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2.3 Thermodynamics

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"'\ I, Module 2,3 Thermodynamics 3-1

'~ Use and/or disclosure is
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Copyright Notice ,, . J

© Copyright. All worldwide rights reserved. No part of this publication may be reproduced,
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Knowledge Levels - Category A, 81, 82 and C Aircraft Maintenance

Licence
Basic knowledge for categories A, B1 and B2 are indicated by the allocation of knowledge levels indicators (1,2 or
3) against each applicable subject. Category C applicants must meet either the category B 1 or the category B2
basic knowledge levels.
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The knowledge level indicators are defined as follows:

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LEVEL 1 \ i
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• A familiarisation with the principal elements of the subject.

Objectives:
• The applicant should be familiar with the basic elements of the subject.
• The applicant should be able to give a simple description of the whole subject, using common words and
examples.
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• The applicant should be able to use typical terms.

LEVEL 2
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• A general knowledge of the theoretical and practical aspects of the subject.
• An ability to apply that knowledge.
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Objectives:
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• The applicant should be able to understand the theoretical fundamentals of the subject.
• The applicant should be able to give a general description of the subject using, as appropriate, typical iI. J
examples.
• The applicant should be able to use mathematical formulae in conjunction with physical laws describing the 'I
subject. ,I
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• The applicant should be able to read and understand sketches, drawings and schematics describing the
subject.
• The applicant should be able to apply his knowledge in a practical manner using detailed procedures.

LEVEL 3
• A detailed knowledge of the theoretical and practical aspects of the subject.
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manner.
Objectives:
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• The applicant should be able to give a detailed description of the subject using theoretical fundamentals
and specific examples.
• The applicant should understand and be able to use mathematical formulae related to the subject.
• The applicant should be able to read, understand and prepare sketches, simple drawings and schematics
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describing the subject.

• The applicant should be able to apply his knowledge in a practical manner using manufacturer's
instructions.
• The applicant should be able to interpret results from various sources and measurements and apply
corrective action where appropriate.
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Module 2.3 Thermodynamics !
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Table of Contents
11
u
Module 2.3 Thermodynamics _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 5
(l
Temperature ____________________________ 5
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The Gas Laws 11
Thermal Expansion 23
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He~ 33
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Refrigeration and Heat Pumps 49
r-c Thermodynamics and the 1st and 2nd Laws 57
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Module 2.3 Enabling Objectives n

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Objective EASA 66 Reference Level
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Thermodynamics 2.3
(a) 2 nI
Temperature: thermometers and temperature scales:
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Celsius, Fahrenheit and Kelvin; Heat definition

Heat capacity, specific heat

Heat transfer: convection, radiation and conduction;
(b) 2
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Volumetric expansion ...,

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First and second law of thermodynamics l I
Gases: ideal gases laws; specific heat at constant volume
and constant pressure, work done by expanding gas
Isothermal, adiabatic expansion and compression, engine I J
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cycles, constant volume and constant pressure,

refriQerators and heat pumps
...,,
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Latent heats of fusion and evaporation, thermal energy, , ,_.J

heat of combustion
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Module 2.3 Thermodynamics
3-4 Use and/or disclosure is
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o Module 2.3 Thermodynamics

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Temperature
11
. ,

U Temperature Scales

o Our common notion of hot and cold has its precise expression in the concept of temperature. As
objects are heated their molecules move faster. In a solid the molecules vibrate more rapidly. In
liquids and gases the molecules move all over in the container at a faster rate of speed. These
variations in speed of the molecules cause objects to expand when they are heated.

This expansion can be used to construct instruments called thermometers. The ordinary
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mercury thermometer uses the expansion of a volume of mercury contained in a bulb to indicate
I: temperature.
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A number of temperature scales are currently in use. The Fahrenheit scale is the one we have
used most extensively. On this scale the freezing point of water is 32° and its boiling point is
212°. The metric scale is the Celsius or centigrade scale. On this scale the freezing point of
water is zero and the boiling point is 100°.

In theory, if we cool any substance enough, we can cause all molecular motion to cease. We
call this lowest possible temperature "absolute zero". Ordinary gases like air would be rock solid
II
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~
at this temperature. Low temperature physicists have never been able to reach this extremely
low temperature in their laboratories. However, they have come close-down to a fraction of a
centigrade degree. Absolute zero is a limiting temperature which can never be reached. Two
other temperature scales are used by engineers and experimental scientists. In both of these
scales the zero of the scale is placed at absolute zero, the coldest possible temperature. These
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scales are the metric Kelvin scale and the English Rankin scale.
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In Table 3-3, the four temperature scales are compared.
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" There are formulas that enable us to change from a centigrade reading to a Fahrenheit reading
and vice versa. These formulas are:
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C =-(F
9
- 32) and F =-C
5
+ 32
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U Note that there are parentheses in the first formula but not in the second formula. Be careful!

There are also formulas that change from a centigrade reading to a Kelvin reading and from a
Fahrenheit reading to a Rankin reading. These formulas are very important to us at this time
since we will have to use absolute temperatures in the gas laws.

o These formulas are:

K=C+273 and R= F + 460

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l...' Module 2.3 Thermodynamics 3-5
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Boiling Freezing Absolute n
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Point of Point of Zero
Water Water

Centigrade 100° 0° -273°

Kelvin 373 273 0

Fahrenheit 212 0 32° -460°

,...,
Rankin 672° 492° 0° l I
Table 3.1: Comparisons of boiling points, freezing points and
absolute zero in different units

Notes:
• Kelvin has no 0 sign in-front of the K. n
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• The accurate conversion factor for DC to K is +273.15

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Figure 3.1: Temperature scale comparison iJ
3-6
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o Problems

1. Change 20°C to degrees F.

2. Change -15°C to degrees F.

3. Change 86°F to degrees C.

4. Change _4°F to degrees C.

5. Change 100°F to degrees R.

o 6. 0
Change 450 R to degrees F.

7. Change 100°C to degrees K.

8. Change 383 K to degrees C.

9. Gas turbine engine performance is very sensitive to variations in the temperature

of the air. All engines are rated with the air at a standard temperature of 59°F.
What is the equivalent Centigrade temperature?

10. On some large commercial turbojet engines, the temperature at the front end of
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the combustion section is approximately 400°C. What is this temperature on the
Fahrenheit scale?

o 11. As air enters the combustion chamber of a turbojet fuel is added and the
temperature is raised to about 3,500°F in the hottest part of the flame. What is this
temperature on the Centigrade scale?
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Module 2.3 Thermodynamics 3-7

Use and/or disclosure is
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Answers

1. 68°F

o 2.
3.
5°F
30°C
11 4. -20°C
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5. 560 0 R

o 6.
7.
-10°F
373 K
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9. 15°C
fl 10. 752°F
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11. 1,930°C

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3-10 Module 2.3 Thermodynamics
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The Gas Laws

We will next discuss the volume and density of gases under varying conditions of temperature

o and pressure. Three gas laws, named after the scientists that discovered them, will be
considered.

ii,u Boyle's Law

A cylinder containing gas is fitted with a light piston. This cylinder contains a certain mass of gas
and therefore a certain number of molecules of gas. The gas has a definite absolute

c temperature. This temperature is a measure of the average speed of the gas molecules in the
sample. Some of the molecules are moving faster and some are moving slower. The average
speed determines the temperature.

o If the temperature of the gas remains constant and the volume of the gas sample is decreased,
the molecules, still moving with the same average speed, are "squashed" into a smaller space
fi (see figure 3.2).
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The result is that the sides of the container experience more collisions per unit time. This results
r -,
in an increase in the absolute pressure the molecules exert on the walls of the container.
U

o Note that a decrease in volume produces an increase in absolute pressure. This is

characteristic of an inverse proportion. We write the equation as:
P,2
-=-
P2
V
V,
o If we cross multiply in the above equation we

o reach the form in which Boyle's Law is usually

written:

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Here P1 and P2 are the absolute pressures

o corresponding to the volumes V 1 and V2

respectively. In working with Boyle's Law, it
must always be remembered to use absolute
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pressures.
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o Figure 3.2: Boyle's Law

u Use andlor disclosure is

governed by the statement
Module 2.3 Thermodynamics 3-11
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EXAMPLE:

A cylinder fitted with a piston contains gas at a pressure of 35.5 Ibs.lin2 as indicated by a
gauge mounted to the outside of the cylinder. The atmospheric pressure is 14.5 Ibs.lin2 if the
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piston is forced down reducing the volume in the cylinder to one fourth of its original volume
while holding the temperature of the gas constant, determine the new reading on the pressure
gauge.

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P1 = (35.5 + 14.5) Ibs.lin2

P1 = 50 ibs.lin2
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Solving for P2 gives,

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P2 = 200 ibs.lin2 absolute

We still must express this new pressure as a gauge pressure since the problem asked for the
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new reading on the pressure gauge. Our final answer is: I I
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P2 = (200 - 14.5) Ibs.lin2= 186 Ibs.lin2
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Charles' Law
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Toward the end of the 18th century, investigations carried out by French physicists, Jacques ~ J
Alexandre Charles and Joseph Louis Gay-Lussac led to the discovery of a relation between the
volume and absolute temperature of gases under conditions of constant pressure. :1
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Let us again consider a sample of gas containing a definite number of molecules. We stipulate
that the pressure on this sample of gas will remain constant. If the pressure is to remain
constant, an increase in absolute temperature must be accompanied by a corresponding
increase in volume (see figure 3.3).
n
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3-12
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We say that the volume is directly proportional to

o the absolute temperature. provided that the
pressure remains constant. We write the

o equation as:

The absolute temperatures must be either

o Kelvin, or Rankin degrees.

