Thermodynamics for energy systems 3 J.J.C. van Lier, N.

Woudstra

2 THE FUNDAMENTALS OF THERMODYNAMICS

2.1 THE THREE LAWS AND THEIR MEANING

Classical thermodynamics is based on three empirical laws from nature that are concerned with visible
amounts of matter. In summing up these laws a specific sequence must be adhered to. Unfortunately,
as a result of the development of thermodynamics, the second and third laws in this sequence were
formulated first and described as the first and the second law of thermodynamics. Only after this was
the first law as we now know it formulated. Because meanwhile the "first law" and "second law" had
become well-known concepts, in modern handbooks the first law in the series of three is described as
the “zeroth law".
Before we continue with the formulating of the zeroth law it is first necessary to define the concept of
“thermodynamic equilibrium”. For this we assume two systems, which each enclose a particular type
of matter and a specific quantity of this matter. Both systems are then brought into contact with each
other in such a way that no matter transfer, no chemical reaction and no nuclear reaction can take
place. In this way they remain completely separate from each other. In addition we assume that the
contact is such that between both systems no energy can be transferred by movement of forces or by
magnetic or electric interaction. The systems are placed directly against each other or at a specific
distance from each other. In practice it appears that with such a contact an energy exchange between
both systems can however occur. This exchange of energy - as appears from a statistical approach - is
completely attributable to an interaction between the molecules available in each system: an
interaction that has its causes in the energy that is bound to these molecules. At a given moment with
such a contact the energy exchange will be such that both systems give out as much energy as they
receive. The term used for this is that both systems are in “thermodynamic equilibrium” with each
other. Experience in practice shows that:

two systems that separately are each in thermodynamic equilibrium with a third system are also
in thermodynamic equilibrium with each other.

This empirical law from nature is referred to as the “zeroth law”. If we want to determine whether two
systems are in thermodynamic equilibrium with each other, this can be done according to the zeroth
law with the help of a third system that functions as the “measuring system”. The preferred choice for
this is a system of which the state is determined by only one single quantity, for example the volume
of a specific amount of liquid of which the change in size can be determined by the change in a
particular height of the liquid.
If the measuring system - in our case the liquid - is first brought into contact with one system and then
with the other system, and if this does not cause any change to the height of the liquid in the
measuring system, then one can conclude that both systems are in thermodynamic equilibrium with
each other.
If, however, a change in the height of the liquid does take place, then it is obviously clear that both
systems are not in thermodynamic equilibrium with each other and that - only by contact - an energy
transfer between both systems is possible. This transfer will take place until both systems are in
thermodynamic equilibrium with each other, or in other words until both systems when making
contact with the measuring system show the same height of liquid. In one system the energy transfer
will lead to a drop in the height of the liquid and in the other to an increase in the height of the liquid.
From this we can conclude that the height of the liquid in the measuring system is a measure of the
amount of energy that can be transferred from one system to the other when they are in contact, or in
other words that it is a characteristic quantity for a system. For many centuries this quantity was
known under the name “temperature” without people actually knowing precisely what meaning should
be attached to the word.
Thermodynamics for energy systems 4 J.J.C. van Lier, N. Woudstra

By means of applying a correlation in the measuring system - referred to as a thermometer - between

the height of the liquid and a specific scale, it is possible to determine the value of the property
temperature via a temperature scale, in an unambiguous way.
The connection between the properties pressure, temperature and volume of a substance can be
expressed in an equation: the so-called "thermal equation of state" of the substance concerned.
If two systems have a different temperature from each other, then an energy exchange will take place
between both systems, when they are brought into contact with each other. However, it is also possible
to isolate a system such that no contact can take place any longer with the surrounding systems that
leads to a temperature equalisation. This is referred to as an "adiabatic system".
Suppose that we have a system - consisting of a particular amount of matter - and that this system is
limited such that we can consider it an adiabatic system. If such a system changes from a state 1 to a
state 2 on account of the input of work, then it appears that the amount of work needed for this is
independent of the way in which the change takes place, thus it is independent of the process that takes
place to change from state 1 to state 2. This means that the amount of energy that can be accumulated
in a substance is only determined by the begin and end states of the system. This means that in a
particular amount of a substance “accumulated” energy is a property. This property is described with
the appropriate name "internal energy".
By basing this explanation on the molecular structure of a substance a good picture can be seen of the
way in which energy is accumulated in some substance or other and of what the property "internal
energy" in fact means. We will have a closer look at this when discussing the various types of energy.
The equation that gives the relationship between the property internal energy and the properties
pressure, temperature and volume is referred to as the "calorific equation of state".
Physicists classify the law that

