Examples in Thermodynamics

Reall Life
R Lif
Examples in
Thermodynamics
Lesson plans and solutions
Eann A Patterson, Editor

Real Life Examples in Thermodynamics

First edition March 2010
Second [electronic] edition September 2011

Copyright © 2010, 2011 Eann A Patterson (editor)
This work is licensed under the Creative Commons Attribution-NonCommercial-

NoDerivs 3.0 Unported License. To view a copy of this license, visit
http://creativecommons.org/licenses/by-nc-nd/3.0/ or send a letter to Creative Commons,
444 Castro Street, Suite 900, Mountain View, California, 94041, USA.
The Editor has no responsibility for the persistence or accuracy of URLs for external
or third-party internet websites referred to in this publication, and does not guarantee
that any content on such websites is, or will remain, accurate or appropriate.
Bounded printed copies can be purchased on-line at www.engineeringexamples.org
This edition is distributed free of charge by the ENGAGE project

(www.EngageEngineering.org), which is supported by the National Science Foundation
under Grant No. 0833076.
Real Life
Examples in
Thermodynamics
Suggested exemplars within lesson plans for Sophomore level courses in

Thermodynamics. Prepared as part of the NSF-supported project (#0431756) entitled:
“Enhancing Diversity in the Undergraduate Mechanical Engineering Population through
Curriculum Change”
Eann A Patterson, Editor
The University of Liverpool

eann.patterson@liverpool.ac.uk
This work was developed during the NSF-supported project (#0431756) entitled:
“Enhancing Diversity in the Undergraduate Mechanical Engineering Population through
Curriculum Change”. Any opinions, findings, and conclusions or recommendations
expressed in this material are those of the authors and do not necessarily reflect the views
of the National Science Foundation. The following members of the project contributed to
the many discussions which led to this production of this volume:
Ilene Busch-Vishniac McMaster University (Project leader)
Patricia B. Campbell Campbell-Kibler Associates Inc
Darrell Guillaume California State University, Los Angeles
Eann Patterson Michigan State University
The comments on an early draft made by Robert D. Handscombe of Handscombe

Associates are gratefully acknowledged.
CONTENTS
page no.
Introduction 5
FIRST LAW CONCEPTS
1. Systems, properties, & pure substances 6
Coffee maker, exploding soup
2. First law of thermodynamics 9
Chips, classroom air-conditioning, photosynthesis, iPod
SECOND LAW CONCEPTS
3. Second law of thermodynamics 13
Large fan (air circulator), cup of tea, geothermal heat engine
4. Entropy 17
Balloons, bicycle tires, turbine, milky coffee
5. Exergy 22
Candy, death, air-powered cars, ‘destructive’ walls, personal performance
POWER CYCLES
6. Vapor Power Cycles 26
Water pistol, kettle, geothermal power plant
7. Gas Power Cycles 30
Spark ignition engine, diesel engine, gas turbine
THERMODYNAMIC APPLICATIONS
8. Refrigeration and heat pumps 35
Personal refrigerator, drinks cooler, dorm room air-conditioning & heating
9. Non-reacting Mixtures 40
Fire extinguisher, landfill gas, desalination
10. Psychrometric applications 44
Sweating water bottle, misted glasses, windshield misting, cooling towers
THERMODYNAMICS OF CHEMICAL TRANSFORMATIONS
11. Reacting mixtures & combustion 48
Birthday candles, cooking pasta, engine heat losses
3
4
INTRODUCTION
These notes are designed to enhance the teaching of a sophomore level course in
thermodynamics, increase the accessibility of the principles, and raise the appeal of the
subject to students from diverse backgrounds. The notes have been prepared as skeletal
lesson plans using the principle of the 5Es: Engage, Explore, Explain, Elaborate and
Evaluate. The 5E outline is not original and was developed by the Biological Sciences
Curriculum Study1 in the 1980s from work by Atkin and Karplus2 in 1962. Today this
approach is considered to form part of the constructivist learning theory3, and a number
of websites provide easy-to-follow explanations of them.
These notes are intended to be used by instructors and are written in a style that addresses
the instructor; however this is not intended to exclude students who should find the notes
and examples interesting, stimulating and hopefully illuminating, particularly when their
instructor is not utilizing them. In the interest of brevity and clarity of presentation,
standard derivations and definitions are not included since these are readily available in
textbooks which these notes are not intended to replace but rather to supplement and
enhance. Similarly, it is anticipated that these lessons plans can be used to generate
lectures/lessons that supplement those covering the fundamentals of each topic.
This is the third in a series of such notes. The others in the series are entitled ‘Real Life
Examples in Mechanics of Solids’ (ISBN: 978-0-615-20394-2) and Real Life Examples
in Dynamics (ISBN: 978-0-9842142-0-4) are available on-line at
www.engineeringexamples.org.
1
Engleman, Laura (ed.), The BSCS Story: A History of the Biological Sciences Curriculum Study. Colorado
Springs: BSCS, 2001.
2
Atkin, J. M. and Karplus, R. (1962). Discovery or invention? Science Teacher 29(5): 45.
3
e.g. Trowbridge, L.W., and Bybee, R.W., Becoming a secondary school science teacher. Merrill Pub. Co.
Inc., 1990.
5
FIRST LAW CONCEPTS
1. Topic: Systems, properties, & pure substances
Engage:
Take a coffee maker (filter machine), flask of water, and, if
you have one, a coffee grinder and beans. The coffee
grinder will make a lot of noise and the process of grinding
beans and preparing the coffee maker to brew coffee should
engage the attention of the class.
Explore:
While preparing to brew your coffee you can discuss closed systems and control volumes
(open systems). The filter machine while it is brewing the coffee can be considered a
closed system in which no mass is transferred across its boundaries, assuming no steam
escapes from it. If you wanted to consider the chemical process in which the coffee is
produced then you might define a control volume as the cone containing the coffee
grounds, i.e., it has a prescribed boundary across which mass flows (water in and coffee
out).
Explain that intensity properties, such as the temperature of the water in the filter
machine, are independent of the size or extent of the system; whereas extensive
properties such mass are dependent on the extent and size of the system. The coffee is
brewed at the same temperature regardless of how much coffee and water you put in the
machine. However, the mass of the system is strongly a function of the amount of water
and coffee in the closed system.
Note that the filter machine is not in equilibrium during the brewing process because
there is a significant temperature gradient. Also, comment on the water being a pure
substance, i.e., uniform and invariable composition, whereas the coffee is not a pure
substance because its chemical composition will change with a change in phase.
Explain:
Take an old filter machine into class and remove its base. Explain that there is a hole in
the bottom of the reservoir connected via a one-way valve to a pipe that runs under the
hot-plate on which the coffee pot sits. The heating element in the hot plate heats the cold
water that is supplied by the pipe from the reservoir. Steam forms in the pipe and the
bubbles are forced along the pipe and up into the hopper containing the coffee by the
increase in pressure caused by the expansion of the heated water. The one-way valve
prevents the hot water and steam returning to the reservoir. The rest of the process is
driven by gravity as the hot water percolates through the coffee grounds and falls into the
coffee pot where it is kept warm by the hot plate.
6
Elaborate:
When the coffee is brewing it drips very slowly into pot; so the flow through the system
is slow and, hence, the level of the water in the reservoir drops very slowly. So, if the
level of water in the reservoir is nearly constant we can assume that the water in the pipe
under the hotplate is being heated at constant pressure. When brewing is started, the
temperature will be ambient ( 21C) and the pressure will be 2158N/m2
(  gh  1000  9.81 0.22) above atmospheric pressure assuming the surface of the
water in the reservoir is 22cm above the pipe under the hot plate. On a temperature-
volume plot, this state lies somewhere between 1 and f (in the T-v diagram below) in the
compressed liquid phase.
Using thermodynamics tables (www.dofmaster.com/steam.html) it is possible to
establish that the specific volume for water at p = 101.325 + 2.158 = 103.483 kPa and T =
21C is v = 0.0010m3/kg with a saturation temperature of 100.5913C, i.e. the head of
water raises the boiling point, ( Tfg) slightly above 100C.
As heat is transferred to the water in the pipe, at constant pressure, its state moves along
1-f until it reaches f when it is saturated water, T fg  100.5913 C.
With further heat transfer the water becomes a two-phase, liquid-vapor mixture and its
state progresses along fg on the T-v diagram. In this state the liquid phase is saturated
liquid and the vapor phase is saturated vapor; and the mixture begins to move up the pipe
and eventually falls on the coffee. The quality of the mixture, x is the ratio of the mass of
vapor to the total mass of the vapor:
mvapor
x
Temperature (C)
mliquid  mvapor Tc
Vapor
Even after moving only 5% of the distance along the p =103.287 kPa
fg line (x = 0.05, T = 100.5913C), the specific Liquid

Liquid-vapor
volume will have increased from 0.0010 to 0.0830 100.591 f
m3/kg, according to the thermodynamic steam tables g
and this expansion is probably sufficient to drive it 1
up the tube to fall onto the coffee. Specific volume
Evaluate:
Invite students to attempt the following examples: 
Example 1.1
For the water in the coffer filter machine already discussed, estimate the energy supplied
by heating when brewing a cup of coffee.
Solution:
Heat transferred to water = change in internal energy of water

These steam tables are available as a download to your iPod Touch or Phone (price: $11.99 at time of
going to print).
7
Using thermodynamic steam tables, internal energy, u1 for water at p = 103.483 kPa and
T = 21C is 88.0347 kJ/kg.
And at p= 103.483 kPa and x = 0.05, internal energy, u2 = 525.5212 kJ/kg
So the change in internal energy, u  u2  u1  525.5212  88.0347  437.4865 kJ/kg.
There is about 260g of water in a mug of coffee so the energy supplied is 114kJ (=
437.48660.26).
Example 1.2
After a tiring trek in the Rocky Mountains, you return to your lodging in Park City Resort
(elevation 6900ft) and place a storage container with 500g of soup in the microwave to
reheat it, forgetting to take off the top. For the sake of simplicity ignore the other
ingredients in the soup and treat it as being pure water and find:
(a) at what temperature will it just start to evaporate?
(b) if the container can withstand an increase in volume of 1/5th before failure, what
would be the quality of the mixture in the container the instant before it bursts?
(c) how much energy must be supplied to induce the container to burst?
Solution:
(a) Approximate pressure at 6900ft ( 2123m)
 patm  gh  101325  1 9.81 2123  80498 Pa
From the thermodynamic tables the saturation temperature at this pressure (x = 0) is
93.6794C, so the water vapor would appear at the temperature, i.e. boiling would begin.
(b) The specific volume of the water at 80.498 kPa and room temperature is 0.001m3/kg.
Note that this value does not change even at saturation temperature. So, a 1/5th volume
change would give a specific volume of 0.0012. From the thermodynamic steam tables,
this specific volume is achieved at a quality of x = 0.0001 for a pressure of 80.498 kPa.
(c) From the thermodynamic steam tables, the internal energy, u
at a room temperature of 21C, u1 = 88.0362 kJ/kg
and for the condition in (b) u2 = 392.5533 kJ/kg
so, the change in internal energy, u2 - u1 = 304.5171 kJ/kg
Thus, the energy required to heat 500g of soup is 152.26kJ (=0.5 kg  304.5171 kJ/kg).
Note: if a 1000W microwave with an efficiency of 64% is used only 704W (= 1100 
0.64) of power will be converted to heat energy, i.e., 704 J/s so it will take 3 minutes and
36 seconds (= 216 seconds = 152,360/704) to supply the 152.26 kJ needed to heat the
soup; plenty of time to catch it before the container bursts!
8
FIRST LAW CONCEPTS
2. Topic: First law of thermodynamics
Engage:
Take some bags of potato chips into class. Share
them with the students.
Explore:
As the students hand the bags of potato chips
round ask them to estimate amount of energy in
the chips that they are eating (about 10 Calories
per chip 41.8kJ). Ask each student to write a list
of processes in which that energy will be expended
by them over the next couple of hours, e.g. heat
loss to the environment, metabolic processes such
as breathing, walking from the class. Ask a few
students to read their lists while you construct a
comprehensive list based on their responses.
Explain:
Let us take the simple case of a student sitting motionless and listening to the lecture.
Then, neglecting physiological processes, we can assume that the energy taken in as food
will be emitted as heat – this a form of the first law of thermodynamics which is that
energy is conserved in all processes.
We can assume that heat transfer from a student in the classroom will occur as a
consequence of convection and radiation to the surroundings; and that conduction
through the feet or body to the chair is negligible. 
A person’s surface area can be estimated from a nomograph4 used by physicians in the
treatment of certain diseases. We can take a typical value to be 1.8 m2. The convective
heat transfer coefficient, hc for a fully clothed person sitting in a chair is5
hc  1.222T 0.299 W/(m2.K)

