Real Life Examples in Thermodynamics: Lesson Plans and Solutions

Real Life

Examples in
Thermodynamics

Lesson plans and solutions

Eann A Patterson, Editor

Real Life Examples in Thermodynamics
CONTENTS
page no.
Introduction and acknowledgements 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
4
Real Life Examples in Thermodynamics
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.
Acknowledgements
Many of these examples have arisen through lively discussion in the consortium
supported by the NSF grant (#0431756) on “Enhancing Diversity in the Undergraduate
Mechanical Engineering Population through Curriculum Change” and the input of these
colleagues is cheerfully acknowledged as is the support of National Science Foundation.
The comments on an early draft made by Robert D. Handscombe of Handscombe

Associates are gratefully acknowledged.
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
5E Lesson Plan No.T1
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.
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
mliquid  mvapor
Even after moving only 5% of the distance along
the fg line (x = 0.05, T = 100.5913C), the
specific volume will have increased from 0.0010
to 0.0830 m3/kg, according to the thermodynamic
steam tables and this expansion is probably
sufficient to drive it up the tube to fall onto the
coffee.
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).
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!
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)
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

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.
 
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  2944  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 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 106
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.
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
tscreen 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 
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/hr 4 or 529W (=
4554187/3600). So for x people in the class we just generated heat equal to about x times the
power consumption of the fan, but it did not turn – why? Ask the students in pairs to discuss this
conundrum.
4
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.
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.
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
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.
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 the 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.
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

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.
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 tables4) 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.
s  0.308 103 
W  exp  exp  23 
k 1.380658 10 
4
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPG/pgConsts.html
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.
For state 2i:

P2i  P2  50.5 kPa and s2i  s1  6.7842 kJ/kg/C from which the quality must be determined:
s2i  s f 6.7842  1.0941
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
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  mcp T
so the temperature, T3 after mixing without heat loss to the surroundings will be
T3 
mmilkTmilk  mcoffeeTcoffee

1 276  9  353  345.3 K (= 72.3C)
mmilk  mcoffee 10
The entropy generated will be S generated  Smixture  (Smilk  Scoffee )
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, Smilk  mmilk sT 3  0.028349  0.0459  1.3012 103 kJ
for coffee before mixing, Scoffee  mcoffeesT 80  0.028349  9 1.0752  0.2743 kJ
for mixture, Smixture  mmixturesT 72.3  0.028349 10  0.9828  0.2786 kJ

hence the entropy generated is
S generated  Smixture  (Smilk  Scoffee )  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
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 environment4. 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 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
4
Schrödinger, Erwin, What is life? Cambridge University Press, Cambridge, 1944.
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
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 engine 5, 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.
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  S0   KE  PE
In this case there is no change in internal energy, kinetic or potential energy of the air, so
X1  m1P0 v1  v0   T0 s1  s0 
5
http://www.fueleconomy.gov/FEG/atv.shtml
 RT RT  P 
And using the ideal gas equation m1P0 v1  v0   m1P0  1  0   m1RT0  0  1 because
 P1 P0   P1 
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
P P  1  105 3.5  107 

Hence X 1  m1 RT0  0  1  ln 1   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/100km6 so 5.58 litres would take you 155 km (= [5.58 / 3.6]  100).
(a) 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).
6
http://www.vcacarfueldata.org.uk/search/vehicleDetails.asp?id=22655
POWER CYCLES
6. Topic: Vapour 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 Dictionary4.
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.
4
www.merriam-webster.com/dictionary/
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.
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
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.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.
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.
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,
Power 216
Win    18 kJ/kg
Flow Rate 12
Work out from turbine,
Power 14400
Wout    1200 kJ/kg
Flow Rate 12
Net. Work,
Wnet  Wout  Win  1200  18  1182 kJ/kg
State 3 (input to turbine): P3  15000 kPa, 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
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’4 or try:
www.animatedengines.com/otto.shtml or auto.howstuffworks.com/engine1.htm
The
Department of Mechanical Engineering at Michigan State University loaned one its cut-away engines to the Art Program at
Okemos High School, Michigan to use as inspiration for a series of paintings. Two of the paintings, by Christine Budd (left) and
Ed Emmerich (right), are reproduced above; all of the paintings are on display at MSU.
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.
4
http://www.youtube.com/watch?v=OXd1PlGur8M&NR=1&feature=fvwp
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:
An Otto engine takes in air from its surroundings
so that:
State 1: P1  101kPa and T1  21 C  294K these
values can be used in the thermodynamic tables5 to
obtain the internal energy, u1  209.774 kJ/kg and
the relative specific volume, vr1  653.54 of air as
an ideal gas.
Process : (an isentropic compression)
If an Otto engine has a compression ratio, r = 9,
v1 vr1
then r  9 and
v2 vr 2
vr1 653.54
vr 2    72.62
9 9
hence from the thermodynamic tables6: 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)
5
http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tables.html
6
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 
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:
Example 7.1
Given that an ideal diesel engine has a cycle as shown,
i.e. the combustion process occurs at constant pressure
rather constant volume as in a spark ignition engine:
Determine the cutoff ratio, rc  V3 V2 i.e. the ratio of
the volumes after and before 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
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  101kPa 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
v2 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?
Solution:
State 1: remains unchanged, i.e. P1  101kPa 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
8. Topic: Refrigeration and heat pumps
Engage:
Acquire (purchase4 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.
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.
4
At the time of writing you could purchase a Personal Mini Fridge Cooler via www.amazon.com for about $40.
In example 7.2 the Brayton gas turbine cycle was introduced. This cycle can be reversed to
produce a refrigerator, i.e.
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.
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.
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 tables5.
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  sg  0.9169 kJ/kg
5
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPC/TSatR134a.html
State 2: (at compressor exit / condenser entry)

