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THE FUNDAMENTALS OF MECHANICAL ENGINEERING

THERMODYNAMICS
W van Niekerk
2013

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Preface
Students can find textbooks in Thermodynamics quite intimidating. The rigorous derivation of
all the laws and equations can be quite complex. Add to that the abstract nature of many of
the concepts used and no wonder Thermodynamics is perceived as difficult. In this document
an effort is made to develop the laws and concepts in an easy to follow, concrete manner. It is
an first, introductory text.
The logical way to explain the conservation of energy is to first cover closed systems (the control
mass) combining heat, work and internal energy in the First Law. Using that as foundation,
the concept of enthalpy is developed and the conservation of energy in open systems (control
volumes) explained. Once the student understands the concept of energy conservation, the
concepts the student now needs to understand are that of reversibility and entropy - be it in
open or closed systems. Once the student is comfortable with reversibility and entropy he/she
should find it easier to understand real systems and the generation of entropy. This approach
is followed in this text and is shown schematically in Figure 1 below.

ii

Figure 1: Overview
But also in the smaller detail, the approach is different. When the First Law for closed systems
(the control mass) is introduced, initially only heat, work and internal energy are taken into
consideration. Potential energy very rarely is relevant during the implementation of the First
Law for closed systems. Examples where potential and kinetic energy are relevant, are done.

Contents
Preface

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 Properties of pure substances


1.1 Properties . . . . . . . . . . . . . . . . . . . . . . . .
1.1.1 Temperature . . . . . . . . . . . . . . . . . .
1.1.2 Pressure . . . . . . . . . . . . . . . . . . . . .
1.1.3 Volume and Mass . . . . . . . . . . . . . . . .
1.2 Single phase systems . . . . . . . . . . . . . . . . . .
1.2.1 Ideal gases . . . . . . . . . . . . . . . . . . .
1.2.2 Real Gases . . . . . . . . . . . . . . . . . . .
1.2.3 Liquids and solids . . . . . . . . . . . . . . .
1.3 Two-phase systems . . . . . . . . . . . . . . . . . . .
1.3.1 Phase change . . . . . . . . . . . . . . . . . .
1.3.2 Quality . . . . . . . . . . . . . . . . . . . . .
1.4 Determining the phase of water . . . . . . . . . . . .
1.4.1 Temperature and pressure . . . . . . . . . . .
1.4.2 Pressure or temperature and specific volume
1.4.3 Temperature or pressure and quality . . . . .
2 Work and heat in closed systems
2.1 Closed and open systems . . . . . . . .
2.2 Work . . . . . . . . . . . . . . . . . . .
2.2.1 The Isobaric Process . . . . . .
2.2.2 The Isothermal Process . . . .
2.2.3 The Adiabatic Process . . . . .
2.2.4 The Isochoric Process . . . . .
2.2.5 Process with Spring Restrained
2.2.6 Non-equilibrium processes . . .
2.3 Heat transfer . . . . . . . . . . . . . .

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CONTENTS

3 The First Law for Closed Systems


3.1 Internal energy . . . . . . . . . . . . . .
3.1.1 Ideal gases . . . . . . . . . . . .
3.1.2 Perfect gases . . . . . . . . . . .
3.1.3 Real gases . . . . . . . . . . . . .
3.1.4 Two phase systems . . . . . . . .
3.1.5 Compressesed liquids . . . . . . .
3.1.6 Solids . . . . . . . . . . . . . . .
3.1.7 Determination of internal energy
3.2 The First Law for closed systems . . . .
3.2.1 Kinetic and potential energy . .
3.2.2 Sign convention . . . . . . . . . .
3.3 Adiabatic processes . . . . . . . . . . . .

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4 The First Law for open systems


4.1 Enthalpy . . . . . . . . . . . . . . . . . . . .
4.1.1 Ideal gases . . . . . . . . . . . . . . .
4.1.2 Perfect gases . . . . . . . . . . . . . .
4.1.3 Real and condensible gases . . . . . .
4.1.4 Compressed liquids and solids . . . . .
4.2 The first law for steady state, open systems .
4.2.1 Shaft work . . . . . . . . . . . . . . .
4.2.2 Heat . . . . . . . . . . . . . . . . . . .
4.2.3 Kinetic energy . . . . . . . . . . . . .
4.2.4 Potential energy . . . . . . . . . . . .
4.2.5 Common open systems . . . . . . . . .
4.3 Calculating heat transfer using specific heats
4.3.1 Compressed Liquids and Solids . . . .
4.3.2 Gases . . . . . . . . . . . . . . . . . .
4.4 Unsteady state processes . . . . . . . . . . . .
5 Reversible Systems
5.1 Reversibility and Irreversibility . .
5.2 Entropy . . . . . . . . . . . . . . .
5.3 Determination of Entropy . . . . .
5.3.1 Ideal gases . . . . . . . . .
5.3.2 Perfect gases . . . . . . . .
5.3.3 Real and condensible gases

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CONTENTS
5.4
5.5

5.6

Entropy and work . . . . . . . . . . . . . . .


Reversible processes . . . . . . . . . . . . . .
5.5.1 Reversible adiabatic processes . . . . .
5.5.2 Reversible processes with heat transfer
5.5.3 Reversible heat engines . . . . . . . .
Enthalpy revisited . . . . . . . . . . . . . . .

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6 Real Systems
6.1 Entropy generation in real systems . . . . . . . . .
6.1.1 Friction . . . . . . . . . . . . . . . . . . . .
6.1.2 Unrestrained expansion . . . . . . . . . . .
6.1.3 Heat transfer over a temperature difference
6.2 The significance of entropy generation . . . . . . .
6.3 Entropy in real systems . . . . . . . . . . . . . . .
6.3.1 Entropy transfer with heat. . . . . . . . . .
6.3.2 Internally reversible systems . . . . . . . . .
6.3.3 Internally irreversible systems . . . . . . . .

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ii

CONTENTS

Chapter 1

Properties of pure substances


1.1

Properties

Substances have properties that are used to identify and describe them. You should be familiar
with four properties from everyday life: temperature, pressure, volume and mass. We measure
the amount of milk by volume and meat by mass. We quantify the hotness or coldness of
air by measuring its temperature. Pressure gives an indication of the force necessary to contain
a fluid.
We distinguish between intensive and extensive properties. Temperature is an intensive property
as its value does not depend on the amount of matter of the substance. A cup of water can be
at 20 C as well as a drop of water. Volume and mass are extensive properties. The mass and
volume of a substance is directly proportional to the amount of matter making up the substance.
A cup of water cannot have the same mass as a drop of water.
Another characteristic of properties is that the value of a property is not dependent on the history
of the substance. We cannot deduct from the temperature at the present moment whether the
temperature was higher or lower at an earlier stage.

1.1.1

Temperature

Temperature is measured in degrees Celsius [ C] or Kelvin [K]. To convert a temperature in C


to K, add 273.15. This means 50 C is the same as 323.15K. It also means that a temperature
difference expressed in degrees Celsius is numerically the same as the difference expressed in
Kelvin. The lowest possible temperature is 0K. Temperature is an intensive variable.1

Temperature can also be measured in F . T [ F ] = 1.8T [ C] + 32. This means that 100 C = 212 F . The
absolute temperature associated with F is Rankine. The temperature in [R] is obtained by adding 459.67 to the
temperature in [F ]

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

1.1.2

Pressure

Pressure (P ) is the force per unit area:


P =

F
A

With F in [kN ] and A in [m2 ], P will be in [kN/m2 ]=[kP a]. Pressure is an intensive variable.
Other common pressure units are:
atmosphere (1atm = 101.325kP a) and
bar (1bar = 100kP a)
Absolute or total pressure
The total pressure is the total force exerted on a surface divided by the area of the surface.
In a gas, the force exerted on a surface is due to the collision of the gas molecules against the
surface. There is a limit at how low total pressure can be. If no force is exerted on a surface the
total pressure is zero. The pressure of a complete vacuum is zero because there are no molecules
colliding with the surface of the container. Absolute pressure (Pabs ) is the pressure measured
above this zero point. The value of total pressure can never be negative.
Atmospheric pressure
Atmospheric pressure (Patm ) is the total pressure caused by the weight of the atmospheric air.
This pressure varies according to location and weather patterns. The average value at sea-level
is 101.325kP a. The average atmospheric pressure for Potchefstroom is 87.0kP a with 99% of
the values between 86.0kP a and 88kP a. The average atmospheric pressures for a few major
cities in South Africa are given in Table 1.1.2 It is clear that the height above sea level plays a
dominating role in determining the average value. Atmospheric pressure is also called ambient
pressure.
Table 1.1: Average atmospheric pressure for a few cities in South Africa.
City
Kimberley
Polokwane
Pretoria
Potchefstroom
Bloemfontein
Johannesburg

Height above sea level [m]


1230
1262
1350
1351
1395
1700

Mean Atmospheric Pressure [kP a]


88.5
88.3
87.5
87.0
86.7
83.5

Gauge pressure
Gauge pressure (Pg ) is the difference between the pressure inside the vessel and outside. The
pressure outside is usually equal to atmospheric pressure but for a vessel submerged in water
2

With acknowledgment to the South African Weather Service.

1.1. PROPERTIES
such as a submarine, the pressure outside may differ from the atmospheric pressure.
Pg = Pabs Patm

If the total pressure of a fluid is lower than the atmospheric pressure, the gauge pressure will
be negative and when it is higher, it will be positive. Except when specifically stated that it
is a total or absolute pressure gauge, the pressure displayed by a pressure gauge is the gauge
pressure. We use a pressure gauge at the petrol station to measure the gauge pressure of the air
in the tires of our cars.
Example
Assume you have inflated the spare tyre of your car to a gauge pressure of 200kP a on the
Highveld where the atmospheric pressure on that day is 85kP a. The absolute (or total
pressure) inside the spare tyre is now 285kP a. You now drive to the sea where the atmospheric pressure on that day is 101kP a. What is the gauge pressure of the spare tyre now?
Solution
If the spare tyre does not leak, the mass of air inside does not change. Let us assume the
volume stayed the same as well as the temperature. Therefore the absolute pressure also
remained the same (this can be shown to be true by using the Ideal Gas Law which is done
later), but the gauge pressure would have dropped to 184kPa. You will have to inflate the
tyre somewhat if you want to use it now.
Hydrostatic Pressure
The pressure exerted by a liquid column with a constant density, is given by the equation:
P =

gh
1000

With in [kg/m3 ], g = 9.81m/s2 and h in [m], P will be in [kP a],.


Example
Assume you go down a mine shaft 1000m deep. Calculate the pressure exerted by a column
of air 1000m high. Assume the air has a density of 1kg/m3 .
Solution
1 9.81 1000
= 9.81kP a
1000
This is in the same range as the change in pressure you will experience traveling from the
Highveld to the coast. The density of the air will change due to the significant change in
pressure - so the assumption of constant air density can be questioned. How will you account
for the change in air density?
P =

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

Figure 1.1: Manometer

Example
A manometer is connected to a pipe filled with air as shown in the figure. The manometer
is filled with mercury. The density of the mercury can be taken as 13600kg/m3 . The height
(h) is 0.2m and the atmospheric pressure 87kP a. Calculate the absolute and gauge pressure
inside the pipe.
Solution
The pressure exerted by the column of mercury is:
Pmercury =

0.2 9.81 13600


= 26.68kP a
1000

The pressure on the surface of the mercury exposed to the atmosphere is equal to 87kP a.
In the other leg of the manometer, at the same elevation, the pressure will also be 87kP a.
Moving upwards from that elevation to the surface of the mercury, will cause a drop in total
pressure. The density of the air is very low, therefore it can be assumed that the pressure
inside the pipe is uniform. Therefore:
Pabs,inside = 87 26.68 = 58.32kP a
The gauge pressure is 26.68kP a. From the figure it is also clear that the pressure inside
the pipe is lower than the pressure inside, therefore it makes sense that the gauge pressure
has a negative value.

1.1.3

Volume and Mass

In thermodynamics, volume and mass are usually combined to form a new property: specific
volume (v). Specific volume is the total volume divided by the total mass v = V /m [m3/kg].

1.2. SINGLE PHASE SYSTEMS


Specific volume is an intensive property. Density () is the inverse of specific volume.3
Example
A cup holds 250m` of boiling hot water at 95 C. The mass of the water is 240.4g. Calculate
the specific volume in [m3 /kg] and the density in [kg/m3].
Solution
Specific volume is the volume divided by the mass: v = V /m. First determine the values of
V and m.
1`
1m3

1000m` 1000`
= 250 106 m3
1kg
m = 240.4g
1000g
= 240.4 103 kg
v = 250106/240.4103
V = 250m`

= 0.00104m3/kg
and = 1/v = 961.5kg/m3

Sometimes the density of a substance is given relative to a reference substance. Then it is called
relative density or the somewhat misleading term, specific gravity (SG). In the case of liquids
(and often solids) the reference substance is usually water at a pressure of 101.3kP a and 4 C
with a density of 1000kg/m3 . The density of mercury is often taken as 13.6. This means its
density is 13600kg/m3
Let us see how P, T and v are interdependent.

1.2

Single phase systems

The term phase refers to a quantity of matter that is homogeneous throughout in both chemical
composition and physical structure. Homogeneity in physical structure means that the matter
is all solid, or all liquid, or all gas. An oil-water mixture consists of two liquid phases - a water
phase and an oil phase. They are both liquids but their chemical compositions differ. The
three phases of water are shown in Figure 1.2 below. The three phases are separated by phase
boundaries with zero thickness.
For single-phase substances, we can alter the values of two intensive properties independently.
For instance, consider water at 100kP a and 50 C (indicated by the ) We can increase the
3

In order to know whether answers you get during calculations are realistic, it is important that you remember
typical values for the variables you will encounter in Thermodynamics. The density of water is approximately
1kg/` or 1000kg/m3 while that of atmospheric air is approximately 1kg/m3 and the specific volume approximately
1m3 /kg.

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

Figure 1.2: The three phases of water.


temperature a few degrees without the water changing phase (starting to boil). We can also
reduce the temperature of the steam (shown by the ) a few degrees without the steam changing
phase (condensing).
Because we can change the value of two intensive properties independently we say a single-phase
substance has two degrees of freedom.4 It means that once we have specified the values of two
independent intensive properties the state of the system is fixed and the values of other intensive
properties are also fixed. The state of the substance is simply the condition of the substance
as described by its properties. If we heat up water, we say its state has changed because its
temperature has changed. There are different ways in which to determine the value of the other
properties.

