example. Using other temperatures to calculate b for curve "Z" would yield the following results: ~ 25ICI501C = 3936K ~ 25IC/85IC = 3976K As we can see. J1n!i T2 T. R2 [3 can be used to compare the relative steepness of NTC thermistor curves. the material constant T = Thermistor temperature (K) To calculate Beta for any given temperature range.15IC = 323.15K T2 = 50"IC + 273.3601 This value of [3 would be referenced as [3O"IC/50lC.269 Isolated Paramagnets exponential approximation between the two. the accuracy of this equation is only approximately ±OSIC over a 50"IC span. although not to the extent that resistance ratio does. the value of [3 before it is used to compare thermistor curves. as with resistance ratios. This approximation is based on simple curve fitting to experimental data and uses two points on a curve to determine the value of. it is important to know what temperatures were used to calculatp. the value of [3 will vary depending upon the temperatures used to calculate the value. However.k*I.265 ~= 0.
values at the low end. band c are equation constants R = resistance in n at temp T To solve for resistance when the temperature is known. three sets of data must be used. This will ensure the best fit for the equation over the range. THERMISTOR TOLERANCE AND TEMPERATURE ACCURACY x = aliT There are two factors to consider when discussing thermistors and their ability to measure temperature. To solve for the constants. the form of the equation is: R = e[ I"2+4+27 Where: x x3 'l'0lhl +1"24+271 X x3 'l'Olh'J 1 b If/=C C The a.oonc over a IOO'IC temperature span. middle and high end are used to calculate the constants.15) a. To solve for temperature when resistance is known. Normally. The first is resistance tolerance and this is defined as the amount of resistance that any part will vary from its nominal value. The SteinhartHart equation is the best method used to describe the RvT relationship and is accurate over a much wider range of temperature than is. yields the following form of the equation: liT = a + b(LnR) + c(LnR)3 Where: T = temperature in Kelvins (K = 'IC + 273. The tolerance on the resistance at any temperature is the sum of: . band c constants can be calculated for either a thermistor material or for individual values of thermistors within a material type. for a temperature range. Using the SteinhartHart equation allows for an accuracy as good as ±o.Heat and Thermodynamics 270 SteinhartHart Thermistor Equation The SteinhartHart equation is an emperically derived polynomial formula which best represents the resistance versus temperature relationship ofNTC thermistors.
for ATP part number Al 004Z2. The other type of thermistor tolerance is known as curve matched or interchangeable.45IC. for ATP part number AI004ZC3. Therefore.88%. These thermistors are normally defined to have a certain accuracy over a range. ATP also provides the curve deviation for parts that are point matched at 25IC. the reference temperature. For example for curve "Z" at 50lC for ATP part number A I 004Z2. Accy = ResTol a or ResTol=Accyea For example. This describes a thermistor that has its tightest resistance tolerance at one temperature. the resistance .4 %!IC. the resistance tolerance would be (±O. A simple equation is used to describe the relationship between resistance tolerance and temperature accuracy. allows for the temperature accuracy to be calculated at any temperature. the resistance tolerance is ±2% @ 25IC.4%!IC) = ±O. Looking at the data for curve "Z" shows that the a at 25IC is 4. the accuracy at 25'IC can be calculated to be (±2% / 4.4%!IC) = ±0. There are two generally accepted methods of describing the tolerance or accuracy of a thermistor. When one is known the other can be calculated. In the data section for NTC thermistors. For 25IC. At temperatures below and above the reference temperature the resistance tolerance will become larger due to the uncertainty in the material curve. Similarly. typically ±O. To calculate the resistance tolerance at 25IC divide the temperature accuracy at the temperature by the a at that temperature.2'IC from OlC to 70'IC. which is normally 25IC.2'IC * 4.2'IC from OlC to 70'IC.271 Isolated Paramagnets • • The closest tolerance at any specified temperature The additional tolerance due to deviation from the nominal curve for the material In any application where the thermistor is to be used to measure temperature it is more appropriate to discuss the temperature accuracy for the device. the temperature accuracy is expressed as ±O. Using this information and the value of. The first is point matched. The accuracy can be calculated if the resistance tolerance and ex are known.
NTC Thermistor Selfheated Parameters Selfheating occurs in a thermistor when current passing through the device is such that the internal heat generated is sufficient to raise the thermistor body temperature above that of its environment. defines the relationship between the applied wattage and the thermistor self heating in ternlS of temperature rise. For temperature sensing applications.8%!IC. The ability of a thermistor to dissipate power is a function of the size of the part. Therefore. lead material and size. is dependent upon a number of factors. method of mounting and any other factor that would contribute to the ability of the part to dissipate heat. Dissipation Factor (t5) The dissipation factor. its geometry. the total resistance tolerance would be: (±2%) + (±1. 8. it is not desirable to selfheat the thermistor to any extent. The deviation due to the curve uncertainty is listed as ±1. to calculate the temperature accuracy at SOlC for Al004Z2: (±3. Other NTC thermistor applications utilize the self heated characteristics inherent to the parts.2%) = ± 3. .8%!IC. This relationship is defined as follows: o=~ /).Heat and Thermodynamics 272 tolerance at 2S'IC is ±2%.8%!IC) = ±O. 8.2%) / (3.T where: P = power dissipated in watts ~ T = the rise in temperature (lC ) The dissipation factor (8) is expressed in units ofmW!IC. A particular value of 8 will con'espond to the amount of power necessary to raise the body temperature of the thermistor by nco Because the dissipation factor.2%.84'IC The a at SCJIC for this material is listed as 3. Therefore. the values listed in the data sheets are for reference only.2% @ SO'IC The at SCJIe for this material is listed as 3.
certain systems can achieve negative temperatures. the value at 56. By contrast. to find the value for. t.0000 . is then moved to an environment where the temperature is 75IC. For measurement will correspond to 63. we would monitor the res!stance value of the part using a multimeter or similar instrument. Temperatures that are expressed as negative numbers on the familiar Celsius or Fahrenheit scales are simply colder than the zero points of those scales.273 Isolated Paramagnets Time Constant (r) The thermal time constant for a thermistor is defined as the time required for a thermistor to change 63. A thermistor that has been in an ambient temperature of 25IC for a period of time long enough for it to reach equilibrium. For example for ATP part number Al 004ZC3. mounting. a system with a truly negative temperature is not colder than absolute . The resistance of the part at that temperature can be calculated using the SteinhartHart equation or an approximation can be used. NEGATIVE TEMPERATURE In physics.6IC should be 2814 0 .2% of the temperature span.2% of the difference between the initial temperature of the thermistor and that of its surroundings when no power is being dissipated by the thermistor. Negative temperatures can be expressed as negative numbers on the Kelvin scale.e. i.632 (7025) = 31. Therefore. The factors that affect t are similar to those that affect 8 and include the mass of the thermistor.6 + 25 = 56. using the equation.6IC. their thermodynamic temperature can be of a negative quantity. The time that the part takes to reach 2814 0 once the part is moved to the new temperature o05IC will correspond the value of 't and will have the units of seconds. that is. The part should start at 25IC where the resistmce should be 10. The value of defines a response time for the thermistor when it has been subjected to a step change in temperature.6IC Therefore the temperature that the part must reach is 56. The thermistor will not immediately indicate a resistance corresponding to the new temperature but rather will exponentially approach the new resistance value. Tt = 0. environment and other factors.