following an isoentropic compression, i.e. s2  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 R134a6, 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  mCp 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,
 h1  h4 
Q in  m
6
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPC/superR134a.html
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
 
 h2  h1   9.718 104  259.995  249.53  0.01 kW
Win  m
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:
State 1: (at the evaporator exit / compressor entry)

Temperature (C)
The refrigerant is a saturated vapor, hence for T1  6

C and using the thermodynamic tables7: 30

20
h1  hg  243.72 kJ/kg and s1  sg  0.9226 kJ/kg
State 2: (at compressor exit / condenser entry) 4
-6
following an isoentropic compression, i.e.  
s2  s1  0.9226 kJ/kg Entropy
7
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesPC/superR134a.html
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:
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
 h1  h4  so m 
qin 0.4465
Q in  m   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
 
 h2  h1   2.941103  266.538  243.72  0.067 kW
Win  m
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.
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.
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 sF i  sI 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:
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 salt and water are 58.44
2
and 18 respectively; so for the mixture
and m f i  i
mmixture mmixture 1 m
M mixture   
N mixture  mi M i  mi M i mmixture  mmixture
1 1 1
M mixture     18.45
So

 mi M i mmixture   m f i M i 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  RuT0 N A ln y A  N B ln yB   RuT0 N A  1 ln y A  N B ln yB   RuT0 ln y A
So for 1kmol of fresh water at 21C, the minimum work will be
Wmin H O  RuT0 ln yH O  RuT0 ln 1 yH O   8.314  294  ln1 0.989  27.2 kJ/kmol
2 2 2
In 2000, the per capita average usage of water in the United States was 1,430 gallons per day4;
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 plants5.
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 106  25  17280 mols
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
4
http://ga.water.usgs.gov/edu/wateruse2000.html
5
Encyclopedia of Desalination and Water Resources (DESWARE), UNESCO Encyclopedia of Life Support
Systems (EOLSS), www.desware.net/desa4.aspx
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 mixture of
air and water vapor. The mixture can be considered to
be made up of ideal gases so the pressure, P, is the
sum of the partial pressures of the air, Pa, and water
vapor, Pv.
In the room the partial pressures are constant and the
water is completely vapor, i.e. it can be represented by
 in the T-s graph. The air 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% humidity4 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.
4
http://www.sciencebits.com/exhalecondense
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:
 a1  m
The mass flow rate of the dry air remains constant, i.e., m  a2  m
a
The mass flow rate of the water vapor increases by the amount which evaporates from the wet b,
 v1  m
m e , i.e. m e  m
 v2
 a 2  1 
mv
So e  m
m  v1 and substituting  
 v2  m e  m
yields m
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

ha2  ha1   2 hv2  he 
1 
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. h g at T1 and T2 respectively, and he
 
is the enthalpy of saturated liquid at T2, i.e. h f2 so hv2  he  h fg2 then
C p T2  T1    2 h fg 2
1 
hg1  h f 2
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 thermodynamic tables is Tsat  p 1.379kPa  11.57 C
The relative humidity,  is defined as the ratio of the mass of

water vapor in air to the maximum mass of water vapor that could
be held at the same temperature, mg, i.e.,
mv P V RvT P
  v  v
m g PgV Rg T Pg
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 chart5 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 breathe
condensing on it. However your breathe will mix with the air in the vehicle and after a few
5
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesMA/psychro.html
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 water6 Air
h f T 35  h3  146.68 kJ/kg, h f T 25  h4  104.89 kJ/kg