1.2.1

Ideal gases

An ideal gas is a hypothetical gas whose molecules/atoms do not attract or repulse each other
and collide elastically with each other and the walls of the container. They are point particles
occupying negligible space. At high temperatures and low pressures,5 the density of gases are
low (the particles will occupy negligible space) and the kinetic energy of the particles much
higher than any possible inter-particle interactions and under these conditions gases are often
considered as Ideal Gases obeying the Ideal Gas Law. In this law, pressure, temperature and
specific volume are combined in one equation: (P v = RT ). R is the ideal gas constant. Its units
are [kP a m3 kg 1 K 1 ] and it has a specific value for every substance as shown in the table
below.6 Tables with the values of the ideal gas constant for different substances can be found
in literature.[1, Table A.5]
4

The number of degrees of freedom are determined by the Gibbs Phase Rule. See Cengel [2, p.759]
As a rule of thumb, a gas can be considered ideal if its temperature is twice its critical temperature and its
pressure half its critical pressure. Critical pressure and temperature are explained in Paragraph 1.3.1
3
6
In literature, the units of R are usually given as [kJ/(kgK)]. This is the same as [(kP am )/(kgK)].
5

1.2. SINGLE PHASE SYSTEMS

Table 1.2: Ideal gas constant for three gases.


Substance
Air
Steam
Helium

R [kP a m3 kg 1 K 1 ]
0.287
0.4615
2.0771

It is clear from the Ideal Gas Law that once we know what the temperature and pressure are,
we can calculate the specific volume using the Ideal Gas Law. In fact, the value of all other
intensive properties (density, viscosity, internal energy etc) ) can now be determined. Knowing
the values of any two variables (P, T ; P, v; T, v) enable us to calculate the value of all other
intensive properties and we say the state is fixed.

Example
Consider air at 25 C and 101kP a. Calculate its specific volume and the mass of 1m3 of air.
Solution

RT
P
0.287 298.15
=
101
= 0.8475m3/kg

v=

m=

V
v

1
0.8475
= 1.180kg
=

Make sure of the units when using the Ideal Gas Law. Temperature is in Kelvin, pressure is
the absolute pressure in kP a and specific volume is in m3 /kg. In the case of gases like air in
everyday use and Helium, the Ideal Gas Law is quite accurate. Usually we do not use the Ideal
Gas Law for steam.7
7

Optional textbook reading: Cengel [2] discuss the question: Is water vapor an ideal gas? and Compressibility factor - a measure of deviation from Ideal Gas Behaviour. See also paragraphs 3.6 and 3.7 in Sonntag [1]
on the same topics.

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

1.2.2

Real Gases

Super-heated steam is usually considered to be a real gas and the specific volumes at different
temperatures and pressures are tabulated in tables known as the steam tables. These are
available in hard copy or as software.
Example
Find the tables for super-heated steam at the back of your textbook.[1, Table B.1.3] (Note
that water refers to the chemical H2 O and is not an indication of the phase. We talk of
solid water, liquid water and water vapor when we refer to the solid, liquid or gas phases.)
Determine the specific volume of steam at 5000kP a and 350C. (0.05194m3/kg).
Now use the Ideal Gas Law to determine the specific volume (0.0575m3/kg). You can
see there is a significant difference between the two values. At low pressures and high
temperatures, the agreement will be better. We will not worry at the moment about how
high is high or how low is low as we will not use the Ideal Gas Law for steam. Even though
you can find the ideal gas constant for steam and other real gases in the tables giving the
ideal gas properties of gases, the Ideal Gas Law is only used for these substances under
special conditions. For instance atmospheric air contains some water vapor and this water
vapor is ususally assumed to obey the Ideal Gas Law.

Example
Steam at 5000kP a has a specific volume of 0.054m3/kg. Find the temperature of the steam.
Solution
You will note that 0.054m3/kg lies between the specific volumes at 350 C and 400 C. You
need to interpolate to find the required temperature. (367.5C)

1.2.3

Liquids and solids

Liquids below their boiling temperature and above their melting temperature(compressed or
sub-cooled liquids) and solids below their melting points are also single phase systems. Because
their molecules are so densely packed, pressure does not have a big influence on their volume.
Liquids and solids are therefore usually considered to be incompressible and that their volume
depends only on temperature. The density of liquids and solids at a single temperature (or
sometimes as function of temperature) can be found in textbooks [1, Table A.3, A.4]. In the
steam tables the properties of liquid and solid water (ice) as function of temperature AND
pressure are tabulated.

1.3. TWO-PHASE SYSTEMS

Example
Find the table for compressed water in the back of your textbook.[1, Table B.1.4] Find the
specific volume of water at 20 C and 500kP a. (0.001002m3/kg)
Now find the specific volume at the same temperature but at 5000kP a. (0.001000m3/kg)
Note that the specific volume stayed essentially constant. The assumption that liquid water
is incompressible is therefore a good assumption.

1.3

Two-phase systems

We will first consider a system consisting of liquid water and water vapor.

1.3.1

Phase change

If we heat up water enough it will start to boil it will undergo a phase change. It is instructive
to study some of the events that occur as a pure substance undergoes a phase change. Consider
water at 101.325kP a in a piston-cylinder assembly. The water is at 20 C, a temperature lower
than the boiling point and therefore it is a single-phase system. It has two degrees of freedom.
The temperature and the pressure can be varied independently without the water changing its
phase. The water is heated while the pressure remains constant at 101.325kP a. The volume
increases slightly as the water is heated and the temperature rises.(Assume the combined effect
of the cylinder and the ambient pressure is 101.325kP a and the piston is frictionless and can
therefore move to accommodate any increase in volume.)
At the boiling point (100 C), vapor starts to form and a two-phase system results. Even though
more heat is added, the temperature will remain constant. With the addition of more heat
only more vapor forms. It is no longer possible to vary temperature and pressure independently
without the system changing phase. If we increase the pressure on the system (by putting on
additional weights on the piston) the vapor will condense, release heat, and a single-phase system
will result once more. If we resume heating at this higher pressure, the temperature will rise to
a higher value before vapor will start to form again. As long as heat is added to a two-phase
system all the liquid will eventually vaporize and a single phase - a saturated vapor, will result.
If the saturated vapor is heated, its temperature will rise and super-heated vapor will form. A
super-heated vapor is also known as a gas. This behavior is shown in Figure 1.3 below. The
constant pressure heating of water will show as a horizontal line on a P v diagram (Figure
1.7).
If the pressure is high enough, no phase separation will take place. The liquid will change from a
liquid-like phase to a gas-like phase without two phases forming. You can see this happening in
Figure 1.3 at 40000kP a. The minimum pressure where no phase separation takes place, is called
the critical pressure. The temperature at the critical pressure is called the critical temperature.
The critical pressure of water is 22.09M P a and the critical temperature 374.14C.
The constant pressure heating of water can also be shown as a vertical line on a T-P phase
diagram (Figure 1.2) The the liquid-gas phase boundary in Figure 1.2 ends in the critical point.

10

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

Figure 1.3: Constant pressure heating of water


As long as two phases are present, the system is at the saturated state. The liquid is called
saturated liquid and the gas, saturated vapor. The temperature is the saturation temperature
and the pressure, the saturation pressure or vapor pressure. The relationship between saturation
pressure and saturation temperature is shown in Figure 1.4

Figure 1.4: Saturation pressure for water as function of temperature


It is clear from this graph that the equilibrium pressure is a unique function of temperature. For
a two-phase mixture, temperature and pressure are no longer independent. Once the pressure
(or temperature) is specified, the temperature (or pressure) and the specific volumes of the
saturated vapor and the saturated liquid are fixed. This seems to imply that two phase systems
have only one degree of freedom because all the variables are fixed once one variable is fixed.
This is true for saturated vapor only and saturated liquid.
Example
Find the saturation pressure, specific volume of saturated water vapor and specific volume
of saturated liquid water at 100 C. (101.325kP a; 1.6729m3/kg; 0.001044m3/kg)

1.4. DETERMINING THE PHASE OF WATER

11

In general we need to know the relative amount of liquid and vapor. We therefore need another
variable bringing to two the number of variables necessary to define the state completely. The
second variable can be specific volume or a variable that we will call quality.

1.3.2

Quality

For a saturated liquid-vapor mixture, the quality (x) is the ratio of the mass of vapor to the
total mass of the two-phase mixture:
x=

mvapor
mliquid + mvapor

The value of the quality varies from zero to unity. For a saturated liquid, x = 0, and for
a saturated vapor, x = 1. Quality is only defined for the saturated condition.8 Using the
saturation tables and the definition of quality, the specific volume of a two-phase liquid-vapor
mixture can be determined:
v = (1 x)vf + xvg

(1.1)

Example
Determine the pressure and specific volume of water at 100 C with a quality of 0.7.
Solution
Because the quality has a value between zero and one, we know it is a two-phase mixture
and the pressure will be the saturated pressure at 100 C, 101.3kP a. The specific volume of
the two phase mixture is calculated using Equation 1.1 and the volumes of saturated liquid
and saturated vapor at 100 C. ( 1.171343m3/kg)
It is also possible to get liquid/solid equilibrium and vapor/solid equilibrium. It is also possible
to get equilibrium between three phases - vapor, liquid and gas. It is the triple point and a pure
substance has only one triple point.
The slope of the solid/liquid equilibrium line for water on a pressure-temperature graph is
slightly negative. This means liquid water under pressure will freeze at a lower temperature
than water under a lower pressure. The slope is positive for substances that contracts upon
freezing.
If the behavior of any substance is plotted on three perpendicular axes, one each for temperature,
pressure and specific volume, a three dimensional shape results as shown in Figure 1.5 below.

1.4

Determining the phase of water

We have four variables that can be used to fix the state of a substance: Pressure, Temperature,
Specific volume and quality. In order to determine the values of the unknown variables once the
8
This means that x can never have a value bigger than unity such as 1.2. If you ever calculate x and find it is
bigger than 1, you have made a mistake somewhere!

12

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

Figure 1.5: PVT Diagram for water


state is fixed, we need to know the phase (solid, liquid or gas) of the substance. Once we know
the phase, we know which table (compressed liquid, saturated liquid, super-heated vapor) to
use. Let us look at common combinations of variables used to fix the state and how to determine
the phase.

1.4.1

Temperature and pressure

We determine the phase by comparing the specified temperature to the saturation temperature
at the specified pressure and comparing the specified pressure to the saturation pressure at the
specified temperature. In effect this means plotting the state on a PressureTemperature Phase
diagram. Only three phases are possible when the pressure and temperature are specified: solid,
liquid and gas. The lines separating the phases as in Figure 1.6 has zero thickness and the state
will either be a solid OR a liquid OR a vapor. The phase boundary between liquid water and
solid water (ice) is almost vertical.
Consider water at 100kP a and 50 C. The specified temperature is lower than 99.62C, the
saturation temperature at 100kP a and the specified pressure higher than 12.34kP a, the saturation pressure at the specified temperature. This means it is a compressed liquid as can be
seen from the position of the  in Figure 1.6. The quality is undefined and if we assume an
incompressible liquid, the volume of the substance is the same as that of the saturated liquid at
50 C, 0.001030m3/kg, which can be read from the tables for saturated water.[1, Table B.1.2]
Consider water at 100kP a and 150 C. Its pressure is lower than 475.9kP a, the saturation

1.4. DETERMINING THE PHASE OF WATER

13

Figure 1.6: PressureTemperature phase diagram for water.


pressure at the specified temperature and its temperature is higher than 99.62C, the saturation
temperature at the specified pressure. This means it is a super-heated vapor as can be seen by
the position of the in Figure1.6. Again the quality is undefined and the specific volume can
be read from the super-heated water vapor tables, 1.93636m3/kg

1.4.2

Pressure or temperature and specific volume

Heating water at a constant pressure (lower than the critical pressure) will first result in a
saturated liquid, then the a two-phase mixture and then a super-heated vapor. The P-v phase
diagram is shown in Figure 1.7. The phase is determined by comparing the specific volume of
the system with the specific volume of the saturated vapor and saturated liquid at the known
pressure or temperature.
Water at 1000kP a and 0.0005m3/kg is a compressed liquid because its specific volume is smaller
than that of the specific volume of the saturated liquid at the same pressure. It is also clear
from the position of the  in Figure 1.7. As the specific volume of a compressed liquid does not
change much with changes in temperature at lower values of temperature as can be seen in
Figure 1.3, it may be difficult to obtain an accurate value for temperature from specified values
of pressure and specific volume. For a compressed liquid, quality is undefined.
Water at 100kP a and 0.01m3/kg is a two-phase mixture as its specific volume lies between that
of the saturated liquid and saturated vapor at 100kP a. It is also clear from the position of the
in Figure 1.7. Its quality can be calculated from Equation 1.1 using the specific volume of
the saturated liquid (0.001043m3/kg), and the saturated vapor (1.694m3/kg) at 100kP a to obtain
a value of x = 0.005291. The temperature is the saturation temperature at 100kP a, 99.62C.
Water at 100kP a and 4.02781m3/kg is a super-heated vapor as its specific volume is larger than
that of a saturated vapor at the specified pressure. It is also clear from the position of the in
Figure 1.7. Its temperature can be determined from the super-heated water tables. In this case
the temperature can be read directly from the tables (600C), but in general, interpolation will
be necessary. Quality is undefined for a super-heated vapor.

14

CHAPTER 1. PROPERTIES OF PURE SUBSTANCES

Figure 1.7: Pressure-Specific Volume phase diagram for water.


When the temperature and specific volume are specified, the phase must first be determined
comparing the specific volume to the specific volumes of the saturated liquid and vapor at the
specified temperature - in effect by plotting the state on a T v diagram (Figure 1.3).

1.4.3

Temperature or pressure and quality

The quality of a saturated liquid is 0 and for a saturated vapor, 1. As quality is undefined for a
sub-cooled liquid and super-heated vapor, if the quality is specified, it means it is a two-phase
mixture and the temperature (or pressure) for the specified pressure (or temperature) can be
read from the tables for saturated water and the specific volume determined from Equation 1.1.

Chapter 2

Work and heat in closed systems


Thermodynamics is the study of energy and energy conversion. Often we are interested in the
conversion of heat into shaft work. The burning of coal or nuclear fission generates heat. This
heat is converted into shaft work which can readily be converted into electricity in a generator.
We will study the different ways of converting heat into work and the limits to this conversion
later. In this chapter we will only look at how work is performed in a closed system. Then we
will also introduce heat transfer.