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Figure 3.3: Charles' Law

o
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u What will be the volume of this quantity of air when the temperature increases to 85°F, and
the pressure stays the same?
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1 ft3 V2
-==-=-
c
--::-- =
475°R 545°R

Note that we have changed the temperatures from degrees Fahrenheit to degrees Rankin,

o because we must express the temperatures in absolute units. Cross multiplying, we obtain:

v = 1 ft3 x545°R =1.15 ft3

2 475 0 R

Failure to convert to absolute temperatures will always lead to incorrect answers when
rl working with the gas laws!
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Module 2.3 Thermodynamics 3-13

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Gay-Lussac's Law

This third gas law relates the absolute pressure

o
to the absolute temperature of a gas when its
volume is held constant.
0+-
cI' t
0+-
cI' t n
Again we consider a certain number of
molecules of gas in a closed container where the ~ a... ~ a... 'I
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volume of the gas is held constant. If we
increase the absolute temperature of the gas,
the average speed of the molecules increases.
As these molecules strike the walls of the
~ ~~ t ~~~ t r1
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container they exert a greater pressure since

they are moving faster (see figure 3.4). + .-0 + .-0
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Using absolute pressures and temperatures the
following simple relationship is obtained:
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Figure 3.4: Gay Lussac's Law

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P,2 P u
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This equation is referred to as Gay-Lussac's Law.
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EXAMPLE: I
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The tyre of a bicycle is filled with air to a gauge pressure of 50.0 Ibs.lin. at 58°F. What is the
gauge pressure in the tyre on a day when the temperature rises to 86°F? Assume that the
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volume of the tyre does not change and the atmospheric pressure is 14.7 Ibs.fin.2

We must first convert to absolute temperatures and pressures.

P1 = 50.0 Ibs.lin2+ 14.7Ibs.lin2= 64.7 ibs.lin2
:]
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Substituting these values into Gay-Lussac's Law gives:

64.7 Ibs/in2 P2
518°R 546°R

Solving for P2, we obtain P2 = 68.2 ibs.lin2. Finally, the new gauge pressure is obtained by
subtracting the atmospheric pressure from P2.

68.2 Ibs.lin2 - 14.7 Ibs.lin2 = 53.5 Ibs.lin2

Module 2.3 Thermodynamics

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The General (Ideal) Gas Law

o The three properties, pressure, temperature, and volume are interrelated for a fixed mass
(number of molecules) of gas in such a way that if two of them change in value the third can

o immediately be determined. Combining the three gas laws the following general gas law can be
written:

r~
I I Note that this equation gives us the three gas laws that we have studied.
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If the temperature of the gas remains constant, we can cancel the temperatures in the
o denominators and obtain:

Boyle's Law
o If the pressure remains constant, we can cancel the pressures in the numerators and obtain:

o Charles' Law

o If the volume remains constant, we can cancel the volumes in the numerators and obtain:

o Gay-Lussac's Law

I:
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o EXAMPLE:

A tank of helium gas has a gauge pressure of 50.2 Ibslin2 and a temperature of 45°F. A piston
'1 decreases the volume of the gas to 68% of its original volume and the temperature drops to
U 10°F. What is the new gauge pressure? Assume normal atmospheric pressure.

[i We must change both temperatures to absolute units. We must change the original gauge
U pressure to absolute pressure. We remember that when the final pressure is obtained it will be
=
in absolute units. We also note that V 2 0.68 V 1 .
[1
u P,V,
2 2 PV
--=- -
T,
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Module 2.3 Thermodynamics 3-15

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We transfer V 2from the numerator on the right to the denominator on the left. We also
transfer T2 from the denominator on the right to the numerator on the left. In this way, we
solve our formula for P2.
P1V 1T2
T1V 2
P2
n
Next we substitute our known values:

P _ (64.9 Ibs/r)(V1)(4't&"R)
2 - (~R)(-&:68V1)

P2 = 88.8 Ibslin2 Absolute n

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P2 = 74.1 Ibslin2 (New Gauge Pressure)

Alternate Form of the General (Ideal) Gas Law

The general gas law tells us that for a fixed quantity of gas, the expression PVIT is constant.
Since PVIT is a constant for a fixed mass of gas, we can set this expression equal to the Ii
product of the mass (m) of the gas and what is referred to as a gas constant (R). This gas U

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constant (R) varies according to the type of gas. Table 3.2 gives values of R for various gases.
We can write:
PV =mR
T

PV= mRT
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If we divide both sides of this equation by V. we obtain:

p=mRT
V
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We remember that the density of any substance is given by: L. J

m :'1
p=-
V U
Values of the Gas Constant, R,
for Some Common Gases
ll J
3
Pa m /kg K ft.lbs/slug OR
Air 287 1,710
Carbon Dioxide 189 1,130
Helium 2,077 12,380
Nitrogen 297 1,770
Oxygen 260 1,550
Water Vapour
Table 3.2: Gas Constants, R
462 2,760
n
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3-16
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o Therefore we can write:

P= pRT

1 The most important application of this formula enables us to obtain the density of any particular
r
U kind of gas if we know its absolute pressure and absolute temperature.

1"1 We write the equation in the form:

LJ

o Note: When comparing the density of one type of gas to another, we need to use equal
temperatures and pressures for each gas (since, as the above equation shows, density

o changes with pressure and temperature changes). The temperature and pressure we use for
this is known as Standard Temperature and Pressure. These are OOC and 1 atmosphere
(273.15 K and 760 mmHg).
o
EXAMPLE:
fl Find the density of air if the temperature is 80°F and the absolute pressure is 2,150 Ibs.lftz

o P
p = RT
2150 Ibs/ft2
= (1710 ft.lbs/slugOR)(5400R)

= 0.00233 slug/ft3

II
LJ Application of the General Gas Law to Compressors
We can apply the general gas law to the flow of air through the compressor of a turbojet engine.

o The function of the compressor is to provide a large quantity of high pressure air to the limited
space of the combustion chamber. The reason for this is that the energy released in the
combustion chamber is proportional to the mass of air consumed. The pressure of the air when
it leaves the compressor is called the compressor discharge pressure (COP) and the ratio of
this to the compressor inlet pressure (CIP) is the compression ratio. That is,

o C . R·
ompresslon atlo = COP
CIP

[] Note that the compression ratio can also be expressed as:

[] Compression Ratio = P2
P,

fl where the 1's refer to the inlet pressure and the 2's to the discharge pressure.
u
Air entering a compressor having a compression ratio of 12.5:1 at a pressure of 14.7 PSIA will
[J leave with a pressure of:

o Use and/or disclosure is

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(12.5)(14.7) = 184 PSIA o
If however, the temperature of the air is increased too much in the compression process the
volume of a quantity of air entering the combustion chamber will not be reduced significantly
and the compressor efficiency will be low.
o
EXAMPLE:
n
A quantity of air occupying 1 cU.ft. at pressure of 14.7 PSIA and a temperature of 59°F enters
the compressor of a turbojet engine having a compression ratio of 12.5:1 and is discharged at
o
a temperature of 2,000°F. With what volume will this quantity of air enter the combustion
chamber? n
Solving our general equation:

PV PV .
o
_1_1 = ~ for V 2Yields
T1 T2 n
V 2 = P1V1T2 = V1(T21( 1 I
TF2 T1) P2 /P1)

Therefore, we can substitute our given values:

3
n,
L )
,

V =(1 ft )(2000+460J(_1_J
2 59+460 12.5
nI I

V2 = 0.379 ft.3 l J

EXAMPLE:
n
With what volume would the quantity of air of the previous problem enter the combustion
chamber if the discharge temperature of the compressor were 750°F instead of 2,000°F? lJ
V =(1 ft 3 )(750+460J(_1_J
2 59+460 12.5
n
V2= 0.187 ft.3 n
We see that the volume of the original cubic foot of air is less (0.187 ft. 3) when the
temperature is 750°F than it is (0.379 ft. 3) when the temperature is 2,000°F. o
Module 2.3 Thermodynamics
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Problems
o 1. A quantity of gas is contained in a cylinder fitted with a piston. The absolute pressure of
the gas is 240 kPa when the volume is 0.15 m 3 . What will the volume be when the
o absolute pressure of the gas is changed to 80 kPa while the temperature is held
constant?

2. A quantity of gas is contained in a cylinder fitted with a piston. The gauge pressure of the
gas in the cylinder is 335 Ibslin2 when the volume occupied by the gas is 72in 3 What is

o the gauge pressure when the volume is decreased to 60 in 3 ? Assume atmospheric

2
pressure to be 151bslin , and assume that the temperature is held constant.

o 3. A sample of nitrogen is held at an absolute pressure of 1.50 atmospheres and a volume

of 7.80 m 3 . A piston gradually reduces the volume to 6.30 m3 . The temperature does not
change. What is the new absolute pressure in atmospheres?

o 4. A volume of 1.35 m 3 of air at 1rc is heated to 42rC while its pressure is held constant.
What is the volume of the gas at this elevated temperature.
r1
LJ 5. A tank of carbon dioxide is maintained at an absolute pressure of 5,000 Ibs/ff. The
temperature is 190°F. What is the density of this carbon dioxide?
f1
U 6. The air pressure and density at a point on the wing of a Boeing 747 flying at altitude are
70 kPa, and 0.9 kg/m 3 respectively. What is the temperature at this point on the wing in

o 7.
degrees Centigrade?

The Goodyear non-rigid airship, the Mayflower, has a volume of 4000 m 3 and is filled with

o helium to an absolute pressure of 100 kPa. The temperature is 2rc. Find the density
and total mass of the helium in the ship.

rU1 8. At an altitude of 8,000 ft. the absolute temperature of air is 500 0 R and the absolute
pressure is 1600 Ibs/ft2 What is the density of air at this altitude?

C 9. A tank of carbon dioxide is maintained at an absolute pressure of 5,830 Ibs/ft2 and a

temperature of 70°F. What is the density of this carbon dioxide?

o 10. A quantity of air occupying 0.9 ft3 at a pressure of 15 PSIA and a temperature of 40°F
enters the compressor of a turbojet engine having a compression ratio of 13:1 and is
discharged at a temperature of 1 ,540°F. With what volume will this quantity of air enter

o the combustion chamber? .

o Use andfor disclosure is

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3-20 Module 2.3 Thermodynamics

Use and/or disclosure is
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Answers
u 1. 0.45m 3
[] 2. 4051b./in 2

3. 1.86 atmosphere

4. 3.26 m3

u 5. 0.007 slug/ft3

u 6.

7.
_ 2°C

0.16 kg/m 3 , 640 kg

8. 0.00 188 slug/ft3

u g. 0.01 slug/ft3

10. 0.3 ft3

u
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11
I.....J

u Use andfor disclosure is

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3-22
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Thermal Expansion
The temperature of a body is a measure of the average kinetic energy of the molecules of that

o body. It follows that molecules of warm liquids and gases move around faster in their containers
than molecules of cool liquids and gases. As a solid is heated its molecules vibrate faster about
their equilibrium positions. As a result of this increased motion of molecules as they are heated,
solids and liquids expand as the temperature is raised.