The unit of Calorie declared on US food packaging is equivalent to a kilocalorie or 4.18kJ.
4
Adelman, P., Casale, T.B., Corren, J., (eds) Manual of allergy and immunology, Lippincott Williams and
Wilkins, Philadelphia, PA, 2002, p.483.
5
Kurazumi, Y., Tsuchikawa, T., Ishii, J., Fukagawa, K., Yamato, Y., Matsubara, N., Radiative and
convective heat transfer coefficients of the human body in natural convection, Building and Environment,
43(12):2142-2153, 2008.
9
where T is the temperature difference between the person and the environment. So if a
clothed person has a surface temperature of 30C, then in a room maintained at 21C they
will experience a convective heat loss of
 
Q convection  hc ATsurface  Tenvironment   1.222  90.299  1.8  303  294   38.19W
There will also be heat loss by radiation to the surroundings which we can assume are at
the same temperature as the air in the room, so

Q radiation  A Tsurface
4
 Tenvironmen
4
t 
where  is the emissivity (   0.90 for typical clothing) and  is the Stefan-Boltzmann
constant (   5.67 108 W/m2). Thus

Q radiation  A Tsurface
4
 Tenvironmen
4
 
t  0.90  5.67  10
8
  
 1.8  3034  294 4  88 W
Hence the total rate of heat loss per person in the class is
Q total  Q convection  Q radiation  38  88  126 W
So for a person sitting doing nothing else, and neglecting the energy required for
physiological processes, it would take 5.5 minutes to loose the energy equivalent to one
chip ([Energy in chip]/[rate of heat loss] = 41800/126 = 332 seconds).
Elaborate:
Consider the design of the air conditioning system required for the classroom with a
capacity of x students who each have a heat loss of 126W and y light fittings of 100W
each plus a 500W LCD projector. Use values of x and y for the class in front of you.
We can express the first law of thermodynamics, that energy is conserved, as an energy
balance, in terms of energy rates:
Rate of change Net rate of Net rate of

of energy in a = energy inflow + energy outflow
system as heat as work
Assuming that the room (the system) is in a steady state (no rate of change of energy in
the system), then the heat outputs from the room will balance the heat inputs, i.e.
(  Q  0 ) because there is no work being done on the system.
The heat generation in the room is given by

Q generation  126 x  100 y  500
and let’s assume x =50 and y =12, then Q generation  126  50  100  12   500  8000 W
If it is desired to keep the room at a steady temperature of 21C with an outside air
temperature of 10C then we must consider the heat loss from the room to its
surroundings. If we assume that the room is surrounded on three sides and above and
10
below by similar rooms, then we need only consider heat loss from one wall. Heat loss
from the one external wall will occur mainly as a consequence of convection, i.e.
Q convection  hc ATsurface  Tenvironment 
where the coefficient of convective heat transfer6, hc is typically 12 W/(m2.K) and A is

the surface area of the wall (e.g. 2.5m  9m)
Q convection  hc ATsurface  Tenvironment   12  (2.5  9)  283  294   2970 W
Consequently, to maintain steady state conditions
 Q  0  Q convection  Q generation  Q aircon
So Q aircon  2970  8000  5030 W

i.e. the air conditioning system must extract 5030W of heat from the room.
Evaluate:
Invite students to attempt the following examples:
Example 2.1
In North America the primary energy consumption per person per year was 6 tonnes oil
equivalent7 (= 6  42 GJ) in 2008. If the maximum amount of solar energy that can be
captured by photosynthesis is 25Wm-2 and assuming that at best 8% is stored as chemical
energy in biomass (typical value for sugar cane), what is the minimum land area needed
to sustain the energy consumption of average person in North America using biomass
alone? Compare this with the population and area of arable farm land.
Solution
Using the first law of thermodynamics, equate energy captured from photosynthesis in
biomass to energy consumption:
Energy captured per unit area by photosynthesis assuming year round growing season
with an average of 12 hours of daylight  0.08  25  365  12  60  60  31.54 MJ/m2
6  42  109
Thus area required per person   7990 m2 (1.97 acres)
31.54  10 6
US population is 309 million living on a land area of 3,537,438 square miles of which
about one quarter is arable or 1.83 acres per person.
6
Emmel, M.G., Abadie, M.O., Mendes, N., New external convective heat transfer coefficient correlations
for isolated low-rise buildings, Energy and Buildings 39(3):335-342, 2007.
7
BP Statistical Review of World Energy 2009.
11
Example 2.2
It takes about 5 hours for a fully charged iPod nano to run out of power when its screen is
left on and all other functions are switched off. Subsequently, it takes about 90 minutes
to re-charge the iPod from a charging unit with a 5V and 500mA output. The same iPod
takes about 24 hours to run out of power when only the audio function is used. Calculate:
(a) the power consumption of the screen and the audio output separately;
(b) when the power will run out if the user switches on the screen for 10 seconds
every 3 minutes (i.e. about once every track).
Solution
Energy from charge, Echarge  VItbattery  5  0.5  90  60  13500 J
(a) Based on the first law of thermodynamics, the energy input (from charging) will be
equal to the energy output, so
Echarge = Powerscreen  tscreen
hence
E 13500
Power consumption of screen    0.75 W
t screen 5  60  60
and
Echarge = Poweraudio  taudio
hence
E 13500
Power consumption of audio    0.15625 W
taudio 24  60  60
(b) as for above but with a combined usage cycle, from first law of thermodynamics
Echarge = Ecycles  ncycles
so,
Energy consumed in single cycle, Ecycle  10  0.75  3  60  0.15625  35.625 J
13500
Number of cycles   378.95
35.625
 10 
Battery life  378.95   3    1200 mins  20 hours.
 60 
12
SECOND LAW CONCEPTS
3. Topic: Second law of thermodynamics
Engage:
Take the largest fan you can find into class, preferably a
pedestal fan or an air circulator. Try to borrow a large floor-
mounted industrial air circulator in order to make a bigger
impression on the class (e.g. www.airmasterfan.com). If this
doesn’t work out, then borrow all of the desk fans from the
staff in the departmental office – this should make an impact.
Run the fan(s) for a minute or so while students prepare for the class. Then switch it off
and ask the students to stand-up and energetically exercise on the spot in an attempt to
make the fan blades go around.
Explore:
Discuss the fact that when the fan is operated, the electricity consumed by the fan
becomes an energy input to the room, i.e. the room gains energy at the rate of 500W (for
a 500W fan), according to the first law of thermodynamics. Due to this work input, Win
(energy), the temperature of the room will begin to rise and as it does so there will be
heat loss to the surroundings until this loss equals the input from the fan, i.e. using the
first law of thermodynamics
E in  E out  Q  W  0
then Win  Q out  hc ATroom  Tenvironment 

thus if the coefficient of convective heat transfer6, hc=12 W/(m2.K) and heat loss is
through one wall to the outdoors (A = 2.59 = 22.5 m2), we have
Win 500
T    1.85 C
hc A 12  22.5
i.e. the fan will cause the temperature of the room to rise by 1.85C. Here we have
assumed that the room is surrounded on three sides and above and below by rooms at
approximately the same temperature so that there is negligible heat transfer across these
boundaries.
Low impact aerobic exercise for a 91 kg (200lb) person burns about 455 Calories/hr8 or
529W (= 4554187/3600). So for x people in the class we just generated heat equal to
8
Ainsworth, B.E., Haskell, W.L.; Whitt, M.C.; Irwin, M.L.; Swartz, A.M.; Strath, S.J.; O'Brien, W. L.;
Bassett, D.R. Jr.; Schmitz, K.H.; Emplaincourt, P.O.; Jacobs, D.R. Jr.; Leon, A. S., Compendium of
Physical Activities: an update of activity codes and MET intensities, Medicine & Science in Sports &
Exercise, 32(9):S498-S516, 2000.
13
about x times the power consumption of the fan, but it did not turn – why? Ask the
students in pairs to discuss this conundrum.
Explain:
The experiment with the fan demonstrates what we know intuitively, i.e., that work can
be converted completely and directly to heat quite easily but that it is rather more difficult
to convert heat to work. A ‘heat engine’ is needed to convert heat into work; there are
many different types of heat engine which share the following characteristics:
i. a high temperature heat source;
ii. only part of the supplied heat is converted to work;
iii. waste heat is rejected to a low-temperature sink; and
iv. they operate on a cycle.
Heat engines are special devices designed to cope with the implications of the second law
of thermodynamics which states that processes occur in a certain, specific direction.
The inability of the heat generated by our aerobic exercise to do work on the fan is an
illustration of the Kelvin-Planck statement of the Second Law of Thermodynamics: ‘It is
impossible for any system that operates on a thermodynamic cycle to receive heat from a
single reservoir and produce a net amount of work’.
Re-engage:
Take a cup of black tea or coffee into class. Now add
milk to it and stir. Blow on it to cool it before taking a
sip.
Explore (part II):

Ask the students to identify the two irreversible
processes that they have just watched you perform, i.e.
mixing the tea and milk together then cooling the tea by
blowing on it.
Explain (part II):

Explain that the second law of thermodynamics states that processes occur in a certain,
specific direction, and so there are irreversibilities in all real processes, e.g. mixing of two
fluids and heat transfer across a finite temperature difference.
This second irreversibility is associated with the Clausius statement of the second law of
thermodynamics: ‘It is impossible for any system to operate in thermodynamic cycle and
produce no effect other than the transfer by heat from a cooler to a hotter body.’
Ask the students to identify other forms or sources of irreversibility with which they are
familiar, e.g. friction, unrestrained expansion, inelastic deformation, chemical reactions.
14
Elaborate:
We know that heat does not on its own transfer from a cold body to a hot one; and yet a
refrigerator arranges for exactly this to happen – heat is removed from the cold food
compartment to the warmer surroundings. However, this does not violate the 2nd law of
thermodynamics because the refrigerator does work and so consumes external energy.
For example: if 4kW of heat needs to be removed from the cold compartment of a
refrigerator to maintain it at 3C (=TL(ow) = 277K) , and the power input is 1.5kW then
conservation of energy (1st law of thermodynamics) requires
Win  Q dumped  Q removed
And so the heat dumped into the surroundings at 21C (=TH(igh) = 294K) is
Q dumped  Q removed  Win  4  1.5  5.5 W
The coefficient of performance is defined as