2.1

Closed and open systems

An important step in any analysis is to define the system we want to study. We distinguish
between open and closed systems. An open system is a properly selected region in space.
It usually encloses a device with mass flowing in and out of the device, such as a hair dryer,
a boiler or turbine. A closed system consists of a fixed amount of mass. No mass can cross
the boundaries of a closed system. A piston-cylinder arrangement is the most common closed
system. We encounter piston-cylinder arrangements in internal-combustion engines, the engine
of steam locomotives and reciprocating air compressors. The piston-cylinder arrangement in an
internal combustion engine is only a closed system during the compression stroke and during
the power stroke. During the other strokes one of the valves is open to either allow the air/fuel
mixture to flow into the cylinder or the combustion products to flow out of the cylinder. The
system boundary separates the system from the surroundings and has zero thickness. Energy
in the form of heat can cross the boundaries of open and closed systems and the system can
perform work or work can be done on the system.
We begin our discussion on work and heat transfer with closed systems. As a closed system
transforms from one state to another, it passes through an infinite number of intermediate states.
We assume that the deviation from equilibrium of these states are infinitesimal. This means
that there are no pressure and temperature gradients in the system and that a single value exists
for all properties of the system at any specific instant. In other words the pressure has a specific
value, temperature has a specific value and specific volume has a specific value at any moment
during the process. Changing form one state to another is called a process. We will encounter
15

16

CHAPTER 2. WORK AND HEAT IN CLOSED SYSTEMS

several types of processes e.g. an isothermal process, where the temperature of the system stays
constant or an isochoric process where the volume stays constant.

2.2

Work

If a force of magnitude F is necessary to move a weight a distance s, the work is given by the
product: W = F s. Consider a gas inside a piston cylinder setup as in Figure 2.1. The gas
is heated, causing the volume to increase.

Figure 2.1: Expansion of gas


The magnitude of the work performed by the system in the process of going from state 1 to
state 2, is given by:
W =

F dx

(2.1)

The force is equal to the pressure of the gas multiplied by the area of the piston. It is usually
easier to work with the identical formulation of Equation 2.1:
Z 2
Wout =
P dV
(2.2)
1

This work is called boundary work because it is performed at the boundary of the system. If
pressure is measured in kP a and volume in m3 , work is in kJ. Work done by the system on the
environment (volume increases) will be a positive number while work done by the environment
on the system (volume decreases) will be a negative number. To determine the magnitude of
W , a relationship is required between the gas pressure at the moving boundary and the volume
of the system. In real processes this relationship may be difficult or even impossible to obtain
because of pressure gradients in the system or an unknown relationship between pressure and
volume. Different process paths between the two states are possible.1
1

Work is said to be a path function because the path followed determines how much work is performed. A
property on the other hand, is a point function, as its value does not depend on the path followed to get to its
present state.

17

2.2. WORK

For a few special processes, the relationship between pressure and volume can be expressed as
a simple mathematical equation. Assuming an quasi-equilibrium process, the pressure inside is
uniform and we can use a single value.

2.2.1

The Isobaric Process

If heat is added to a gas in a frictionless piston-cylinder arrangement such as in Figure 2.1,


the volume will increase but the pressure inside will remain constant because the force exerted
on the system by the combined effect of the weight of the piston and the atmosphere does not
change during the process. P is therefore a constant and can be taken out of the integral sign
in Equation 2.2 and the equation for work becomes:
Wout = P (V2 V1 )
The process can also be presented graphically:

Figure 2.2: Constant pressure process.


The work performed is equal to the area under the graph. Sometimes calculating the area under
the graph is the only way to calculate the magnitude of work.

2.2.2

The Isothermal Process

If the volume is increased while the system is kept at a constant temperature (by adding heat)
and if the Ideal Gas Law (P = mRT/V ) is assumed, then the process path on a P-V graph will be
an hyperbole as shown in Figure 2.3. In general Equation 2.2 can be integrated by substituting
P from the Ideal Gas Law to give an equation for Wout :
Wout = mRT `n

V2
V1

18

CHAPTER 2. WORK AND HEAT IN CLOSED SYSTEMS

Figure 2.3: Isothermal expansion of a gas

Example
One kilogram of air at 25 C and 100kP a in a piston cylinder arrangement is compressed
slowly to a pressure of 200kP a. Heat is released at a sufficient rate to keep the temperature
constant during the process. Calculate the work.
Solution
The initial and final volumes can be calculated using the Ideal Gas Law: V1 = 0.8557m3
and V2 = 0.4278m3
Wout = mRT `n

V2
V1

= 1 0.287 298.15 `n

0.4278
0.8557

= 59.3kJ
The value is negative because work was performed on the air in order to raise its pressure.
In order to have a positive numerical value, the answer is reported as:
Win = 59.3kJ

If the integration cannot be done analytically, it may be necessary to do a numerical integration.


Consider the isothermal expansion of steam. Steam cannot be assumed to be an ideal gas and a
convenient number of intermediate points (A and B) on the P -V diagram must be determined
and the area under the P-V curve determined numerically as shown in Figure 2.4.

19

2.2. WORK

Figure 2.4: Isothermal expansion of steam

2.2.3

The Adiabatic Process

In an adiabatic process, the system is well insulated so that no heat transfer takes place between
the system and the environment. If ideal gas behavior can be assumed and if the specific
heats (Paragraph 3.1.2) for the gas can be assumed constant (usually the case for the
mono-atomic gases He, Ar, Ne and Kr), the relation between pressure and volume during a
quasi-equilibrium process, is given by the following equation.2
PV k = c

(2.3)

The exponent k is equal to the ratio of the specific heats Cp and Cv . Its value can be found in
a table of ideal gas properties.3 The numerical value of the constant (c) for each process will
be different and must be determined from the conditions at some stage of the process for
instance the initial conditions P1 and V1 . This equation gives a relationship between pressure
and volume and Equation 2.2 becomes:
Wout = c

V2

V1

c
1k

V k dV


1k
1k
V2
V1

If a gas is compressed, the kinetic energy of the particles is increased by the approaching boundary much like a cricket ball being hit by a bat and the temperature of the gas rises. The
temperature of a gas that is expanded adiabatically, drops. The reason is that the particles
colliding with the expanding boundary, must perform work to move the boundary and transfer some of their kinetic energy to the moving boundary and therefore the temperature drops.
2
3

See Paragraph 3.3 for the derivation.


Sometimes is used instead of k.

20

CHAPTER 2. WORK AND HEAT IN CLOSED SYSTEMS

A common mistake is to assume the temperature in an adiabatic process remains


constant. Although there is no heat transfer, there is energy transfer in the form of work.

2.2.4

The Isochoric Process

In an isochoric process the volume stays constant and no work is performed. The area under a
the curve of an isochoric process drawn on a P -V diagram is zero.

2.2.5

Process with Spring Restrained Piston

If the piston is restrained by a linear spring, the P -V relationship of the process will be a
straight line. The area under a straight line is easily determined. The work can be determined
by drawing the process on a graph and calculating the area under the P-V line.

2.2.6

Non-equilibrium processes

In all the previous cases we assumed quasi-equilibrium processes - therefore uniform conditions
prevailed inside the system. Although this is often a good assumption, there are cases where it
is clearly not a valid assumption. In order to calculate the work done in such cases, integrate
Equation 2.1 using the external force acting on the system.
Example
Air at 25 C and 600kP a is contained in a piston cylinder arrangement with a cross sectional
area of 0.1m2 . The initial volume of the air is 1m3 . The mass of the piston is 0.1kg. The
atmospheric pressure is 87kP a. The piston is kept in position by a pin as shown in the
sketch. The pin is removed and the piston moves rapidly upward until it hits the stops.
The final volume is 3m3 . Calculate the work.

Solution
The combined effect of the weight of the piston and the atmospheric pressure means the
piston will exert a pressure of 96.81kP a on the air once it is free to move. This is the
pressure necessary to lift the piston and push away the atmosphere. The pressure exerted
by the air on the piston will be more than 96.81kP a. The moment the pin is removed the
pressure difference acting on the piston will cause the piston to accelerate upwards. The

21

2.3. HEAT TRANSFER

piston will come to a standstill against the stops and the kinetic energy of the piston will
be converted into heat and sound. The work performed by the air is therefore
Wout = 96.81(3 1) = 193.62kJ

2.3

Heat transfer

Heat is defined as the form of energy that is transferred across the boundary of one system to
another system, at a lower temperature, by virtue of the temperature difference between the
two systems. A substance does not contain heat. Heat is only identified as it crosses the system
boundary. In actual fact the heat transfer takes place because the particles of the two systems
collide with each other. The particles of the hotter substance has higher molecular energy than
the particles of the colder substance. During a collision, some of the energy of the hot particle
is transferred to the cold particle. This increases the kinetic energy of the cold particle and
causes the temperature of the colder substance to rise. So heat transfer is actually kinetic
energy transfer on the molecular level. The heat that enters the system ends up increasing the
kinetic energies of the molecules and/or atoms of the system it entered. Temperature gives an
indication of the average kinetic energy of the particles of a substance the higher the kinetic
energy, the higher the temperature.

22

CHAPTER 2. WORK AND HEAT IN CLOSED SYSTEMS

Chapter 3

The First Law for Closed Systems


We have already encountered work and heat as two forms of energy. In order to complete the
picture, another type of energy, internal energy, must be taken into consideration. These three
forms of energy will later be combined in the First Law of Thermodynamics.

3.1

Internal energy

Consider the heating of one kilogram of Helium in a rigid stationary container from 300K to
600K. The heat necessary is 1558kJ. No work was performed as the volume stayed constant and
the system remained stationary. Therefore the energy added to the system as heat, is absorbed
by the molecules of the gas. It increased the kinetic energy of the individual Helium atoms. To
name three:1
Translational kinetic energy
Rotational kinetic energy
Vibrational kinetic energy
The sum of all these microscopic energies is called the internal energy of a substance. It can be
shown that specific internal energy is a property. The symbol for specific internal energy
is u and its units are [kJ/kg]. The total internal energy of a system is U [kJ] and is equal to
m u. Because specific internal energy is a property, it is one of the variables that can be used
to fix the state of a substance. For a single phase system it means if we know the value of the
internal energy and either the value of temperature or pressure or specific volume, the state is
fixed and the value of the other properties can be determined.
The change in internal energy is calculated using the following equation [1, Equation 14.30]:
 


P
du = Cv dT + T
P dv
T v

(3.1)

1
Optional textbook reading. A more elaborate discussion of molecular forms of energy is given in par 2.6 of
Sonntag [1]

23

24

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

Where Cv is the constant volume specific heat. It is defined as the amount of heat necessary to
raise the temperature of a substance (at constant volume) by one degree.

3.1.1

Ideal gases

For an ideal gas it is assumed that the atoms or molecules do not attract or repulse each other.
Therefore there is no energy associated with inter-particle interactions. The distance between
particles is therefore irrelevant from an energy point of view. This means that the internal
energy of an ideal gas is only made up of the kinetic energies of individual particles and that
internal energy is not influenced by changes in density or pressure. The same is clear from
Equation 3.1. For an ideal gas P/T is equal to R/v and the term in the square brackets reduces
to zero. The change in internal energy for an ideal gas is therefore only dependent on the change
in temperature and can be calculated as follows:
Z T2
u2 u1 =
Cv dT
(3.2)
T1

To avoid having to integrate Equation 3.2 every time, the internal energy of ideal gases as
function of temperature (relative to a reference temperature Tref where the value of uref is set
to a chosen value), is tabulated as function of temperature.2 A table giving the internal energy
of air under the assumption of ideal gas behavior, is given in Borgnakke and Sonntag, Table
A7.1 [1].
Example
Calculate the temperature and specific volume of air at 200kP a with a specific internal
energy of 315.64kJ/kg.
Solution
From the table of the ideal gas properties of air [1] it can be determined that the temperature
corresponding to the given internal energy is 440K. The Ideal Gas Law can now be used to
calculate the specific volume: 0.6314m3/kg
Note that because of the assumption of ideal gas behavior, internal energy and temperature
are no longer independent and both cannot be specified to fix the state of the system.
Therefore u can only be used in combination with P and v.

The internal energy is independent of pressure, therefore there is only one column - giving the value of internal
energy for the tabulated values of temperature. The reference to pressure that usually appears in the heading of
such tables, is because the values of entropy, a property we have not encountered yet, is calculated at a certain
pressure, usually 100kP a.

25

3.1. INTERNAL ENERGY

3.1.2

Perfect gases

Cv for a few gases as function of temperature are shown in Figure 3.1.

Figure 3.1: Cv values for Helium, Air and Steam (at two pressures)
From Figure 3.1 it is clear that the Cv of Helium stays essentially constant.3 In this text it
will be assumed that the Cv of the mono-atomic gases (Helium, Argon, Neon and Krypton), is
independent of temperature and that they obey the Ideal Gas Law. They are then collectively
called Perfect Gases. Equation 3.2 is now easily integrated to give the change in internal
energy for perfect gases:
u2 u1 = Cv (T2 T1 )

(3.3)

Example
Helium at 400kP a and 300 C is heated to 600 C while the pressure changes to 500kP a.
Determine the change in volume and the change in specific internal energy.
Solution
Using Equation 3.3 and the Ideal Gas Law:
u2 u1 = Cv (T2 T1 )
= 3.116 (600 300)
= 934.8 kJ/kg
3
In order to reduce the range of the y-axis, the units of Cv in Figure 3.1 is in
values with the right units in calculations.

kJ/kmolK .

Take care to use

26

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

R T2 R T1

P2
P1
2.0771 873.15 2.0771 573.15
=

500
400
= 0.651 m3/kg

v2 v1 =

It is important to note the following:


The value for Cv found in tables is usually at a specific temperature but for a Perfect
Gas can be used at any temperature.
Even though this is not a constant volume process, Equation 3.3 is still valid. It is
valid for any perfect gas for any process: isobaric, isochoric, unspecified.... and can be
used to calculate the change in internal energy as long as the change in temperature
is known.
For a perfect gas, it is only possible to calculate the change in internal energy. This
means that the internal energy of a perfect gas does not have a value that can be used
to define the state. For perfect gases it is therefore necessary to use two of the other
three intensive properties (P, T, v) we are familiar with at the moment to define the
state.
As a perfect gas is a special kind of ideal gas, a change in pressure has no effect on
(the change in) internal energy.
The temperature difference calculated in C is the same as the temperature difference
calculated in Kelvin.
In the Ideal Gas Law, the temperature must be in Kelvin.