the internal energy of a substance is a property

as "the first law" of thermodynamics. Although this is indeed a fundamental law, on which this current
discourse is also based, we will still not class this law as “the first law” but a law that arises from this,
namely a statement which is generally easier to understand.
To arrive at this statement we first consider the system that - for the purpose of increasing the internal
energy - has absorbed energy (referred to as the first system) and the system that has looked after this
supply of energy (referred to as the second system) together. The amount of energy given out by the
second system will result in a decrease in the accumulated energy in this system and lead to a new
state of equilibrium in the system. Because for each of the two systems the change to the internal
energy is equal to the energy given off by and received by the systems respectively, the result will be
that both systems have reached a new state, but that the amount of energy in both systems together has
not changed.
From this it can be concluded that in the case of interaction between a number of systems that together
form one energetic isolated whole, the total amount of energy remains unchanged. In other words it is
not possible to design a machine that produces energy from nothing (a perpetual motion machine).
This important “empirical law” is written in the following words:

energy can not be created from nothing and can also not be destroyed.

It is this formulation that in general is considered to be the “first law” of thermodynamics. We will
continue to use this formulation in the rest of this book.

According to the first law the total amount of energy at the beginning and the end of a state change
effected by a system must remain the same. This makes it possible to define an energy balance for the
system with the state change concerned.
Thermodynamics for energy systems 5 J.J.C. van Lier, N. Woudstra

The first law says nothing about the process of a state change. This is covered by the second law of
thermodynamics, which very clearly states that some state changes are not possible and that other are.
There are different formulations of the second law that in fact all come to the same thing. The most
common formulation is as follows:

work can be transformed completely into heat, but heat can not be transformed completely into
work.

We will return to the formulations later on.

The second law is extremely important to the process designer. It makes it possible to determine in
advance if a particularly wanted state change can be realised and what can be done to make the state
change concerned take place in an optimal way from the energetic point of view. It also enables the
designer to calculate the development of all the properties in advance and thereby to construct the
apparatus required.
At the end of this section it is useful to again point out that the laws of thermodynamics are concerned
with visible amounts of matter, that is with the average behaviour of a very large number of atoms and
molecules together respectively. One must also not forget that we are not in a position with a
collection of atoms and molecules respectively - thus with a given amount of a substance - to
separately influence the movement of each atom or molecule respectively.
However we can base our theory on the behaviour of one atom or molecule respectively and we can
then with the help of probability theory determine the behaviour of a large number of atoms or
molecules together, respectively. The statistical laws of averages that follow from this observation are
laid down in statistical thermodynamics and appear to be completely in agreement with the laws of
classical thermodynamics: the thermodynamics that was developed in the years when mankind had
absolutely no picture of the structure of matter.
It is also useful to mention here that the equations of state that we arrived at by experiment show the
relationship between the properties of a substance that is completely in equilibrium with itself, that is
of a substance in which the molecules have reached their most likely state. For the transition of a
substance from one state of equilibrium to another it takes some time for molecules to reach their most
likely state. However this time is extremely short and is even so short that in most technical processes
the molecules of the substance involved at every moment of the state transition have sufficient
opportunity to approach their most likely state so closely that the correlation between the statuses at
any moment is practically identical to the correlation in a status of perfect equilibrium.

2.2 ENERGY AND TYPES OF ENERGY

Energy is a difficult concept to define. One definition that people intuitively understand very well and
furthermore is very concise, is as follows:

energy is a non-material “something” that is able to bring about a change to or in material

objects.