We're going to return to the idea of how temperature is related to molecular motion later, but
first let's look at what happens to materials when they change temperature. Let's say that
you've got a jar lid that's stuck and you want to get it off. How can you do this? One common
way is by running the jar under hot water so that the jar lid expands and can come off the jar.
Thinking back to our model of solids, if temperature is a measure of how fast things are moving,
when a solid heats up, the molecules vibrate about their normal positions. At higher
temperature, they vibrate more and the material actually grows in size. When a material is
cooled, the molecules don't move as much and the material shrinks.
11
If we look at a long strip of metal, with length La, we might want to find out what its change in

o length is under certain conditions. This is important, for instance, in building roads that must
undergo temperature extremes. Experimentally, we find that the change in length is directly
related to the change in temperature and to the initial length of the bar. The dependence on the

u initial length of the bar comes about because there are that many more molecules moving, so
the change in length will be greater than that of a shorter bar.

o But let's think back to the jar. When you heat the lid, you're also heating the glass, too. Doesn't
the glass also expand? The answer is that it does, but it expands less than the material from
which the lid is made. This means that we somehow have to account for the fact that different

u materials expand or contract by different amounts under the same temperature change.

Let's try to arrange these materials on a scale. The way we account for the different rates of
u rc different materials in out equation is via the coefficient of linear expansion, CI.. CI. has units of
(pronounced 'per degree Celsius') .
rl
LJ

[1
L.;

u
u

[J Use and/or disclosure is

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Linear Expansion
A rod of a substance will increase its length for a given temperature change. The increase in
length depends on the original length of the rod, the temperature change, and the material of
J
the rod. The increase in size of the object comes about by the fact that an increase in
temperature results in a n increase in kinetic energy of the molecules or atoms which make up
the material. Increasing the movement of the molecules forces it to occupy more space.
o
We define alpha (a), the coefficient of linear expansion. Tables of values of alpha for various
substances are found in handbooks of physics.
n
The formula is:
n
L..l

~L =a Lo~T
In this formula,

Lo = the original length of the rod n

l._

a = the coefficient of linear expansion

i1L =
the change in length of the rod
i1T = the change in temperature
n
Area Expansion
Two-dimensional solid bodies also experience thermal area expansion. The formula is as
[J
follows:

M =2o.Ao~T
o
In this formula, n
Ao
a
M
=
=
=
the original area of the body
the coefficient of linear expansion
the change in area of the
n
body
COEFFICIENTS OF LINEAR EXPANSION (a) n
i1T = the change in U
temperature SUBSTANCE· perFo
Aluminum 13 x 10-6 n
Brass 10 x 10-6
.1
Concrete (varies) 5 x 10-6 n
\J
Copper 9.4 x 10-6
Glass (Pyrex) 1.6 x 10-6 n
Ice 28 x 10-6
u
Iron

Lead
6.6 x 10-6

16 x 10-6
n
Steel 11 x 10-6
n
l .. J
Table 3.3: Coefficients of Linear Expansion

3-24 Module 2.3 Thermodynamics

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(j Volume Expansion
Three-dimensional solid bodies experience volume expansion.
U
II tN =31l VotlT
lJ In this formula:

o Vo
Il
= the original volume of the body
= the coefficient of linear expansion
tlV = the change in volume of the body
[1 tlT = the change in temperature

Expansion of Liquids and Gases

We have a minor problem with our expression for the thermal expansion of solids, which is that
it only works for solids. Neither liquids nor gases have a fixed shape when left on their own. The

c expression also fails if you have to consider the expansion of a solid in all directions.
~ is called the coefficient of volume expansion. For solids, ~ is approximately equal to 31l. This
is true only when the change in volume is small compared to the original volume. The problem
[-I
, , is that for liquids and gases, ~ is very large and this formula sometimes won't work.
LJ
Liquids also experience thermal
o expansion. We introduce beta
(~), the coefficient of volume
COEFFICIENTS OF VOLUME EXPANSION (f.I)
LIQUIDS perFo
expansion. There are also tables
\1 of the coefficients of volume Ethyl Alcohol 0.60 x 1 r
expansion.
Methyl Alcohol 0.66 x 10~

o Benzene 0.69 x 10~

t, Gasoline 0.58 x 10~
I I
U
Table 3.4: Coefficients of Volume Expansion

Generally, liquids expand more than solids, and gases much more than liquids, for any given
change in temperature. This is because the molecules of liquids are not tied to each other and
have more room and freedom to vibrate than do the molecules or atoms in solids. The
molecules of gases of course, are completely free to move, and thus will move much more
vigorously when heated than either solids or liquids

o
u
o
"U Use and/or disclosure is
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on page 2 of this chapter.
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LJ
The Interesting Case of Water
Most materials expand when heated and contract when cooled. Water is an exception. Between
n
lJ
O°C and 4°C, water actually expands when cooled. Above this range, it behaves normally.
Water therefore has its greatest density at 4°C. This turns out to be quite important for things
that live underwater. In the winter, you notice that the top of a pond always freezes first. As the
temperature decreases, there is a temperature gradient in the water. The top will be cooler than
the bottom because it is in contact with the cold air. When the water on the top of the lake
reaches 4°C, it becomes denser and sinks to the bottom of the lake, being replaced by warmer
water from the bottom. The water that is now on top cools to 4°C, and so on, until the whole
n
lake is at 4°C. The surface water cools even more, but now it is less dense than the water below
it, so it stays on the top of the lake and turns to ice (which is even less dense than cold water). If
the ice sank instead of floating, the lake would freeze all the way through and pretty much
n
everything inside would die. The layer of ice additionally acts as an insulator, keeping the rest of
the water away from the surface and the colder environment. n
EXAMPLE:
n
,~

A steel rail of length 140 ft. Is laid down when the temperature is 20°F. What is the increase in
length of this rail when the temperature is 95°F?

~L = a Lo~T 6 o
n
~L = (11 x 10· / F) (140 ft.) (75 OF)
~L = 0.116 ft.

EXAMPLE:

An aluminium tank has volume 35 ft.3 What is the increase in volume of this tank when the
temperature increases from 30°F to 90°F?
n
It should be noted that a solid block of a substance increases in volume as the body is heated.
Also, a container has a bigger volume as the temperature of the container increases.
n
l J

n
~V = 3a Vo~T U
~ V = 3 (13 x 10·6fF) (35 ft. 3 ) (60 OF)
~V = 0.0819 ft.3

n
J

3-26 Module 2.3 Thermodynamics

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EXAMPLE:

The manager of an airport accepts delivery of 1,000 gallons of avgas on a cool evening when
the temperature is 35°F. This avgas completely fills a 1,000 gallon aluminium tank. A warm
front moves in the next morning and the temperature rises to 95°F. How much avgas will
n, , overflow?
u If the avgas costs £1.25/gal. what is the loss to the airport?

For the gasoline:

/iw /:;.V = 13 Vo/:;.T

/:;.V = (0.58 x 1 0-3fF) (1,000 gaL) (60 OF)
=
/:;.V 34.8 gal.

For the tank:

[i /:;.V= 13 Vo/:;.T
U /:;.V = 3(13 x 10-6/ oF) (1,000 gaL) (60 OF)
/:;.V = 2.3 gal.

The new volume of the avgas is 1,034.8 gal. and the new volume of the tank is 1,002.3 gal.
We note that 32.5 gallons of avgas will overflow!

Loss £1.25/gal. x 32.5 gal. = £40.63.

[J EXAMPLE:

(I A motorist puts 20.1 gallons of petrol in his gas tank on a hot summer day when the
G
temperature is 95°F. He uses 0.1 gal. in driving home. The temperature falls to 45°F that
evening after a cool front has moved into the area. How many gallons are in his tank the next
o morning when he leaves for work?

/:;.V = 13 Vo/:;.T
/:;.V = (0.58 x 10-6/ oF) (20 gaL) (50 OF)
/:;.V = 0.58 gal.

There are 19.42 gallons of petrol in his tank the next morning!

flw
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\J Use and/or disclosure is
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3-28
ITS Integrated Training System
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r'lI Problems
,

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1, A 90 ft aluminium rail is put in place on a hot summer day when the temperature is 85°F.
What is the decrease in length of this rail when the temperature is 35 OF?

2. A 150 ft. steel rail is put in place when the temperature is 35°F, What is the increase in
length of this rail when the temperature is 95°F?
[l..,
3. A concrete bridge is laid down in sections with some space between sections to allow for
• expansion. The length of one section is 250 ft. The lowest recorded temperature in the
[)
~
area is - 45 OF and the highest recorded temperature is 115 OF. How much space should
the builders leave between each section?
11
L) 4. The volume of an aluminium tank is 200 gallons on a day when the temperature is 30 OF.
It is completely filled with gasoline from a supply truck. The temperature rises to 70°F

I" i
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when a warm front moves in. How many gallons of gasoline overflow?

,-,
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on page 2 of this chapter. © Copyright 2010
rl
 Integrated Training System
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3-30 Module 2.3 Thermodynamics

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n
© Copyright 201 0 on page 2 of this chapter.
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nu Answers

1. 0.0585 ft
rl 2. 0.099 ft.
U
3. 0.20 ft
4. 3.7 gallons

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Module 2.3 Thermodynamics 3-31

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3-32
TIS Integrated Training System
Module 2.3 Thermodynamics
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n
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r1 Heat
LJ
We recall that temperature is a measure of the average kinetic energy of molecules or atoms in
II a gas, and therefore the average velocity, of the molecules of the substance whose temperature
II
~ is being measured.

[, Heat is a measure of the total energy of molecular motion. The more molecules that are moving,
.I the greater is the heat energy. Let us compare a teaspoon of water at 100°F with a cup of water
l.!
at 50°F. The molecules of water in the teaspoon are moving faster than the molecules of water
rl in the cup. However, since we have so many more molecules in the cup, the heat energy in the
u cup is greater than the heat energy in the teaspoon. If the teaspoon of water is placed on a
large block of ice and the cup of water is also placed on this block of ice, the cup of water at
,p ,
50°F would melt more ice than the teaspoon of water at 100°F.
LJ
There are definite units for measuring heat energy. The units are the Btu (British thermal unit)
and the metric units, the large Calorie (written with a capital "C") and the small calorie.