1 1
COP      2.67
Qdumped Qremoved  1 5.5 4  1
An ‘ideal’ reversible refrigerator operating between two temperatures, TLand TH is known
as a Carnot refrigerator and has a coefficient of performance defined as
1 1
COP    16.29
TH TL  1 294 277  1
This is the ideal coefficient of performance for a refrigerator operating between these
temperatures. Real refrigerators, such as the one mentioned above, have lower values
due to the 2nd law of thermodynamics.
Similarly, an ideal, reversible heat engine is known as a Carnot engine and has the
highest efficiency of any heat engine operating between these two temperatures
TL 277
th  1   1  0.058
TH 294
It is clear that a larger temperature difference will produce a greater efficiency.
Evaluate:
Example 3.1
Calculate the maximum efficiency of a heat engine for your home using a geothermal
source with a constant all-year temperature of 50F (=10C) about 50ft below ground?
Solution
Assume the maximum temperature difference is achieved in winter when the lowest
temperatures are 0F (=-18C), so
15
TL 255
th  1   1  0.099 or about 10%.
TH 283
Example 3.2
Discuss what the Carnot efficiency means in terms of the design of a heat pump and why
you can’t achieve this efficiency in a design for your home using geothermal energy.
16
SECOND LAW CONCEPTS
4. Topic: Entropy
Engage:
Take a pack of children’s balloons into class. Hand one to
each student. Ask the students to blow up their balloons
and place them in a tidy pile in a corner of the room.
Of course you will not end up with a tidy pile! Unless you
have a little static electricity around as in the photograph.
Explore:
Ask the students what they feel when they gather round a barbeque on a late Fall day, or
when they light the gas on the stove on a cold day. The answer should be heat! Ask
them to discuss in pairs how the pile of balloons is analogous to heat from the gas stove
or barbeque. Invite a couple of pairs to offer their explanation.
The balloons have a tendency to disperse; it is impossible to make a pile of them unless
we use a box or a net to constrain them. Energy behaves in same way. Energy will
always disperse unless it is constrained from doing so. Our most common experience of
this dispersion is heat transfer as in the case of the gas stove or barbeque. The measure of
energy dispersion is entropy.
Explain:
Rudolf Clausius expressed his statement of the second law of thermodynamics as
Q
 T
 0
where  means the integral or sum around a cycle, and Q is the heat entering the
system at a point in the cycle and at temperature T.
Clausius called the quantity on the left of the above equation ‘entropy’, which is denoted
by S and
Q
dS 
T
so  dS 0
For a reversible process the equality applies, but for all other processes more entropy is
transfered out of the system than into it.

It is impossible for any system to operate in thermodynamic cycle and produce no effect other than the
transfer by heat from a cooler to a hotter body.
17
The third law of thermodynamics defines the absolute value of entropy: the entropy of a
pure crystalline substance at absolute zero temperature is zero. For a pure crystalline
substance at absolute zero temperature we have no uncertainty about the state of its
molecules which leads to a second definition of entropy based on statistical mechanics
S  k  ln W
where W is number of microstates that are consistent with the given macrostate and k
(=1.38065810-23) is the Boltzmann constant (named after Ludwig Boltzmann who
proposed the above relationship) and is the ratio of the molar gas constant to Avogadro’s
number.
At absolute zero temperature, there is no thermal motion of the molecules and there is
only one way to arrange the molecules, so there is only one microstate consistent with the
macrostate, i.e. we are certain about the state of the molecules and
W  1 and S  1.380658  10 23 ln 1  0
So the statistical thermodynamics definition of entropy proposed by Boltzmann agrees
with that of Clausius at absolute zero temperature.
When the balloons are constrained in a box or net there are fewer configurations, perhaps
two dozen (ln 24 = 3.18), that they can assume compared to the thousands of
configurations (ln 2000 = 7.6) which they can assume when they are free to disperse
around the room; thus their ‘entropy’ is higher in the dispersed state.
Elaborate:
For an ideal gas the change in entropy between two states is given by
T2 P
ds  c p ln  R ln 2
T1 P1
where cp (from thermodynamics tables9) is the specific heat capacity at constant pressure
and R (=0.287 kJ/kgK) is the universal gas constant. Note that s is used to indicate
specific entropy or entropy per unit mass.
We can consider air as an ideal gas and when it escapes from a puncture in our bicycle
tire, the air experiences a change in entropy of
T2 P 290 101
ds  c p ln  R ln 2  1.005 ln  0.287 ln  0.308 kJ/kgK
T1 P1 294 310
assuming the temperature drops by 4C from an ambient temperature of 21C and the
tires were pressurized at 45psi (310 kPa). In other words, the air disperses taking its
internal energy with it and this dispersion can be quantified by the increase in its entropy
of 0.308 kJ/kgK.
We can use Boltzmann’s equation to calculate the increase in the number of macrostates
present in 1 gram of escaping air, i.e.
9
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPG/pgConsts.html
18
s  0.308  10 3 
W  exp  exp  23 
k 1.380658  10 
this is an enormous number of microstates which is beyond the range of the editor’s
calculator.
This tendency to disperse can be used to do work for us which is what happens in a
turbine. For instance, steam is generated in a pressurized boiler (using a heat source
derived from burning a fuel) at 2.8MPa and 420C and is exhausted from the turbine at
boiling point and half an atmosphere.
The entropy at the entry (1) and exit (2) states for the turbine can be found using the
steam tables (www.dofmaster.com/steam.html):
State 1: T1  350 C and P1  2800 kPa so s1  6.7842 kJ/kg/C
State 2: T2  100 C and P2  50.5 kPa so s2  7.6905 kJ/kg/C
These can be represented on a T-s diagram as shown below. In the ideal, reversible case
there would be no increase in entropy and the process can be described as isentropic
(constant entropy) resulting in end state 2i.
P1=2800kPa
T1=350C
P1 =2800 kPa
1
Temperature (C)
350 P2 =50.5 kPa
steam
turbine Wout
100 2
2i
P2=50.5kPa
T2=100C Specific entropy, s
For state 2i:
P2i  P2  50.5 kPa and s 2i  s1  6.7842 kJ/kg/C from which the quality must be
s2 i  s f 6.7842  1.0941
determined: x2i    0.8758
s fg 6.4972
In order to define the efficiency of the turbine we need to introduce ‘enthalpy’. Enthalpy
is defined as the sum of the internal energy of the substance and the product of its
pressure and volume, and can be expressed as h = u + pv. For state 2i,
h2i  h f  x2i h fg
where hf and hfg can be found in the steam tables for T2 = 100C and P2 = 50.5kPa.
Hence, h2i  h f  x2i h fg  341.6059  0.8758  2304.7903  2360 kJ/kg
19
The efficiency of the turbine can be defined as the ratio of the actual enthalpy change to
the ideal (isentropic) enthalpy change, i.e.
h1  h2
 II 
h1  h2i
where h1 and h2 can be found in the steam tables i.e.
State 1: T1  350 C and P1  2800 kPa so h1  3121.86 kJ/kg
State 2: T2  100 C and P2  50.5 kPa so h2  2682.5 kJ/kg
h1  h2 3121.86  2682.5
hence  II    0.577 or 57.7%
h1  h2i 3121.86  2360
This is known as second-law efficiency and can be expressed in terms of useful work
(Wuse) to reversible (Wrev) work, i.e.  II  Wuse Wrev for a work-performing device and
 II  Wrev Wuse for a work-consuming device.
Evaluate:
Example 4.1
Determine the entropy generated when 1oz of milk from the refrigerator is added to an
insulated 9oz mug of coffee. Where/what is this entropy?
Solution
Assume the refrigerator is at 3C and the coffee at 80C and that milk and coffee can be
considered equivalent to water. The first law of thermodynamics can be used to consider
the heat transfer that occurs during mixing in the absence of any external work or heat
input; so that the heat transfer to the milk must equal the heat transfer from the coffee, i.e.
Qgained by milk = Qlost by coffee and Q  mc p T
so the temperature, T3 after mixing without heat loss to the surroundings will be
T3 
mmilk Tmilk  mcoffeeTcoffee

1 276  9  353  345.3 K (= 72.3C)
mmilk  m coffee 10
The entropy generated will be S generated  S mixture  ( S milk  S coffee )
Now, using the steam tables for water at T = 3, 80, and 72.3C, s = 0.0459, 1.0752, and
0.9828 kJ/kg/C respectively.
So, for milk before mixing, S milk  mmilk sT 3  0.028349  0.0459  1.3012  10 3 kJ
for coffee before mixing, S coffee  mcoffee sT 80  0.028349  9 1.0752  0.2743 kJ
20
for mixture, S mixture  mmixture sT 72.3  0.028349  10  0.9828  0.2786 kJ

hence the entropy generated is
S generated  S mixture  ( S milk  S coffee )  0.2786  (0.0013  0.2743)  3.0127  10 3 kJ (3J)
Example 4.2
Measure the temperature adjacent to the interior and external walls of your room; and
calculate the entropy generation in the wall as a consequence of heat transfer through the
wall.
Solution
Solving this example for the editor’s study in December in Michigan
Tint  68 F  19.44 C  292.44 K
Text  28 F  2.22 C  270.78 K
and Q out  hc ATroom  Tenvironment 

thus, if the coefficient of convective heat transfer6, hc =12 W/(m2.K) and heat loss is
through one wall to the outdoors (A = 2.74.05 = 10.935 m2) we have
Q out  12 10.935292.44  270.78  2842 W
We can consider the wall to be a closed system since there is no mass transfer. Assuming
the temperatures on each side of the wall to approximately constant (changing very
slowly) then the rate of change of entropy across the wall is zero, i.e.
dS system
 0  Sin  Sout  S gen
dt
 Q   Q 
or       S gen  0
 T in  T out
2842 2842
so S gen    0.778 W/K
270.78 292.44
21
SECOND LAW CONCEPTS
5. Topic: Exergy
Engage:
Take some individually wrapped candy, or small
packets of nuts into class that have the energy
content and nutritional values on the packet.
Share them around the class.
Explore:
As the students enjoy the treat, remind them about
the analysis in lesson 2 where we estimated the
time required to loose, by heat loss, the energy
gained from eating a chip while sitting doing nothing else; about 5½ minutes per chip.
Then, ask the students, working in pairs, to consider how and why the heat is generated.
Explain: 
The second law of thermodynamics requires that entropy is created in all real processes;
during the metabolic processes in our bodies entropy is generated as heat and needs to be
dispersed. All living organisms continually generate entropy in every process and during
every event, so that they progress towards a state of maximum entropy in which they are
in complete equilibrium with the environment, i.e. death. Living organisms remain alive
by continually drawing negative entropy, known as exergy from the environment10.
Plants use sunlight as their source of exergy (negative entropy) and animals eat plants or
other animals to gain their exergy. Thus, to be really useful, the labeling on food packets
should include the exergy content.
Engineering systems are described as being in a ‘dead state’ when they are in
thermodynamic equilibrium with their environment, i.e. at the temperature and pressure
of the environment with zero velocity and relative elevation (KE = PE = 0) and
chemically inert. In a dead state a system has no potential to perform work because there
is no ‘available energy’, or exergy.
Elaborate:
Exergy is a measure of the available energy of a system relative to its dead state. Of
course we cannot always run a system down to its dead state, unlike the battery a mobile