Purely physically seen, this description is not perfect. For example it ignores the fact that mass and
energy are equivalent. However, in order to determine “what” in a technical process must be taken into
account for energy balance, it is quite sufficient. So we will use this description as a basis for our
further considerations. If the non-material energy is bound to a material body, this body is then
referred to as an "energy carrier".
There now follows a description of the most important types of energy that we can distinguish.

Work
Thermodynamics for energy systems 6 J.J.C. van Lier, N. Woudstra

Is the energy that is supplied to a system or given off by a system as a result of the force that is applied
by the adjoining system to the boundary surface of the system concerned.
If the force is applied in the same direction as in which it acts, then energy in the form of work is
supplied to the system concerned. If the force is applied in the opposite direction to that in which it
acts, then energy in the form of work is given off by the system concerned. The following is an
illustration of this.
part of the system
boundary

part of the shaft that

is considered as the
system

shear forces exerted on

the system by the
gas adjacent part of the shaft

Figure 2.2.1 Figure 2.2.2

System formed by gas Shear forces on the boundary surface at the place where it runs
in a cylinder, with through the shaft
movable forces on the
boundary surface

If the plunger in the cylinder in Figure 2.2.1 applies a force F to the enclosed gas (the system!) on the
boundary surface between the plunger and the gas, then when the plunger moves in a downwards
direction it supplies work to the gas. When the plunger moves in an upwards direction then work is
supplied by the gas to the plunger.
To supply work to a system the force applied by the adjoining system on the boundary surface does
not have to work perpendicular to the boundary surface. So - if the boundary surface of a system also
runs through a shaft - shearing forces will be exerted at the point of the sectional plane of the adjacent
part of the shaft (the bordering system) on the boundary surface of the system concerned (Figure
2.2.2). These shearing forces rotate on the boundary surface together with the shaft. If the shearing
forces operate in the direction of rotation then work is supplied to the system concerned via the shaft.
If the shearing forces operate in the opposite direction, then the shaft gives off work to the bordering
system. The shearing forces that operate on a mass particle in a liquid flow with friction are also an
example of movable forces that are in the actual boundary surface (Figure 2.2.3).
Thermodynamics for energy systems 7 J.J.C. van Lier, N. Woudstra

δw
(w + dy) dt
δy

τ + δδyτ dy

τ
w dt

Figure 2.2.3
Deformable mass particle with shear force on the
boundary surfaces

In general one can say that the work supplied to a system is equal to the scalar product of the force
(applied to the system by the adjoining system) and the (covered) distance. If this scalar product is
negative, this means in fact that work is given off by the system!

Kinetic energy
Is the energy available in a system as a result of the speed of physical mass.
If we provide work to an amount of mass m and if the work supplied only has an increase in the speed
of this mass as a result, then we can write:

Potential energy
Is the energy available in a specific amount of mass as the result of the location of this mass in a force
field (gravity field or magnetic field).
If a “mass particle”is at rest in a force field, then the force fields that act on this particle will be
neutralised by forces that are applied by the adjoining systems on the boundary surface of the mass
particle involved. The result of these forces will be equivalent to the force field, but in the opposite
direction.
If the mass particle moves in the force field, then these forces cover a distance. If the movement is in
the direction of the forces, then work is supplied to the mass particle. This added energy is
accumulated in the mass particle and forms the increase in the potential energy. The increase in the
potential energy of a mass particle during the movement of the mass particle in a force field is
therefore equivalent to the negative value of the scalar product of the force field and the distance.
When setting up an energy balance one must realise that the force field itself is fixed in place can
therefore not be moved by the mass particle concerned. For the static observer the force field operating
on a moving mass particle in setting up an energy balance only has an increase in the potential energy
as a result. The static observer sees the energy necessary for the increase in the potential energy
supplied either by the surrounding systems - via the forces that these systems exert on the boundary
surfaces of the mass particle involved - or by a change to the kinetic energy of the mass particle. An
observer who moves with the system only sees the force field increase in size.
Thermodynamics for energy systems 8 J.J.C. van Lier, N. Woudstra

Internal energy
Is the energy that according to the first law is available as a property of a specific substance.
From atomic physics we know that matter (gaseous, liquid or solid) is made up of molecules. Each
molecule on account of its movement (translation, vibration and/or rotation) and on account of the
forces that the surrounding molecules exercise on it, represents a certain amount of energy. If we now
supply energy (for example work in the case of an adiabatic isolated system), then this energy will be
absorbed by the molecules and this will result in a change to the movement and/or the location of the
molecules. In other words: the structure of the system changes. So it is more elegant to change the
description of the internal energy given above as follows:

the internal energy of a substance is the energy available in the substance as a result of its
molecular structure.