The definitions are:

n
v 1 British thermal unit (Btu) = the amount of heat needed to raise the temperature of 1
Ib of water 1°F
I-!
U 1 Calorie = the amount of heat needed to raise the temperature of 1 kilogram of
water 1°C

(Note: 1 Calorie =4186 J, 1 Btu =0.252 CaL)

o 1 calorie = the amount of heat needed to raise the temperature of 1 gram of water
1°C

1 Celsius Heat Unit (CHU) = the amount of heat needed to raise the temperature of 1
Ib of water 1°C

(Note: The CHU is a mix of English and Metric units and is rarely used).

When we talk about the heat content of fuel (which must be burned to be released) -
commonly called the heat of combustion, we talk about Calories per lb. of fuel, or Btu per lb. of
fuel, or Joules per kg of fuel. Since 1 Btu =252 calories, and 1 calorie =4.186 Joules, there are
r-
I I
1055 Joules in 1 Btu. And since 1 lb. = 2.2 kg, 1 Btu/lb. = 2326 J/kg.
U We note that the Calorie is the famous dietary Calorie. The body stores excess food as fat and
we measure the Calories in a certain foodstuff by burning these foodstuffs and measuring the
heat produced!

In the solution of heat problems, we will limit our discussion to the English system, since this is
the system that is most often encountered in our society.

Module 2.3 Thermodynamics 3-33

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As heat is added to a body its temperature increases. However, the same amount of heat
added to a piece of aluminium and a piece of copper will not produce the same temperature
change. Aluminium and copper have different "specific heats".
The important equation is the following:

Q=wCdT (when using English units)

In this equation:

Q = heat gained or lost (Btu)

w = weight of the body (lb.)
C = the specific heat of the substance Btu/lb. of
t:,.T = the temperature change (OF or OR)

Q=mCdT (when using Metric units)

In this equation:

Q = heat gained or lost (J)

m
C
=
=
mass of the body (kg)
the specific heat of the substance (J/kgOC)
n
t:,.T = the temperature change (OC or K) l
u
It is important to note that this equation deals with substances that are not changing their states ,,"")
of matter. Another equation will deal with heat added or lost as a body changes from one state I,
;",,"
I
(solid, liquid, or gas) to another.

Since there are two equations, (depending on whether you are using English or Metric units)
there are also two sets of Specific Heat Capacity constants.
n
Table 3.5 shows various specific heats of substances in English and Metric units.

n
')
!J

3-34 Module 2.3 Thermodynamics

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,Ir"!,
U SPECIFIC HEAT CAPACITIES

Liquids J/kg K Btu/lbOF

Acetic acid 2130 0.51
:-

Ii
1
Alcohol 2930 0.70
l..J Ammonia 470 0.11
Paraffin 2140 0.51

o Petroleum
Turpentine
Water, fresh
2090
1980
4190
0.50
0.33
1.00
r:
u
Water, sea 4°C 3940 0.93

Metals
Aluminium 912 0.212
Antimony 214 0.051
Copper 389 0.093
Gold 130 0.031
Iron 460 0.110
Lead 130 0.031
1"1
u Mercury
Nickel
138
452
0.033
0.108
(! Platinum 134 0.032
lJ Silver 234 0.056
Tin 230 0.055

o Zinc

Solids
393 0.094

o Asbestos
Ashes
Asphalt
84
84
80
0.20
0.20
0.19
Brick 92 0.22
Carbon 71 0.17
[1 Coal 1310 0.314
I ' Coke 850 0.203
Ll Concrete 1130 0.27
Cork 2030 0.485
Glass 840 0.20
Granite 750 0.18
Graphite 710 0.17
Ice 2110 0.504
Wood 2300 - 2700 0.55 - 0.65

n
I '
~
Table 3.5: Specific Heat Capacities of some
common substances

o
r1
L Use and/or disclosure is
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Gases have a different specific heat capacity depending upon whether they are held at constant ,-,
I I
volume or constant pressure. Therefore all gases, as well as having a specific heat capacity, tJ
also has a value of its ratio of Cp to Cv .

For example:

Specific Heat Capacity of Dry Air:

at Constant Pressure, 1004 J I K kg

un
at Constant Volume, 717J/Kkg
n
u
C ,'I
Therefore Yair =- p
Cv
=1.4 i
I I
I
'--."

Also C p - Cv = R (the ideal gas constant we saw in Chapter 4).

Since both Rand yare always positive values, and greater than 1, Cp is always greater than
Cv .

EXAMPLE:
'i""I
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I

rI
How much heat must be supplied to raise the temperature of a 32 lb. aluminium fitting from
60°F to 90°F?
:1
Q =wCf,T (imperial) o
Q = (0.212 BtU) (32 Ibs.)(30°F)
Ib.ft. o
Q = 204 Btu. n
, 1

,"'-1
EXAMPLE:
I!
How much heat is given up as 100 Ibs. of sea water cools from 90°F to 50°F?

Q = wCf,T (imperial)
J
Q = (0.93 BtU) (100 Ibs.)(40°F)
Ib.ft.

Q =3720 Btu.

Module 2.3 Thermodynamics

3-36 Use and/or disclosure is
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l.J
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'1
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I ' club66pro.co.uk question practice aid
'-'

Heat Exchange
When hot bodies and cool bodies are mixed heat exchange occurs. The heat lost by the hot

o body equals the heat gained by the cold body:

Heat Lost =Heat Gained

nU On each side of this equation there is a wCI::;.T term. In writing an expression for I::;.T, we always
express this change as the larger temperature minus the smaller temperature.
r-:
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EXAMPLE:
f:
• I

LJ If 5,000 Ibs. of sea water at 100°F are mixed with 7,000 Ibs. of ordinary water at 40°F, what is
the final temperature of the mixture?
ji We note that, if the final temperature is T, the temperature 100° is more than T and the
-L.....' temperature 40° is less than T. Therefore the temperature change of the sea water is (100 -
T) and the temperature change of the ordinary water is (T - 40).

Heat Lost = Heat Gained

In setting up the wCI::;. T left and right members of the above equation, we will not include the
units. However we will note that the weights must be in Ibs. and the temperature changes in
Fahrenheit degrees.

(0.93) (5,000) (100 - T) = (1.00) (7,000) (T - 40)

465,000 - 4,650 T =7,000 T - 280,000

745,000 = 11,650 T

T = 63.9 of

(1
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U Use and/or disclosure is
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Cooling and Heating Curves
When a substance changes phase, that is it goes from either a solid to a liquid or liquid to gas,
the energy, it requires energy to do so. The potential energy stored in the inter-atomic forces
n
,-

between molecules needs to be overcome by the kinetic energy of the motion of the particles
before the substance can change phase. n
If we measure the temperature of the substance which is initially solid as we heat it we produce
a graph like Figure 3.5. n
n
'J

n
[I

\
phase change
(vapourlsatlon)
n
[,

n
,)
B -........,..-C
\ phase change
n
i !
l.......

(me~tlng))

Energy Input

Figure 3.5: Temperature change with time. Phase

changes are indicated by flat regions where heat
energy used to overcome attractive forces between
molecules i'"I
, j

Starting a point A, the substance is in its solid phase, heating it brings the temperature up to its
melting point but the material is still a solid at point B. As it is heated further, the energy from the
heat source goes into breaking the bonds holding the atoms in place. This takes place from B to
C. At point C all of the solid phase has been transformed into the liquid phase. Once again, as 11
energy is added the energy goes into the kinetic energy of the particles raising the temperature, U
(C to 0). At point 0 the temperature has reached its boiling point but it is still in the liquid phase.
From points 0 to E thermal energy is overcoming the bonds and the particles have enough ",:1
kinetic energy to escape from the liquid. The substance is entering the gas phase. Beyond E, LJ
further heating under pressure can raise the temperature still further is how a pressure cooker
works.

Note the temperature stays constant during the state changes of melting and boiling. ."'l
[1
i1
3-38 Module 2.3 Thermodynamics I
\-_ ....
I
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Note: Since 'fusion' (meaning 'to melt') is the opposite of 'solidification', the Latent Heat of
Fusion is the same as the Latent Heat of Solidification. Also, since 'vaporisation' is the opposite
of 'condensation', the Latent Heat of Vaporisation is the same as the Latent Heat of
Condensation.

A heating curve summarises the changes:

solid ~ liquid ~ gas

The principle of latent heat (especially of vaporization) is what is behind the operation of the
fridge and air conditioning system, water injection of gas turbine engines, and the cooling effect
you feel when you perspire.
r.~~
U That principle is that if you make a fluid vaporize, it extracts heat (latent heat) to cause it to
vaporize, but the fluid does not change temperature.
Latent Heat of Fusion and Vaporisation
The energy required to change the phase of a substance is known as a latent heat. The word
latent means hidden. When the phase change is from solid to liquid we must use the latent heat
of fusion, and when the phase change is from liquid to a gas, we must use the latent heat of
vaporisation.

The latent heat energy required is given by the formula:

Q=mL

where m is the mass of the substance and L is the specific latent heat of fusion or vaporisation
which measures the heat energy to change 1 kg of a solid into a liquid.

Some values of Specific Latent Heats of Fusion and Vaporisation are shown in table 3.6.
I 1
!
w
Specific
r 1 Specific Freezing latent heat Boiling
I Substance latent heat of Temperature of Temperature
'--'
fusion kJ/kg °C vaporisation °C
r ~I kJ/kg
l "
U Water 334 0 2258 100
Ethanol 109 -114 838 78
Chloroform 74 -64 254 62
Mercury 11 -39 294 357
Sulphur 54 115 1406 445
Hydrogen 60 -259 449 -253
Oxygen 14 -219 213 -183
l'- Nitrogen 25 -210 199 -196
\
l-.J Table 3.6: Latent heats, freezing points and boiling points of some common
substances

Module 2.3 Thermodynamics 3-39

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"

Further Discussion on Latent Heat

Each time water changes physical state, energy is involved.

In the vapour state, the water molecules are very energetic. The molecules are not bonded with
each other, but move around as single molecules. Water vapour is invisible to us, but we can
feel its effect to some extent, and water vapour in the atmosphere is a very important factor in
-,
weather and climate.
;I
i~ j

In the liquid state, the individual molecules have less energy, and some bonds form, break, then
re-form. At the surface of liquid water, molecules are continually moving back and forth from the
liquid state to the vapour state. At a given temperature, there will be an equilibrium between the
number of molecules leaving the liquid, and the number of molecules returning.
n
In solid water--ice--the molecules are locked together in a crystal structure: U
a framework. They are not moving around, and they contain less energy.