3.1.3

Real gases

For real gases, inter-particle distance is important because there may be energy associated with
inter-particle interactions (attraction or repulsion). From Table 3.1, the influence of pressure on
the internal energy of steam at 400C is clear.
Note that at low pressures, internal energy does not vary much with pressure. This is because
at low pressures, the steam molecules are far apart and the energy associated with their interaction, small. As the pressure rises to higher values and especially close the critical point, internal
energy is very sensitive to pressure. For a real gas it is necessary to know the value of two
variables to fix the state. Any two of the variables we have encountered thus far (Temperature,
Pressure, specific volume or specific internal energy) can be used.

27

3.1. INTERNAL ENERGY

Table 3.1: Influence of pressure on the specific internal energy of steam at 400 C.
Pressure (kP a)
10
100
1000
10000
25000

3.1.4

Specific Internal Energy (kJ/kg)


2968.9
2967.9
2957.3
2832.4
2430.1

Two phase systems

For two-phase systems, pressure and temperature are no longer independent. For a saturated
liquid (x = 0) and a saturated vapour, (x = 1) the value for internal energy can be read directly
from the table for saturated water at the appropriate temperature or pressure. Note that the
internal energy of the saturated liquid at 0.01C is taken as zero.
For a saturated two-phase mixture, a calculation must be done. Quality (x) has already been
defined as the mass of vapor in a 1kg two-phase mixture. Quality can now be used to calculate
the internal energy of a two-phase mixture from the internal energy of the saturated liquid (uf )
and the saturated vapour (ug ) as follows:
u = (1 x)uf + xug

3.1.5

Compressesed liquids

The internal energy for compressed (or sub-cooled liquids) as function of temperature and pressure can be found in the steam tables. For incompressible substances, pressure will not affect
inter-particle distances and it usually assumed that the internal energy of sub-cooled liquids and
solids are not affected by pressure as shown in Table 3.2.
Table 3.2: Influence of pressure on the specific internal energy sub-cooled water at 100 C.
Pressure (kP a)
101.325
1000
10000

Specific Internal Energy (kJ/kg)


419.0
418.7
416.1

The internal energy for liquid water is therefore assumed to be only a function of temperature.
This means that the internal energy for liquid water can be read from the tables for saturated
water. For example the internal energy of water at 10M P a and 100 C is assumed to be equal
to the internal energy of saturated liquid water at 100 C even though the saturation pressure
is only 101.325kP a.

28

3.1.6

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

Solids

Usually constant specific heats are assumed for solids. Then the change in internal energy can be
calculated using Equation 3.3. However, because of the small change in volume during heating,
the values of Cv and Cp are essentially equal and often no distinction is made between the two
or only Cp is tabulated. This is discussed in more detail in Paragraph 4.3.1

3.1.7

Determination of internal energy

Once the value of two independent properties are known the state is fixed and the value of the
other properties can be determined. Let us consider a few examples where internal energy is
involved.
Temperature and pressure.
The three phases of water as function of pressure and temperature are shown in Figure 1.6. The
first step is to determine the phase as explained in Paragraph 1.4.1 by determining the position
of the state relative to the phase boundaries.
Example
Determine the specific internal energy and specific volume of water at 100kP a and 50 C.
Solution
From the position on the phase diagram ( in Figure 1.6), it is clear that it is a compressed liquid. Assuming that uT ,P = ufsat@T : u = 209.3kJ/kg and also for volume,
v = 0.001012m3/kg . Quality is not defined for a compressed liquid.

Example
Determine the specific internal energy and specific volume of water at 100kP a and 150 C.
Solution
The state is indicated by the in Figure 1.6. From the position on the phase diagram, it
is clear that it is a super-heated vapor. From the tables for super-heated water vapor, we
can read the values for u = 2582.75kJ/kg and v = 1.93636m3/kg . Quality is not defined for a
super-heated vapor.
Note that on a P-T diagram, the state can never lie on the line separating the phases. The
line has zero thickness and therefore, for a specific temperature and pressure, the phase will be
either a liquid or a vapor.
Temperature or pressure and internal energy
The phase is determined by comparing the internal energy of the system with the internal
energy of the saturated vapor and saturated liquid at the specified pressure or temperature. If
the specified value for internal energy falls inside the dome , it is a two phase mixture and the
temperature is the saturation temperature. The quality can now be determined and from the
quality, the specific volume.

29

3.1. INTERNAL ENERGY

Figure 3.2: Phase diagram for water.

Example
Determine the temperature, specific volume and quality of water at 200kP a with an internal
energy of 2808.6kJ/kg.
Solution
The specified internal energy is bigger than the internal energy of saturated vapor at 200kP a,
2529kJ/kg and therefore it is a super-heated vapor. From the tables for super-heated water
vapor at 200kP a, the temperature that corresponds with the specified internal energy, is
300 C. The specific volume is 1.31616m3/kg. Quality is not defined for a super-heated vapor.

Example
Calculate the internal energy at 100kP a of a two-phase water mixture with a quality of 0.2.
(835.1kJ/kg)

Example
Determine the pressure of steam at 200 C with an internal energy of 2656kJ/kg
Solution
The specified value for internal energy is bigger than than the internal energy of saturated
vapor at 200 C, 2595kJ/kg and it is therefore a super-heated vapor. From the tables for
super-heated steam, it is clear that the internal energy of steam at 200 C and 100kP a
is bigger; and the internal energy at 200 C and 200kP a smaller than the specified value,
2656kJ/kg. The pressure of the system must therefore be between 100kP a and 200kP a.
Interpolation is therefore required. (156kP a).

30

3.2

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

The First Law for closed systems

The First Law simply states that energy cannot be destroyed or created merely converted
from one form to another. In a coal fired power station, heat is converted into work and
electricity. The First Law gives the relation between the three forms of energy encountered so
far heat, work and internal energy. Consider the closed system in Figure 3.3 undergoing a
process. Usually the substance contained in the piston-cylinder arrangement is taken as the
system. Heat is added to the system, it expands and raises the piston, performing work.
Work

Heat
State 1

State 2

Figure 3.3: Closed system undergoing a process


The First Law states that energy is conserved. This means that the energy in the beginning,
the total internal energy U1 , plus the energy transferred to the system, the heat Qin , must equal
the the work done by the system, Wout , plus the energy in the system at the end of the process,
the total internal energy U2 . In mathematical terms:
U1 + Qin = Wout + U2
or:
Qin = m(u2 u1 ) + Wout
Example
One kilogram of steam in a piston-cylinder arrangement is at 200 C and 300kP a. The steam
is heated to 400 C in a constant pressure process. Calculate the heat that must be added
in order for the process to take place as described.
Solution
The First Law is used: Qin = m(u2 u1 ) + Wout
The work performed in a constant pressure process:
Wout = P (V2 V1 ) = 300(1.03151 0.71629) = 94.57kJ Done by system
The First Law now becomes:
Qin = (2965.53 2650.65) + 94.57 = 409.45kJ Required by system
Note that less than 25% of the energy added as heat is converted into work.

31

3.2. THE FIRST LAW FOR CLOSED SYSTEMS

3.2.1

Kinetic and potential energy

Whereas internal energy is on a microscopic level, the system can also undergo changes in energy
on a macroscopic level. If the center of gravity of the system changes height in a gravitational field
or changes velocity because of interactions between the system and the environment, the energy
associated with these changes must be taken into consideration and the First Law becomes:
2

Qin

m(V 2 V 1 ) mg(Z2 Z1 )
= U2 U1 +
+
+ Wout
2000
1000

where V is the velocity of the center of gravity of the system (in m/s) and Z is the height of the
center of gravity of the system (in meters). Usually the changes in kinetic and potential energy
are much smaller than the other terms and can safely be ignored. But there are instances where
it must be taken in to consideration:
Example
A lead bullet at 20 C traveling at 250m/s comes to a complete standstill against a target
plate. Calculate the temperature of the bullet after impact.
Solution
The bullet will exchange heat with the target plate but let us calculate the temperature
before any heat transfer takes place. Therefore it is an adiabatic process and 1 Q2 = 0.
The volume of the bullet will change with the change in temperature, doing some work
against the atmosphere. As can be seen from the thermal expansion coefficient for lead
( = 0.00003283K 1) the change in volume will be small and therefore it is assumed that
Wout is negligible. Assuming that the specific heat of lead is independent of temperature
and pressure, the change in internal energy is given by u = Cv T (from Equation 3.1).
The First Law becomes:
2

V1
Cv (T2 T1 ) =
2000
The specific heat of lead at 25 C is 0.13kJ/kgK .[1, Table A.3] Therefore the temperature of
the bullet after impact is 260 C. If the bullet traveled at the speed of sound ( 300m/s), it
would have reached its melting temperature (326.9C).
The two assumptions should now be checked. With the final temperature known, the change
in volume can be calculated as well as the change in specific heat. It is left to the reader to
do.

Example
A vertical piston/cylinder arrangement with a cross sectional area of 0.002m2
(D = 50.46 mm) contains 1kg saturated liquid water at 100kP a. The water is va-

32

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

porized at constant pressure until saturated vapor results. Calculate the heat required.
Solution
The height of the column of the liquid water will be 0.521m and the height of the vapor
column will be 846m. The center of gravity in each case is height/2. The setup is stationary
so the kinetic energy does not change and the First Law becomes:
Qin



Z2 Z1
+ P (v2 v1 )
= m (u2 u1 ) + g
1000
846 0.521
+ 100(1.693 0.001)
= (2506.06 417.3) + 9.81
2 1000
= 2088.7 + 4.147 + 169.2
= 2262kJ

It is clear that even with this extreme change in elevation of the center of gravity, that the
contribution of the change in potential energy is still small relative to the other terms.

3.2.2

Sign convention

Equation 2.1 gives the work done BY a system undergoing a process from state 1 to state 2:
Wout =

V2

P dV

V1

If work is performed BY the system (the volume increases), the value of Wout will be > 0 and if
work is done ON the system, the value of Wout will be < 0. In this text, Wout will be changed
to Win to ensure that the numerical value is > 0.
The heat transfer for an Ideal Gas undergoing a iso-choric process from state 1 to state 2, is
given by:
Q=m

T2

Cv dT

T1

If heat is ADDED to the system, the value of Q will be > 0, and if heat is RELEASED by
the system the value of Q will be < 0. This is true for other processes also. In this text the
appropriate subscript (in or out ) will be used to ensure that the value of Q is always > 0.

3.3

Adiabatic processes

The first law can be used to derive Equation 2.3 for an adiabatic process for a perfect gas.
PV k = c

33

3.3. ADIABATIC PROCESSES


which is the same as:
P2
=
P1

V1
V2

k

The first law in differential form:


Q = dU + W
For an adiabatic process Q = 0, for an ideal gas, dU = mCv dT and for a quasi-equilibrium
process, W = P dV . This gives:
mCv dT = P dV
Dividing the left hand side of the equation by mRT and the right hand side by P V , the following
equation results for a Perfect Gas:
V1
Cv T2
ln
= ln
R
T1
V2
Which can be written as:


T2
T1

 Cv
R

V1
V2

From the Ideal Gas Law it follows that:


T2
P2 V2
=
T1
P1 V1
The last two equations can be combined to give:
P2
P1

Cv
R

Cv

V1 ( R
V2

+1)

Noting that that Cp Cv = R and after some manipulation, the following equation results:
P2
=
P1

V1
V2

 Cp
Cv

V1
V2

k

which is the equation we set out to derive. From the above it also follows that:
T2
=
T1

P2
P1

 k1
k

V2
V1

1k

v2
v1

1k

It is important to remember the conditions: Adiabatic, quasi-equilibrium process, Perfect Gas.

34

CHAPTER 3. THE FIRST LAW FOR CLOSED SYSTEMS

Chapter 4

The First Law for open systems


An open system allows mass flow across its boundaries. Mass flow rate is measured in [kg/s].
Many of the systems engineers work with, are open systems. For instance the turbines, boilers
and pumps in large-scale power generation plants are open systems. A turbine performs shaft
work at a certain rate and the units of shaft work are [kJ/s] which is the same as kilo-Watts, [kW ].
The heat transfer rate is also measured in [kW ]. The energy content of a flowing substance is
given by enthalpy.

4.1

Enthalpy

Consider a pipe connected to a container. A fluid is flowing in the pipe and into the container.
The pressure of the container remains constant at P . A pressure P is therefore necessary to
push the fluid into the container. The work necessary to move one kilogram of fluid against
this pressure of P , is P v [kJ/kg]. This is called flow work. The rate at which work must
be performed to push the fluid into the container is mP
v [kW ]. The rate at which internal
energy is entering the container with this fluid, is mu
[kW ]. As Pressure and Specific volume
are both properties it is convenient to group flow work and internal energy together to form a
new intensive property, enthalpy (h):
h = u + P v [kJ/kg ]

(4.1)

The change in Enthalpy is calculated using the following equation:[1, Equation 14.28]


 
v
dh = Cp dT + v T
dP
T P

(4.2)

We now consider the the determination of enthalpy for Ideal gases, Perfect gases and Real and
condensible substances.
35

36

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS

4.1.1

Ideal gases

The enthalpy of an ideal gas is not dependent on pressure because the internal energy of an ideal
gas is not dependent on pressure and P v = RT so h = u + RT and pressure does not appear
in this equation. It also follows from Equation 4.2. For an ideal gas, (v/T )P = R/P and the
term in square brackets reduces to zero. The change in enthalpy of an ideal gas can therefore
be calculated by performing the following integration:
Z T1
h2 h1 =
Cp dT
(4.3)
T2

The amount of heat necessary to raise by one degree, the temperature of one kilogram of a
substance in a constant pressure process (without phase change) is defined as the constant
pressure specific heat:


1 Q
Cp =
m T p
where Cp is the specific heat , Q the amount of heat in [kJ] and T the temperature of the
substance in Kelvin or Celsius. Because work is done when heating a gas at constant pressure,
more heat must be supplied to raise the temperature of a gas at constant pressure than would
have been the case if the volume stayed constant - therefore Cp > Cv . Also Cp Cv = R.
Equations for Cp for various ideal gases are available in literature [1, Table A.6] and can be
used in Equation 4.3 to calculate the change in enthalpy [1, Example 5.8]. In order to simplify
matters, the enthalpy for various ideal gases relative to a reference temperature Tref where href
was set equal to a chosen value, were calculated and are available in literature. Air is usually
assumed to be an ideal gas and its enthalpy as function of temperature can be found in literature
[1, Table A 7.1].