A substance with a negative temperature is not colder than absolute zero." Generally.. However.. the number of particles in the lower energy states and in the higher energy states becomes equal. .« ) K. . . thermal energy is constantly being exchanged between the various modes. Rather. However.Heat and Thermodynamics 274 zero. .. and no way to get to a negative temperature.. a system with a negative temperature is hotter than the same system with an infinite temperature. (This is a consequence of the definition of temperature in statistical mechanics for systems with limited states. temperatures colder than absolute zero are impossible.. As Kittel and Kroemer put it. "The temperature scale from cold to hot runs +0 K. . vibrational. it is possible to create a system in which there are more particles in the higher energy states than in the lower ones.. electronic. +00 K. .. temperature as it is felt is defined by the kinetic energy of atoms (heat). . and nuclear modes of a system determines the macroscopic temperature. temperature is more generally defined by statistical mechanics than just kinetic energy. for some cases it is possible to isolate one or more of the modes. rotational. 0 K. TEMPERATURE AND DISORDER The distribution of energy among the various translational. +300 K. in fact. 300 K. . but rather it is hotter than infinite temperature. In practice the isolated modes still exchange energy with the other modes" but the time scale of this exchange is much . particles move into higher and higher energy states.) By injecting energy into these systems in the right fashion. This situation can be characterised as having a negative temperature. In a "normal" system. and as the temperature becomes infinite. Heat and Molecular Energy Distribution Negative temperatures can only exist in a system where there are a limited number of energy states. .. Since there is no upper bound on momentum of an atom there is no upper bound to the number of energy states available if enough energy is added.. As the temperature is increased on such a system.
Since the energy flow is predominantly within the spin sy~tem. Nuclear Spins In the case of electronic and nuclear spin systems there are only a finite number of modes available. the energy levels are split. meaning that they correspond to the same energy. thus slightly more atoms should be in the lowerenergy state (for the purposes of this example . Upon application of a magne:ic field. vibrational. The reason for this is that there are an infinite number of these types of modes and adding more heat to the system increases the number of modes that are energetically accessible. When an external magnetic field is applied. A definition of temperature can be based on the relationship: T = dqrev ds The relationship suggests that a positive temperature corresponds to the condition where entropy. In the absence of a magnetic field. one would expect such a twospin system to have roughly halfthe atoms in the spinup state and half in the spindown state.275 Isolated Paramagnets slower than for the exchanges within the isolated mode. qrev' is added to the system. since those spin states that are aligned with the magnetic field will have a different energy than those that are antiparallel to it. some of the atoms will tend to align so as to minimize the energy of the system. it makes sense to think of a spin temperature that is distinct from the temperature due to other modes. S. often just two. corresponding to spin up and spin down. One example is the case of nuclear spins in a strong external magnetic field. and thus the entropy. and nonspin related electronic and nuclear modes. energy flows fairly rapidly among the spin states of interacting atoms. This is the "normal" condition in the macroscopic world and is always the case for the translational. but energy transfer between the nuclear spins and other modes is relatively slow. In this case. these spin states are degenerate. increases as thermal energy. In the absence ofa magnetic field. since this maximizes entropy. rotational.
. then ~ must itself be negative. This reduction in entropy with the addition of energy corresponds to a negative temperature. It is possible to add energy to the spin system using radio frequency (RF) techniques. In this case.. at some point more than half of the spins are in the spinup position.~' exp(f3H) . initially this drives the system towards a 50/50 mixture. the trace to converge.Heat and Thermodynamics 276 we'll assume the spindown state is the lowerenergy state).... The Hamiltonian for a single mode of a luminescent radiation field at frequency v is H=(hv. corresponding to a positive temperature. Semiconductor Lasers This phenomenon can also be observed in many lasing systems.=. wherein a large fraction of the system's atoms (for chemical and gas lasers) or electrons (in semiconductor lasers) are in excited states. ~H must be positive semidefinite. the thermal conductivity will decrease with increasing temperature. This is referred to as a population inversion. The density operator in the grand canonical ensemble is p.Trexp(f3H)· For the system to have a ground state. adding additional energy reduces the entropy since it moves the system further from a 50/50 mixture.:.. Since we started with over half the atoms in the spindown state. So if hv < J! and H is negative semidefinite. typically in a defined temperature range. Negative Temperature Coefficient A negative temperature coefficient (NTC) occurs when the thermal conductivity of a material rises with increasing temperature. For most materials. and the density operator to be generally meaningful.. Materials with a negative temperature coefficient have been used in floor heating since 1971. implying a negative temperature .u)a.. The negative temperature . so the entropy is increasing. However.. This causes atoms to flip from spindown to spinup.
and may infrequently cause fires. Such is the importance of the B constant value.. The ·. . which is governed by an Arrhenius equation over a wide range of temperatures: R = A exp (BIT) where R = resistance A.and are based on a conduction model.hence. Since the N j + cation has less positive charges than the Mn3+ cation so to maintain charge neutrality a M~+ is converted to a Mn4+ cation for each of the substituted Ni2+ cations. which can damage wooden floors. the material becomes insulating.ralue of B strongly depends on the energy required to dissociate the charge carriers that are used for the electrical conduction from these defect centres.either elements or compounds. B = constants T = absolute temperature (K) The constant B is related to the energies required to form and move the charge carriers responsible for electrical conduction . and behaves as an insulator as low temperatures and becomes more conducting as temperature increases. Practical and commercial NTC resistors aim to combine modest resistance with a value ofB that provides good sensitivity to temperature. A common commercially available NTC thermistor material is MnjO4 which can be doped with varying amounts ofNiO. mattresses etc. One of the main reasons that semiconductors are so useful for thermistors is that their electrical properties can be controlled and enhanced by 'doping' or alloying with impurities . that it is possible to characterize NTC thermistors using the B parameter equation: R = rooeB/T where roo = RO eB/TO RO = resistance at temperature TO Therefore. A semi conductor is intermediate between an insulator and a conductor. Most ceramics exhibit NTC behaviour. bean bag chairs.277 Isolated Paramagnets coefficient avoids excessive local heating beneath carpets. many materials that produce acceptable values of B include materials that have been alloyed or possess variable cation valence states and thus contain a high natural defect centre concentration. NTC thermistors are generally manufactured from pressed die chip of semiconducting material .often a sintered ceramic oxide . as the value of B decreases.