In order to obtain a particular state change in a substance a given amount of energy must be supplied
to the substance. The amount can be determined experimentally and shows the increase in the internal
energy with the state change concerned.
Normally it is not possible to calculate the absolute magnitude of the internal energy available in a
substance. So for most substances people limit themselves in practice to the experimental
determination of the increase in the internal energy in relation to a certain reference state. In general
this state is described as “the zero point". So for water the triple point of water is chosen as the zero
point, because this point can be reproduced with extreme accuracy. The internal energy of the water at
this point has been defined as zero in the international tables for the thermodynamic properties of
water and steam.

Heat
Is the name for the energy that at the point of the boundary line between two systems flows across this
boundary line only because the two systems are not in thermal equilibrium with each other.
With this energy exchange the state of both systems changes in such a way that the property
"temperature" of both systems become closer to each other. When both systems together have reached
a thermal equilibrium then the temperatures of both systems are equal to each other and also the
amounts of energy given off and absorbed by each system are also equal to each other. At this point
one can say that energy transfer does not happen any more. It is therefore possible - and this also
sounds somewhat simpler - to state that heat is the name for the resulting amount of energy that at the
point of the boundary line between two systems flows across this boundary line only as a result of a
temperature difference between the two systems.
In the statistical approach to internal energy it already became apparent that each substance is built up
out of molecules that demonstrate a certain energy. If now two systems are brought directly into
contact with each other, an energy exchange will take place on the boundary line between the two
systems between the molecules building up the substances in each of the two systems. This can be
because of collisions of the molecules with each other on the boundary line (energy transfer by
conduction and convection respectively) or because of an exchange of photons (energy transfer by
radiation). If the energy transfer in one direction is greater than in the other direction, then the net
result is the transfer of a certain amount of energy (the so-called resulting amount of energy) from the
one substance to the other. If the energy transfer is the same in both directions then in fact no energy is
transferred (the resulting amount of energy is nil!) and the substances in both systems are in
equilibrium with each other in accordance with the zeroth law.
A graduator for the amount of energy that a particular amount of a substance can give off on account
of its molecular structure is the property "temperature". The statistical approach described above helps
to make us understand that the temperature of the matter, which gives off the heat of the net energy
flow, is an important parameter for the value of the energy of this net energy flow. As will now
Thermodynamics for energy systems 9 J.J.C. van Lier, N. Woudstra

become clear, this is confirmed by the second law. This has led in practice to a temperature being
ascribed to the energy flow “heat”, being the temperature of the system that is giving off the heat.
In the formulation of the concept of heat, heat has been referred to as the "resulting amount" of energy
that at the point of the boundary line between two bodies flows across this boundary line only as a
result of a temperature difference between both systems. Because an energy balance always deals with
the resulting amount of energy, from now on the net energy flow will be described as the energy flow
that results from the difference in temperature. The definition of the concept ‘heat’ is then:

the energy that at the point of the boundary line between two systems flows across this
boundary line only as a result of a temperature difference between both systems.

Heat is a type of energy that shows a certain similarity to the type of energy work. Both forms are an
amount of energy that at the point of the boundary line is given off or absorbed by a system
respectively. They are not themselves available in the system concerned so that both types of energy
only exist during an energy exchange between the system concerned and the surrounding systems.

Electrical energy
Is the energy that is released when electrically charged particles in this system move from a higher
potential to a lower potential.
Electrical energy - just like work and heat - only appears during an energy exchange. Of the two forms
of energy work and heat, work shows the greatest similarity to electrical energy, because in the ideal
case electrical energy can be completely converted into work and the other way round. This is not the
case with heat!