4.1.2

Perfect gases

In this text it will be assumed that the specific heats of mono-atomic (He, Ne, Ar) are not
dependent on temperature.1 It will also be assumed that they obey the Ideal Gas Law and
Equation 4.3 becomes:
h2 h1 = Cp (T2 T1 )
(4.4)
It is however now only possible to calculate the change in enthalpy.

4.1.3

Real and condensible gases

If a substance is condensible under the process conditions or the ideal gas assumption is not
valid, enthalpy is a function of phase, temperature and pressure and its value found in tables.
The phase of the substance must first be determined (compressed liquid, saturated liquid/vapor,
two-phase or super-heated). The Pressure-Enthalpy diagram is shown in Figure 4.1. Note that
the enthalpy is also relative to a reference point (in the case of water, the triple point) where
1

See Figure 3.1 If Cv is constant, Cp is also because Cp Cv = R

37

4.1. ENTHALPY

enthalpy is taken to be zero. The quality is used to calculate the enthalpy of a two phase mixture
(in the same way as the internal energy of a mixture) as follows:
h = xhg + (1 x)hf

Figure 4.1: Pressure-Specific Enthalpy diagram for water.

4.1.4

Compressed liquids and solids

Because of the small value of v for liquids and solids, the P v term Equation 4.1 is much smaller
than u, so the change in enthalpy with pressure is also small and it can be assumed that the
enthalpy of a compressed liquid (and solid) is the same as that of a saturated liquid (and solid)
at the same temperature - as long as the difference between the pressure and the saturation
pressure at the temperature is not too large.
To simplify matters even further, constant specific heats can be assumed for liquids and solids2
- as long as no phase change takes place. Then the change in enthalpy can be calculated by
Equation 4.4. The value for specific heats for solids and liquids are available in literature [1,
Table A.3]3
2

The specific heat of liquid water at 25 C and 100kP a is 4.183kJ/kgK . It stays essentially constant except
close to the freezing (0 C) and boiling point (99.6 C) where it rises by less than one percent.
3
Often no distinction is made between Cp and Cv because the work performed when a solid or liquid is heated
at constant pressure is small because of the small change in the already small value of specific volume. Therefore
the additional heat that must be supplied to compensate for the work performed over and above the heat
necessary to increase the internal energy, will be negligible and their values will be essentially the same. Also it
is not common practice to heat a liquid at constant volume because of the high pressures generated because the
liquid cannot expand.

38

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS

4.2

The first law for steady state, open systems

If the system boundaries are rigid and conditions inside the system boundaries are steady4 then
there will be no accumulation of mass or energy in the system. If the state and flow-rate of the
streams leaving and entering the system also does not change with time, then the rate at which
energy flows out of the system must be equal to the rate at which energy flows into the system.
This is true for many systems and the First Law can be written down after inspection. The rate
at which energy is entering the system is set equal to the rate at which energy is leaving the
system.

4.2.1

Shaft work

In a closed system, boundary work is performed usually in a piston-cylinder arrangement. By


connecting the piston to a crankshaft as in an internal combustion engine, boundary work is used
to provide the energy necessary to rotate the crankshaft which in its turn turns the wheels of the
car or whatever load is connected to the engine. In the process boundary work is transformed
into shaft work. If this process takes place continuously, the shaft will rotate at a certain speed
under a certain torque, delivering mechanical power at a certain rate. This is called rate of shaft
work or power and the unit is [kW ]. In turbo machines, direct energy transfer between a fluid
and the blades attached to the shaft takes place.
Turbines convert the enthalpy of the incoming stream into shaft power. For compressible substances (gases), both internal energy and flow energy are converted into work and both temperature and pressure will decrease. For an incompressible substance no expansion takes place
and therefore the molecules cannot transfer their energy to a moving boundary and only flow
energy is converted into work and only the pressure will drop. Any change in the internal energy
is due to friction and turbulence in the turbine. In the case of gas and steam turbines, heat
loss is prevented as far as possible because energy lost as heat cannot be converted into work.
The rate of heat loss is therefore usually small in comparison to the rate at which energy enters
and leaves the system with the fluid and unless otherwise stated, turbines are assumed to be
adiabatic. Consider the turbine in Figure 4.2 below.
m

out
W

Figure 4.2: Steady state turbine


The only energy (in the form of internal energy plus flow energy) entering the system is the
4

The pressure inside a deflating tank will change with time and this is therefore an unsteady system.

4.2. THE FIRST LAW FOR STEADY STATE, OPEN SYSTEMS

39

enthalpy of the inlet stream. It enters the system at a certain mass flow rate m
in [kg/s].
Energy leaves the system as shaft work and also with the outlet stream - assuming an adiabatic
turbine. The first law states that the rate at which energy flows IN must equal the rate at which
energy flows OUT of the system. In mathematical terms:
out
mh
in = mh
out + W
The rate of energy transfer is [kg/s kJ/kg = kJ/s] or kW . The W stands for Watt. The rate
shaf t is called power and its unit is also [kW ]. The term work
of mechanical energy output W
is often used when talking about power. It is technically not correct but the true meaning is
usually clear from the context.
Example
Calculate the power delivered by the turbine shaft if the steam at the inlet of the turbine in
the figure above is at 1M P a and 500 C. The steam at the outlet is saturated vapor and at
5kP a. The flow-rate is 20kg/s.
Solution
The enthalpy of the steam entering the turbine is 3478.44kJ/kg . The enthalpy of the steam
at the outlet is 2561.45kJ/kg. Rearranging the energy balance:
out = m(h
W
in hout )
= 20(3478.44 2561.45)
= 18340kW

4.2.2

Heat

Heating and cooling are common and important processes. The equipment is designed in a
specific way as to maximize the rate of heat transfer. In the radiator of a car, fins are attached
to the outside of the water tubes to increase the heat transfer area in contact with air. An
important process in a power station is the generation of steam. Liquid water is fed to a boiler
and vaporized to produce steam. The only primary sources of heat are: combustion (usually
coal), nuclear radiation (usually the fission of uranium atoms), solar radiation or geothermal
heat. Consider the generic heater in the figure below.
Energy (as internal and flow energy) enters the system with the fluid flowing into the heater as
well as the heat supplied to the heater. This must equal the rate at which energy leaves the
system with the out-flowing fluid. In mathematical terms:
mh
in + Q in = mh
out

(4.5)

40

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS

Figure 4.3: Generic Heater

Example
Municipal water at 25 C and 300kP a is pumped through a solar water heater. The water
must be heated to 55 C. The solar water heater delivers heat at a rate of 1.2kW to the
water. At what rate must the water be circulated to ensure the stated outlet temperature?
A typical household geyser holds 150` water. How long will it take to heat up the geyser
from 25 C to 55 C?
Solution
Rearranging Equation 4.5 and getting the values for enthalpy from the saturated liquid
tables at the corresponding temperatures:
Q in
hin hout
1.2
=
230.2 104.87
kg
60s
= 0.0095747
s
min
kg
= 0.5745
min

m
=

The time necessary to heat up 150` of cold water (assuming 1kg = 1`):
t = 150kg

s
= 4.35h
0.0095747kg

Using Equation 4.4 and Cp = 4.183kJ/kgK results in h = 125.33kJ/kg while the values for
saturated liquid water (used in the calculation above) results in a value of 125.49kJ/kg.
The forms of energy considered are: enthalpy, heat, work, kinetic and potential energy. When
all are included the First Law for open systems becomes:(Assuming that heat is added to the
system and power delivered by the system.)
2

Q in +

V
gZin
m
hin + in +
2000 1000

out +
=W

V
gZout
m
hout + out +
2000
1000

For calculations with the First Law for open systems, the following relations are very useful. It

4.2. THE FIRST LAW FOR STEADY STATE, OPEN SYSTEMS

41

states that the volumetric flow rate is equal to the mass flow rate times the specific volume and
also to the flow velocity times the area of the pipe (perpendicular to the flow direction):
 3


hm i
m
kg m3
q
= mv

=VA
m2
s
s kg
s

4.2.3

Kinetic energy

While the change in kinetic energy through a system is often low and therefore usually ignored,
there are instances where it is important. A rocket is propelled by the gases produced by the
combustion of the rocket fuel. The higher the velocity of the exhaust gases, the faster the rocket
will travel. In a rocket, a diverging nozzle is employed to convert as much as possible of the
enthalpy of the exhaust gases into kinetic energy to maximize the velocity of the rocket. In the
process the temperature and pressure of the exhaust gas drop. The ideal is that the pressure of
the exhaust gases at the exit of the nozzle is equal to ambient.
Example
Consider a rocket propelled by compressed air. The air at the inlet to the nozzle is at
700K and 500kP a and at the outlet of the nozzle the temperature dropped to 460K and
the pressure to 100kP a. Determine the velocity of the air at the outlet of the nozzle. It can
be assumed that the inlet velocity is negligible.
Solution
The heat loss will be very small compared to the rate at which energy flows through the
nozzle and therefore it is assumed that the nozzle is adiabatic. Letting m
= 1kg/s, an energy
balance over the nozzle gives:
2

hin = hout +

V out
2000

Getting the values for enthalpy from the table [1, Table A 7.1] enables us to calculate the
velocity at the outlet of the nozzle:
V out = (2000(713.56 462.34)) /2 = 708.9m/s
1

Under the assumption of ideal gas behaviour, pressures are irrelevant here. They are however
necessary to calculate the maximum possible outlet velocity by making use of the concept
of an ideal nozzle. The calculation of the maximum possible velocity will be done in later
chapters.

4.2.4

Potential energy

The change in potential energy is often much smaller than the change in the other terms in the
First Law and is often not taken into consideration. However if the change in elevation is large,
it must be taken into consideration:

42

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS

Consider the Drakensberg pumped storage scheme. During times of low electricity demand,
water is pumped from the Kilburn dam (water surface 1256 m above sea level) to the Driekloof
dam (water surface 1702 m above sea level). During times of high demand, electricity can be
generated by reversing the flow direction of the water. The flow rate when generating electricity
is 312m3 /s. Assuming frictionless flow and zero turbulence, calculate the power output of the
turbine. Assume the water temperature in the Driekloof dam is 15 C and the ambient pressure
at the Kilburn dam is 100kP a.
The water at the dam surface is equal to the ambient pressure. Assuming a density of air of
1kg/m3 the ambient pressure at the surface of the Driekloof dam can be calculated as 95.6kP a.
Because there is no friction or turbulence, the internal energy will stay constant and because of
the small change in pressure and the small value of v, it is assumed that the enthalpy (h = u+P v)
also stays constant. Because the rate of heat loss (or gain) of the water will be much less than
the rate energy is passing through the pipe (mh)

it is assumed that the pipe is adiabatic. Also


assume that the change in kinetic energy is negligible.
The First Law now becomes:

out = mg
W
(Zin Zout ) = 1365M W
1000

4.2.5

Common open systems

Because open systems are so varied, it is usually the best practice to formulate the First Law
for each individual case. All the energy terms entering the system are written down and set
equal to all the energy terms leaving the system. In the examples below, kinetic and potential
energies are ignored. This may not be always valid.
Just as energy is conserved, mass is also conserved. If there are more than one inlet and/or
outlet stream, care must be taken to take all streams into account
a) Valves
Valves are used to control flow rate or reduce pressure. Valves do not perform work. The
rate at which energy flows through the valve mh
is much larger than any heat loss or gain
by the substance as it passes through the valve. Therefore a valve is usually assumed to be
adiabatic.

Figure 4.4: Valve


Therefore:
hin = hout
b) Compressors/pumps

4.2. THE FIRST LAW FOR STEADY STATE, OPEN SYSTEMS

43

A compressor is used to raise the pressure of a gas and a pump to raise the pressure of a
liquid. Both require power to accomplish this. Unless stated otherwise, compressors and
pumps are assumed to be adiabatic.

Figure 4.5: Compressor and Pump


An energy balance gives:
in = mh
mh
in + W
out
c) Condenser
In a condenser, heat is removed and a vapor turned into a liquid. A condenser does not
perform or require power.

Figure 4.6: Condenser


An energy balance gives:
mh
vapor = mh
liquid + Q out
d) Evaporator / Boiler
Liquid flows to an evaporator and is evaporated by the addition of heat as shown in Figure
4.3. Usually no specific measures are taken to superheat the vapor and the vapor and liquid
may be close to equilibrium. In power stations steam is produced in boilers from high pressure
liquid water. Usually the steam is also significantly super-heated before leaving the boiler.
An energy balance (from Figure 4.3) gives:
mh
liquid + Q in = mh
vapor
e) Heat exchanger

44

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS


In a heat exchanger heat is transferred from a hot fluid to a colder fluid without the two fluids
mixing. An example is the radiator of a car where the water releases heat to the ambient air
and returns to the engine. The two fluids are separated by a conducting medium (usually
a metal). A schematic presentation of a counterflow heat exchanger is shown in Figure 4.7.
Also shown in Figure 4.7, is an often used symbol for a heat exchanger.

Figure 4.7: Heat exchanger


The system boundary is shown as a dotted line in Figure 4.7. Doing an energy balance over
the system boundary, results in the equation below. It is assumed that the rate at which heat
is exchanged between the two streams is much larger than possible heat exchange between
any (or both) of the streams and the environment and this exchange with the environment
is therefore ignored.
m
h hh |in + m
c hc |in = m
h hh |out + m
c hc |out
does not appear in the energy balance because it
Note that the rate of energy transfer (Q)
does not cross the system boundary.

4.3

Calculating heat transfer using specific heats

In general, the First Law is used to calculate the amount of heat transferred during a process.
We will now consider a few special cases of heat transfer in single phase systems.