hence the NTC thermistors exhibit a decrease in resistivity with increasing temperature. surprisingly. This phenomenon is also described by the change in the temperature coefficient of resistance: ex = (l/R) dR/dT ex = BI T3' It is therefore clear thatthe temperature coefficient of resistance is inversely proportion to the temperature.Heat and Thermodynamics 278 The electrical conduction is therefore increase by an electron hopping mechanism between the M~+ and Mn4+ ions on equivalent sites in the crystal lattice. as the t(. and decreases when the temperature.mperature increases. This results in a greater proportion of electrons being able to move around and carry charge . the more current a material can conduct and therefore the resistivity has decreased . Temperature To get things started. It is also possible to dope the Mn30 4 with other combinations of impurities such as CoO and CuO. and. Negative Temperature Coefficient of Reactivity In a nuclear reactor." In watercooled nuclear reactors. a closed system can be described by a negative temperature. Due to these properties of semiconductors. increases. A reactor with a negative temperature coefficient of reactivity is therefore inherently selfcontrolling and safe. the predominant reactivity changes are brought about by changl:s in the temperature of the coolant water. be hotter than the same system at any positive temperature. and viceversa. In this case the temperature coefficient is negative. temperature changes can introduce reaclivity changes. This property is called the "temperature coefficient of reactivity.. which means that an increase in coolant temperature causes a decrease in reactivity. we need a clear definition of . NEGATIVE TEMPERATURE MEAN Under certain conditions. the energy ofthe electrons increases due to the increased thermal energy available and therefore enables them to be promoted to the conduction band.the more electrons that are mobile and can carry charge.
. treating S I and S2 together. . is "How will the energy of S3 be distributed between S 1 and S2?" With a total energy E." Actually various kinds of "temperature" appear in the literature of physics (e. in some sense the most fundamental. will occur with any significant prouability. The combined system. the rate of change of entropy. must be the same for both systems. S has many possible internal states (microstates). For convenience.279 Isolated Paramagnets "temperature. on average. as the combined system mov'. A simple counting argument tells us that only one particular division of the energy.E2) reaches a maximum when N 1*N2 is stationary with respect to variations of EI and E2 subject to the total energy constraint. S. N(El. the total energy E3 being constant. Each state corresponds to a particular division of the total energy in the two subsystems S 1 and S2. kinetic temperature.E2) isjust the product of the number of states allowed in each subsystem. That number. since EI + E2 = E.E2) = Nl(EI)*N2(E2). The atoms ofS3 can share the total energy in many ways. The important question. Many microstates can correspond to the same division. Let's say there are N different states. colour temperature).s towards a state of maximal total entropy.. Our intuitive notion is that two systems in thermal contact should exchange no heat. and call this the entropy. S. physicists prefer to frame the question in terms of the logarithm of the number of microstates N. E. It's the one with the overwhelmingly largest number of microstates for the total system S3. per unit change in energy. Let's call the two systems S 1 and S2.e. El in SI and E2 in S2. N(El. consideration of which will lead us LO a useful quantitative definition of temperature. We can easily see from the above analysis that two systems are in equilibrium with one another when (dS/dE)l =(dS/dE)2' i. can be S3.g. Otherwise. The relevant one here is the one from thermodynamics. N(El. if and only if they are at the same temperature. and. energy will tend to flew from one subsystem to another as S3 bounces randomly from one microstate to another.
Negative Temperature Not all systems have the property that the entropy increases monotonically with energy. Imagine an ideal "spinsystem". gives the system a total energy of NuB. E is zero when half of the spins are up and half are down. In some cases. from z~ro. one spin .are the number of atoms with spin up and down respectively. So long as dS/dE is always positive. pointing down. where u is the magnetic moment of each atom and if and N. a set ofN atoms with spin 112 on a onedimensional WIre. asymptotically approaching positive infinity as the energy increases. T. to the system. is (N+ . so thatthe equilibrium condition becomes the very simple T 1 = T2' This statistical mechanical definition of temperature does in fact correspond to our intuitive notion of temperature for most systems. The lowest possible energy state. increasingly faster with increasing total energy. If we now add a quantum of energy.Heat and Thermodynamics 280 We define the temperature. as energy is added to the system. For common situations. iIl"a magnetic field of strength B. The total energy of the system. or configurations. actually decreases for some range of energies. The only degree of freedom allowed to them is spinflip: the spin of a given atom can point up or down. i. size uB. so ill this case is log( 1) = O. So temperature increases with increasing energy. or particles in a harmonic oscillator potential.e. by liT == dS/dE.. The entropy is the log of the number of microstates. T is always positive. adding energy always increases the number of available microstates. Notice that with this definition. There is only one configuration of the system at this energy. all the spins pointing down. and temperature of absolute zero. all the spins must point down. the number of available microstates.N)*uB. The atoms are not free to move from their positions on the wire. like a collection of free particles. It is negative when the majority are down and positive when the majority are up.
that the timescale for energy to flow from the spins into other degrees of freedom is very large compared to the timescale for thermalization of the spins among themselves. Ifwe remove one quantum of energy from the system. and put them in thermal contact.. so the entropy is 10g(N). as the energy increases toward maximum.281 Isolated Paramagnets is allowed to flip up. heat will flow from the negativetemperature system into the positivetemperature system. half of the spins up. Atoms always have other degrees of freedom in addition to spin. In fact the maximal entropy occurs for total energy zero. and the coupling between atomic spins sufficiently strong. there are a total of N(N . the entropy does not go on increasing forever. and the entropy is again zero. temperature starts off positive. i. It makes sense to define the "spintemperature" of a collection of atoms. and the temperature is rising as well. only certain degrees of freedom of a particle can have negative temperature. as we add more and more energy. Then it makes sense to talk about the temperature of the spins separately from the . with all spins up. we allow one spin down. the temperature becomes negative infinite. so long as one condition is met: the coupling between the atomic spins and the other degrees of freedom is sufficiently weak. with half of all spins up. Ifwe add another quantum of energy. The entropy is increasing quickly. but always negative. The entropy goes on increasing as the energy is lowered. it is hotter than when it is has positive temperature. approaches positive infinity as maximum entropy is approached. There is a maximum energy. When the system has negative temperature. At this maximal energy. Thus. If we take two copies of the system. one with positive and one with negative temperature. However. there is again only one microstate. So we have created a system where. half down. There are N possibilities. At this energy there are N available microstates. usually making the total energy of the system unbounded upward due to the translational degrees of freedom that the atom has. +NuB. for this system.1)/2 allowable configurations with two spins up.e. After that. coming down in magnitude toward zero.