Alternatively you can go to http://caloriecount.about.com/calories-sweets-ic1900 and display the nutrition
information (in the style of a packaging label) for many types of candy or other foods.
10
Schrödinger, Erwin, What is life? Cambridge University Press, Cambridge, 1944.
22
phone. Exergy is destroyed during all real processes. It can only be conserved in
reversible processes and can never be created. This is a consequence of the second law
of thermodynamics. In heat transfer processes the destruction of exergy is related to the
creation of entropy:
X destroyed  T0 S generated
Heat can be considered to contain exergy since in the appropriate circumstances it is able
to perform useful work. The exergy level of heat depends on the temperature at which
the heat is available and the temperature at which heat can be rejected and this is
maximized in the Carnot cycle for which the efficiency is
TL
  1
TH
in these circumstances the exergy is given by
 T 
X  Q1  L 
 TH 
The exergy of a system at a specified state is the sum of the internal, kinetic and potential
energies of the system where the internal energy is taken as the total useful work output
as the system undergoes a reversible process from the specified state to the dead state
which is equivalent to the enthalpy of the fluid contained in the system, so that
X  U  U 0   p0 V  V0   T0 S  S0   KE  PE
Exergy is sometimes known as the irreversibility, I where for a system producing work
I  Wrev  Wuse  X destroyed
where Wuse and Wrev are useful and reversible work and need to be interchanged when
considering a system consuming work.
Evaluate:
Example 5.1
(a) Measure the temperature adjacent to the interior and external walls of your room;
and calculate the exergy destroyed in the wall as a consequence of heat transfer
through the wall.
(b) How is this related to value of the entropy found in Example 4.2?
Solution:
(a) Solving this example for the editor’s study in December in Michigan:
Tint  68 F  19.44 C  292.44 K
23
Text  28 F  2.22 C  270.78 K
and Q out  hc ATroom  Tenvironment 

thus if the coefficient of convective heat transfer6, hc=12 W/(m2.K) and heat loss is
through one wall to the outdoors (A = 2.74.05 = 10.935 m2) we have
Q out  12 10.935292.44  270.78  2842 W
We can consider the wall to be a closed system since there is no mass transfer. Assuming
the temperatures on each side of the wall to be approximately constant (changing very
slowly) then the rate of change of exergy across the wall is zero, i.e.
dX system
 0  X in  X out  X destroyed
dt
 T   T 
Or using Q 1  0   Q 1  0   X destroyed  0
 T in  T  out
 270.78   270.78 
so X destroyed  2842 1    1    210.5 W
 292.44   270.78 
(b) Alternatively, the same answer could have been obtained by using the value of the
entropy generated which was calculated in Example 4.2 as 0.777W/K and multiplying it
by the temperature of the environment, T0=270.78K (i.e. X destroyed  0.777  270.78)
Example 5.2
Cars running on compressed air are a reality, see for example: www.mdi.lu.
(a) Use an exergetic analysis to calculate how much work can be performed by the
compressed air in the tank of a typical car with a capacity of 175 litres (0.175m3)
containing air compressed to 350bar (35000 kPa) at 25C.
(b) If about 15% of the 32MJ/litre exergy content of 87 Octane gasoline fuel is
converted to motive force in a typical car powered by an internal combustion
engine11, how many litres of gasoline is the tank of air equivalent to when used in
90% efficient air motor.
Solution:
(a) Assume the air in the tank to be at state 1, and T1=T0=25C where subscript 0 refers
to the state in the environment, we can calculate the mass of air stored in the tank using
the ideal gas equation
11
http://www.fueleconomy.gov/FEG/atv.shtml
24
P1V 35  106  0.175

m1    71.6 kg
RT1 287  298
Considering the exergy of the system:
X  U  U 0   p0 V  V0   T0 S  S 0   KE  PE
In this case there is no change in internal energy, kinetic or potential energy of the air, so
X 1  m1 P0 v1  v0   T0 s1  s0 
 RT RT  P 
And using the ideal gas equation m1P0 v1  v0   m1P0  1  0   m1RT0  0  1
 P1 P0   P1 
because T1=T0 and, similarly for an ideal gas
T1 P
ds  c p ln  R ln 1
T0 P0
 P
T0 s1  s0   T0  c p ln 1  R ln 1    RT0 ln 1
T P
so
 T0 P0  P0
Hence
 P0 P1   1  105 3.5  107 
  
X 1  m1 RT0   1  ln   71.6  287  298    1  ln 5 
  2.97  107 J
 3.5  10 1  10 
7
 P1 P0 
(b) So the available energy is 29.7MJ and MDI claim to achieve 90% efficiency in their
air motors giving 26.8MJ of motive energy available.
One litre of 87 Octane gasoline has an energy (exergy content) of 32MJ/litre and 15% of
this energy gets used to generate motive energy, i.e. 4.8MJ/litre. So the AirPod has a
range equivalent to about 5.58 litres (= 26.8 / 4.8).
An equivalent size gasoline-powered car (e.g. Ford Focus) has an urban cycle fuel
consumption of about 3.6 litres/100km12 so 5.58 litres would take you 155 km (= [5.58 /
3.6]  100).
MDI claim their AirPod, which can carry 3 to 4 people, will have a range of 220km (137
miles) at a maximum speed of 70km/hr (44 mph).
12
http://www.vcacarfueldata.org.uk/search/vehicleDetails.asp?id=22655
25
POWER CYCLES
6. Topic: Vapor Power Cycles
Engage:
Take a child’s water pistol with a large reservoir
into class together with a bucket and an electric
kettle. If the windows in the room open, then
perhaps you can fire the water pistol out of the
window, otherwise use the bucket!
At the same time boil the kettle and produce clouds of steam. Perhaps you could ask a
pair of students to hold down the kettle switch (until it boils dry) and to pump the water
pistol (until it runs dry).
Explore:
Ask the students to describe the water pistol and kettle in engineering terms, i.e. what
type of devices are they?
Answers: a pump: ‘a device that raises, transfers, delivers or compresses fluids’ and a
boiler: ‘a vessel used for boiling; the part of a steam generator in which water is
converted into steam’ according to the Merriam-Webster Online Dictionary13.
The water pistol and the kettle represent half of a vapor power cycle – the half in which
we have to deliver work (via the pump) and heat transfer (via the boiler). You could
pump some water (from the bucket) into the kettle with the water pistol to illustrate the
relationship.
Explain:
We can draw the half of a Rankine cycle represented by the water pistol (pump) and
kettle (boiler) as shown below and also plot it on a temperature-entropy plot.
qin
boiler P1 =2800 kPa

 
Temperature (C)
 350 P2 =50.5 kPa

qin

pump
Win
Win 

Specific entropy, s
13
www.merriam-webster.com/dictionary/
26
For the typical temperature and pressure range illustrated in the T-s plot, the enthalpies
can be determined from the steam tables (www.dofmaster.com/steam.html):
State 1: P1  50.5 kPa and saturated water (x = 0) so
h1  h f  341.6059 kJ/kg, v1  v f  0.0010 m3/kg and s1  s f  1.0941 kJ/kg/C.
State 2: P1  2800 kPa and s2  s1  1.0941 kJ/kg/C

Work done between 1 and 2, Win  v1 P2  P1   0.00102800  50.5  2.7495 kJ/kg
Hence the work input is equal to the change in enthalpy using the first law of
thermodynamics. Noting that enthalpy is the internal energy of a substance plus the work
done against the ambient pressure. So,
Win  h2  h1
and h2  h1  Win  341.6059  2.7495  344.3554 kJ/kg
State 3: P3  P2  2800 kPa and T3  350 C so
h3  3121.8607 kJ/kg and s3  6.7842 kJ/kg/C

And, the heat supplied by the boiler is
qin  h3  h2  3121.8607  344.3554  2777.5053 kJ/kg.
Elaborate:
Two further components are necessary to complete a closed vapor power cycle, i.e. a
turbine and a condenser. We can add them to the schematic of the power plant and
complete the plot of the cycle on the T-s diagram, as shown below.
qin
boiler P1 =2800 kPa

 
Temperature (C)
 Wout
350 P2 =50.5 kPa
turbine qin
 Wout
pump
Win
Win
 qout 
 
condenser
Specific entropy, s
qout
State 4: P1  P4  50.5 kPa and s4  s3  6.7842 kJ/kg/C which corresponds to a saturated

mixture. In order to find the quality of the mixture we need from the steam tables,
s f  1.0941 kJ/kg/C and s fg  6.4972 kJ/kg/C
27
s4  s f 6.7842 - 1.0941
thus x   0.8758 and
s fg 6.4972
from the steam tables h f  341.6059 kJ/kg and h fg  2304.7903 kJ/kg
so h4  h f  xh fg  341.6059  0.8758  2304.7903  2360.0888 kJ/kg

Now, again using the first law of thermodynamics for the ideal process (ds = 0)
Wout  h3  h4  3121.8607  2360.0888  761.7719 kJ/kg
The efficiency is defined as the ratio of the net work and heat supplied, i.e.,
Wout  Win 761.7719  2.7495
th    0.2733 or 27%
qin 2777.5053
This is the best efficiency that a power plant operating over this cycle can achieve
because it does not involve any irreversibilities, i.e. the processes in the pump and turbine
are isentropic (constant entropy) and there are no pressure losses in the boiler or
condenser. We can draw an actual cyclic including these irreversibilities as shown below
by the solid lines.

Temperature (C)


Specific entropy, s
Evaluate:
Example 6.1
At a particular location a hot spring is available to provide a heat source for a vapor
power cycle of a power station and not far away a meltwater river from a glacier is
available to provide a heat sink. The hot spring has a flow of 1500 litres/sec at 98C and
the meltwater river a flow of 5600 litres/sec at 1C. Design a vapor power cycle for a
8MW power station using heat exchangers to input and remove heat from the working
fluid and assuming an 80% isentropic efficiency in the turbine and pump with no pressure
losses in the boiler or condenser. Attempt to minimize the environmental impact of the
power plant.
28
Example 6.2
At a power station the 216kW feedwater pump supplies 12 kg/s of water to the boiler
which in turn provides steam at 15MPa, 600C to the turbine. The turbine provides
14.4MW of output and exhausts the steam at 10kPa. Calculate the efficiency of the
power cycle assuming that the power station operates on a non-ideal vapor power cycle
but that there are no pressure losses in the condenser or boiler.
Solution:
Work input via pump, p =15MPa
Power 216 
Win    18 kJ/kg 
Flow Rate 12
Temperature (C)
Qin (boiler) Work (turbine)
Work out from turbine, p =10kPa