4.3.1

Compressed Liquids and Solids

= 0) is
The rate at which energy must be supplied to heat a liquid in an open system (W
given by: Q in = m(h
out hin ). Often the pressure is unknown although it is known that the
water remains liquid. For instance, the inlet and outlet temperature of cooling water flowing
through a heat exchanger is often displayed by temperature gauges. In domestic applications,
only the temperatures of the different water streams flowing through a geyser or solar water
heater or a heat pump may be known. In such cases it can safely be assumed that the enthalpy
of the compressed liquid is independent of pressure as discussed in Paragraph 4.1.4. The change
in enthalpy is now given by dh = Cp dT . For liquid water Cp is not strongly dependent on
temperature and the heat transfer rate can be now be calculated by:

4.4. UNSTEADY STATE PROCESSES

Q in = mC
p (Tout Tin )

45

(4.6)

If a solid or a liquid in an open container is heated at constant pressure (for instance a cup of
water) the heat transfer can be calculated by using the First Law for a closed system. Making
the same assumptions as above, this gives:
Qin = m((u2 u1 ) + P (v2 v1 ))
= m((u2 + P2 v2 ) (u1 P1 v1 )
= m(h2 h1 )
= mCp (T2 T1 )
The values of Cp are available in literature. See [1, Table A.3] for liquids and [1, Table A.4]
for solids. It is usually assumed that Cp = Cv . In the software program EES, no distinction
between Cp and Cv is made for solids and only C, the specific heat, can be selected.
The fact that work is ignored, also means that the type of process becomes irrelevant. Only
the change in internal energy is taken into consideration. Liquids and solids are usually not
heated under constant volume conditions because the pressure rises dramatically during heating
because of their low compressibility.
If in doubt about the validity of any of these assumptions, use the First Law.

4.3.2

Gases

For gases the volume will change and work in a closed system cannot be ignored. For a Perfect
Gas undergoing a constant pressure process, the heat transfer rate in an open system is given
by Equation 4.6 and for a closed system the equation derived in Paragraph 4.3.1 for liquids and
solids,
Qin = mCp (T2 T1 )
can be used. For constant volume processes in a closed system, Cv instead of Cp must be used.
For an Ideal Gas, compressed liquid or solid, if the value of the specific heat as function of
temperature is known, the value at the average temperature can be used.

4.4

Unsteady state processes

Many important processes are not steady state. If a pressure vessel springs a major leak, it is
important to know how the temperature and pressure inside will change with time. Filling a
closed tank with a gas or a liquid is another example of unsteady state processes. A general
unsteady state process is shown in the figure below:
Unlike steady state processes, the amount of mass inside the system boundary does change with
time during an unsteady state process. Like energy, mass is also conserved and a mass balance
for the process in Figure 4.8 are:

46

CHAPTER 4. THE FIRST LAW FOR OPEN SYSTEMS

Figure 4.8: Unsteady state process

m1 + min = m2 + mout

(4.7)

The summation signs are used to emphasize that more than one stream can flow into and more
than one stream can flow out of the system. Assuming a stationary system an energy balance
for an unsteady state process (in [kJ]) can be written as:
m1 u1 + (mh)in + Ein = m2 u2 + (mh)out + Eout
Where E accounts for all the other forms of energy (in [kJ]): heat, boundary and shaft work and
kinetic energy.
Example
Consider a rigid adiabatic tank. Initially the tank is completely empty m1 = 0. Air at 300K
now flows into the tank until the pressure rises to 400kP a. Calculate the final temperature.
Solution
No work is done and no heat is exchanged. Therefore the energy balance becomes:
min hin = m2 u2
From a mass balance it is clear that m2 = min and therefore u2 = hin . The enthalpy of air
at 300K is 300.47kJ/kg. The temperature of air with a specific internal energy of 300.47kJ/kg
is 419.2K
The flow energy of the air that flowed into the tank is converted into internal energy and
because of the rise in internal energy, the temperature also rises. Note also that the final
pressure does not have any influence on the final temperature.

Chapter 5

Reversible Systems
5.1

Reversibility and Irreversibility

Consider a simple pendulum as shown in Figure 5.1 below. When the bobbin is released at
an elevated position, the bobbin accelerates in the gravitational field and potential energy is
converted into kinetic energy - as well as dissipated by friction at the pivot point, friction
between the air and the pendulum and also because of turbulence in the air caused by the
movement of the bobbin through the air.

Figure 5.1: A Simple Pendulum


At its lowest end the bobbins kinetic energy is at its maximum and its potential energy at its
minimum. Then the bobbin decelerates and kinetic energy is converted into potential energy
again until the bobbin reaches its highest elevation at the opposite end. The bobbin will swing
back and forth until all its energy has been dissipated by friction and turbulence and the bobbin
comes to a standstill at the lowest elevation. In order to keep the pendulum swinging, the
environment has to do work on the pendulum to overcome the effect of friction and turbulence
- like in a grandfather clock where the energy is supplied by a spring or weights. A frictionless
pendulum in an evacuated space can in principle keep on swinging forever. In such a (reversible)
pendulum, conversion between kinetic and potential energy takes place without any losses.
47

48

CHAPTER 5. REVERSIBLE SYSTEMS

The two factors that make a pendulum irreversible are friction and turbulence which converts
the kinetic and potential energy into heat which cannot be - even in theory, be fully converted
back into potential or kinetic energy again. In the absence of these two factors the pendulum
would have been reversible. Unrestrained expansion is another factor that makes a process
irreversible. Consider a balloon that bursts. In order to restore the air that was inside the
balloon to its original condition, work is required (to compress the air) as well as heat exchange
with the environment (to lower the temperature after compression). The fact that outside action
is required to restore the system to its original condition means the process is irreversible. It is
possible (in principle) to expand air in a reversible manner. Consider an adiabatic frictionless
piston cylinder arrangement with compressed air inside. Initially the piston is restrained by
sand on top of the cylinder as shown in Figure 5.2 below:

Figure 5.2: Reversible expansion of gas.


Grains of sand are removed one by one, allowing the gas to expand slowly enough to ensure that
the pressure and temperature of the air inside stays uniform. The process can now be reversed
by placing the grains of sand back on the piston, compressing the gas slowly until the original
state has been reached.1
Consider energy conversion during this expansion process. In the expansion of the gas, work is
performed by the air molecules colliding with the piston, moving it upward. Some of the kinetic
energy of the colliding molecule is therefore converted into work and the kinetic energy of the
molecule is reduced. The total kinetic energy of the air molecules therefore drops. The internal
energy (and the temperature) of the gas will therefore also decrease. During the compression of
the gas, work is performed on the gas and the temperature will rise again to its original value.
The air inside a balloon that bursts in a vacuum (unrestrained expansion) does not perform work
- and assuming an adiabatic process, the internal energy of the gas remains constant. Assuming
air to be an ideal gas, the temperature of the gas will also remain constant. To compress the
gas again, work must be performed on the gas and its temperature will rise. To return the gas
to its original temperature, heat must be removed from the gas.
Heat transfer across a temperature difference is another factor that makes processes irreversible.
Consider a piston cylinder arrangement containing 1kg of saturated liquid water at 100 C. In
order for heat to be conducted across the walls of the container at a finite rate, heat at a slightly
higher temperature than 100C must be available. Let us assume a Thermal Energy Reservoir
1

It can be argued the effort from outside is necessary to remove and replace the grains of sand. If this
experiment was actually performed, it would have been a valid argument. But conducting this as a thought
experiment, no effort is required to remove the grains of sand, suspend them in the gravitational field and replace
them again. Even in a thought experiment, it is necessary to perform work when compressing the gas from the
balloon.

49

5.2. ENTROPY

(TER)2 at 110 C supplies the heat and the water boils at constant pressure until a saturated
vapor results as shown in Figure 5.3 below.

Figure 5.3: Irreversible heat transfer


In order to reverse the process a TER at a lower temperature than 100 C must be available to
act as a heat sink. Lets assume heat is rejected to a TER at 90 C. The vapor condenses at
constant pressure and a saturated liquid at 100 C results again - so the water inside the piston
cylinder is restored to its original condition, but the environment has changed. The temperature
of the 2258kJ of heat necessary to vaporize the water, has changed from 110 C to 90 C. In
a reversible process there will be no temperature gradient and the heat will be absorbed and
rejected at the same temperature - making it possible to reverse the process without changing
the temperature of the heat.
Although not relevant in processes considered here, mixing of two dissimilar substances is also
irreversible. Once the coffee granules have dissolved in the water, the water and coffee granules
cannot be restored to its original condition without considerable effort. We have considered four
factors that make processes irreversible:
Friction and turbulence
Unrestrained expansion
Heat transfer over a finite temperature gradient
Mixing of dissimilar substances
In order to quantify the degree of (ir)reversibility, a new property, entropy is defined.

5.2

Entropy

From a statistical viewpoint, entropy is described as a measure of molecular disorder. Molecular


disorder can be described in terms of position and in terms of velocity. For instance, particles
at rest can be ordered or disordered. Also, particles moving at different velocities and directions
are more disordered than particles all moving at the same velocity and direction. In the gas
phase, the molecules move about at random, collide and change direction. Therefore the entropy
2

A TER is a body with an infinitely large heat capacity (and constant volume) and can therefore supply and
receive heat without its temperature changing. Because its volume stays constant, the TER also does not perform
any work.

50

CHAPTER 5. REVERSIBLE SYSTEMS

of a substance should be higher in the gas phase and lower in the solid or liquid phase. Also,
according to the kinetic gas model, the higher the internal energy of a gas, the higher the kinetic
energy of the gas molecules. Therefore entropy should rise as heat is added to a gas, when a
solid melts or a liquid boils to form a vapour. This leads to the first very important statement3
about entropy:
Entropy transfer accompanies heat transfer. In a reversible system this enables us to
calculate the change in entropy using the definition of entropy:
dS =

Q
T

(5.1)
reversible

where Q is the differential amount of heat exchanged in a reversible process and T the temperature of the system boundary. In a reversible system there will be no temperature gradients in
the system.
To illustrate how the flow of heat leads to a change in entropy, consider 1kg of saturated liquid
water at 100kPa in a closed system. The water is heated at constant pressure (and therefore
also at constant temperature) until it is a saturated vapor. The heat necessary to vaporize the
water is 2 258kJ as calculated from the First Law. Because the temperature remains constant
during the process, the equation above is easily integrated to give the change in entropy for the
water upon evaporation:
S =

Qin
2258
kJ
=
= 6.057
T
99.63 + 273.15
K

If the water is condensed again and the heat released at the equilibrium temperature, the
system is back at its original condition and the heat is still at the same temperature it has
been supplied to the system. In this case the evaporation and condensation were done infinitely
slowly in order to make sure that the vapor and liquid were at the same temperature and there
were no temperature gradients.
Lets consider a process where the temperature changes. A perfect gas is heated at constant
pressure from T1 to T2 The heat required is given by:
Q = Cp dT
replacing Q in the definition of entropy and integrating gives:
s = Cp

T2
T1

dT
T1
= Cp `n
T
T2

(5.2)

It is possible, working from a suitable reference point, to calculate the value of entropy at any
state. It can be shown that the value of entropy so calculated is independent of the calculation
path and depends only on the reference state and the end state. This is a necessary and sufficient
condition to make the following statement:
3

In this chapter we will encounter a few of these statements about the nature of entropy

51

5.3. DETERMINATION OF ENTROPY

Entropy is a property Entropy can therefore be used in the specification of the state of a
substance. For a single phase substance, if the value of two independent properties are fixed,
the state is fixed. Entropy cannot be measured but can only be calculated. It is therefore an
abstract property - like the momentum of a particle.

5.3

Determination of Entropy

We distinguish between three types of substance: Real and condensible substances, Ideal gases
and Perfect gases (Ideal gases with a specific heat independent of temperature). As with other
properties a distinction is made between specific entropy - the entropy per kilogram of substance,
using the lowercase s with units of [kJ/kg K] and total entropy using uppercase S with units
of [kJ/K].

5.3.1

Ideal gases

An equation giving the change in the entropy of an ideal gas can be derived using the differential
form of the First Law for a closed system. Consider a unit mass:
q = du + w
For a reversible process w = P dv and for an ideal gas, P = RT
v and du = Cv dT . Using these
equations and the definition of entropy to replace the appropriate terms in the First Law, the
following equation results:
T ds = Cv dT + RT

dv
v

dividing by T and integrating gives:


s2 s1 =

T2

Cv dT + R `n

T1

v1
v2

(5.3)

Using the Ideal Gas Law v = RT /P to get rid of the volume terms in the equation above and
remembering that Cp = Cv + R and rearranging, the following equation results:
s2 s1 =

T2

T1

Cp

dT
P2
R `n
T
P1

(5.4)

Equation 5.4 is similar to Equation 5.2 but with a term to account for change in pressure. In
general the specific heat Cp is not a simple function of temperature and in order to prevent
having to do the integration every time a value for entropy is required, the entropy of different
ideal gases as function of temperature, at 100kP a, relative to some reference point has been
calculated and tabulated. To find the entropy at a pressure other than 100kP a the equation
above is rewritten to only give the change in entropy with pressure:

52

CHAPTER 5. REVERSIBLE SYSTEMS

sT ,P = soT R `n

P
100

(5.5)

Where sT ,P is the entropy at the specified temperature and pressure and soT is the entropy at
the specified temperature but at 100kP a. Its value can be found in tables giving the properties
of gases under the assumption of ideal gas behaviour.
Example
Calculate the entropy of air at 200kP a and 25 C
Solution
s200kP a;25C = so298.15K Rair `n
= 6.863 0.287`n

P
100

200
= 6.664kJ/kg K
100

The answer seems logical as one can expect the molecular disorder to decrease as the pressure
increases.
Because entropy is a property it can be used to define the state of the air. Because air is a single
phase substance the value of two independent properties must be specified to fix the state.
For specified values for entropy and temperature, the pressure can be determined directly from
Equation 5.5 but for specified values for entropy and pressure, an iterative procedure may be
necessary to determine temperature from the tabulated values4 . Once the values of temperature
and pressure are known, the Ideal Gas Law can be used to calculate the specific volume.

5.3.2

Perfect gases

For the mono-atomic (ideal) gases (Ar, Ne, He, Kr, Zn) Cp is virtually independent of temperature and collectively they are called perfect gases. For a Cp 5 independent of temperature
Equation 5.4 is easily integrated to give the change of entropy with temperature and pressure:
s2 s1 = Cp `n

T2
P2
R `n
T1
P1

The change of entropy with temperature and specific volume is obtained by integrating Equation
5.3
s2 s1 = Cv `n
4

T2
v2
+ R `n
T1
v1

Use the values in the example above to illustrate this for yourself
Tables giving the properties of gases usually give the values at a specific temperature. Under the assumption
of a constant specific heat this value can be used at any temperature.
5

53

5.4. ENTROPY AND WORK

In this case, because it is only possible to calculate the change in entropy, it is not possible to
use entropy as one of the variables that define the state. The same is true for internal energy
and enthalpy - because, for a perfect gas, only the change in u and h can be calculated. A
combination of two other variables (P, T, v) must be used to fix the state.