equal to the mean kinetic energy of molecules. Nuclear and electron spin systems can be promoted to negative temperatures by suitable radio frequency techniques. This condition can easily be met for the case of nuclear spins in a strong external magnetic field. and the rderences therein. yet seems difficult. The most often given answer to this question is something like "no. IS A NEGATIVE KELVIN TEMPERATURE POSSIBLE? Thermodynamics is older than the atomistic view of matter. probably because we cannot feel it. As follows. a simplified statistical concept of temperature is discussed and used to explain the state of matter in lasers as well as the technique to attain very low temperature (adiabatic demagnetization). Temperature is usually taken as simple. is much simpler. for instance. hence thermodynamic quantities such as temperature are not defined atomistically. but this is an equality. . because we all can feel it. It is. But have we ever tought of explaining it to an alien who does not feel it? It would be very difficult. Entropy. because at zero K.. Let's have a closer look at that equality between temperature and mean kinetic energy of molecules.Heat and Thermodynamics 282 temperature of the atoms as a whole. moreover. molecules are not moving anymore and we cannot have less than zero motion. as we probably know. it is certainly interesting to discuss it because it helps understand the concept of temperature. not a definition. The definition of temperature allows negative absolute temperatures. and see what we can get out of this." This answer. What is correct in the abovecited answer is th~t negative Kelvin temperature cannot be achieved by cooling. as well as applications of negative temperature systems as RF amplifiers. ignores that temperature is not defined as motion of molecules. while not completely wrong. etc. Various experiments in the calorimetry of negative temperatures. for certain systems. But do such temperature have any empirical meaning? While this might be questionable. not even zero K can be achieved by cooling.
speed Maxwellian distribution of particle speeds The Maxwellian distribution of molecular speeds for three different temperatures. the particles must somehow accomodate this energy. When the system is heated. low temperature. this can only happen if some change from a low to a high energy state.1ber of molecules at low speed. But certainly. temperature is determined by the ratio of the number of molecules at high speed to the nUr. In this model. the distribution of molecular speeds depends on temperature. A model can help us understand this relationship. energy is transferred to it. there is a small fraction of molecules having high speed. while the fracition of molecules with low speed becomes smaller but does not vanish. Obviously. nobody expects all molecules to have the same speed. The image (Maxwellian distribution) shows the distribution of molecular speeds for three different temperatures. To keep things simple.283 Isolated Paramagnets Statistical Model In a gas made of tiny hard billard balls temperature is proportional to mean kinetic energy of the particles. a system is assumed that can have but two levels of energy. Conversely. E(hi) and E(lo): the particles either have energy or they have not. This fraction increases with temperature. o . Eyen at.
more and more particles change from the low energy level to the high energy level (note that the levels themselves are unchanged). grows and N(lo) decreases so the logarithm becomes less negative and temperature rises.DeltaE/k T = In [N(hi)/N(lo)] HEATING AND COOLING If heat is added. is populated at the cost of E(hi). but one particle changed his place from low to high level. On the other hand. where C a constant (at a given temperature) N(i) the number of particles with energy E(i) E(i) is the energy portion. The energy of the whole ensemble rises because now there are more particles on the high energy level. the number of particle with high energy. if energy is withdrawn from a body. N(hi).Heat and Thermodynamics 284 What is the number of particles that will be on the ith energy level? The answer is given by the Boltzmann distribution: N(i) = C*exp (E(i)/kT). E(lo). Try calculating the temperature for the system shown in picture (two level model). The value of the logarithlil becomes more and more negative lim N(hi) >() N(IO) In[' l Mlk J e N(hl') = N(lo)J . according to our simplifying assumption it is either nought or it is something k the Boltzmann constant T absolute temperature For only two levels of energy the ratio of the population of these levels is: N(hi)/N(lo) = exp (DeltaE/kT) where " DeltaE = E(hi)E(lo) Solving this equation for T . the low energy level.
a hotter body is required. we have negative absolute temperature. Infinite temperature cannot be reached anyway by heating. as well as the picture. but because heat flows from high temperature to low temperature. Can such a state be realised? Yes. only an finite amount of energy is needed to get infinite temperature in this model. To heat a body. of a system is infinite If both levels are equally populated. . it can. show that a state of matter to which negative absolute temperature can be attributed has more energy than the states at usual temperatures. so that N(hi)+N(lo) lim /illlk In[N(hi)] N(lo) =00 The value of the temperature becomes infinite (note that DeltaE does not change). but not by cooling. The formula. INFINITE TEMPERATURE System At infitine Temperature At equally populated levels. because more particles are at high energy level than at low energy level. absolute temperature of a system is negative As soon as the high energy level is populated more that the low energy one. NEGATIVE ABSOLUTE TEMPERATURE System at Negative Absolute Temperature If more particles are at the upper level than at the lower one. as a diagram of the logarithm versus the ratio shows. but not the energy. N(hi) = N(lo) and the logarithm vanishes. although not because of the energy needed. from the expression can be concluded that it must be difficult to reach absolute zero.285 Isolated Paramagnets and temperature goes towards zero. Since number of particles are always finite. temperature. Also.