How do you make water evaporate? Here is a bowl of water. Make the
water evaporate. Go ahead.

How did you make the water evaporate? Probably you added heat. You
might have put it out in the sun, or possibly put it over a fire. To make
water evaporate, you put energy into it. The individual molecules in the water absorb that 'I1,1,
,c, J
energy, and get so energetic that they break the hydrogen bonds connecting them to other
water molecules. They become molecules of water vapour. Evaporation is the change of state
from liquid to vapour. In the process of evaporation, the molecule absorbs energy. This energy 'l
is latent heat. Latent means hidden, so latent heat is "hidden" in the water molecule--we can't l..J
feel it, but it is there. Wherever that individual molecule of water vapour goes, it takes that
latent heat with it. To get the molecule of water vapour to become liquid again, we have to take
the energy away, that is, we have to cool it down so that it condenses (condensation is the
change from the vapour state to the liquid state). When water condenses,
it releases latent heat.
:1
, I
,_ .J

Now, how do you make ice melt? Here is a block of ice, water in the solid ......
, I
state. Make it melt. Go ahead. •I
l J

Again, you probably melted the ice by adding energy. The additional
energy was absorbed by the individual molecules of water, which became ~
l j
so energetic that they broke some of the hydrogen bonds holding the ice crystal together, and
became liquid (that is, the ice melted). This energy is also latent heat, and each molecule of the :"l
liquid water is holding that latent heat. To change the liquid water back to ice, you have to take [
, J
that latent heat away, or in other words, cool the water.

Water could change directly from the frozen state to the vapour state without passing through
the liquid state first. This process is called sublimation. Water can also change from the
vapour state to the frozen state without passing through the liquid state. This is usually called
deposition, and is what you see when frost forms on grass or windows on a cold night.
(Sometimes the term sublimation is used when water changes state in either direction, that is,
from solid to vapour, or vapour to solid).

'1I
3-40 Module 2.3 Thermodynamics j, 1
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,J
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The really important thing to remember is that each time water changes state, energy is
absorbed or released. This energy is latent heat. Latent heat is the energy absorbed or
released when a substance changes its physical state. Latent heat is absorbed upon
evaporation, and released upon condensation to liquid (as in clouds). Latent heat is also
absorbed when water melts, and released when it freezes.

How much heat does it take to get water to change state? if the water is at a temperature of
100 degrees C (that is, the boiling point, or 212 degrees F) it takes an additional 540 calories of
heat to convert one gram of water from the liquid state to the vapour state. When the vapour
converts to the liquid state, 540 calories of energy will be released per gram of water. If you are
converting solid water (ice) to liquid water at 0 degrees C, it will require about 80 calories of·
heat to melt one gram of ice, and the 80 calories will be released when the liquid water is frozen
to the solid state.

Solid Liquid Gas

80 calories
--==~ 540 calories

O· C <)==_.--100" C
Freezing Cooling Condensing
80 calories~::::':::==-;;:? 100 calories 540 calories
n
L Latent heat of fusion-80 calories Latent heat of vaporization-540 calories

Figure 3.6: Ice, water and water-vapour

Water does not have to be at the boiling point to evaporate. if you don't believe this, set a pan
of water out in the sun and watch it slowly disappear. The sun's heat is not boiling the water,
but it is evaporating it. in a given amount of water at a given temperature, some molecules of
Ii,w water will have more energy than others, so some molecules will be able to evaporate, while
others remain in the liquid state. The lower the temperature of the water, the more energy is
required for evaporation. if the water is liquid at a temperature of 0 degrees C, the latent heat of
r",
, I vaporization is 597 cal/g, compared to 540 cal/g at 100 degrees C. in between, at 50 degrees
L C, an input of 569 cal/g would be required for evaporation.

It will take a total of about 720 calories per gram to sublimate water, that is change it directly
from ice at 0 degrees C, to vapour at 100 degrees C: this includes 80 calories from latent heat
of fusion (melting) + 100 calories to raise the temperature of the water 100 degrees C + 540
calories to make the liquid water evaporate (latent heat of vaporization). Similarly, about 720

Module 2.3 Thermodynamics 3-41

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calories per gram will be released when water is changed directly from vapour to ice, the
process called deposition.

Methods of Heat Transfer

Heat can be transferred from one place to another by one or more of the following processes:
~
Convection is the transfer of heat by the actual
movement of the warmed matter. Heat leaves a coffee •I
J, )
convection
cup as the currents of steam and air rise. Convection
is the transfer of heat energy in a gas or liquid by
movement of currents. Think of air and water currents!
(it can also happen is some solids, like sand.) The water
heat moves with the fluid. Consider this: convection is ;-or!

responsible for making macaroni rise and fall in a pot c. J

of heated water. The warmer portions of the water are
less dense and therefore, they rise. Meanwhile, the "l
cooler portions of the water fall because they are '-" i)

denser. ,.,
Figure 3.7: Heat - convection I
i, j
I
Conduction is the transfer of energy
through matter from particle to particle. It is
the transfer and distribution of heat energy
from atom to atom within a substance. For
example, a spoon in a cup of hot soup ;-.
becomes warmer because the heat from the , I,
l 1
soup is conducted along the spoon.
Conduction is most effective in solids-but it
can happen in fluids. Have you ever noticed direction of heat flow
that metals tend to feel cold? Believe it or
not, they are not colder! They only feel
colder because they conduct heat away from
your hand. You perceive the heat that is Figure 3.8: Heat - conduction
n
LJ

. leaving your hand as cold. 'I

Radiation: Electromagnetic waves that directly transport ENERGY through space. Sunlight is a •J
form of radiation that is radiated through space to our planet at the speed of light without the aid
of fluids or solids. The energy travels through nothingness! Just think of it! The sun transfers
heat through 93 million miles of space. Because there are no solids (like a huge spoon)
touching the sun and our planet, conduction is not responsible for bringing heat to Earth. Since
there are no fluids (like air and water) in space, convection is not responsible for transferring the
heat. Thus, radiation brings heat to our planet.

n
• J

•J
Module 2.3 Thermodynamics
3-42 Use andfor disclosure is
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on page 2 of this chapter.
© Copyright 2010
"'"
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Integrated Training System

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Heat Transfer
We know that heat flows through insulating materials from the warm side to the cool side, It is
possible to predict how many Btu will flow through a given insulator in a given amount of time.

The equation is:

Q kMT THERMAL CONDUCTIVITIES

-=-- (Btu-IN./FT.2 -HR._OF)
t L
Air
r: The equation is less difficult than it
0.17
i....; seems at first. We will carefully Corkboard 0.30
define each symbol.
Cotton 0.54
Q = heat flow in Btu
t = time in hours Fiberboard 0.42
A = the surface area of the
insulation in square feet Foam Plastic 0.30
!1T = the temperature difference
in of Glass Wool 0.27
L = the thickness of the
insulation in inches Table 3.7: Thermal conductivities of some
.--,
I, : ' k =
the thermal conductivity of the common materials
u material from which the insulation is made

EXAMPLE:

An outside wall of a house has total cross-sectional area of 2,000 ft.2 The thickness of the
fibreboard insulation is 3 inches. The inside temperature is 70°F and the outside
temperature is 20°F. What is the heat loss per hour through this outside wall?

Q kA!1T
t
= L

Q (0.42 Btu in.! ft 2 hrOF)(2,000 ft)(50 F)

=
r -".~ t 3 in
\ I
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Q
- = 14,000 Btu!hr

C t

r~)
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.,
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3-43
Module 2.3 Thermodynamics
Use and/or disclosure is
governed by the statement TIS Integrated Training System
on page 2 of this chapter. © Copyright 2010
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3-44 Module 2.3 Thermodynamics

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Problems

1. How much heat must be supplied to raise the temperature of 67 Ibs. of ethyl alcohol
from 32°F to 76°F?

2. How much heat is given up as 780 Ibs. of steel cool from gO°F to 45°F?

3. If 1 lb. of vodka (alcohol) at gO°F is mixed with 0.2 lb. of water at 40°F what is the final
temperature?

4. If 3 Ibs. of hot water at 200 OF are poured into a 1.5 Ibs. aluminium container at 40 OF,
what is the final temperature?
!i
u A house has an outside wall area of 3,000 ft2 These walls are insulated with corkboard
5.
4 in. thick. The inside temperature is 75°F and the outside temperature is 15°F. What is
the heat loss per hour through these outside walls?

n
u

Module 2.3 Thermodynamics 3-45

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3-46 Module 2.3 Thermodynamics
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TIS Integrated Training System governed by the statement
© Copyright 2010 on page 2 of this chapter.
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Answers
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1. 2,064 Btu
2. 3,860 Btu
3. 79°F
0
4. 180 F
5. 13,500 Btu/hr

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Integrated Training System
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3-48 Module 2.3 Thermodynamics

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.~ ,
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: Refrigeration and Heat Pumps
First of all, did you know that there is no such thing as cold? You can describe something as
cold and everyone will know what you mean, but cold really only means that something contains
I I
'-' less heat than something else. All there really is, is greater and lesser amounts of heat. The
definition of refrigeration is The Removal and Relocation of Heat. So if something is to be
r '-
t ! refrigerated, it is to have heat removed from it. If you have a warm can of pop at say 80 degrees
u Fahrenheit and you would prefer to drink it at 40 degrees, you could place it in your fridge for a
while, heat would somehow be removed from it, and you could eventually enjoy a less warm
pop. (oh, all right, a cold pop.) But lets say you placed that 40 degree pop in the freezer for a
while and when you removed it, it was at 35 degrees. Even "cold" objects have heat content that
can be reduced to a state of "less heat content". The limit to this process would be to remove all
J) heat from an object. This would occur if an object was cooled to Absolute Zero which is -273° C
U or -460° F. They come close to creating this temperature under laboratory conditions and
strange things like electrical superconductivity occur
n
\ .

u How do things get colder?

Things get cold because they lose heat by one or more of the following methods:

• Radiation
• Conduction
o • Convection

o
u
r-.