5.3.3

Real and condensible gases

Values for entropy are tabulated in the steam tables for saturated water (as a function of pressure
or temperature) and for super-heated water (as a function of pressure and temperature). Note
also that the entropy of saturated liquid water at the triple point (0.01C and 0.6113kPa) is
(arbitrarily) chosen as zero.
For a single phase substance, once the values of two independent properties are specified, the
state is fixed while for a two phase mixture, temperature and pressure are no longer independent
and only one of the two can be specified. For a specific set of variables, it is therefore important
to first determine the phase.
Example
Calculate the temperature and enthalpy of steam at 10kP a with an entropy of 7kJ/kg K
Solution
The value for entropy is larger than the value for entropy for the saturated liquid at this
pressure (0.6493kJ/kg K) but smaller than the value for the saturated vapor (8.1502kJ/kg
K) This means that it is a two phase liquid and the temperature is the equilibrium value at
10kP a, 45.81C. To determine the enthalpy of the two phase mixture (TPM), the quality
must be known. This is calculated from the value of the entropy:
sT P M = sg x + sf (1 x)
7 = 8.1501x + 0.6492(1 x)
x = 0.8467
hT P M = 0.8467 2584.63 + (1 0.8467)191.81 = 2217.7kJ/kg
According to the steam tables, the entropy of saturated liquid water at 100kPa is
1.3026kJ/kg K and of saturated water vapor, 7.3594kJ/kg K. The change in entropy
upon vaporisation is therefore 6.0568kJ/kg K. This is the same as the value calculated
from the definition of entropy.

5.4

Entropy and work

From the definition of entropy, it is clear that the entropy during an adiabatic reversible process
will stay constant. During the adiabatic reversible expansion of a gas in a piston/cylinder setup,

54

CHAPTER 5. REVERSIBLE SYSTEMS

work is performed but the entropy does not change. This means that work is free of entropy.
This is also the case for open systems. As steam flows through an adiabatic reversible turbine,
the entropy of the steam does not change (the entropy at the inlet and the outlet will be the
same) although the turbine delivers power. From this follows the third very important statement
about entropy:
There is no entropy transfer associated with energy transfer as work or power. This
is in contrast to heat, where heat transfer leads to a change in entropy - as is evident from the
definition of entropy in Equation 5.1.

5.5

Reversible processes

Because no heat transfer takes place, the entropy during an adiabatic reversible process does
not change. Now consider heat exchange between a system and a heat source. For this process
to be reversible, the system and the heat source must be at the same temperature. From the
definition of entropy, it is clear that the increase in the entropy of the system will be the same
as the decrease in the entropy of the heat source and this leads to the fourth very important
statement about entropy:
For reversible processes, the total entropy (Stotal = Ssystem +ST ER ) remains constant6 .
This means that for a reversible process, we can do an entropy balance. This principle will now
be demonstrated for the following reversible processes:
Closed and open adiabatic systems
Closed and open systems with heat transfer
Heat engines and heat pumps - a special type of closed system.

5.5.1

Reversible adiabatic processes

Adiabatic reversible processes are known as isentropic processes.


Closed systems
Consider the reversible adiabatic compression of a gas

For a more elaborate proof of this statement see [2, p.307].

55

5.5. REVERSIBLE PROCESSES

Because no heat flow has taken place and because there is no entropy transfer associated with
work, it follows from the definition of entropy Equation 5.1 that S2 = S1
Example
Calculate the work required to compress 1kg of Helium at 300K adiabatically and reversibly
from 100kP a to 200kP a
Solution
The entropy will stay constant during this process and assuming Helium to be a perfect gas:
s2 s1 = Cp `n

T2
P2
R `n
=0
T1
P1

T2 is now the only unknown and its value can be calculated from the equation above as
359.6K and work from the First Law (Q = 0):
Win = m(u2 u1 ) = m Cv (T2 T1 ) = 3.1156(359.6 300) = 185.7kJ

Open systems
For an adiabatic, steady, open system it means that the rate at which entropy is entering the
system with mass flow will be the same as the rate at which it is leaving the system with mass
flow. For a system with only one inlet and one outlet:
ms
i = ms
u
Example
Steam at 400C and 400kP a flows to a reversible adiabatic turbine at a rate of 1kg/s. The
pressure at the outlet is 100kP a. Calculate the power delivered.
Solution
An energy balance for the turbine gives:
out
mh
in = mh
out + W
Because this is an adiabatic reversible turbine, the entropy at the outlet will be the same
as the entropy at the inlet (sin = 7.8984 kJ/kgK ). We therefore know the the value of two
variables at the outlet, fixing the state. At a pressure of Pout = 100kP a and an entropy
of sout = 7.8984 kJ/kgK the enthalpy of steam is 2906 kJ/kg and the power delivered by the
turbine:
out = m(h
W
in hout ) = 3273 2906 = 367kW

56

CHAPTER 5. REVERSIBLE SYSTEMS

Pumping an incompressible liquid


Ignoring potential and kinetic changes and replacing enthalpy (h) with u + P v, the First Law
for an adiabatic pump becomes:
in + uin + Pin vin = uout + Pout vout
W
In a reversible pump there will be no friction, turbulence or unrestrained expansion and the
internal energy will not change. Assuming a constant specific volume:
in = v(Pout Pin )
W
A more rigorous derivation can be found in Thermodynamics by S Klein and G Nellis [3, p. 404]

5.5.2

Reversible processes with heat transfer

Heat is usually supplied by a heat source or rejected to a heat sink (often the environment).
If we can assume assume a uniform temperature inside the source or sink and an infinite heat
capacity its temperature will not change and we call it a Thermal Energy Reservoir (TER). For
a TER we also assume a constant volume (so no work is performed). The change in entropy of
a TER can be calculated using the definition of entropy.
Example
Assume that the environment is a heat sink at 25 C. Calculate the change in the total
entropy of the environment with the addition of 20M J of heat.
Solution
From the definition of entropy:
dS =

Senvironemnt =

Q
T

reversible

20 000
= 67kJ/K
25 + 273.15

Closed systems
When the system release (absorbs) heat its entropy will decrease (increase) but the entropy of
the TER receiving (supplying) the heat will increase (decrease) by the same amount because
the total entropy must stay constant.

57

5.5. REVERSIBLE PROCESSES

Example
One kilogram of steam at 200kP a and 400 C is expanded at constant temperature to
200kP a in a piston cylinder arrangement exchanging heat with a TER at the same
temperature. Determine the work without making any assumptions.
Solution
R
The equation W = P dV can be integrated numerically but that would not be an exact
solution. So another strategy must be devised. The First Law for closed systems:
Qin = m(u2 u1 ) + Wout
The initial and final temperatures and pressures are known, so the u1 and u2 can be read
from the steam tables. The amount of heat exchanged is calculated from an entropy balance.
The change in the entropy of the steam is equal to the change in the entropy of the TER
supplying the heat:
QT ER,out
m(s2 s1 ) =
TT ER
Entropy can be read from the steam tables and QT ER calculated:
QT ER,out = (8.5434 8.2217) (400 + 273.15) = 216.55kJ
QT ER,out is equal to Qsteam,in . The First Law therefore gives:
Wout = 216.55 (2967.85 2966.69) = 215.39kJ
of work done by the system on the environment. It is important to note the sign of Q. The
formulation of the First Law used here is valid for heat supplied to the system while work
is performed by the system. In this case the heat was supplied to the system and the heat
term in the First Law are positive. Had heat been released by the system, the heat term in
the First Law would have been negative.

Open systems
For an open system it means that the rate of change of the entropy of the TER must be equal
to the rate of change on the entropy of the substance. For a process where heat is supplied by
the TER:
Q T ER,out
= ms
out ms
in
TT ER

58

CHAPTER 5. REVERSIBLE SYSTEMS

Example
Air at 300K and 100kPa is compressed at constant temperature to 200kPa in an reversible
compressor at a rate of 2kg/s exchanging heat with a TER at the same temperature.
Determine the power required.
Solution
During compression, the temperature of the air will rise. In order to maintain a constant
temperature, heat must be released. An enthalpy balance gives:
in = mh
mh
in + W
out + Q out
Assuming air to be an ideal gas, enthalpy is not dependent on pressure and hin = hout . This
means that the power required is the same as the heat transfer rate. In order to calculate
the heat transfer rate an entropy balance is performed. Because this is a reversible process,
the total entropy stays constant and the rate at which the entropy of the air decreases must
be the same as the rate at which the entropy of the TER increases:
m(s
in sout ) =

Q T ER,in
TT ER

For air:
sin sout = m(s
o300K (so300K Rair `n

200
))
100

and the heat transfer rate becomes:


Q = 300 2 0.287`n 2 = 119kW
and:

5.5.3

out = Q = 119kW
W

Reversible heat engines

A heat engine is used to convert heat into (shaft) work. Heat engines form the basis of electricity
generation where they are used to convert the heat released by the burning of coal or fissile
nuclear material or solar energy to shaft work to turn an electric generator and also in automobile
engines where the heat released by the combustion of gasoline is converted to the work necessary
to turn the wheels of the car.
Consider a reversible heat engine called the Carnot cycle. Saturated water at high pressure
and temperature enters a boiler and leaves the boiler as saturated vapor at the same pressure.
The saturated vapor enters an adiabatic reversible turbine and shaft work is produced. The
two-phase mixture that leaves the turbine is almost completely condensed at constant pressure
and temperature and enters an adiabatic reversible pump with an outlet pressure equal to the
inlet pressure of the boiler. This saturated liquid enters the boiler to complete the cycle. The

59

5.5. REVERSIBLE PROCESSES

components and flow direction of the Carnot heat engine is shown in Figure 5.4 below. The
high temperature TER supplies heat at the evaporating temperature and steam condenses at
the same temperature as that of the low temperature TER.

Figure 5.4: Carnot Heat Engine


A coal-fired power plant (and most nuclear plants) contains a somewhat similar heat engine.
The burning of coal (or fission of uranium atoms) supplies high temperature heat to the heat
engine and low temperature heat is rejected to the environment.
If we take the reversible heat engine as a black box with high temperature heat entering and
power and low temperature heat leaving as shown in Figure 5.5, entropy can be used to calculate
the maximum rate that power can be produced from high temperature heat.

Figure 5.5: Black Box Heat Engine


Because all the processes involved are reversible the total entropy will be constant and therefore
the rate at which the entropy of the high temperature TER decreases, will be the same as the
rate at which the entropy of the low temperature TER increases. No mass flow is taking place
across the boundaries of the heat engine.
Q H
Q L
=
TH
TL
The first law states that the energy must be conserved. The pump will consume a little of the
energy produced by the turbine. Therefore the net work is the work delivered by the turbine
minus the work consumed by the pump. For the heat engine an energy balance gives:

60

CHAPTER 5. REVERSIBLE SYSTEMS

nett + Q L
Q H = W
Because a heat engine usually rejects its heat to the environment, and this heat is of no value,
while QH costs money to generate, QL is usually eliminated from the two equations above to
give the reversible power for a heat engine:
nett = Q H
W

TL
1
TH

Example
A reversible heat engine receives heat at a rate of 10kW from a high temperature reservoir
at 1000K and rejects heat to the environment at 25 C. Calculate the power delivered.
Solution


25 + 273.15

Wnett = 10 1
1000
nett = 7kW
W

This is quite high. In actual fact, a coal power station typically converts a third of the energy
in the coal into electricity.
This cycle can be reversed to give a heat pump - a device that pumps heat against the
temperature gradient from a low temperature to a higher temperature. This principle can be
used to extract heat from the environment, raise its temperature and use this high temperature
heat to heat domestic water.
Example
A typical domestic hot water cylinder contains 200kg of water. Calculate the heat necessary
to raise the temperature from 15 C to 60 C using an electrical resistance heater and a
reversible heat pump extracting heat from the environment at 15 C.
Solution
Assuming a specific heat of 4.184kJ/kg K for water the heat necessary is:
Q = mCp (T2 T1 ) = 200 4.184(60 15) = 37 656kJ
This heat has to be supplied by the resistance heater. A reversible heat pump will require
(It is left to the reader to show that this equation is also valid for heat pumps):
Wnett





288.15
TL
= QH 1
= 37 656 1
= 5 086kJ
TH
333.15

5.6. ENTHALPY REVISITED

61

The heat pump therefore requires only 13.5% of the energy required by the resistance heater.
The running cost will be lower but additional capital outlay will be necessary. Heat pumps will
therefore be at their most economical where there is a constant consumption of hot water - so
the saving in running cost can cover the capital expenditure associated with the purchase of the
heat pump.
A refrigerator also uses this principle to pump heat from the inside of the refrigerator (at a low
temperature) to the environment at a higher temperature.

5.6

Enthalpy revisited

Enthalpy is defined as the sum of internal energy (u) and what is often called flow energy
(P v) which is often difficult to conceptualize. The application of the First Law on open, steady
state, reversible processes, gives another view of enthalpy that may make the concept of flow
energy easier to grasp. Consider water flowing in an adiabatic pipe. Also replace enthalpy (h)
with u + P v or rather u + P :
ui +

V 2i
gZi
Pe
Ve2
gZe
Pi
+
+
= ue +
+
+
i
2000 1000
e
2000 1000

The four types of energy represented here are: u: internal energy, P : flow energy, 12 V 2 : kinetic
energy and gZi : potential energy. If there is friction or turbulence, some of the flow, kinetic or
potential energy will be converted into internal energy. In a reversible system there is no friction
and the internal energy will not change and the First Law above reduces to:
Pi
Vi2
gZi
Pe
Ve2
gZe
+
+
=
+
+
i
2000 1000
e
2000 1000
This is also known as the Bernoulli equation and its units are [kJ/kg]
Example
A man uses a hose pipe to wash debris from the gutters of his house. The exit of the hose
pipe is 3m higher than the inlet of the hose pipe at the tap. Due to a nozzle at the end of
the hose pipe the water is accelerated from 5m/s at the inlet to an unknown value at the
outlet. The municipal pressure of the water at the tap is 300kP a and the ambient pressure
85kP a. Assuming a constant density of 998kg/m3 for the water and reversible (frictionless)
flow, calculate the velocity at the outlet of the nozzle.
Solution
From the Bernoulli equation:
300
52
85
V2
9.81 3
+
=
+
+
998 2000
998 2000
1000

62

CHAPTER 5. REVERSIBLE SYSTEMS

Therefore:
Vout = 19.92m/s
Because the specific volume of the water stays constant, the change in flow energy is directly
proportional to the change in pressure. As the pressure drops (flow energy decreases) the
water is accelerated (kinetic energy increases) and the elevation increased (potential energy
increases).
Assuming a very long thin adiabatic hose pipe with high friction (with no change in kinetic
and potential energy) all the flow energy will be converted into internal energy. From the
First Law the rise in the temperature of the water can be calculated:
Pin Pout
= u = Cv T

(300 85)
= 0.052C
4.184 998
This is a small change in temperature and is usually ignored.
T =

Because the change in pressure for incompressible substances is directly proportional to the
change in flow energy, the perception develops that (P v), flow energy (pressure) is the main
source of energy, also for compressible substances. This is not correct. Consider the Helium
turbine in Paragraph 5.5.1
The internal energy changes by:
u = Cv (Tin Tout ) = 3.11 (700 461.8) = 742.23kJ/kg
while the flow energy (P v = RT ) changes by:
P v = R(Tin Tout ) = 2.077 (700 461.8) = 494.74kJ/kg
The total is the same as in the example: 1237kJ/kg. The internal energy supplies the bulk
of the power. For substances whose volume is not that dependent on pressure - in the case of
gases, those with a smaller value of R - the fraction of the power supplied by flow energy will
be even smaller. A turbine running on air at the same inlet temperature and between the same
pressure limits, will deliver 191kJ/kg with only 52kJ/kg supplied by flow energy.
In the case of a turbine powered by liquid water, the internal energy will change very little and
the power is completely due to the change in flow energy. Internal energy changes only due to
irreversibility.