In most lasers atoms are excited electronically to a high energy level. the energy of . Note that. Prior to laser light emission of the whole system. and a negative absolute temperature can be ascribed to the system. the number of atoms in the parallel equals that in the antiparalle! state. let us look at magnetism due to electron spin. To get a rough idea of the subject. This is an example for the previously stated assertion that one does not need infinite energy to get infinite temperature. Still submerged in liquid helium. The technique is that of adiabatic demagnetization. both systems at infinite temperature and at negative absolute temperature can be prepared. This phenomenon can be used to cool samples of suitable materials (specific magnetic properties are required). the energy of the parallel state is lowered and energy of the antiparallel state goes up. Each electron can be seen as a tiny magnet. Our formula says that if two states differ in energy but are equally populated. Systems at Infinite Temperature Systems at infinite temperature are used to attain the lowest temperatures possible. then the temperature is infinite.Heat and Thermodynamics 286 Thus one has to add energy to get negative absolute temperature. Let us look first at negative temperature. so it is equally probable to find each orientation. atoms are not excited by heating. Without a field. At the very first moment. A sample is cooled down to the temperature ofliquid helium. as expected. It has been emphasized that such states cannot be reached by adding heat to a body. except that it can have only two orientations in an external magnetic field. these "electron magnets" are randomly oriented. more atoms have to be excited than are not. Energy of both states is equal. But these states are no more energetically equivalent in the presence of an external magnetic field. If an external field is applied. In fact. Systems at Negative Absolute Temperature Nevertheless. a magnetic field is applied to it. namely parallel to the field and antiparallel to it.
The energy that was transferred to the helium bath cannot go back to the sample. so most of the time the system will be close to that distribution. The above given Boltzmann relation holds true for multi Ip. Can these temperatures be attributed to such systems. of course. but the larger the fluctuation. This is how some of the lowest available temperatures are attained. Hence in this step. too? Looking at the limits of this two level model may help to elucidate further the concept of temperature. but not the energy. while the populations of the antiparallel and the parallel states are gradually equalized. Now we can clarify what it means when it is said that a system must be in thermal equilibrium: A system is in thermal equilibrium if particle number on each energy level follows the Boltzmann distribution. Keep in mind that the systems are dynamic. of a system is infinite . temperature. the sample cools down. on the contrary! Because it is at infinite temperature. So the model fails when there are only a few particles on each level. The energy is transferred as heat from the sample to the helium bath. Now the relation Ekin = 3/2kT At equally populated levels. Now the sample is insulated from the helium bath and the external magnetic field is reduced to zero. the less it is probable. particles exchanging energy continually. For systems with an infinite number of states infinite temperature would also mean infinite energy. each level must be populated enough to avoid random fluctuations of particle number. Its temperature changes from infinity to that of the helium bath. SYSTEMS WITH IV''JRE THAN TWO ENERGY LEVELS Usual systems have more than two excited states and hence more than two energy levels. Random fluctuations cause deviations from this distribution. the system will now lose energy as anti parallel states change to parallel.vel systems. First.287 Isolated Paramagnets the sample does not rise.
Boris E. If we put negative temperature into the Boltzmann formula. Negative absolute temperature is not an equilibrium quantity. N(hi) the logarithm vanishes. It follows that in system that have inversely populated states. Translational states thus cannot be described by the above model. Free particles that store energy in their translational motion cannot have negative Kelvin temperature. SK Ma Course in Thermodynamics . these states cannot be in thermal equilibrium with all other states of the same system. DK Science Encyclopedia (Revised Edition) by Susan McKeever and Manyn Foote. the function value goes up exponetially. in contradiction to our conclusions above.Heat and Thermodynamics 288 If both levels are equally populated. so that = N(lo) and In[N(hi)] N(lo) shows that. Statistical Physics. REFERENCES N(hi)~N(lo) lim Mlk =00 • • • • • A Guide to Physics: Thermodynamics. the number of translational states is very large. Of course it is not possible to keep populating levels like this. infinite temperature means infinite energy. . Landau and E. and Max Dresden. Volume II. D. Revised Printing. For a system with a Volume of about 1 cm 3 there are more translational states than molecules. In fact. Each energy ievel must be populated more than its iower neighbour. L. Lifshitz Statistical Mechanics. and Quantum Mechanics by Gerald D. Nadgorny. Statistical Physics. M. (Series in Thermal and Fluids Engineering) by Joseph Kestin. near infinite. Mahan.
Liquid vapor Liquid vapor liquid water Fig. and water vapour. so there can be heat transfer to or from the system. as given by SB&VW. is "a quantity of matter that is homogeneous throughout. We wish to find the relations between phases and the relations that describe the change of phase (from solid to liquid. water. To start we consider a system consisting of a liquid and its vapour in equilibrium.13 ________________________ Power Cycles with TwoPhase Media BEHAVIOUR OF TWOPHASE SYSTEMS The definition of a phase. which are enclosed in a container under a moveable piston. including the work done and the heat transfer. A system which has three phases is a container with ice. Twophase System in Contact with Constant Temperature Heat Reservoir . The system is maintained at constant temperature through contact with a heat reservoir at temperature." Common examples of systems that contain more than one phase are a liquid and its vapour and a glass of ice water. or from liquid to vapour) of a pure substance.
: curve Fig.. D J!1~ " ! .. P = peT)... These values are called the saturation pressure and saturation temperature. there is a onetoone correspondence between the temperature at which vaporization occurs and the pressure.... For a singlephase ideal gas we know that the curve would be Pv... Ifboth phases are present.... c:~"'~ : .. in addition to the equation of state. For the twophase system the curve looks quite different.Heat and Thermodynamics 290 emperature Fig. any quasistatic process at constant T is also at constant P.. Let us examine the pressurevolume behaviour of a liquidvapour system at constant temperature.. In summary. Relation for a Liquidvapour System For a pure substance. This means there is an additional constraint for a liquidvapour mixture. Vapor :!'""__A /salu~on . for two phases in equilibrium. The consequence is that we only need to specify one variable to determine the state of the system. Liquid salLnliocl cum: B \'oIume. Ifwe specify Tthen P is set. V ... Pv Diagram for Twophase System Showing Isotherms .. __ /...
The regions of the diagram in which the system will be in the liquid and vapour phases respectively are indicated. The behaviour shown is found for all the isotherms that go through the vapour dome. there are two bounding situations. there is no transition from liquid to vapour and the fluid goes continu0usiy from a liquidlike behaviour to a gastype behaviour. bounded by the liquid saturation curve on the left and the vapour saturation curve on the right.291 Power Cycles with TwoPhase Media Several featuros{}fthefigme should be noted. There is a distinct nomenclature used for systems with more than one phase. This behaviour is unfamiliar. In the zone where both liquid and vapour exist. there is a region in which liquid and vapour can coexist. If we put heat into a saturated vapour it is referred to as superheated vapour. First. Third. the behaviour of isotherms at temperatures below the "critical point" in the region to the right of the vapour dome approach those of an ideal gas as the pressure decreases." Outside of this regime. In this. At a high enough temperature. the terms "vapour" and "gas" seem to be used interchangeably. When the last trace of vapour condenses. and the ideal gas relation is a good approximation in this region. . for water the critical temperature is 374°C and the associated critical pressure is 220 atmospheres. This is roughly domeshaped and is thus often referred to as the "vapour dome. When the last trace of liquid evaporates the state becomes saturated vapour (or dry vapour). due to the small compressibility of most liquids. specifically at a temperature corresponding to the pressure at the peak of the vapour dome. the state becomes saturated liquid. the equilibrium state will be a single phase. Nitrogen at room temperature and pressure (at one atmosphere the vaporization temperature of nitrogen is 77 K) is a superheated vapour. Second is the steepness of the isotherms in the liquid phase. mainly because the temperatures and pressures are not ones that we typically experience.