30C
2 =100%
1 atm
From a psychrometric chart21 at T1=20C and 1  50 %

Water  
h1  39.5 kJ/kg dry air, 35C
100 kg/s
1  0.00725 kg H20/kg dry air,
v1  0.84 m3/kg dry air
And using T2  30 C and 1  100 % Air

20C Water
1 =50%
h2  100.0 kJ/kg
25C
1 atm 100 kg/s
2  0.0273 kg H20/kg dry air 
 a1  m
Mass balance for the dry air m  a2  m
a
Mass balance for the water m  a1  m

3  m  a2 or m
4 m 3 m  a (2  1 )
4  m
Energy balance from the first law of thermodynamics
 m h   m h
in out
 3 h3  m
so 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
6
THERMODYNAMICS OF CHEMICAL TRANSFORMATIONS
10. Topic: Combustion & reaction mixtures
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 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
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 ]

20H 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 tables4.
i.e. h f CO  -393,520 kJ/kgK; h f H O  -241,820 kJ/kgK; h f O  h f H  h f 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
20H 42 2 2
hR   456000  2.13  400  298C20H42  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 tables5.
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N2

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.
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
4
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesComb/formation.html
5
e.g. http://v5.sdsu.edu/testhome/Test/solve/basics/tables/tablesIG/igN2.html
 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; h f O  h f H  h f 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CH4  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H2O  7.5841902N2  386293 Hence,

applying the first law of thermodynamics to the flame in a control volume with W  0
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 
  MnF  16 1.316 105  2.106 104 kg/s or 0.294 liters/s

And for methane, M  16 , so m
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; h f O  h f H  h f N  0 kJ/kgK
2 2 2 2 2
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H2O  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

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 Diversity in the Undergraduate Mechanical Engineering
Population through Curriculum Change”
Edited by Eann A Patterson, Michigan State University
ISBN: 978-0-9842142

Real Life Examples in Thermodynamics: Lesson Plans and Solutions

Uploaded by

Copyright:

Available Formats

Real Life Examples in Thermodynamics: Lesson Plans and Solutions

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Real Life Examples in Thermodynamics: Lesson Plans and Solutions

Uploaded by

Copyright:

Available Formats

Real Life

Lesson plans and solutions

Eann A Patterson, Editor

Introduction and acknowledgements 5

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

FIRST LAW CONCEPTS

1. Topic: Systems, properties, & pure substances

FIRST LAW CONCEPTS

2. Topic: First law of thermodynamics

Rate of change Net rate of Net rate of

 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

For state 2i:

where h1 and h2 can be found in the steam tables i.e.

The entropy generated will be S generated  Smixture  (Smilk  Scoffee )

for mixture, Smixture  mmixturesT 72.3  0.028349 10  0.9828  0.2786 kJ

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 

P P  1  105 3.5  107 

6. Topic: Vapour power cycles

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

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

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

And for the boiler, qin  h3  h2  3579.7767  209.8324  3369.94 kJ/kg

7. Topic: Gas power cycles

P2v2 P1v1 V T  T   689.9 

P3v3 P2v2  T  v   1610.5 

h3  qin  h2  804.1  894.957  1699.057 kJ/kg

so from thermodynamics tables: h3  1699.07 kJ/kg and Pr 3  687.88

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

8. Topic: Refrigeration and heat pumps

And is represented on a T-s diagram as shown. This assumes

State 2: (at compressor exit / condenser entry)

h3  h f  77.26 kJ/kg and s3  s f  0.2924 kJ/kg

The refrigerant is a saturated vapor, hence for T1  6

h3  h f  91.49 kJ/kg and s3  s f  0.3396 kJ/kg

9. Topic: Non-reacting mixtures

And there is a corresponding relationship for volume known as Amagat’s law

and 18 respectively; so for the mixture

10. Topic: Psychrometric applications

If the air-vapor mixture is an ideal gas then h  fnT  and

The relative humidity,  is defined as the ratio of the mass of

where Pg  Psat at the considered temperature. So for the relative

So Pv  Psat  0.95  5.3516  5.08 kPa

h f T 35  h3  146.68 kJ/kg, h f T 25  h4  104.89 kJ/kg

From a psychrometric chart21 at T1=20C and 1  50 %