Power 14400
Wout    1200 kJ/kg Work (pump)
Flow Rate 12 

Net. Work, Qout (condenser)
Wnet  Wout  Win  1200  18  1182 kJ/kg
State 3 (input to turbine): P3  15000 kPa, Specific entropy, s
T3  600 C, so using the steam tables h3  3579.7767 kJ/kg and s3  6.6764 kJ/kg/C
State 4 (output from turbine): P4  10 kPa
Work output of turbine is known and can be equated to the change in enthalpy using the
first law of thermodynamics
Wout  h3  h4 so h4  h3  Wout  3579.7767  1200  2379.7767 kJ/kg
Hence from the steam tables for P4  10 kPa and h4  2379.7767 kJ/kg
T4  Tsat  45.8328 C, s4  7.5084 kJ/kg/C  s3  and x  0.9143 ,
so it is wet steam implying that  should have been drawn further to the left along the
isobar where it becomes an isotherm.
State 1 (inlet to pump):
thus at the pump input/condenser outlet, P1  P4  10 kPa, T1  T4  45.8328 C and x  0
so from the steam tables
h1  h f  191.8324 kJ/kg and s1  s f  0.6493 kJ/kg/C
Now, using the first law of thermodynamics for the work input by the pump
Win  h2  h1 so h2  h1  Wout  191.8324  18  209.8324 kJ/kg
And for the boiler, qin  h3  h2  3579.7767  209.8324  3369.94 kJ/kg
wnet 1182
So the thermal efficiency, th    0.3507 or 35%.
qin 3369.94
29
POWER CYCLES
7. Topic: Gas Power Cycles
Engage:
If you have a cut-away internal combustion engine in
your department, then arrange for it to be delivered to
your class. In addition, or alternatively, you can show
an animation of a four-stroke engine by searching in
Youtube for ‘Awesome Engine Animation’
(http://www.youtube.com/watch?v=OXd1PlGur8M&N
R=1&feature=fvwp) or try:
www.animatedengines.com/otto.shtml or
auto.howstuffworks.com/engine1.htm
Explore:
Explain the processes underway in each stroke of the engine. On the Animated Engines
website you can control the speed of the cycle which allows you to explore the process in
more detail.
Explain:
Discuss how an internal combustion engine (or a jet engine) differs from the vapor power
cycle used in a power station because (a) the working fluid always remains in the gaseous
phase and; (b) it is an open cycle (as opposed to closed cycle) in which the working fluid
is replaced at the end of each cycle instead of recycled.
However, the ideal closed vapor power cycle and ideal open gas cycles look remarkably
similar when plotted on a temperature-entropy (T-s) diagram with the closed cycle
operating between two pressures and the open cycle between two specific volumes.
Ideal Closed Vapor Power (Rankine) Cycle Ideal Open Gas Power (Otto) Cycle
P
v
t.
t.
ns
ns
co
co


Temperature (C)
Temperature (C)
qin Wout Wout


P
qin t.
v
t.
ns
ns
co
co
Win  
 qout 
qout

Specific entropy, s Specific entropy, s
30
In an open power cycle,  is an isentropic compression of the fuel-air mixture by the
piston,  is a constant volume heat transfer (addition) during combustion of the fuel,
 is an isentropic expansion as the piston is pushed down the cylinder and  is a
constant-volume heat transfer (rejection) as the exhaust gases are pushed out of the
cylinder.
Elaborate:
co
ns
An Otto engine takes in air from its
t.

s
surroundings so that:
Pressure (MPa)
4.9
co qin
ns
State 1: P1  101 kPa and T1  21 C  294K t.
s Wout
these values can be used in the thermodynamic 2.1

tables15 to obtain the internal energy, 
u1  209.774 kJ/kg and the relative specific
qout
volume, vr1  653.54 of air as an ideal gas. 0.1 
Process : (an isentropic compression)
v2=v3 v1=v4=9v2
If an Otto engine has a compression ratio, r = 9, Specific Volume, v
v1 vr1 v 653.54
then r    9 and vr 2  r1   72.62
v2 vr 2 9 9
hence from the thermodynamic tables14: T2  689.9 K and u2  504.015 kJ/kg.
P2v2 P1v1 V T  T   689.9 

Now,  so P2  P1 1  2   P1r  2   101 9     2133 kPa
T2 T1 V2  T1   T1   294 
Process : (constant volume heat transfer)

If 17g of gasoline (with a Gross Calorific Value, GCV = 47,300 kJ/kg) is injected into the
cylinder and completely combusts, then the heat addition will be
qin  m  GCV  0.017  47300  804.1 kJ
And applying the first law of thermodynamics for the isentropic compression by equating
the heat input to the change in internal energy, noting that we can consider internal
energy rather than enthalpy for the constant volume process,
qin  u3  u2 so u3  qin  u2  804.1  504.015  1308.115 kJ/kg
so from the thermodynamic tables: T3  1610.5 K and vr 3  5.683 .
P3v3 P2v2  T  v   1610.5 

Now,  so P3  P2  3  2   2133    1  4979.26 kPa
T3 T2  T2  v3   689.9 
14
http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tables.html
31
Process : (isentropic expansion)

v4 vr 4
Again r    9 and vr 4  rvr 3  9  5.583  50.247
v3 vr 3
so from the thermodynamic tables: T4  787.83 K and u4  582.45 kJ/kg
Process : (constant-volume heat transfer (rejection))
Again, using the first law of thermodynamics to equate heat transfer to the change in
internal energy
qout  u4  u1  582.45  209.774  372.676 kJ/kg
Finally, wnet  qin  qout  804.1  372.676  431.424 kJ/kg
wnet 431.424
Giving a thermal efficiency, th    0.5365 or 53.6%
qin 804.1
Evaluate:
Pressure (MPa)
co
co ns
Example 7.1: ns t.
t. s
Given that an ideal diesel engine has a cycle
s qin  Wout
as shown, i.e. the combustion process occurs  
at constant pressure rather constant volume
as in a spark ignition engine: qout
0.1 
v2 v1=v4=18v2
Determine the cutoff ratio, rc  V3 V2 i.e. the ratio of theSpecific

volumesVolume, v before
after and
combustion at which the ideal diesel engine must operate if it is to achieve the same
thermal efficiency with the same fuel input as the spark ignition engine represented by
the ideal Otto cycle above but with twice the compression ratio.
Solution
wnet
By definition: th  and th  0.5365 , qin  804.1 kJ/kg
qin
so wnet   th qin  0.5365  804.1  431.424 kJ/kg
And wnet  qin  qout so qout  qin  wnet  804.1  431.424  372.676 kJ/kg
Also, by applying the first law of thermodynamics
32
qout  u4  u1  372.676 kJ/kg and qin  h3  h2  804.1 kJ/kg

(note: qin does not happen at constant volume so it is necessary to use enthalpy, i.e.
h  u  pv )
State 1: remains unchanged, i.e. P1  101 kPa and T1  21 C  294K and from
thermodynamic tables15: u1  209.774 kJ/kg and the relative specific volume,
vr1  653.54
v1 vr1 v 653.54
So for a compression ratio of 18, r    18 and vr 2  r1   36.31
v2 vr 2 18 18
State 2: given vr2 = 36.31 then from the thermodynamic tables: T2  882.6 K and
h2  894.957 kJ/kg.
P2v2 P1v1 T   882.6 

now,  so P2  P1r  2   10118     5457.71 kPa
T2 T1  T1   294 
From qin  h3  h2  804.1 kJ/kg,
h3  qin  h2  804.1  894.957  1699.057 kJ/kg

And from the thermodynamic tables: T3  1548.03 K
P2 v 2 P3 v3 v
Process  occurs at constant pressure, so  becomes T3  3 T2
T2 T3 v2
v3 T3 1548.03
and by definition, the cutoff ratio, rc     1.75 4
v 2 T2 882.6
Example 7.2
The ideal cycle for a gas turbine, known as the Brayton cycle, has a constant pressure
process of heat rejection as shown below. If it were operated over the same temperature
range as the diesel engine in the previous example but with the pressure ratio of the Otto
cycle above, what would be the thermal efficiency?
qin
Pressure (MPa)
co Heat
co ns Exchanger
n st t.  
.s qin s Wout

 Wout Turbine
Compressor
0.1

 qout 
 Heat
Exchanger
condenser
v2 v1=9v2
Specific Volume, v
qout
33
Solution:
State 1: remains unchanged, i.e. P1  101 kPa and T1  21 C  294K and from
thermodynamic tables14: h1  294.17 kJ/kg and the relative pressure, Pr1  1.2917
Process : (compression of gas)
P2
Relative pressure at the compressor outlet, Pr 2  Pr1  9  1.2917  11.6245
P1
Hence from thermodynamics tables: T2  546.91 K and h2  552.22 kJ/kg
Process : (expansion of gas)
The gas is heated to T3  1548.03 K in the heat exchanger
so from thermodynamics tables: h3  1699.07 kJ/kg and Pr 3  687.88
P4 1
and Pr 4  Pr 3     687.88  76.43
P3 9
so from thermodynamics tables: T4  903.38 K and h4  936.72 kJ/kg.
Hence, using the first law of thermodynamics
win  h2  h1  522.22  294.17  228.05 kJ/kg
and wout  h3  h4  1699.07  936.72  762.37 kJ/kg
thus, wnet  wout  win  762.37  228.05  534.32 kJ/kg
And qin  h3  h2  1699.07  522.22  1176.85 kJ/kg
wnet 534.32
Hence by definition, th    0.454 or 45.5%
qin 1176.85
34
THERMODYNAMICS APPLICATIONS
8. Topic: Refrigeration and heat pumps
Engage:
Acquire (purchase or borrow) a portable refrigerator, prepare
yourself a picnic meal and pack it into the refrigerator. Take the
refrigerator to class, open it and start to eat your picnic – the
more elaborate the better; include items that obviously need to
be refrigerated, e.g. fruit juice, yoghourt …
Explore:
Remind the students of the Clausius statement of the second law of thermodynamics: ‘It
is impossible for any system to operate in a thermodynamic cycle and produce no effect
other than the transfer by heat from a cooler to a hotter body’. Point out that a
refrigerator transfers heat from its cold box to the warmer room, i.e. ‘the transfer by heat
from a cooler to a hotter body’ hence there has to be another ‘effect’.
Ask students what impact a refrigerator has on a room. Someone will mention the noise
and you can talk about the compressor doing work, i.e. the ‘effect’ required by the
Clausius statement.
Explain:
Remind them about the Carnot cycle, the most efficient cycle operating between two
temperatures. It consists of two isotherms and two adiabats (processes involving no heat
transfer, only work) as shown in the diagram below.
Tc
Liquid Vapor
 
Temperature (C)
 
Liquid-vapor
Entropy
Discuss the fact that the power cycles in the previous two chapters (lessons) go around
this ideal cycle clockwise where as for a refrigeration cycle it is necessary to go around
anti-clockwise.