low specific volume state. During this process. At this point. however. .1 MPa Saturatedliquid tine MIlA B Saturaledv~pot line Volume Fig. For water at temperatures near room temperature. heat is transferred to the system.Heat and 1hermodynamics 292 D 1 UP. the pressure is fixed because the temperature is constant. Constant Pressure Curves in Tv Coordinates Showing Vapour Dome Lines of constant pressure in temperaturevolume coordinates. As the piston is withdrawn. Inside the vapour dome the constant pressure lines are also lines of constant temperature. all the liquid will have been transformed into vapour and the system again behaves as a singlephase fluid. starting from a high pressure. The behaviour in this region is liquidlike with very little compressibility. the volume changes little until the boundary of the vapour dome is reached. as mentioned above. since the expansion is isothermal (we specified that it was). the behaviour would be essentially that of a perfect gas in this region. Once this occurs. It is useful to describe the situations encountered as we decrease the pressure or equivalently increase the specific volume. 0. The specific volume will increase at constant pressure until the right hand boundary of the vapour dome is reached. the behaviour is qualitatively like that of a perfect gas. the specific volume increases through more liquid evaporating and more vapour being produced. As the pressure is decreased. To the right of the vapour dome.
for state b..293 Power Cycles with TwoPhase Media Critical Point M' Saturatedvapor Line Gas (vapor) State 01 vapot in mixture State 01 vapo r in Mixture Liquid + gas I I .e_.specific volume of gas phase. v$ =. The states IJ and c denote the conditions at which all the fluid is in the liquid state and the gaseous state respectively. is the ratio of the total volume to the total mass of the system . The total mass of the system is given by total mass = m = liquid mass + vapour mass = m + mg _ f The volume of the system is Volume of liquid = V = mtf f Volume of liquid = Vg = mgvg Total volume = V = nlJ'f+ mgvg. The average specific volume for this condition is v =.average specific volumeof twophase system We can relate the average specific volume to the specific volumes for liquid and vapour and the mass that exists in the two phases as follows. i. The average specific volume. ''! v ". v. For condihons corresponding to specific volumes between these two values. Specific Volumes at Constant Temperature and States within the Vapour Dome in a Liquidvapour System We define notation to be used in what follows. Fig. the system would exist with part of the mass in a liquid state and part of the mass in a gaseous (vapour) state.. The specific volumes corresponding to these states are v/=.specific volume of liquid phase.
but the volume. Liquid Vapour Equilibrium in a Twophase Medium WORK AND HEAT TRANSFER WITH TWOPHASE MEDIA We examine the work and heat transfer in quasis!atic processes with twophase systems. The system is kept at constant temperature through contact with a heat reservoir at temperature T.vI In reference to Figure. For a fixed mass. For definiteness. V. Fig. and denoted by X: m X =m I : m g = quanlity of a liquidvapour system In terms of the quality and specific volumes. ab ac = v vI Vg vI = X =quality. The pressure is thus also constant.X) vI ab = v .Heat and Thermodynamics 294 _ mivi +mgvg v= = average specific volume. can change. the volume is proportional to the specific volume so that point in Figure must move to the left or the right as V changes. IrII +mg The fraction of the total mass in the vapour phase is called quality. and hence the quality. consider the system to be a liquidvapour mixture in a container whose volume can be varied through movement of a piston. also changes because mass is . the average specific volume can be expressed as v = Xv g + (1 .Vj ac = Vg . This implies that the amount of mass in each of the two phases.
vf) dmfg · The change in internal energy. u) of the phase as.hf )dmjg" The heat needed for the transfer of mass is proportional to the difference in specific enthalpy between vapour and liquid. so that the specific internal energy and the specific enthalpy for the liquid phase and the gas phase are also constant. the quantity of heat needed is .295 Power Cycles with TwoPhase Media transferred from one phase to the other. The change in volume can be related to the changes in mass in the two phases as. mfg' therefore. The work done is given by dW= PdV= P(vg . The internal energy of the system can be expressed in terms of the mass in each phase and the specific internal energy (internal energy per unit mass. For a finite change in' mass from liquid to vapour. !l.vf) dmfg . In terms of dmfg the volume change of the system is dV= (Vg . U=urf+u~g dU= ulmf + ugdmg = (ug . We wish to find the heat and work transfer associated with the change in mass in each phase.dmf = mass transferred from liquid to vapour. dV= vgdm g + vlmf The system mass is constant (m = mf + mg = constant) so that for any changes dm = 0 = dmf + dmg. Note that the specific internal energy of the twophase system can be expressed in a similar way as the specific volume in terms of the quality and the specific internal e"nergy of each phase: u=Xug + (IX) u f Writing the first law for this process: dQ=dU+dW =(u g uf)dmfg +P(Vg vf)dmfg = [(u g +Pvg)(uf +Pvf)]dmfg = (hg . We can define the quantity dmfg = dmg = .U. can be found as follows.uf ) dmfg . The pressure and temperature are constant.
This is 2257 kJ/kg.001044 m3/kg. • The difference in enthalpy between liquid and vapour. The heat input to the system is the change in enthalpy between .1013 MPa. From these. is 2676 kJ/kg and the specific enthalpy of the liquid. occurs often enough so that it is tabulated also.6729 m3/kgand the specific volume of the liquid is 0. The expression for the amount of heat needed. the heat flowing into.= Ml (enthalpy change) f The heat needed per unit mass. ~f is 419 kJ/kg. for water: • At 100°C. or out of. we make use of the fact that problems involving heat and work exchanges in twophase media are important enough that the values of the specific thermodynamic properties that characterize these transformations have been computed for many different working fluids. hfg . liquid to vapour (heat of vaporization). q.h ). is a particular case of the general result that in any reversible process at constant pressure. q. • The specific enthalpy of the vapour. Heat is absorbed if the change is from solid to liquid (heat of fusion). h . • What is the change in internal energy per unit mass of fluid vaporized? In addressing these questions.Heat and Thermodynamics 296 Q = (hg . • The specific volume of the vapour is 1. A numerical example is furnished by the vaporization of water at 100°C: • How much heat is needed per unit mass of fluid vaporized? • How much work is done per unit mass of fluid vaporized? . the system is equal to the enthalpy change. for transformation between the two phases is q:JL:(hg hf):hfg' mfg The notationm hfg refers to the specific enthalpy change between the liquid state and the vapour state. or solid to vapour (heat of sublimation). the vapour pressure is 0.