In a summary of the types of energy people also normally mention chemical energy and atomic
energy. This is not completely correct, because these terms are only intended to indicate that energy is
given off by a chemical reaction or a nuclear reaction and how much energy this is - under particular
conditions!. What type of energy is given off plays no part in this naming convention. That completely
depends on the substances that react with each other and the process taking place (the measure of
irreversibility). As an explanation we shall look at what takes place during a chemical reaction.

In a chemical reaction a change takes place in the configuration of electrons in the substances reacting
with each other, whereby completely new bonds are created between the atoms concerned. Before the
reaction the substances involved each have a certain amount of internal energy. After the reaction a
new substance is available that itself also contains a certain amount of internal energy. Both before
and after the reaction there is no other energy available in the substances involved than the internal
energy!
The total amount of internal energy after the reaction will, because of a different binding of the atoms,
differ from the total amount of internal energy before the reaction. In the case of a decrease in the total
internal energy this difference is the energy given off to the surrounding systems, and in the case of an
increase in the total energy it is the energy supplied by the surrounding systems.
During the reaction an increase in volume or a decrease in volume also occurs as a rule. This means
that in the case of a volume increase the work of expansion is given off via the boundary line to the
surrounding systems and in the case of a volume decrease work of expansion is supplied from the
surrounding systems. The decrease in the total amount of internal energy (positive or negative) less the
work of expansion given off (positive or negative) is the net amount of energy that is given off by the
system as a result of the chemical reaction. This amount of energy in a process whereby at the end of
the process the newly-formed substance still has the original temperature and pressure (see Figure
2.2.4), is described as chemical energy (by the chemists called: “heat of reaction”).
Thermodynamics for energy systems 10 J.J.C. van Lier, N. Woudstra

TA ,p A TB ,p B TC ,p C

chem. reaction
A + B C

chemical energy =
energy that will be transferred as TA = TB = TC and
pA = pB = p C (this energy can be used for other purposes)

Figure 2.2.4
Energy flow - referred to as chemical energy - as a result of a
chemical reaction between two substances A and B

In the case of a positive value this energy can be used for other purposes and in the case of a negative
value this extra energy must be supplied by the surrounding systems in order to achieve the chemical
reaction.

A similar approach can also be made for a process with a nuclear reaction, however it must be
understood that with a nuclear reaction the nuclei themselves react with each other and in this way
form new atoms.
In atomic physics people often talk about binding energy. By this is understood the amount of energy
that is necessary to completely separate the nuclear particles of a nucleus from each other. It is
therefore not energy that is accumulated in the nucleus and which can be freed by a reaction. Quite the
opposite: it is actually the amount of energy that would have to be supplied to "break" the link
between the nuclear particles. In spite of this, the binding energy can be used as a measure for the
amount of energy that atoms represent. So, for example, in a nuclear reaction one must consider the
difference between the binding energy of the newly-formed atoms and that of the original atoms. If
this difference is positive, then it costs more energy to separate the particles from each other after the
reaction than before the reaction. According to the law of conservation of energy, this difference must
be released by the nuclear energy reaction.

2.3 CONCEPTS AND CONVENTIONS IN THERMODYNAMICS

Thermodynamics is based on three empirical laws of nature: the zeroth, the first, and the second law.
By taking these three laws as a starting point, by introducing certain concepts, and by stating certain
conventions, a whole theory is built up using consistent reasoning. Of great importance here is that the
concepts introduced are described as well-defined as possible and that the conventions stated are
adhered in a consistent way. There must also not be any misunderstanding about what is understood
by the names of the various types of energy.
Of extreme importance is the correct understanding of the concept of the type of energy referred to as
heat. When people did not have a (good) picture of the structure of material, it was not clear what
happened during the contact between two substances at different temperatures. People thought then
that with this contact a sort of mysterious fluid (described as calorique in French literature) flowed
from the one substance to the other. So people introduced a separate energy unit for this fluid: the
calorie in the old system of technical units. In addition many names developed over the years point to
this old interpretation, such as specific heat, heat capacity, heat conduction, heat transfer and heat
content. The quantities referred to by these names are often in a particular profession quantities that
make a simple calculation method possible. There is absolutely no objection to the use of these
Thermodynamics for energy systems 11 J.J.C. van Lier, N. Woudstra

quantities as long as people realise what actually happens according to modern statistical
interpretation. The following is an illustration of this:

In the wall of any apparatus the temperature of the material the wall is made from is not the
same at all places. This means that - if one thinks of the wall as being divided into a large
number of small parts - these parts are not in thermal equilibrium with each other. So it follows
that energy must flow through the wall, trying to bring the parts into thermal equilibrium with
each other. If we want to calculate such an energy flow in a particular cross-section, then we can
consider this cross-section as a plane that divides the wall into two systems with differing
temperatures. According to our convention we must describe the energy flow at the boundary
line - the energy flow that only arises as a result of the difference in temperatures! - as "heat
flow". Whoever has to calculate the energy flow in the entire wall will therefore in the selected
boundary surface have to deal with an energy flow that is indicated by the name heat flow. It is
therefore not so strange that he or she continues to talk of a heat flow through the wall and
about conduction of heat in the wall. For the purpose of the calculation this is the obvious term
to use, and does not lead to an incorrect result! In essence, however, energy flows through the
wall only because the molecules of the wall exchange energy with one another. Thus there is
internal energy available in the wall and not some sort of mysterious fluid "heat".

There now follow below the descriptions of a number of concepts that are mostly used in the
elaboration of the three main laws. The sequence of the descriptions of these concepts is not
alphabetic: the aim is to connect the concepts together in a logical way. For this reason the first
description is that of the concept “process”.
By a process is meant an event whereby one of more energy carriers change from one state of
equilibrium to another as the result of external influences. With a process a clear differentiation must
be made between the cause of the process and the progress of the state changing by the energy carriers
during the process. The same progress can namely have different causes. We shall come back to this
later.

The area or equipment involved in a process that must especially be considered is set off from the
entire area or from all the other equipment by means of a boundary line or boundary surface and
described as a system. A boundary line or boundary surface respectively can be fixed (for example
when considering a particular apparatus) or movable (for example when considering a particular
amount of gas that expands during the process).
If forces are brought to bear by the adjoining systems at the point of the boundary line or boundary
surface respectively of the system concerned and these forces move with the movement of the
boundary line or boundary surface respectively in a direction opposite to that of the forces, then with
the movement of the boundary line work is given off by the system concerned to the adjoining
systems. For example, if the system is made up of a certain amount of gas with a volume V and at
pressure p, then - assuming that no friction occurs on the boundary surfaces - as a result of the law
“action is reaction”, equally large pressure will be exerted on the gas by the surrounding systems, but
in the opposite direction. In the case of a volume expansion dV the reaction forces exerted by the
surrounding systems move in the opposite direction to that of the reaction forces. This means that the
gas with the volume expansion dV supplies an amount of work dW = pdV to the surrounding systems.
If the boundary surface of a system is chosen such that energy can not flow anywhere across the
boundary surface as a consequence of a difference in temperature between the chosen system and the
adjoining systems, then this is referred to as an adiabatic system. The boundary surface is then also
referred to as an adiabatic wall.
With systems, a difference is made between closed and open systems. In closed systems the transport
of mass across the boundary lines of the system - and therefore also of energy linked to mass! - is not
possible. This also means that we are dealing with the same mass. In open systems the transport of
Thermodynamics for energy systems 12 J.J.C. van Lier, N. Woudstra