At the time of writing you could purchase a Personal Mini Fridge Cooler via www.amazon.com for about $40.
35
In example 7.2 the Brayton gas turbine cycle was introduced. This cycle can be reversed
to produce a refrigerator, i.e.
qin qout
Heat Heat
Exchanger Exchanger
   
Wout Win
Turbine
becomes Turbine
Compressor Compressor
 Heat   Heat 
Exchanger
condenser Exchanger
condenser
qout qin
Brayton Power Cycle Brayton Refrigeration Cycle

Temperature (C)
And is represented on a T-s diagram as
shown. This assumes isentropic
compression from  to  and 
expansion from  to . For a Brayton 
gas power cycle the arrows would be
reversed on the T-s diagram, i.e., the
cycle would run clockwise. 
Entropy
Elaborate:
A Brayton refrigeration cycle operates using gas as a refrigerant just as the power cycle
uses gas as the working fluid. This approach is fine in certain applications such as
aircraft cabin cooling or the liquefaction of air. However, in domestic refrigerators it is
more usual for the refrigerant to change phase as heat is transferred from the cold zone.
Thus, one heat exchanger is known as an evaporator and one as a condenser; in addition
the expansion achieved by the turbine is performed by an expansion valve.
Warm Zone
qout

Condenser
Temperature (C)
  Liquid
Vapor
Win TH 
Expansion
Compressor
Valve
TC 

 
Evaporator
condenser Liquid-vapor
qin
Cold Zone Entropy
36
So consider a refrigerator sitting in a room at 20C if the food compartment is to be

maintained at 4C, using CF3CH2F as the refrigerant which is more commonly known as
R134a then from thermodynamic tables15.
State 1: (at the evaporator exit / compressor entry)
The refrigerant is a saturated vapor, hence for T1  4 C:
h1  hg  249.53 kJ/kg and s1  s g  0.9169 kJ/kg
State 2: (at compressor exit / condenser entry)
following an isoentropic compression, i.e. s 2  s1  0.9169 kJ/kg
The pressure corresponds to saturation pressure at 20C, i.e. p2  0.57160 MPa
And the refrigerant is superheated, so using the tables of superheated R134a16,
h2  259.995 kJ/kg
State 3: (condenser exit/expansion valve entry)
The refrigerant is saturated liquid, hence for T3  20 C
h3  h f  77.26 kJ/kg and s3  s f  0.2924 kJ/kg
State 4: (expansion valve exit / evaporator entry)

The expansion through the valve is a throttling process that involves no change in
enthalpy, i.e. h4  h3  77.26 kJ/kg.
If the design specification is to cool a 75cl bottle of champagne from room temperature
(20C) to 4C in five minutes, then ignoring the glass bottle and assuming champagne to
have the thermodynamical properties of water, the heat to be transferred out of the
champagne is
Qchampagne  mC p T2  T1   0.75  4.1855  4  20  50.226 kJ
Q 50.226
So Q in  champagne   0.16742 kW
time 5  60
Also, using the first law of thermodynamics to equate heat transfer to the change in
enthalpy, Q in  m h1  h4 
qin 0.16742
so m    9.718 10 4 kg/s
h1  h4  249.53  77.26
The compressor work input can be found using the first law of thermodynamics to equate
work done to the increase in enthalpy
15
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPC/TSatR134a.html
16
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPC/superR134a.html
37
 
Win  m h2  h1   9.718  10 4  259.995  249.53  0.01 kW
So by definition, the coefficient of performance is
Q 0.16742
  in   16.46
Win 0.01
Note that the maximum coefficient of performance is given by a Carnot cycle for which
TC 277
 max    17.3
TH  TC 293  277
Of course, in reality, the champagne will not be chilled in 5 minutes because the effect of
the thick glass bottle has been neglected and heat transfer through the wall of the
refrigerator has been ignored. In addition, the refrigerant temperature in the evaporator
will be lower than in the food compartment and its temperature in the condenser will be
higher than the surroundings both of which adversely affect the performance.
Evaluate:
Invite the students to attempt the following examples:
Example 8.1
A soft drinks cooler is designed to chill six cans in 5 minutes from room temperature at
20C to 4C. If the metal of the cans is neglected and losses through the wall are ignored
then find the coefficient of performance if it is assumed that the refrigerant (R134a) is
10C warmer than the surroundings in the condenser and 10C cooler than the cold box
in the evaporator.
Solution:

Temperature (C)
State 1: (at the evaporator exit / compressor entry)

The refrigerant is a saturated vapor, hence for 30

T1  6 C and using the thermodynamic tables17: 20
h1  hg  243.72 kJ/kg and 4

-6
s1  s g  0.9226 kJ/kg  
State 2: (at compressor exit / condenser entry) Entropy
following an isoentropic compression, i.e. s2  s1  0.9226 kJ/kg

The pressure corresponds to saturation pressure at 30C, i.e. p2  0.77006 MPa from the
thermodynamic tables17
And the refrigerant is superheated, so h2  266.538 kJ/kg
State 3: (condenser exit/expansion valve entry)
The refrigerant is saturated liquid, hence for T3  30 C from the thermodynamics tables:
38
h3  h f  91.49 kJ/kg and s3  s f  0.3396 kJ/kg
State 4: (expansion valve exit / evaporator entry)

The expansion through the valve is a throttle process that involves no change in enthalpy,
i.e. h4  h3  91.49 kJ/kg.
For six 0.33litre cans
Qcans  mC p T2  T1   2  4.1855  4  20  133.936 kJ
Q 133.936
So Q in  cans   0.4465 kW
time 5  60
Also, applying the first law of thermodynamics to the evaporator
Q in  m h1  h4  so m 
qin 0.4465
  2.94110 3 kg/s
h1  h4  243.72  91.94
The compressor work input is given by the first law of thermodynamics as
 
Win  m h2  h1   2.941103  266.538  243.72  0.067 kW
So the coefficient of performance is
Q 0.4465
  in   6.655
Win 0.067
Example 8.2
In motels air-conditioning and heating of guest rooms is often provided by a heat pump
fitted beneath the window. In air-conditioning mode it operates on the same cycle as a
refrigerator with the interior heat exchanger operating as the evaporator transferring heat
out of the room at TC to provide cooling and the exterior heat exchanger acting as the
condenser transferring heat into the surroundings at TH. A reversing valve is used to
convert the unit to a heat pump with the exterior unit operating as the evaporator
absorbing heat at TC and the interior heat exchanger operating as a condenser to transfer
heat into the room at TH.
Outline the design of such of unit for your own room and in particular calculate the flow
rate and power required for the compressor.
39
9. Topic: Non-reacting Mixtures
Engage:
Take a CO2 fire extinguisher into class and

discharge it for a short period to produce a cloud
of white gas. This is spectacularly noisy and so
will attract the attention of the students. The unit
responsible for maintaining fire extinguishers in
your institution will almost certainly have one
that they will lend you, or may come to class and
do the demonstration for you.
Explore:
Discuss with the students that air is a mixture of gases including oxygen (typically about
21%), nitrogen (about 79%), and other gases such as argon and carbon dioxide in very
small concentrations. For instance, carbon dioxide is present in the atmosphere at
approaching 385 parts per million or 0.000385%; so by discharging a relatively large
amount of CO2 from the fire extinguisher a local step-change in the concentration is
produced. Of course carbon dioxide is heavier than oxygen so it initially settles on the
floor which would shut off the supply of oxygen from a fire and hence halt the
combustion process.
The carbon dioxide and the other gases in the atmosphere do not react with one another
but are mixed together as a result of the second law of thermodynamics which ensures a
gradual process of dispersion to achieve maximum entropy as in the case of the balloons
in lesson 4. So the carbon dioxide from the fire extinguisher will not stay on the floor but
will gradually disperse and mix with the oxygen and nitrogen in the air.
Explain:
Define the apparent molecular weight, M of such a mixture as simply the sum of the
products of the molar fraction and molecular weight of each component.
j
M   yi M i
i 1
where yi is the molar fraction and Mi the molar weight of the ith component. Also, by
definition, the apparent molecular weight is ratio of the mass of a substance, m to the
number of moles, N i.e. M = m/N.
40
Discuss that in an ideal gas, molecules are sufficiently sparsely populated that the
behavior of one molecule does not influence another. Explain that real gases can closely
approximate this behavior when they are at low pressure or high temperatures relative to
their critical point, such that
PV  ZRT
where Z is the compressibility factor. To obtain the compressibility factor, most charts
are based on the reduced pressure and reduced temperature which are the actual absolute
pressure and temperature values divided by the critical pressure and temperature of fluid
species being studied. A typical compressibility chart can be found at:
http://www.ent.ohiou.edu/~thermo/property_tables/gas/Zfactor.html
For mixtures, Dalton’s law assumes that each component of a gas behaves as an ideal gas
as if it were alone at the temperature and volume of the mixture, i.e.,
k
Pmixture   Pi Tmixture ,Vmixture 
i 1
And there is a corresponding relationship for volume known as Amagat’s law

k
Vmixture   Pi Tmixture , Pmixture 
i 1
Elaborate
The entropy change during the mixing of gases such as occurred after the fire
extinguisher was discharged can be shown to be
S mixing   N i s F i  s I i    Ru  N i ln yi
i i
where Ni is the number of moles of the ith component of the mixture, sI and sF are the
initial and final specific entropies, yi is the mole fraction of the ith component and Ru is
the universal gas constant. This can be used to calculate the minimum energy required to
separate fluids by assuming the mixing is reversible, i.e. that the work required for
separation is equal to the exergy destroyed in mixing
Wmin  X destroyed  T0 S generated   RuT0  ni ln y
i
In order to sequestrate carbon dioxide generated during the combustion process in power
stations, it is necessary to separate it from the exhaust gases. If we assume that the mole
fraction of carbon dioxide is one third and the separation is to be performed at 100C
(after cooling of the gases in a heat exchanger) then
Wmin
 8.314  373  1  ln 0.3  3734 J/mol
n
And since a mole of carbon dioxide has a molecular mass, M = 44 (=12+(162)) and
M  m n so substituting:
41
Wmin
 3734  44  164 kJ/kg
m
You can look up the carbon dioxide production and generating capacity for your local
power plant at http://carma.org/dig/show/energy+plant. Using data for the editor’s local
coal-fired power-station which generates 0.83 kg of CO2 per MJ of power so, assuming
an ideal process, 13.6% (=0.83164/1000) of the energy generated would be required to
sequestrate the carbon dioxide it produces.
Evaluate:
Example 9.1
Determine the minimum daily power required to obtain enough fresh water for your
needs from seawater.
Solution
The minimum energy required is obtained by assuming the mixing of fresh water and sea
water is reversible, i.e. work required for separation is equal to the exergy destroyed on
mixing
Wmin  X destroyed  T0 S generated   RuT0  N i ln y
i
The average salinity of seawater is 3.5% by mass so the mass fraction of salt,
m f salt  0.035 and of water is m f H O  0.965 (=1-0.035); and the molecular masses of
2
salt and water are 58.44 and 18 respectively; so for the mixture
and m f i  i
mmixture mmixture 1 m
M mixture   
N mixture  mi M i m 
 i i mixture
M m  mmixture
1 1 1
M mixture     18.45
 m  
So
 mi M i mmixture  f i Mi 0.035 0.965

58.44 18.0
And the mole fraction of water is given by
yH 2O  m f H O
M mixture 18.45
 0.965   0.989
2 M H 2O 18.0
Now, when the number of moles in a mixture of A and B, N mixture  N A  N B and NA>>1,
the minimum work to separate 1 mol of substance A from a mixture of Nmixture mols is the
difference between minimum work required to separate the initial mixture and the
minimum work required to separate the remaining mixture, i.e., with 1 kmol removed,
which is
Wmin 1kmol   Ru T0  N A ln y A  N B ln y B    RuT0  N A  1 ln y A  N B ln y B    Ru T0 ln y A
42
So for 1kmol of fresh water at 21C, the minimum work will be