Carnot cycle with twophase medium A Carnot cycle that uses a twophase fluid as the working medium. This is much larger than the work done.629 m3/kg] = 0.297 Power Cycles with TwoPhase Media liquid and vapour.169 x 106 J/kg. The processes in the cycle are as follows: • Start at state a with saturated liquid (all of mass in liquid condition).088 x 10 6J/kg. :: tI.e " • c d '/ 'I [cycle In Pv coordinates] [cycle In Ts coordinates] [cycle in hs coordinates] Fig. . Figure in Ts coordinates. The work done 1S P( vg ..1013 x 106 Pa x [1. During this process a quantity of heat qH per unit mass is received from the heat source at temperature T2• • Reversible adiabatic (i. Most of the heat input is used to change the internal energy rather than appearing as work. Carry out a reversible isothermal expansion to b(a ~ b) until all the liquid is vaporized. isentropic) expansion (b ~ c) lowers the temperature to T\. THE CARNOT CYCLE AS A TWOPHASE POWER CYCLE TA"frb ~~~~~. The boundary of the region in which there is liquid and vapour both present (the vapour dome) is also indicated.vf) = 0. During .. Generally state will be in the region where there is both liquid and vapour.w or from the tabulated values as 2. Figure gives the cycle in Pv coordinates.e.vf)which has a value of P(vg . ~_.U = q . it is only for a perfect gas with constant specific heats that cycles in the two coordinate representations have the same shapes. Note that the form of the cycle is different in the Ts and hs representation. and Figure in hs coordinates. hf ¥. The change in internal energy per unit mass (ufg ) can be found from /). and is equal to 2.257 x 106 J/kg. . . • Isothermal compression (c ~ d) at to T\ state d.
is abe!and the heat rejected. (hb hc)+(ha hd ) 11= (hbha) . are not horizontal as they are in the latter. The combined first and second law is dp Tds=dh· p For a constant pressure reversible process. In the Ts diagram the heat received. is dee! The net work is represented by abed. The heat received and rejected per unit mass is given in tenns of the eilt~talpy . The slope of a constant pressure line in hs coordinates is thus. To see their shape we note that for these twophase processes the isotherms are also lines of constant pressure (isobars)..e." the different states as qH=hbha qL = hd . in terms of the work done during the isentropic compression and expansion processes. however. qH. qH Area abef T2 In the gs diagram.. qH qH (hb . heat qL per unit mass is rejected to the source at T I . since P = pel). • Reversible adiabatic (i. The isotherms in the former. qL. (Oh) p = T= constant. the isentropic processes are vertical lines as in the Ts diagram.Heat and Thermodynamics 298 this compression. dqrev = Tds = dh.11 . isentropic) compression (d ~ a) in which the vapour condenses to liquid and the state returns to a.) The thermal efficiency is _ wnet _ qH +qL _ (hb ha)+(hd hc) 11. slope of constant pressure line for twoos .. whieh correspond to the shaft work done on the fluid and received by the fluid.hc' (In accord with our convention this is less than zero. phase medium.ha ) or. The thermal efficiency is given by 11 = wnet = Area abed =1.
489. t1.7045 kJ/kgK.. S b = S c III the isentropic expansion process. sb: hb = hvapor (300°C) = hg (300°C) = 2749 kJ/kg sb = svapor (300°C) = Sg (300°C) = 5. calculate the enthalpy as h = Xhg + (1 . i.8? Neglect the changes in kinetic energy at inlet and outlet of the turbine and pump. Using the definition of quality.293K =0. which is at temperature Tc.T~ T. • We now need to find the quality at state c. To obtain these the approach is to use the fact that S = constant during the expansion to find the quality at state and then. llthennal = llCamot =1 .had. we need to find the enthalpy changes between states b and c. Xc. wnere the fluid is all vapour. g X _ • c • _scsf(Tc ) .e. and noting that Sc = X~ + (1 Xc)sp we obtain.299 Power Cycles with TwoPhase Media Carnot Steam Cycle • Heat source temperature = 300°C • Heat sink temperature = 20°C What is the (i) thermal efficiency and (ii) ratio of turbine work to compression (pump) work if • All processes are reversible? • The turbine and the pump have adiabatic efficiencies of 0. • For the reversible cycle. 573K To find the work in the pump (compression process) or in the turbine. S 8 (Tc) . we know Tb.hbc' and the change between a and d. =1. knowing the quality.Sf (Tc ) S fg (Tc )  scsf(Tc) • The quantity S c is the massweighted entropy at state c.X) hI We know the conditions at state b. t1. hb. .
hb .354 x 83.hc = Wturbine = 2749 .353 < X c . The quality at state d is X d = 3.1 kJ/kg + 0.Xc) hfat Tc· Substituting the values.Heat and Thermodynamics 300 The quantity sJJc)is the entropy of the liquid at temperature Tc' • The quantity sjT) is the entropy of the gas (vapour) at temperature Tc' • The quantity t1sfg (Tc) = t1sliquid~gas at Tc' We know: Sc = sb = 5..3706 = 0. Sfg = 8.1669.8 kJ/kg.353 x 2538. We can apply a similaT process to find the conditions at state d: Xd = .253  0. hc = XChg + (1 .646. !1had = 1344950.4 = 1079.8 = 393.2966 8. Substituting the numerical values..96 kJ/kg = 950.6 kJ/kg.96 kJ/kg = 1669. hc = 0.3 kJ/kg. The quality at state c is thus.646 x 2538. Also sd = sa = sf at 300°C.7045  0. The turbine work/unit mass is the difference between the enthalpy at state b and state c. The ratio of turbine work to compression work (pump work) is .7045 kJ/kgK.3706 kJ/kgK.4 kJ/kg. The work of compre~sion (pump work) is !1had = hahd.3706 The enthalpy at state is.2966 = 0..Sd s/(Td ) sg(Td)s/(Td ) Sc s/(Td ) s/g(Td ) We have given that Tc = Td. • X c = 5.1 kJ/kg + 0. The enthalpy at state d is hd =Xjzg + (IXd)hf = 0.647 x 83." .. 8.