11
\ '
u Radiation Conduction
Figure 3.9: Summary of radiation, conduction and convection
r.
L
The latter two are used extensively in the design of refrigeration equipment. If you place two
objects together so that they remain touching, and one is hot and one is cold, heat will flow from
the hot object into the cold object. This is called conduction. This is an easy concept to grasp
and is rather like gravitational potential, where a ball will try to roll down an inclined plane. If you
r~1

I i were to fan a hot plate of food it would cool somewhat. Some of the heat from the food would be
U carried away by the air molecules. When heat is transferred by a substance in the gaseous
state the process is called convection. And if you kicked a glowing hot ember away from a
(1
I !
bonfire, and you watched it glowing dimmer and dimmer, it is cooling itself by radiating heat
U away. Note that an object doesn't have to be glowing in order to radiate heat, all things use
combinations of these methods to come to equilibrium with their surroundings. So you can see
1\ that in order to refrigerate something, we must find a way to expose our object to something that
( \

L: is colder than itself and nature will take over from there. We are getting closer to talking about
the actual mechanics of a refrigerating system, but there are some other important concepts to
discuss first.

o Use and/or disclosure is

governed by the statement
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The States of MaUer

They are of course; solid, liquid and gas. It is important to note that heat must be added to a
substance to make it change state from solid to liquid and from liquid to a gas. It is just as
n
l.J

important to note that heat must be removed from a substance to make it change state from a .r), I
gas to a liquid and from a liquid to a solid. ,_ i

The Magic of Latent Heat :/

! )
U
Long ago it was found that we needed a way to quantify heat.
Something more precise than "less heat" or "more heat" or "a great n!
'j

deal of heat" was required. This was a fairly easy task to accomplish. 1" j

They took 1 Lb. of water and heated it 1 degree Fahrenheit. The

amount of heat that was required to do this was called 1 BTU (British
Thermal Unit). The refrigeration industry has long since utilized this
definition. You can for example purchase a 6000 BTu/H window air
n
conditioner. This would be a unit that is capable of relocating 6000
BTU's of heat per hour. A larger unit capable of 12,000 BTUIH could
also be called a One Ton unit. There are 12,000 BTU's in 1 Ton.
Figure 3.10: Raising
11b of by water 1°F

To raise the temperature of 1 LB of water from 40 degrees to 41 degrees would take 1 BTU. To ,~
, .
raise the temperature of 1 LB of water from 177 degrees to 178 degrees would also take 1 BTU. '~-'

However, if you tried raising the temperature of water from 212 degrees to 213 degrees you
would not be able to do it. Water boils at 212 degrees and would prefer to change into a gas
~
n1, ,

rather than let you get it any hotter. Something of utmost importance occurs at the boiling point
of a substance. If you did a little experiment and added 1 BTU of heat at a time to 1 LB of water,
you would notice that the water temperature would increase by 1 degree each time. That is until
you reached 212 degrees. Then something changes. You would keep adding BTU's, but the
water would not get any hotter! it would change state into a gas and it would take 970 BTU's to
vaporize that pound of water. This is called the Latent Heat of Vaporization and in the case of
water it is 970 BTU's per pound.

So what! you say. When are you going to tell me how the refrigeration effect works? Well hang :I,
:J
in there, you have just learned about 3/4 of what you need to know to understand the process.
What keeps that beaker of water from boiling when it is at room temperature? if you say it's
because it is not hot enough, sorry but you are wrong. The only thing that keeps it from boiling
is the pressure of the air molecules pressing down on the surface of the water. When you heat
that water to 212 degrees and then continue to add heat, what you are doing is supplying
sufficient energy to the water molecules to overcome the pressure of the air and allow them to
escape from the liquid state. If you took that beaker of water to outer space where there is no air
pressure the water would flash into a vapour. If you took that beaker of water to the top of Mt.
Everest where there is much less air pressure, you would find that much less heat would be
n
tJ
needed to boil the water. (it would boil at a lower temperature than 212 degrees). So water boils
at 212 degrees at normal atmospheric pressure. Lower the pressure and you lower the boiling :'l
point. Therefore we should be able to place that beaker of water under a bell jar and have a : I
i. __ J

vacuum pump extract the air from within the bell jar and watch the water come to a boil even at
room temperature. This is indeed the case!

3-50 Module 2.3 Thermodynamics

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."
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)

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on page 2 of this chapter.
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,

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A liquid requires heat to be added to it in order for it to overcome the air pressure pressing down
II
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on its' surface if it is to evaporate into a gas. We just learned that if the pressure above the
liquids surface is reduced it will evaporate easier. We could look at it from a slightly different
angle and say that when a liquid evaporates it absorbs heat from the surrounding area. So,
finding some fluid that evaporates at a handier boiling point than water (i.e. lower) was one of
the first steps required for the development of mechanical refrigeration.

Chemical Engineers spent years experimenting before they came up with the perfect chemicals
for the job. They developed a family of hydroflourocarbon refrigerants which had extremely low
r1 boiling points. These chemicals would boil at temperatures below 0 degrees Fahrenheit at
U atmospheric pressure. So finally, we can begin to describe the mechanical refrigeration
process.
Ii
u
(Low Pressure) Compre550r (High Pressure)
~ ~
[
C 0) )~\ (
u ( ~ C
0)
(
C 0)
(
rl
, , C 0)
LJ
Evaporator Metering Conden5er

o
r--',
(Accepts heat)
Device
(Rejects heat)
-, I
, I
Figure 3.11: Main components of a refrigeration system
L
There are 4 main components in a mechanical refrigeration system. Any components beyond
these basic 4 are called accessories. The compressor is a vapour compression pump which
uses pistons or some other method to compress the refrigerant gas and send it on it's way to
the condenser. The condenser is a heat exchanger which removes heat from the hot
compressed gas and allows it to condense into a liquid. The liquid refrigerant is then routed to
the metering device. This device restricts the flow by forcing the refrigerant to go through a
,---,- small hole which causes a pressure drop. And what did we say happens to a liquid when the
u pressure drops? if you said it lowers the boiling point and makes it easier to evaporate, then you
are correct. And what happens when a liquid evaporates? Didn't we agree that the liquid will
absorb heat from the surrounding area? This is indeed the case and you now know how
refrigeration works. This component where the evaporation takes place is called the evaporator.
The refrigerant is then routed back to the compressor to complete the cycle. The refrigerant is
used over and over again absorbing heat from one area and relocating it to another. Remember
the definition of refrigeration? (The removal and relocation of heat.)

I:
LJ Use and/or disclosure is
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r-' on page 2 of this chapter. © Copyright 201 0
Integrated Training System
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So what is a refrigerant?
Remember that a refrigerant, in order to cool the space, must evaporate at the temperature of
n
l J
the space. So in the case of an air conditioning unit, we need a chemical which will evaporate
(boil) at the temperature of the room you are trying to cool. In the case of a fridge, you need a
chemical which will boil at the temperature of the inside of the fridge. There are hundreds of
chemicals which will do this. Several of the commonest are as follows:
'l
U
Boiling · ,
~ j
Refrigerant Formula temperature Properties Applications
°c
Penetrating odour,
soluble in water.
Ammonia NH3 -33 harmless in concentration Large industrial plants
up to 1/30%, non
flammable, explosive

C CI 2F2 Little odour, colourless as

Small plants with
gas or liquid, non
R12 Chlorodi- -29.8
flammable, non corrosive
reciprocating I"""'
fluoromethane of ordinary metals, stable
compressors. :J
Non flammable, non .'1
Commercial plants with
R11 C CbF 8.9 corrosive non toxic,
centrifugal compressors. :J
stable

Little odour, colourless as

gas or liquid, non toxic,
Packaged air il
, I
conditioning units where ( j
R22 CH CI F2 -40.8 non irritating, non
size of equipment and
flammable, non
economy are important.
corrosive, stable

C CI 2 F2 Offers approx. 20%

(73.8%) more refrigeration
R500 -33 Similar to R12 r-.
CH 3CH F2 capacity than R12 for
i
(26.2%) same compressor.
i1
C CI F2 (48.8%) Non flammable, non
R502 CCI -45.6 toxic, non corrosive,
Capacity comparable to (I
R22. '. I
F2 - CF3 (51.2%) stable I. J

F 3CCH 2F
R134a Tetrafluoro- -26.6
Non flammable, non
toxic, non corrosive,
Totally replaces other
Freon types for auto and
--,
ethane stable aircraft applications ,,· ,II
Table 3.8: Some common refrigerants
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3-52 Module 2.3 Thermodynamics
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The range of refrigerants beginning with the 'R' prefix (R12, R22 etc.) are complex compounds
of fluorocarbons or hydrofJourocarbons collectively known as 'Freon'.

Other chemicals could be used and have been used in the past. Methyl bromide is a refrigerant
but has almost completely been phased out for safety and environmental reasons. Carbon
dioxide (dry ice) has also been used as a refrigerant (infact at one time Carbon Dioxide and
'---I
I i Ammonia were the only two refrigerants in use) but is no longer used because other complex
U formulas are much more efficient.

r: So is water a refrigerant?
\
lJ Remember that a refrigerant, in order to cool the space, must evaporate at the temperature of

I,
I '
the space. Unless the room you are trying to cool, or the inside of your fridge, is 1000C or
more, water will not work as a refrigerant at normal atmospheric pressure. You would have to
U reduce the pressure to almost nothing before water will boil at DoC (0.089 PSI to be exact). This
is impractical. However, if you want to cool something which is very hot (i.e. over 1000C) like
ri the rods of a nuclear reactor, then pouring water on it will do the job. In turning to steam
I 'i
L.J (evaporating) the rods are cooled. This is how cooling towers work - water is poured onto the
hot object at the base of the cooling tower. The water turns to steam and rises (because water
vapour is lighter than air) and expands, which forces it to cool (Charles' Law). The cooled
steam condenses into water which runs down the inside of the cooling tower and back onto the
hot object where the process repeats. So you have water, as a refrigerant, cooling an object in

o much the same way as Freon or Ammonia cools the interior of your car, office or fridge.

But also, water can vaporise at temperatures below 100°C, thus missing out the boiling process.
n
I , Hence water which exudes from the pores of your skin when you are hot (sweat) evaporates,
L and in changing state absorbs the heat from your skin, and cools you. Again water is a
refrigerant. However, to be efficient, it usually helps to have a breeze over the skin to help the

c evaporation process.