Chapter 6

Real Systems
Real systems are characterized by friction, turbulence, unrestrained expansion, temperature
gradients and mixing of dissimilar substances and are therefore irreversible. Molecular disorder
increases and the total entropy is no longer constant but is constantly increasing.

6.1

Entropy generation in real systems

A few numerical examples will now be done to illustrate how entropy is generated in real systems.

6.1.1

Friction

In thermal fluid systems friction is generally between the fluid and the containing surface. Turbulence will cause friction between fluid molecules.
Example
In an refrigerator, saturated liquid freon flows through a thin capillary tube. Due to fluid
friction the pressure drops and because of the drop in pressure, the liquid boils and a two
phase liquid results. Because this is an adiabatic process, the enthalpy stays constant and
because a vapor has a higher enthalpy than a liquid, the temperature of the resulting two
phase mixture must be lower than the temperature of the initial saturated liquid. (The
liquid must sacrifice some of its internal energy to provide the energy to form a vapor.)
Calculate the entropy before and after the capillary tube. Assume the freon at the inlet is
saturated R134 liquid at 35 C and the pressure downstream is 100kP a
Solution
For an adiabatic capillary tube:
hin = 100.9kJ/kg = hout

63

64

CHAPTER 6. REAL SYSTEMS

From the pressure and enthalpy at the outlet the rest of the variables can be calculated:
T = 26.4 C and x = 0.385. The entropy increased from 0.3714kJ/kgK to 0.4106kJ/kgK
It is clear that the entropy increased and that entropy has therefore been created. The cause
of this increase is friction in the capillary tube.

6.1.2

Unrestrained expansion

When gas is expanded in a piston/cylinder arrangement, the molecules of the gas is restrained
by the piston. The molecules collide with the moving piston, transferring their energy to the
piston. In a reversible process no pressure gradient in the gas exists. If the rate of expansion
is increased, a pressure gradient may develop and the pressure at the moving boundary may be
lower. Then the amount of work performed by the system decreases. (W = P V ) The faster
the expansion takes place, the more unrestrained it becomes, the bigger the pressure gradient
becomes and the lower the amount of work performed.
Example
Consider a balloon, containing 1kg of air at 100kP a and 25 C bursting in an evacuated
adiabatic container. The final pressure in the container is 10kP a. Calculate the change in
the entropy of the air.
Solution
Because the process is taking place in a vacuum, the pressure at the boundary of the expanding gas is zero. No work is therefore performed. Because no heat transfer takes place
the internal energy stays constant. For an ideal gas the internal energy is not dependent on
pressure and therefore the temperature of the gas does not change. The change in entropy
is therefore given by:
s2 s1 = R`n

10
kJ
P2
= 0.287`n
= 0.66
P1
100
K

It is clear the the entropy at the end of the process is more than at the beginning and
because this is an adiabatic process, that entropy has been created.
If a balloon bursts in the earths atmosphere, the pressure at the boundary of the expanding
gas is equal to the ambient pressure and some work is necessary to push away the atmosphere
therefore some work will be performed and the temperature of the gas will drop. However
this is still not a reversible process and a pressure gradient will exist causing the loud sound
when a balloon bursts.

6.1.3

Heat transfer over a temperature difference

A temperature difference is necessary to provide the driving force for heat transfer. In reversible
systems we assumed an infinitely small temperature difference leading to an infinitely slow rate

6.2. THE SIGNIFICANCE OF ENTROPY GENERATION

65

of heat transfer. In real systems a finite temperature is necessary to make a finite rate of heat
transfer possible.
Example
Consider a system consisting of two TERs. The one at 400K and the other at 300K. 100kJ
of heat is transferred between them. Calculate the change in entropy of the system.
Solution
The heat will flow from the 400K TER to the 300K TER. The entropy of the 400K TER
will decrease:
100
kJ
S400K =
= 0.25
400
K
The entropy of the 300K TER will increase:
S300K =

kJ
100
= 0.33
300
K

The total change is an increase of 0.0833 kJ/K


In principle it is possible to install a heat engine between the two TERs above and generate
work from the 100kJ of heat released by the high temperature TER. A reversible heat engine
will generate no entropy. In the irreversible process above the ability of the high temperature
heat to do work was destroyed and in the process, entropy was generated.

6.2

The significance of entropy generation

In the previous chapter entropy was considered from a statistical viewpoint. (Entropy is a
measure of molecular disorder.) Entropy can also be defined as: Entropy gives an indication
of the unavailability of heat, internal energy and enthalpy to perform work. It is
clear from the examples in Paragraph 6.1 that the generation of entropy is associated with a
reduced work output.
Example
Consider two piston cylinder arrangements containing 1kg of Helium at 25 C The Helium
in the first cylinder is at atmospheric pressure (85kP a) and the other at 170kP a. Calculate
the difference in entropy between the two. Calculate the work performed if both of them
are expanded isentropically to the ambient pressure of 85kP a
Solution
As the temperatures are the same, the difference in entropy is given by:
s85kP a s170kP a = 0.287`n

85
kJ
= 0.199
170
kg K

66

CHAPTER 6. REAL SYSTEMS

The entropy of the Helium at 170kP a is the lower of the two. The Helium at ambient
pressure cannot do any work. For the calculation of work done in the expansion of the
Helium at 170kP a, the First Law can be used. But first the temperature after expansion to
85kP a has taken place has to be calculated:
T2 = T1

P2
P1

 k1
k

85
= 298.15
170

 1.6671
1.667

= 225.9K

The First Law for an adiabatic system:


Wout = m Cv (T1 T2 ) = 3.116(298.15 225.9) = 225kJ
It is clear that the Helium at the higher pressure can perform more work than the Helium
at the lower pressure. Also the Helium at the higher pressure has the lower entropy. This
illustrates the fact the entropy is an indication of the unavailability of internal energy to do
work.
This has implications for the efficiency of converting internal energy, enthalpy and heat into
work. As entropy is generated in real systems, the ability of the internal energy, enthalpy and
heat to perform work, will decrease. The generation of entropy should therefore be minimized
if work output is to be maximized.

6.3

Entropy in real systems

In order to determine where entropy is generated in the system, the flow and generation of
entropy in the system must be studied:
As all the energy in boundary and shaft work as well as kinetic and potential energy is
available to perform work, they are free of entropy. As stated before: There is no entropy
transfer associated with the transfer of energy as work or power.
Entropy is also a property. Therefore the rate of entropy transfer associated with mass
transfer in an open system is equal to ms[
kJ/Ks]. The entropy associated with the mass
in a closed system is equal to ms[kJ/K ].
In any real process, entropy is generated (S gen > 0) in open systems and (Sgen > 0) in
closed systems . In a reversible process the total entropy stays constant (Sgen = 0 or
S gen = 0)
Entropy transfer is also associated with heat transfer. The entropy transferred with heat
is determined by the temperature of the heat where it crosses the system boundary.
The transfer of entropy with heat transfer will now be considered in more detail:

67

6.3. ENTROPY IN REAL SYSTEMS

6.3.1

Entropy transfer with heat.

The fact that entropy transfer accompanies heat transfer, follows from the definition of entropy
and the definition of entropy enabled us to calculate the change in entropy of a TER exchanging

heat. For a heat transfer rate of Q:


S =

Q
TT ER

S is the rate at which the entropy of the TER is changing and it can therefore be seen as a
stream of entropy that flows out of or into a TER. Consider two TERs at different temperatures, say 400K and 300K, connected by a conducting material. The conducting material is the
system (the upright rectangle shown in Figure 6.1). The temperature of the system boundary
is the same as that of the TER where the TER and the system is in contact. At a heat transfer
rate of 100kJ/s from the TER at 400K, entropy flows at a rate of 100/400 = 0.25kJ/s K from
the TER. As energy is conserved, the rate of heat transfer into the TER at 300K will be the
same as the rate out of the TER at 400K - 100kJ/s but the rate at which entropy flows into the

TER at 300K is 100/300 = 0.33kJ/s


K. This means that entropy is being generated in the

system at a rate of 0.33 0.25 = 0.083kJ/s K.

Figure 6.1: Genration of Entropy during heat transfer.


The generation of entropy can take place inside and/or outside the system. Sometimes it may
be advantageous to manipulate the location of the system boundary to place the cause of irreversibility either inside the system or outside in the environment. This can result in one of
two types of system.

6.3.2

Internally reversible systems

By locating all irreversibilities outside the system boundary, an internally reversible system
results. The principles of reversible processes (Sgen = 0) can now be applied on the system by
using the concept of entropy transfer. This sometimes make it possible to solve problems that
could not be solved otherwise.
Example
One kilogram steam in a piston cylinder arrangement at 300kP a and 200 C is compressed at
constant temperature to a pressure of 400kP a, releasing heat to the environment. Calculate
the work required analytically.

68

CHAPTER 6. REAL SYSTEMS

Solution
Because there is not a simple relationship between the pressure, volume and temperature
for steam, work has previously been determined numerically (Paragraph 2.2.2). However,
the First Law contains a work term and can be used if the amount of heat exchanged can
be determined. The heat exchange takes place over the temperature difference between the
steam and the environment and this is an irreversible process and entropy is generated.
The entropy generated can only be calculated if the amount of heat transferred is known
and that is what we want to determine! So we are stuck. But by defining the steam
as the system, an internally reversible process results and the entropy transfer across the
system boundary can be calculated because the temperature of the boundary is uniform
and constant. The irreversibility is located outside the system and does not influence the
calculations. An entropy balance can be done for the steam. The change in entropy of
the steam is equal to the transfer of entropy because it is an (internally) reversible process.
m(s1 s2 ) =

Qout
Tsystem boundary

The heat released can now be calculated:


Qout = Tboundary m(s1 s2 ) = (200 + 273.15)(8.1579 7.1706) = 467.14kJ
From the First Law (heat is released therefore the negative sign):
Win = m(u2 u1 ) +1 Q2 = (2659.85 2646.83) 467.14 = 454.12kJ
The work is negative. This means work was required to compress the steam, which makes
sense. Note that the internal energy changed due to the change in pressure because steam
is not an ideal gas. For an ideal gas the heat exchange would have been equal to the work.

6.3.3

Internally irreversible systems

Because entropy generation impacts negatively on the efficiency of energy conversion into work,
it may be necessary to include the irreversibility in the system to quantify its efficiency. In the
case of turbines and compressors the irreversibility is necessarily part of the system and must be
taken into consideration. The efficiency of internally irreversible systems are often determined
by comparing their real performance to the performance of a reversible system.
Turbines
The actual power delivered by turbine divided by the power a reversible turbine (with the same
outlet pressure) would have delivered:
turbine =

actual
W
isentropic
W

69

6.3. ENTROPY IN REAL SYSTEMS


is called the isentropic efficiency.

Example
Suppose the steam turbine on page 55 is not isentropic but has an isentropic efficiency of
90% Calculate the power delivery and outlet temperature of the actual turbine.
Solution
The isentropic power the turbine delivers is 367.3kW . The actual power is therefore:
actual = 0.9 367.3 = 330.6kW
W
As a smaller fraction of the energy in the steam has been converted into power, the outlet
temperature of actual turbine will be higher than that of the isentropic turbine. An energy
balance for the actual turbine:
actual + mh
mh
in = W
out,actual
gives a value of 2943kJ/kg for the actual outlet enthalpy that corresponds to 234.3C for
Tout,actual which is higher than the isentropic outlet temperature of 215.8C

Compressors
The power required by an isentropic compressor will be lower than the power required by a real
compressor because of turbulence and friction in the real compressor. Therefore the efficiency
for compressors is given by:
compressor =

isentropic
W
actual
W

Example
Saturated steam at 100kP a flows at a rate of 1kg/s to a compressor with an adiabatic
efficiency of 80%. The pressure at the outlet of the compressor is 200kP a. Calculate power
required by the turbine and the outlet temperature.
Solution
isentropic
W
The power required is given by the efficiency: compressor = W
actual The isentropic power
required, is given by an enthalpy balance:
mh
in + Wisentropic = mh
out,isentropic
The outlet enthalpy of the isentropic turbine is found by interpolation at 200kP a and an
entropy of 7.3593kJ/kg K to be 2803kJ/kg. This gives isentropic power required:
isentropic = 2803 2675 = 128kW
W

70

CHAPTER 6. REAL SYSTEMS

And the power required by the actual compressor as:


actual = 128/0.8 = 160kW
W
The actual outlet temperature can be found by doing an enthalpy balance over the actual
compressor:
mh
in + Wactual = mh
actual
This gives an outlet enthalpy for the actual compressor of 2835kJ/kg. The temperature of
steam at this entalpy and 200kP a, is 182.7C

Bibliography
[1] Borgnakke C and Sonntag RE. Fundamentals of thermodynamics, 7th ed. Wiley.
[2] Cengel YA and Boles MA. Thermodynamics: An engineering approach, 4th ed. McGraw-Hill.
[3] Klein S and Nelles G Thermodynamics Cambridge University Press

71