mass across the boundary lines of the system - and therefore also of energy linked to mass - is
possible. The mass in the system is completely or partly replaced but the total amount of mass in the
system can remain the same.
The word “property” has already been used a number of times. By this is meant an amount or value,
which may or not be measurable, which with an arbitrary equilibrium of a system can only have one
particular value. The difference in the value of a property between two states of equilibrium (begin
and end states of a process) is independent of the way the process develops between the two states of
equilibrium.
The relationship between a property and other properties in a state of equilibrium can be expressed in
a function - the equation of state - and is also often shown in diagrams: the so-called state diagrams.
If one wants to further study the development of the properties between two states of equilibrium in a
system, then one uses the term state change. A differentiation can be made here between a quasi-static
state change and a non-static state change. In the case of a quasi-static state change the state change
takes place such that the relationship between the properties at any moment is approximately equal to
that in a state of equilibrium. The progress of the properties can then be shown in a state diagram: the
so-called state change line. In the case of a non-static state change, the relationship between the
properties during the state change can not be determined.
It is usual to give particular processes a special name. One process that often comes up in
thermodynamics is the so-called reversible process. This is a process whereby all the systems that take
part in the process can be returned to their original starting state at the end of the process. If this is not
the case for one or more of the systems, then the process is referred to as an irreversible process. It
appears in practice that it is not possible in any real process to return all the systems to their original
starting state. The extent to which people can more or less succeed in this determines the so-called
irreversible character of the process.
While reversible processes do not occur in practice, in thermodynamics a lot of attention is paid to
these processes. This is because that as a rule for an irreversible process with a quasi-static state
change a reversible process can be thought of with the same state change, but brought about by an
entirely different cause. By now comparing both processes with each other a good picture can be
obtained of the irreversible nature of the process concerned, and it may be possible to diminish the
irreversible character of the process and thereby achieve a better energetic efficiency.
Frequently it is possible when studying a process to choose the boundary lines of the system
concerned such that this system could also have formed part of a reversible process. One can then say
that the system itself has demonstrated a reversible process. When studying the state changes of this
system, we can make use of the properties of a reversible process without restrictions.

If a system by means of a process returns to its original starting state, then this system has
demonstrated a cyclic process. As a rule such a system will be formed by a certain amount of mass.
This mass can possibly undergo a state change in the execution of the cyclic process.
If the cyclic process takes place in a collection of equipment, then if required this set of equipment can
also be chosen as a system. The system will then not demonstrate the cyclic process itself but will limit
the areas in which the cyclic process takes place.
If work is given off by a cyclic process then the process is referred to as a work process. If a cyclic
process results - with help of work supplied to it - in heat being extracted from a system with a lower
temperature and supplied to a system with a higher temperature, then this is referred to as a cooling
process.
If any mass flows during a process through or in the system under consideration and if this flow occurs
such that at any arbitrary point in the system the properties of the mass available or flowing at that
point does not change with time, then the process by or in the system respectively is described as a
stationary process. If this concerns an open system, then one can also refer to it as a system with
stationary flow.
Thermodynamics for energy systems 13 J.J.C. van Lier, N. Woudstra

2.4 APPLICATION OF THE FIRST LAW

2.4.1 Energy balance

If in a process a particular apparatus or a particular area is defined as a system and if this system is
watched by an observer during the process, then - according to the first law that no energy can be lost
or be created from nothing - the difference seen by the observer in the energy supplied to the system
and the energy given off by the system at the point of the boundary line must be absorbed into the
system itself. Because the first law is an empirical law of nature, it must also be possible for the
observer to ascertain this increase in energy in the system. For the energy expert this creates the
possibility to set up the following general energy balance for a system:

energy supplied on the boundary line of a system by the surrounding systems =

increase of the energy in the system + energy given off by the system to the surrounding
systems on the boundary line of the system.

Of great importance is from which "observation point" the energy expert sets up the energy balance,
because in the energy balance only the types of energy must be taken into account that can be
ascertained by the observer from the observation point concerned. Two different observation points for
a particular system can thereby at first glance result in two different energy balances. However the
reader can be reassured that in a further elaboration of these two energy balances a certain connection
turns out to exist between these two energy balances. From all this we can conclude that the choice of
observation point when setting up an energy balance must be done in a very well-considered manner.
This choice can namely have a large influence on the simplicity of the total calculation.

For the"increase of the energy in the system" item of the energy balance we could initially limit
ourselves to the increase of the internal energy of the substance to be processed in the system.
However, it goes without saying that here we must take into account the increase of all types of energy
that can be accumulated in the system and can be verified by us. We must therefore also take into
account the material of the equipment that is also measured as part of the system.
For a system that demonstrates a cyclic process or for a system with stationary flow, the increase in the
system is equal to zero. The energy balance in this case is as follows:

energy supplied on the boundary line of a system by the surrounding systems =

energy given off on the boundary line of the system to the surrounding systems.