Heat Pumps
II
\ '
A heat pump is a machine or device that moves heat from one location (the 'source') to another
cJ location (the 'sink' or 'heat sink'), using work. Most heat pump technology moves heat from a
low temperature heat source to a higher temperature heat sink. Common examples are food

o refrigerators and freezers and air conditioners and reversible-cycle heat pumps for providing
thermal comfort.
Ci
Heat pumps can be thought of as a heat engine which is operating in reverse. One common
U type of heat pump works by exploiting the physical properties of an evaporating and condensing

o a refrigerant. In heating, ventilation, and cooling (HVAC) applications, a heat pump normally
refers to a vapour-compression refrigeration device that includes a reversing valve and
optimized heat exchangers so that the direction of heat flow may be reversed. Most commonly,
heat pumps draw heat from the air or from the ground. Air-source heat pumps do not work well
when temperatures fall below around -5°C (23°F).

According to the second law of thermodynamics heat cannot spontaneously flow from a colder
rl
u location to a hotter area; work is required to achieve this. Heat pumps differ in how they apply
this work to move heat, but they can essentially be thought of as heat engines operating in

o reverse. A heat engine allows energy to flow from a hot 'source' to a cold heat 'sink', extracting a

Module 2.3 Thermodynamics 3-53

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, J

fraction of it as work in the process. Conversely, a heat pump requires work to move thermal
energy from a cold source to a warmer heat sink.

Since the heat pump uses a certain amount of work to move the heat, the amount of energy
deposited at the hot side is greater than the energy taken from the cold side by an amount
equal to the work required. Conversely, for a heat engine, the amount of energy taken from the
hot side is greater than the amount of energy deposited in the cold heat sink since some of the
heat has been converted to work.
n
u

'1
[
,
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:"1
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Figure 3.12. A heat pump's vapour-compression refrigeration

cycle: 1) condenser, 2) expansion valve, 3) evaporator, .-,
I '
4) compressor. ;J
The working fluid, in its gaseous state, is pressurized and circulated through the system by a
compressor. On the discharge side of the compressor, the now hot and highly pressurized gas
is cooled in a heat exchanger called a condenser until it condenses into a high pressure,
moderate temperature liquid. The condensed refrigerant then passes through a pressure-
lowering device like an expansion valve, capillary tube, or possibly a work-extracting device
such as a turbine. This device then passes the low pressure, barely liquid (saturated vapour)
refrigerant to another heat exchanger, the evaporator where the refrigerant evaporates into a
gas via heat absorption. The refrigerant then retums to the compressor and the cycle is
repeated.

In such a system it is essential that the refrigerant reaches a sufficiently high temperature when
compressed, since the second law of thermodynamics prevents heat from flowing from a cold ,.-,
fluid to a hot heat sink. Similarly, the fluid must reach a sufficiently low temperature when : I
allowed to expand, or heat cannot flow from the cold region into the fluid. In particular, the lJ
pressure difference must be great enough for the fluid to condense at the hot side and still
evaporate in the lower pressure region at the cold side. The greater the temperature difference,
the greater the required pressure difference, and consequently more energy is needed to
compress the fluid. Thus as with all heat pumps, the energy efficiency (amount of heat moved
per unit of input work required) decreases with increasing temperature difference. Thus a
ground-source heat pump, which has a very small temperature differential, is relatively efficient.
(Figures of 75% and above are quoted.)
,<" I
U

3-54
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11
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r~,
Due to the variations required in temperatures and pressures, many different refrigerants are
available. Refrigerators, air conditioners, and some heating systems are common applications
LJ that use this technology.

In HVAC applications, a heat pump normally refers to a vapour-compression refrigeration

device that includes a reversing valve and optimized heat exchangers so that the direction of

o heat flow may be reversed. The reversing valve switches the direction of refrigerant through the
cycle and therefore the heat pump may deliver either heating or cooling to a building. In the
cooler climates the default setting of the reversing valve is heating. The default setting in
warmer climates is cooling. Because the two heat exchangers, the condenser and evaporator,
r1
\
~.
I, must swap functions, they are optimized to perform adequately in both modes. As such, the
efficiency of a reversible heat pump is typically slightly less than two separately-optimized
machines.

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Module 2.3 Thermodynamics 3-55

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3-56 Module 2,3 Thermodynamics il

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ri
U Thermodynamics and the 1st and 2nd Laws
We have already seen, the three thermodynamic processes. Here is a brief recap:
r1
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Lj Boyle's Law
Pressure and volume are inversely proportional to each other, providing temperature remains
constant (i.e. if you decrease the volume of a gas, its absolute pressure will increase by the
same proportion).

This is an ISOTHERMAL process (ISO means 'equal' and THERMAL means 'temperature')

Charles' Law
{I Volume and temperature are directly proportional to each other, providing the pressure remains
U constant (i.e. if you increase the absolute temperature of an unrestrained volume of gas, its
volume will increase by the same proportion).

This is an ISOBARIC process (BARIC means 'pressure')

Gay Lussac's Law

Pressure and Temperature are directly proportional to each other, providing the volume remains
constant (i.e. if you increase the absolute temperature of a confined gas, its absolute pressure
will increase by the same proportion).

This is an ISOCHORIC process (CHORIC means 'volume' or 'size')

I'LJ
Note that all three processes involve absolute pressures and temperatures, those pressures
which include atmospheric pressure, and temperatures measured in Kelvin or degrees Rankin.
[!
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An Adiabatic Process
Another definition to know is that of ADIABATIC. That is:

When a change in the volume and pressure of the contents of a system takes place
without exchange of heat between the system and its surroundings.

Although there is no flow of heat, the system temperature can change as heat energy can be
i1 converted to mechanical work and vice versa.
I :
G
It is easy to appreciate how Charles' Law and Gay Lussac's Law are NOT adiabatic processes,
since heat clearly must cross the boundary of the system (in both systems heat is added). It
makes no difference to the definition of adiabatic if the heat is added in the form of fuel, which is
subsequently ignited, or the gas is heated from an external heat source such as a flame.

c A little more difficult to determine, is whether Boyle's Law is an adiabatic process or not. It is
true that no heat is added whilst the gas is compressed, but the natural tendency is for the gas
(1 to rise in temperature as it is compressed (as Charles law tells us). The key then, to performing
U a compression under Boyles's Law is to compress the gas so slowly, that any heat which builds
up leaks away before it has a chance to show itself in the form of a temperature rise. The fact

o
n
u 3-57
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'. J
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that heat is leaking away (through the casing of the system) precludes it from being an adiabatic .....,
\ i
process. l J

The definition of adiabatic does not differentiate between heat being added (as in Charles' and :l
Gay Lussac's Laws), conventionally considered positive, and heat removed (as in Boyle's Law), 1J
conventionally considered negative.

One example of a process which is adiabatic, is that of an air compressor. Inside the cylinder of
an air compressor, as the volume is rabidly reduced, the air is compressed so quickly, that any
n
rise in temperature does not result in any loss of heat through the cylinder walls - the air being
removed from the cylinder before the heat has a chance to escape. However, if you put your
hands on the air compressor that supplies the air-lines around your hangar, you will almost
certainly find it to be hot. The conclusion is then that an adiabatic process exists mainly in rl
· I
theoretical terms only, and is very difficult to achieve in practice. I• .J'

Thermodynamic Work ~
Most thermodynamic processes are carried out in order to do work - the combustion of fuel ,, )

inside your car engine, or inside an aero engine for example. But as we saw previously, to do
work, there must be some movement, and a force in the same direction as that movement.

Consider a piston inside a cylinder as shown

spark plug valves ,I
in Figure 3.13. After both valves are closed,
I J
the gas is ignited and it expands. This
expansion pushes the piston down the
cylinder, with a considerable force. Hence,
'I
!
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work is done and can be calculated by

Work = Force x Distance

But the force on the piston is given by ,....,,

,
, I

piston U
Force = Pressure x Area

Where the Pressure is the pressure of the

crankshaft gas in the cylinder, and the Area is the
piston face area.
C1

Figure 3.13: An internal combustion engine

converts chemical energy into heat energy and
then into mechanical work :I
• I
:J

Module 2.3 Thermodynamics

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1.1
o Hence our Work formula is now
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I,
U Work = Pressure x Area x Distance where 'distance' is the
movement of the piston

Force
t If we simplify the diagram as shown in Figure 3.13, you
will see that the distance that the piston moves,
multiplied by the Area of the piston, equates to the
increase in volume of the gas as it burns.

i-I
U Area
rlI
I
t
L! Distance
t
o Figure 3.14: A simplified heat
engine

r:u Our formula for work then becomes:

o Work =Pressure x Change in Volume

,( ,,
i.e. Work =P IlV Where 'Il' (delta) indicates a
'change in' the quantity V
L
"UI
I This is the standard formula for Work done in a thermodynamic process (it is only applicable to
processes where the volume changes, if the volume does not change, no work is done). It
applies regardless of the direction of work, so if an external force is applied to the piston, the
r", volume of gas in the cylinder will reduce. The work required to reduce the volume is given by
I i
u the same formula.

Thermodynamicists often simplify the formula to

Work =PV
o It makes certain assumptions, for example, that the pressure remains constant as the gas
expands. In a piston engine, this is not the case, as the pressure rises to a peak as the gas is
r--i
\ r burned, then reduces as the piston is displaced. It is however, a fair assumption to make, in the
L.;
case of a gas turbine engine, as the gas in the combustion chamber is burned, and expands at
constant pressure. Even in the case of the piston engine however, the above formula can still
fl
\ i be used in conjunction with some complex calculus (which is not part of the EASA Part-66
u
syllabus, and way beyond the scope of these notes).

rlu Use andlor disclosure is

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Internal Energy
Whenever a gas increases in temperature, the molecules of the gas vibrate and move around il
l )
more vigorously. It is this increased kinetic energy that actually produces the increased
pressure as they collide with each other and with the walls of the container in which it is n
confined. This kinetic energy is directly proportional to the absolute temperature in the gas. )J
Thermodynamicists call the sum of this kinetic and potential energies in the gas, "Internal
Energy", symbol U, and is measured in Joules. :j
! I
: J
When the temperature of a gas is increased, it will increase in volume (and provide work) or
increase in internal kinetic and potential (due to a rise in pressure) energies - that is, increase 'I'
,

Internal Energy, or more likely, a combination of both volume and internal energy changes. ..1

Enthalpy n,
, I
The combination of internal energy, and pressure and volume are the most likely things to ',_ J

change whenever a gas is heated. Since this happens so often in thermodynamics, it is all
grouped together and given its own name and unit. It is called "Enthalpy" and given a symbol
H. It is simply the sum of the internal energy plus the pressure volume product.

Thus Enthalpy H =U + PV
Remember that PV is the work done when a gas expands when it is heated.