not surprisingly. • For a cycle with adiabatic efficiencies of pump and turbine both equal to 0. the efficiency and work ratio can be found as follows.hd = l'lcompression (ha  hd ) = actual work to achieve given pressure difference = 491.285 A question arises as to whether the Carnot cycle can be practically applied for power generation. l'lthermal = 0.4 kJ/kg. We can check the efficiency by computing the ratio of net work (wnet = Wturbine .) Substituting the numerical values. We can find the turbine work using the definition of turbine and compressor adiabatic efficiencies.wcompression) to the heat input (Tcrjg)' Doing this gives. These can be closely approximated by a boiler for the heat addition process and a condenser for the heat rejection.7 kJ/k.6 kJ/kg. = ha ' .he) = actual turbine work received. The thermal efficiency is given by = Wnet heat input = wturbine .he' = l'lturbine (hb . we obtain for the thermal efficiency with nonideal components.75. an efficient turbine can . we use the definition of compressor (or pump) adiabatic efficiency: W compressIOn . hd ) (hb ha . Further.301 Power Cycles with TwoPhase Media Wturbine wcompression =2. the same value as the Carnot equation. The relation between the enthalpy changes is wturbine = hb . Substituting the numerical values.)(ha.wcompression heat input = (hb he. the turbine work per unit mass is 863. The value of the enthalpy at state is a' 1442.8 (nonideal components). The heat absorbed and the heat rejected both take place at constant temperature and pressure within the twophase region. For the compression process.
Heat and Thermodynamics 302 produce a reasonable approach to reversible adiabatic expansion. when the working medium is not an ideal gas (i. the low work per cycle. THE CLAUSIUSCLAPEYRON EQUATION Until now we have only considered ideal gases and we would like to show that the properties u.e. the products of combustion which provide the heat can be cooled only to the highest temperature of the cycle. are true state variables and that the I st and 2nd laws of thermodynamics hold. The source will thus be at varying temperature while the system requires constant temperature heat addition. because the steam is expanded with only small losses. In summary. which is much more compatible with the characteristics of twophase media and available machinery for carrying out the processes. but the rate of power generation may be lower than desired and there can be appreciable heat transfer to the surroundings. The difficulty occurs in the compression part of the cycle. a twophase medium). Also. Equilibrium between the two phases cannot be maintained and the approximation of reversibility is not reasonable. and the irreversibility in the heat transfer from the heat source. Isothermal heat addition under this circumstance is difficult to accomplish. so there will be irreversible heat transfer. If compression is carried out slowly. there is equilibrium between the liquid and the vapour. s. h. so that the heat addition no longer takes place in the twophase region. Rapid compression will result in the two phases coming to very different temperatures (the liquid temperature rises very little during the compression whereas the vapour phase temperature changes considerably). the practical application of the Carnot cycle is limited because of the inefficient compression process. An elegant way to do this is to consider a Carnot cycle for a two . We examine the Rankine cycle. if the heat source and the cycle are considered together. For high efficiency we need to do this at a higher temperature than the critical point. the upper limit on temperature for operation in the twophase flow regime. etc. Another circumstance is that in a Carnot cycle all the heat is added at the same temperature.
'if. Heat is absorbed between states a and b. Carnot Cycle Devised to Test the Validity of the Laws of Thermodynamics Consider the infinitesimal Camot cycle abed shown in Figure. v. This can then be viewed as an experimental proof of the general validity of the 1st and 2nd laws ofthermodynamics! T p T T • efT v. The idea is to run a Camot engine between temperatures T and T . which gives the slope of the vapour pressure curve. . for the infinitesimal cycle considered above. the amount of heat Q=mh must be supplied to the system. We could then measure the vapour pressure curve for various substances and compare the measured slope to the ClausiusClapeyron equation. The working fluid need not be an ideal gas and may be a twophase medium changing phases.om the 1st and 2nd laws of thermodynamics the thermal efficiency for a Camot cycle can be written as 11= Q W = QQR TTR Q =T· Hence. We can then derive an important relation known as the ClausiusClapeyron equation. To state the fact that all Camot engines operated between two given temperatures have the same efficiency is one way of stating the 2nd law of thermodynamics. dW Q = T(TdT) dT =T T . To vaporize an arbitrary amount of mass.dT for a twophase medium and to let it undergo a change in phase. v Fig.303 Power Cycles with TwoPhase Media phase medium.
we need to integrate Equation. .=~= m(vg  vJ )dp dT mhJg T Rearranging terms yields the ClausiusClapeyron equation. v « v ~. This is an important problem in physical chemistry but we shall not pursue it further here except to mention that if • Variations in heat of vaporization can be neglected. Making these approximations.(P . Jg g P f the integration can be readily carried out. To do so. which defines the slope of the vapour pressure curve: dp = hJg dT T(vgvJ) The beauty is that we have found a general relation between experimentally measurable quantities from first principles (1 st and 2nd laws of thermodynamics). h 1 R T . the resulting expression is ~~ ~ dp hfgP dp lnp Jg = +lnC.. Substituting Equations we get . and dW can be viewed as the area enclosed by the rectangle abed: dW= pm (Vg .dp ) m (Vg . i?T hr.!!.Heat and Thermodynamics 304 The work along be and da nearly cancel such that the net work is the difference between the work along ab and cd. In order to plot the ClausiusClapeyron relation and to compare it against experimentally measured vapour pressure curves. and • The specific volume of the liquid is small compared to that or the vapour phase.vf) dp . • The vapour phase is assumed to be an ideal gas. ~ const. the ClausiusClapeyron equation becomes hJg dT dT T2R P R T2 · Carrying out tp.e integration.Vj) .Vj) = m(vg .. the heat of vaporization and the specific volumes must be known functions oftemperature.
Ts. with transition of liquid to vapour. . directly related to the heat of vaporization. The quality decreases from unity at point b to Xc < 1. the volume changes slightly. • a ~ b: Heat added at constant temperature T2 (constant pressure). In this process. [Pv coordinates) [Ts coordinates] [hs coordinates) Fig. a Cooling Water e Fig. Rankine Power Cycle with Twophase Working Fluid A schematic of the components of a Rankine cycle is shown in Figure. • b ~ c: Isentropic expansion through a turbine. The processes in the Rankine cycle are as follows: • d ~ e: Cold liquid at initial temperature Tl is pressurized reversibly to a high pressure by a pump. and hs coordinates in Figure. Rankine Cycle Diagram. • e ) a: Reversible constant pressure heating in a boiler to temperature T2 . • c ~ d: Liquidvapour mixture condensed at temperature Tl by extracting heat.305 Powe