Wmin H O   RuT0 ln yH O  RuT0 ln1
2 2

yH 2O  8.314  294  ln 1 0.989  27.2 kJ/kmol
In 2000, the per capita average usage of water in the United States was 1,430 gallons per
day17; this is equivalent to 5.413 m3 or 5415kg which is 301kmols (=5415/18), so to
produce each persons daily requirement by desalination would require
Minimum energy required  27.0  301  8183 kJ [per day per person]
This 2.273kWh (=8183/3600) each day for every person or 0.42kWh/m3 (=2.273/5.413)
which compares to 3 to 28 kWh/m3 for typical (non-ideal) industrial plants18.
Example 9.2
Consider landfill gas at 30C being pumped into a tanker truck with a volume capacity of
25m3 and design pressure of 1.77MPa. If a molar analysis of the landfill gas has shown it
to be 52% methane (M=16); 46% carbon dioxide (M=44); and 2% hydrogen (M=2) then
calculate the apparent molecular weight, M.
Solution:
j
M   yi M i  0.52  16   0.46  44   0.02  2   28.6 kg/kmol
i 1
where yi is the mole fraction and Mi the molar weight of the ith component. If we assume
the mixture to be an ideal gas then
N mixture 
PV mixture 
1.77 10  25  17280 mols
6
RuTmixture 8.314  308

And by definition the apparent molecular weight is the ratio of the mass of the mixture to
the number of moles, so the mass of the mixture in the tanker is
m  MN  28.6  17.280  494 kg
17
http://ga.water.usgs.gov/edu/wateruse2000.html
18
Encyclopedia of Desalination and Water Resources (DESWARE), UNESCO Encyclopedia of Life
Support Systems (EOLSS), www.desware.net/desa4.aspx
43
10. Topic: Psychrometric applications
Engage:
Take a bottle of water into class. Make sure that the bottle is
really cold so that it will ‘sweat’ in class. Place it on a napkin
then show it to the students so they can see the ring mark.
If you wear glasses, take them off and breathe on the lenses then
invite all of the students in the class wearing glasses to do the
same and show the results to those who are not wearing glasses.
Also borrow a wet and dry bulb thermometer from the lab.,
preferably in the form of a sling psychrometer.
Explore:
Ask students working in pairs to discuss the connection between the sweating water
bottle, the steamed up glasses, and the early morning dew on the grass. Invite a couple of
pairs to provide their thoughts on the issue.
Explain:
The air in the room can be considered as a
Temperature (C)
t
tan
Vapor
mixture of air and water vapor. The mixture can Liquid
ns
co
v
be considered to be made up of ideal gases so the T1
room temperature
p
pressure, P, is the sum of the partial pressures of 

cold surface temperature 
the air, Pa, and water vapor, Pv. Tdp
sa
tu
ra
In the room the partial pressures are constant and

te
Liquid-vapor
d
va
p
the water is completely vapor, i.e. it can be

or
represented by  in the T-s graph. The air Entropy sg

adjacent to the bottle is cooled at constant vapor
pressure until it reaches the saturation line, i.e. Tsat at , which is also known as the dew-
point and liquid water is formed.
Your breathe is at about 35C and 95% humidity19 i.e. a mixture of water vapor and in
the ratio of masses of 0.95 to 0.05. When this mixture meets the cold surface of the
glasses it is cooled to below the dew-point and the water vapor condenses.
At night, thin, exposed objects radiate their heat at a faster rate than it can be replaced
and so they cool relative to the environment. The air adjacent to them also cools and if it
cools below its dew-point then droplets of liquid water will form. If this process occurs
is followed by sub-zero temperatures at night, then the dew freezes to form a frost.
19
http://www.sciencebits.com/exhalecondense
44
Elaborate:
Spin the sling psychrometer and obtain wet and dry bulb temperatures for the room.
When the wet bulb thermometer is spun in the unsaturated air some water evaporates
from the wet bulb. This process can be analyzed by considering the motion of the air
relative to the bulb; the air goes from state  before passing across the wet bulb to state
 after passing across the wet bulb.
mv PvV RvT Pv Rv
By definition the specific humidity is    
ma PaV RaT Pa Ra
0.622 Pv
Substituting for P  Pa  Pv and given that Rv Ra  0.622 gives  
P  Pv
So for a wet bulb temperature of 15C (= T2) the vapor is saturated and the saturation
pressure can be obtained in the thermodynamic tables15 as 1.7051 kPa and
0.622 Pv 0.622  1.7051  10 3
2    0.01068
P  Pv 101  1.7051  10 3
Mass flow rates:
The mass flow rate of the dry air remains constant, i.e., m a1  m a2  m a
The mass flow rate of the water vapor increases by the amount which evaporates from the
wet b, m e , i.e. m v1  m e  m v2
yields m e  m a 2  1 
mv
So m e  m v 2  m v1 and substituting  
ma
1st law of thermodynamics applied to the process with no heat transfer and no work is:
E in  E out or m a ha1  m v1 hv1  m e he  m a ha2  m v2 hv2
Now substituting for m e , dividing by m a and rearranging yields for specific humidity
prior to passing over the wet bulb
1 

ha2  ha1   2 hv2  he 
hv1  he
If the air-vapor mixture is an ideal gas then h  fnT  and

ha2  ha1  C p T2  T1 
Note that hv1 and hv2 are the enthalpy of saturated vapor, i.e. hg at T1 and T2 respectively,
 
and he is the enthalpy of saturated liquid at T2, i.e. h f2 so hv2  he  h fg 2 then
C p T2  T1    2 h fg 2
1 
hg1  h f 2
45
Again from the thermodynamic tables at T2 = 15C, h fg 2  2465.91 kJ/kg and

h f 2  62.99 kJ/kg; and for a dry bulb temperature, T1  20 C then hg1  2538.1 kJ/kg so
specific humidity in the room is
1.00515  20  0.01068  2465.91
1   0.00861
2538.1  62.99
0.622 Pv P 0.00861 101
Now, also   so Pv  and Pv1   1.379 kPa
P  Pv 0.622   0.622  0.00861
Hence the dew-point at this pressure from the Schematic of
thermodynamic tables is Tsat  p 1.379 kPa  11.57 C Psychrometric Chart
The relative humidity,  is defined as the ratio of the
%
mass of water vapor in air to the maximum mass of
59
=
water vapor that could be held at the same temperature,
mg, i.e.,  =0.00861
Tdp 11.5C
T=
mv P V Rv T P 2 15
  v  v C
m g Pg V R g T Pg
T1=20C
where Pg  Psat at the considered temperature. So for the relative humidity of the room
Pv1 1.379
1    0.590 or 59%
Psat 1 2.339
The same calculation can be performed on a psychrometric chart20 as shown above.
Evaluate:
Invite the students to attempt the following examples:
Example 10.1
In the morning when you get into your car which has been standing out overnight in
temperatures at about freezing, the windshield starts to mist up from your breathe.
Determine the temperature to which the screen must be raised by the screen heater to
prevent the misting.
Solution:
You exhale at about 34C and 95% relative humidity, and from the thermodynamics
tables15 Psat  5.3516 kPa at T  34 C
So Pv  Psat  0.95  5.3516  5.08 kPa
And from the thermodynamics tables, Tsat  33.1 C for 5.08kPa which is the dew-point
for the air breathed out so the windshield must be warmer than 33.1C to prevent your
20
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesMA/psychro.html
46
breathe condensing on it. However your breathe will mix with the air in the vehicle and
after a few minutes the average temperature in the car might have risen from about 0C to
16C depending on the size of the car and the number of passengers. At the same time
the relative humidity might have halved to around 50%. A psychometric chart can be
used to estimate the dew-point in these conditions, i.e. Tdp = 5C so the surface of the
wind shield would need to be at least 5C to prevent misting.
Example 10.2
After leaving the condenser of a power station, water enters the top of a cooling tower as
a spray and falls over baffles to the bottom where it is recirculated to the power plant. At
the same time air enters the tower at the bottom and is sucked up by a fan and billows out
of the top generating huge white clouds in certain weather conditions.
The water enters the tower at 35C and 120kg/s and is cooled to 25C by the air that
enters at 20C, 50% relative humidity and atmospheric pressure. If the air leaves
saturated at 30C, calculate required the flow rate of the air.
Solution:
From the thermodynamic tables for saturated water15
h f T 35  h3  146.68 kJ/kg, h f T  25  h 4  104 .89 kJ/kg Air
30C
2 =100%
From a psychrometric chart21 at T1=20C and 1  50 % 1 atm
h1  39.5 kJ/kg dry air,

Water  
1  0.00725 kg H20/kg dry air, 35C
100 kg/s
v1  0.84 m3/kg dry air

And using T2  30 C and 1  100 %
h2  100.0 kJ/kg
Air
20C  Water
1 =50% 25C
 2  0.0273 kg H20/kg dry air 1 atm 100 kg/s

Mass balance for the dry air m a1  m a2  m a
Mass balance for the water m 3  m a 1  m 4  m a  2 or m 3  m 4  m a ( 2  1 )

Energy balance from the first law of thermodynamics
 m h   m h
in out
so m 3 h3  m a h1  m 4 h4  m a h2
So combining the above two

m 3 h3  h4  120146.68  104.89 
m a    85.87 kg/s
h2  h1   h4  2  1  100  39.5  104.89  0.0273  0.00725
47
THERMODYNAMICS OF CHEMICAL TRANSFORMATIONS
11. Topic: Reacting mixtures and combustion
Engage:
Take a cake with a candle, a large glass jar and stop watch into
class. Light the candle. Invite the students to make sealed
bids on how long it will take the candle to be extinguished
when it is covered with the jar. The prize for the nearest
correct answer is the cake.
A cup cake would be fine so that you can cover the cake and
candle with the jar. Alternatively, if you are feeling generous,
use a larger cake that can support the weight of the glass jar
when you put it over the candle; and award a slice to the
nearest answers.
Explore:
Before placing the jar over the candle, discuss the process that is occurring as the candle
burns. The material of the candle is mainly solid paraffin, typically C20H42, i.e. with a
generic chemical formula of CnH2n+2 which is the same as methane, CH4 or octane, C8H18
which is the main component of gasoline; so not surprisingly it is very combustible.
Combustion is a chemical reaction between a fuel (paraffin) and an oxidant (oxygen in
the air) which results in a set of products (carbon dioxide and water) and heat
heat
C20H42 + 30.5O2  20CO2 + 21H2O
If sufficient heat is generated, then the products emit light generating the flame observed
on the candle.
Invite two students to join you in dowsing the candle; give one the stop-watch and the
other the glass jar.
Explain:
When the candle is burning in the room, there is an excess of oxygen available for
combustion. This is the state when the jar is initially placed over the candle. When the
candle goes out there is no oxygen left to react with the paraffin so combustion is
arrested. There is a point somewhere in between when there is exactly the right amount
of oxygen; this is known as the ‘theoretical amount of air’.
It is usual practice to idealize air to be 21% oxygen and 79% nitrogen on a molar basis
and ignoring the smaller percentages of other gases present, such as argon and carbon
48
dioxide which are less than 1%. So for combustion in air the chemical reaction can be
written as
heat
C20H42 + a(O2 + [0.79/0.21] N2)  bCO2 + cH2O + dN2
And the stoichiometric coefficients: a, b, c and d can be found by applying the law of
conservation of mass to carbon so b  20 ; to hydrogen so c  21 ; to oxygen so
2a  2b  c and a  30.5 ; and finally to nitrogen so d  3.76a  114.68 . Thus
heat
C20H42 + 30.5(O2 + 3.76N2)  20CO2 + 21H2O + 114.68N2
So the number of moles of air required for complete combustion of paraffin is 145.18
(=30.5+30.53.76) moles of air per mole of fuel – the theoretical amount of air. It can be
turned into an air-fuel mass ratio by multiplying it by the ratio of the molecular masses of
air (28.97) and paraffin, (324 [=2012+422]), i.e.,
28.97
Air-fuel mass ratio  145.18   12.98
324
As the candle burns inside the jar, the oxygen is used up until there is insufficient to
allow complete combustion of the paraffin and so not all of the carbon is converted into
carbon dioxide resulting in the black deposit on the inside of the glass, i.e., soot.
Elaborate:
An energy balance can be used to evaluate the heat generated during the
reaction/combustion process. If it is assumed that it is paraffin vapor evaporating from
the wick which is reacting with the surrounding air, then this allows a control volume to
be considered in which the reactants (paraffin vapor and air) are entering and the products
of combustion (carbon dioxide, water and nitrogen) are leaving. Thus for the control
volume applying the first law of thermodynamics to equate the change in enthalpy to the
net heat transfer and work done
Q W
   no h f  h o  ni h f  h i
n F n F P R
where n F is the molar flow rate of the fuel, the subscripts i and o refer to the inlet and
outlet gases respectively, and P and R to the products and reactants respectively. h f is the
enthalpy of formation which is the energy released or absorbed when the compound is
formed from its elements at the standard reference state (25C, 1 atm) and h is the
change in enthalpy relative to the standard reference state.
So work, W is zero for the candle and given
heat
C20H42 + 30.5O2 + 114.68N2  20CO2 + 21H2O + 114.68N2
the energy balance becomes
49
Q
 [ 20h f  h CO  21h f  h H O  114.68h f  h N ]
n F 2 2 2
-[ h f  h C  30.5h f  h O  114.68h f  h N ]
20 H 42 2 2
The enthalpy of formation of paraffin (C20H42) is -456,000kJ/kmol and treating it as an