Infact, Enthalpy is the amount of energy in a gas which is capable of doing work.

The First Law of Thermodynamics

If you have understood this chapter so far, you will be pleased to know that we have already
covered the First Law of Thermodynamics. It is best thought of by thinking of the air/fuel
mixture that enters your car engine cylinder. It enters at about 15°C and standard atmospheric
pressure. When it is ignited to release all its internal chemical energy as heat energy, it will
expand, push the piston with a certain pressure, and provide work. The chemical energy of the
fuel (before it is ignited) is measured in J/kg, of the order of around 10 MJ/kg.

You would be forgiven for thinking that all the heat energy (symbol Q) released on burning can ,,""",
be transformed into work (Symbol W), thus: .I J.

Heat energy added to system (Q) =Work done by system (W)

However, now imagine that you walk around the car and put your hand over the exhaust. Two
things you will notice; one is that it is considerably hotter than it went into the engine, and two;
that it is considerably higher pressure than when it went into the engine. This is because not all
of the heat energy added to the gas can be turned into useful work, some of the heat energy
added to the gas will leave via the exhaust in the form of Internal Energy (symbol U). Our n,
,
formula is now: lJ
Heat energy added to the system (Q) =Work done by the system (W) plus a change in II
, J

Internal Energy (U) I

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Module 2.3 Thermodynamics

3-60 Use andlor disclosure is
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r-'! Or in its simplest terms

I
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Q=W+U
f1
u This is the mathematical version of the 1st Law of Thermodynamics.

o =
It is typical for chemistry texts to write the first law as fl.U Q - W. It is the same law, of course -
the thermodynamic expression of the conservation of energy principle. It is just that W is defined
as the work done on the system instead of work done Qy the system. In the context of physics,
n
u the common scenario is one of adding heat to a volume of gas and using the expansion of that
gas to do work, as in the pushing down of a piston in an internal combustion engine. In the
Jl'
context of chemical reactions and process, it may be more common to deal with situations
I
[ ! where work is done on the system rather than Qy it.
u

Engine designers of course try to minimise the internal energy (U) rise which is wasted through
fi
Lj
the exhaust, and maximise the Work output, thus making most efficient use of the chemical
energy locked away in the petrol. But as we will see in the 2 nd Law of Thermodynamics, an

o engine of 100% thermal efficiency (where all the heat energy is transformed into work) is not
possible, theoretically as well as practically.

o During the mid-eighteenth century, when the 1st law of thermodynamics was discovered, it was
thought possible that an engine could be produced which ran off the heat energy (internal
energy) in the exhaust of another engine. Indeed, it seemed possible theoretically to run an
engine off its own exhaust. This led to much research into such a machine, which would have
been the invention of perpetual motion. This same research led only to the conclusion that such
a machine, and with it, perpetual motion, was impossible, and a new law which described this
impossibility, the Second Law of Thermodynamics ...

The Second Law of Thermodynamics

The First Law of Thermodynamics is really a prelude to the second. It states that the total
energy output (as that produced by a machine) is equal to the amount of heat sLipplied,
Generally, energy can neither be created nor destroyed, so the sum of mass and energy is
always conserved.

Physicists attempting to transform heat into work with full efficacy quickly learned that always
n some heat would escape into the surrounding environment, eternally doomed to be wasted
energy (recall that energy can not be destroyed). Being obsolete, this energy can never be
Ic..J• converted into anything useful again.
(1
u One physicist noted for significant experiments in this field is the Frenchman, Sadi Carnot. His
ideal engine, so properly titled the 'Carnot Engine,' would theoretically have a work output equal
I' to that of its heat input (thus not losing any energy in the process). However, he fell into a
U similar trap as in the first law, and failed to conduct his experiments as would naturally occur.
Realizing his error, he concluded (after further experimentation) that no device could completely
make the desired conversion, without losing at least some energy to the environment. .

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Carnot created an equation he employed to prove this statement, and which is currently used to
show the thermodynamic efficiency of a heat machine: n
· .
effIClency = 1 -TL
-
TH n
(the efficiency of a heat machine is equal to one minus the low operating temperature of the
machine in degrees Kelvin, divided by the high operating temperate of the machine in degrees
Kelvin). For a machine to attain 100% efficiency, temperatures of absolute zero would have to
be incorporated. Reaching absolute zero is later proved impossible by the Third Law of
'l
Thermodynamics (which would surface in the late 19th century).
U

The irrevocable loss of some energy to the environment was associated with an increase of
disorder in that system. Scientists wishing to further penetrate the realm of chaos needed a
n
variable that could be used to calculate disorder. Thanks to mid-nineteenth century physicist,
R.J.E. Clausius, this Pandemonium could be measured in terms of a quantity named entropy1 n~ .J
(the variable S). Entropy acts as a function of the state of a system - where a high amount of
entropy translates to higher chaos within the system, and low entropy signals a highly ordered
state. n
Like Carnot, Clausius worked out a general equation, his being devoted to the measurement of
entropy change over a period of time: (change)S = Q I T (the change in entropy is equal to the
amount of heat added to the system [by an invertible process] divided by the temperature in
n
degrees Kelvin). The beauty of this equation is that it can be used to compute the entropic C'l
change of any exchange in nature, not solely limited to machines. This development brought i, I
thermodynamics out of the industrial workplace, and opened the possibility for further studies
into the tendencies of natural order (and lack therefore of), eventually extending to the universe
as a whole.
n l ,J

r-;
Applying this knowledge to nature, physicists found that the total entropy change (change in S) ! I
always increases for every naturally occurring event (within a closed system) that could be then U
observed. Thus, they theorized, disorder must be continually augmenting evenly throughout the
universe. When you put ice into a hot cup of tea (aristocrats of the Victorian era were constantly
thinking of tea), heat will flow from the hot tea to the cold ice and melt the ice in the beloved
beverage. Then, once the energy in the cup is evenly distributed, the cooled tea would reach a ,.--,
maximum state of entropy. This situation represents a standard increase in disorder, believed to
be perpetually occurring throughout the entire universe.
:L)I

'I
1 - Entropy - Specifically is a measure of randomness or disorder in a system. Darrell Ebbing, in the textbook
,'- _JI
General Chemistry, very usefully suggests thinking of a deck of cards. A new pack fresh out of the box, arranged
by suit and in sequence from ace to king, can be said to be in its ordered state. Shuffle the cards and you put them
into a disordered state. Entropy is a way of measuring just how disordered that state is and of determining the
likelihood of particular outcomes with further shuffles. Of course, if you wish to have any observations published in
n
'. ,J

a respectable journal you will need also to understand additional concepts such as thermal non-uniformities, lattice ,....,
distances, and stoichometric relationships, but that's the general idea.
;I
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Module 2.3 Thermodynamics :n·,

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•I
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o
_1
The second law of thermodynamics (also known as 'the entropy law' or 'law of entropy') was
formulated in the middle of the nineteenth century by Clausius and Thomson following Carnot's
earlier observation that, like the fall or flow of a stream that turns a mill wheel, it is the "fall" or
flow of heat from higher to lower temperatures that motivates a steam engine. The key insight
I I
, I
U was that the world is inherently active, and that whenever an energy distribution is out of
equilibrium a potential or thermodynamic "force" (the gradient of a potential) exists that the

c world acts spontaneously to dissipate or minimize. All real-world change or dynamics is seen to
follow, or be motivated, by this law. 80 whereas the first law expresses that which remains the
same, or is time-symmetric, in all real-world processes the second law expresses that which
changes and motivates the change, the fundamental time-asymmetry, in all real-world
processes. Clausius coined the term "entropy" to refer to the dissipated potential and the
second law, in its most general form, states that the world acts spontaneously to minimize
n
I !
potentials (or equivalently maximize entropy), and with this, active end-directedness or time-
asymmetry was, for the first time, given a universal physical basis. The balance equation of the
U
second law, expressed as 8 > 0, says that in all natural processes the entropy of the world
always increases, and thus whereas with the first law there is no time, and the past, present,
and future are indistinguishable, the second law, with its one-way flow, introduces the basis for
telling the difference.
ff
u The active nature of the second law is intuitively easy to
grasp and empirically demonstrate. If a glass of hot liquid,
for example, as shown in Figure 16-3, is placed in a colder
room a potential exists and a flow of heat is spontaneously
produced from the cup to the room until it is minimized (or
r-
the entropy is maximized) at which point the temperatures
lJ are the same and all flows stop.

The glass of Ii~uid at temperature TI is placed in a room at

I temperature TI such that the disequilibrium produces a field
potential that results in a flow of energy in the form of heat
from the glass to the room so as to drain the potential until it
is minimized (the entropy is maximized) at which time
thermodynamic equilibrium is reached and all flows stop.

o Figure 3.15: Heat transfer

This refers to the conservation of energy in that the flow
from the glass equals the flow of heat into the room.

from a hot space to a

less-hot space

o The two laws have far reaching ramifications in physics and the real world. One such is that no
heat engine can ever be 100% efficient, unless the exhaust temperature (known as the 'sink'
temperature) is absolute zero. Absolute zero is both theoretically and practically impossible to
achieve. Another ramification is the fact that no thermodynamics process can be reversed,
precisely due to the first law which states that not all the heat energy supplied can be turned

o into work.

The closest one can come to a fully reversible process is forcing a flow through a constricted
pipe. Ideal means no boundary layer losses. As the flow moves through the constriction, the
Iiu

o Use andfor disclosure is

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on page 2 of this chapter.
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pressure, temperature and velocity change, but these variables return to their original values
downstream of the constriction. The state of the gas returns to its original conditions and the
change of entropy of the system is zero. Aerodynamicists call such a process an isentropic
process. Isentropic means constant entropy.

The second law states that if the physical process is irreversible, the combined entropy of the
system and the environment must increase. The final entropy must be greater than the initial
entropy for an irreversible process: n
L ,

Summary r,
i i
Thermodynamics is the study of the inter-relation between heat, work and internal energy of a I-,•

system.

The British scientist and author C.P. Snow had an excellent way of remembering the three laws
(including the 3 rd law):
n
I I
1. You cannot win (that is, you cannot get something for nothing, because matter and l" J

energy are conserved).

2. You cannot break even (you cannot return to the same energy state, because there is
always an increase in disorder; entropy always increases).
n
\..- j

3. You cannot get out of the game (because absolute zero is unattainable).
n
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Module 2.3 Thermodynamics

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n
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