ideal gas such that h  C p T and C p  2.13 kJ/kg K. For carbon dioxide, oxygen,
nitrogen and water the enthalpy of formation in can be found in thermodynamic tables21.
i.e. h f CO  -393,520 kJ/kgK; h f H O  -241,820 kJ/kgK; hf O  hf H  hf N  0 kJ/kgK
2 2 2 2 2
Now for the reactants which enter the combustion control volume at 400K:
hR  h f  C p T C  30.5h f  h O  114.68h f  h N
20 H 42 2 2
hR   456000  2.13  400  298C20H 42  30.5  0  3029O2  114680  2971N2
hR  22,684 kJ/kmol
where h values are obtained from the ideal gas data for each gas in the thermodynamic
tables22.
Similarly for the products given a temperature in the candle of 1400K:
hP  20h f  h CO  21h f  h H O  114.68h f  h N
2 2 2
hP  20   393520  55907 CO2  21   241829  43447 H 2O  114.68  34936N 2

hP  6,911,821 kJ/kmol
Hence, from the first law of thermodynamics, remembering W  0
Q
 6911821  (22684)  6889 MJ/kmol K (C20H42)
n F
So if the candle (molecular mass = 324) burns at 1g/min (1.66610-5 kg/s) or
5.1410-8kmols/s (=1.66610-5/324), then the heat transfer is 354W
(=5.1410-8  6889106).
Evaluate:
Example 11.1
What flow rate of natural gas is required to raise two liters of water to boiling point in
five minutes in order to cook pasta? You may assume that the gas ring is at a steady
temperature of about 450K and the flame temperature is 1600K.
21
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesComb/formation.html
22
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesIG/igN2.html
50
Solution:
The first law of thermodynamics can be used to equate the energy to heat the pan and
water to the heat supplied by the gas flame.
Energy input required for water
 mC p T  2  4.18  100  21  660.44 kJ
A stainless steel pan large enough to cook pasta in this quantity of water would have a
mass of about 1.8kg,
so energy input required for the pan
 mC p T  1.8  5.2  100  21  739.44 kJ
And the heat transfer rate,
Q  660.44  739.44 5  60   4.667 kW
ignoring the heat losses from the pan.
Now, natural gas is mainly methane so we can approximate the combustion process to
heat
CH4 + 2O2 + 7.58N2  CO2 + 2H2O + 7.58N2
So applying an energy balance based on the first law of thermodynamics
Q
 [ h f  h CO  2h f  h H O  7.58h f  h N ]
n F 2 2 2
-[ h f  h CH  2h f  h O  7.58h f  h N ]

4 2 2
The enthalpy of formation of paraffin (C20H42) is -74,850kJ/kmol (from the

thermodynamic tables22) and treating it as an ideal gas such that h  c p T and
C p  2.2 kJ/kg K.
Also h f CO  -393,520 kJ/kgK; h f H O  -241,820 kJ/kgK; hf O  hf H  hf N  0 kJ/kgK
2 2 2 2 2
Now for the reactants which enter the combustion control volume at 450K
hR  h f  C p T CH  2h f  h O  7.58h f  h N
4 2 2
hR   74850  2.2450  298CH 4  24546O2  7.584436N2  31799 kJ/kmol

Similarly for the products given a flame temperature of 1600K
hP  h f  h CO  2h f  h H O  7.58h f  h N
2 2 2
hP   393520  67580CO2  2 241829  52844H 2O  7.5841902N2  386293

Hence, applying the first law of thermodynamics to the flame in a control volume with
W  0
51
Q combustion
 386293  (31799)  354494 kJ/kmol K (C20H42)
n F
Now applying the first law of thermodynamics to heating the water and pan
 Q 
Q required  Q combustion     n F
 n F 
Q required 4.667
so n F    1.316  105 kmol/s
Q  354494
 n F 
And for methane, M  16 , so m  Mn F  16 1.316 10 5  2.106 10 4 kg/s or 0.294
liters/s
Example 11.2
When a car is cruising on the highway at 70mph, its fuel consumption is 35mpg and the
engine output is 60hp, estimate the rate of heat transfer from the combustion process if
the fuel is assumed to be liquid octane and the temperature in the exhaust is about 900K.
Assume the ambient temperature is 25C.
Solution:
At 70mph the car will use 2 gallons/hour (= 0.007570m3/hr =2.110-6m3/s)
And, the density of octane is 703kg/m3 so the mass flow rate,
m  703 2.1106  1.48103 kg/s
Octane is C8H18 with a molecular mass, M  132 ,
m 1.48  103
so by definition n F    1.119 10 5 kmol/s
M 132
Assuming complete combustion
heat
C8H18 + 12.5O2 + 47N2  8CO2 + 9H2O + 47N2
And applying the 1st law of thermodynamics, the energy balance is
Q W
  [ 8h f  h CO  9h f  h H O  47h f  h N ]
n F n F 2 2 2
-[ h f  h C H  12.5h f  h O  47h f  h N ]
8 18 2 2
The enthalpy of formation of liquid octane is -249,950kJ/kmol and C p  2.23 kJ/kg K

(from the thermodynamic tables22).
Also h f CO  -393,520 kJ/kgK; h f H O  -241,820 kJ/kgK; hf O  hf H  hf N  0 kJ/kgK
2 2 2 2 2
52
Now for the reactants which enter the combustion control volume at 298K
hR  h f  C p T C H  12.5h f  h O  47h f  h N
8 18 2 2
hR   249950C8H18  20  0O2  7.580  0N2  249950 kJ/kmol
Similarly for the products given a flame temperature of 900K

hP  8h f  h CO  9h f  h H O  47h f  h N
2 2 2
hP  8 393520  28041CO2  9 241829  21924H 2O  4718221N2  4046590

So, with W  60 hp  60  745.699 87  44742 W the energy balance becomes
Q W
  hP  hR
n F n F
and Q  n F hP  hR   W  1.119  105  4046590   249950  44.742  2.26 kW
53
NOTES
54
Sophomore Thermo Course: Suggested exemplars within lesson plans
NOTES FOR INSTRUCTORS ON EXAMPLE APPLICATIONS

Prepared as part of the NSF-supported project ( #0431756) entitled:
“Enhancing
Enhancing Diversity in the Undergraduate Mechanical Engineering
Population through Curriculum Change”
Edited by Eann A Patterson, University of Liverpool

Examples in Thermodynamics

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Examples in Thermodynamics

Hochgeladen von

Copyright:

Verfügbare Formate

Reall Life

Lesson plans and solutions

Eann A Patterson, Editor

Lesson plans and solutions

Real Life Examples in Thermodynamics

Copyright © 2010, 2011 Eann A Patterson (editor)

This work is licensed under the Creative Commons Attribution-NonCommercial-

Bounded printed copies can be purchased on-line at www.engineeringexamples.org

This edition is distributed free of charge by the ENGAGE project

Lesson plans and solutions

Suggested exemplars within lesson plans for Sophomore level courses in

Eann A Patterson, Editor

The University of Liverpool

The comments on an early draft made by Robert D. Handscombe of Handscombe

FIRST LAW CONCEPTS

1. Topic: Systems, properties, & pure substances

fg line (x = 0.05, T = 100.5913C), the specific Liquid

and this expansion is probably sufficient to drive it 1

up the tube to fall onto the coffee. Specific volume

FIRST LAW CONCEPTS

2. Topic: First law of thermodynamics

Rate of change Net rate of Net rate of

The heat generation in the room is given by

where the coefficient of convective heat transfer6, hc is typically 12 W/(m2.K) and A is

Consequently, to maintain steady state conditions

 Q  0  Q convection  Q generation  Q aircon

So Q aircon  2970  8000  5030 W

SECOND LAW CONCEPTS

3. Topic: Second law of thermodynamics

then Win  Q out  hc ATroom  Tenvironment 

Explore (part II):

Explain (part II):

The coefficient of performance is defined as

SECOND LAW CONCEPTS

350 P2 =50.5 kPa

The entropy generated will be S generated  S mixture  ( S milk  S coffee )

for mixture, S mixture  mmixture sT 72.3  0.028349  10  0.9828  0.2786 kJ

Text  28 F  2.22 C  270.78 K

and Q out  hc ATroom  Tenvironment 

SECOND LAW CONCEPTS

Text  28 F  2.22 C  270.78 K

and Q out  hc ATroom  Tenvironment 

P1V 35  106  0.175

6. Topic: Vapor Power Cycles

boiler P1 =2800 kPa

 350 P2 =50.5 kPa

State 2: P1  2800 kPa and s2  s1  1.0941 kJ/kg/C

State 3: P3  P2  2800 kPa and T3  350 C so

h3  3121.8607 kJ/kg and s3  6.7842 kJ/kg/C

boiler P1 =2800 kPa

State 4: P1  P4  50.5 kPa and s4  s3  6.7842 kJ/kg/C which corresponds to a saturated

from the steam tables h f  341.6059 kJ/kg and h fg  2304.7903 kJ/kg

so h4  h f  xh fg  341.6059  0.8758  2304.7903  2360.0888 kJ/kg

Work out from turbine, p =10kPa

7. Topic: Gas Power Cycles

qin Wout Wout

Specific entropy, s Specific entropy, s

P2v2 P1v1 V T  T   689.9 

Process : (constant volume heat transfer)

P3v3 P2v2  T  v   1610.5 

Process : (isentropic expansion)

Determine the cutoff ratio, rc  V3 V2 i.e. the ratio of theSpecific

qout  u4  u1  372.676 kJ/kg and qin  h3  h2  804.1 kJ/kg

P2v2 P1v1 T   882.6 