When setting up an energy balance one may ask oneself when one must take into account an energy
flow called heat on the boundary line. In order to determine this we can look along the boundary line
and check if a temperature difference exists anywhere along the boundary line that can lead to an
energy flow. Here we must be mindful of the fact that in the case of a reversible process this
temperature difference approaches zero.
A general convention in thermodynamics is that a heat flow is considered to be positive if it is
supplied to the system and negative if it is given off by the system. This convention must be strictly
adhered to because it is determining for the definition of the property arising from the second law,
entropy.
It is also normal in energy technology when setting up an energy balance to classify the energy flows
“work” and “electric energy” as positive if they are given off by the system and negative if they are
supplied to the system. We will also keep to this convention although a deviation from this convention
will have no influence on the further elaboration of thermodynamics.
Both of these sign conventions mean that from now on with the setting up of a general equation for the
energy balance of a system that is part of a process, we must classify the energy flow “heat”
Thermodynamics for energy systems 14 J.J.C. van Lier, N. Woudstra

represented by Q as one of the terms that indicate the supplied energy and we must classify the energy
flows"work" and "electrical energy" represented by W and P respectively as terms that indicate the
energy given off.

Q1 Q1

W W

Q2 Q2

Figure 2.4.1 Figure 2.4.2

System with cyclic System with cyclic
process, whereby the process, whereby the
direction of the energy direction of the energy
flows is drawn to reflect flows is drawn according
the actual situation to conventions

One can now ask oneself if these sign conventions must also be adhered to when "drawing a picture"
of a particular process. The drawing of a picture of a particular process serves in the first place to
obtain a good insight into the process. This means that in a figure, if it is all possible, the direction of
the energy flow must be drawn corresponding to the actual direction. This drawing method does not
have any drawbacks when drawing up a formula for the process as long as with the drawing up of the
equations one translates the direction of the energy flow in the figure into the direction that has been
agreed upon when drawing up the equations. So the figure for a system in which a power cycle is
described will be easiest to understand if it is drawn according to Figure 2.4.1. When drawing up a
formula for the energy balance of the system concerned in our minds the figure must acquire the form
shown in Figure 2.4.2. The general energy balance is now:

With the elaboration of this calculation it will appear that Q2 has a negative value!

Below we shall now set up the energy balance of a system that is formed by an infinitely small mass
particle of a fluid flow: a cube with sides dx, dy and dz. We are concerned here with a closed system
with a mass equal to [Link].
The energy balance can be set up by a static observer who sees the particle moving through a spatial
coordination system. The observer sees the surrounding systems apply force to the particle on the
surface boundaries as a result of the pressure in the particle itself (action = reaction) and as a
consequence of the shear stress caused by the mutual friction between the flowing particles. The
observer also sees these forces move with the particle. For the static observer this means that - if these
forces operate in the opposite direction to the movement - work is given off by the system concerned
to the surrounding systems or - if the forces operate in the same direction as the movement - work is
supplied to the system by the surrounding systems. If in the period dt during the flow the particle
undergoes an increase in volume, then the observer sees the forces on the boundary surfaces also move
Thermodynamics for energy systems 15 J.J.C. van Lier, N. Woudstra

as a result of the increase in volume. For the observer this means he or she sees the particle give off
work to the surrounding mass.

z
field force on mass = Ffield force .ρ.[Link]

dy

[Link]

dz y
x dx
δp
(p + .dx).[Link]
δx

motion of mass in direction of x-axis

Figure 2.4.3
Mass particle and the forces operating on it in the x-direction.
The field force operates in x-direction

If a temperature gradient exists in the fluid flow, then the observer also sees a temperature difference
between the mass particle concerned and the surrounding mass. For the observer this means an energy
exchange with the surrounding systems only as a consequence of the temperature difference. This
energy exchange on the boundary lines is accounted for under the name heat (the energy dQ in the
time period dt). According to the drawing convention this energy is included in the energy balance as
supplied energy (with a positive or negative value!).
For the observer, the difference in the supplied energy and the energy given off results in an increase
in the internal energy and an increase in the kinetic energy and - in the case that the coordinate system
itself is in a force field - also an increase in the potential energy.
As we are concerned with the principle of setting up an energy balance, we will not set up the energy
balance for a mass particle moving in a completely arbitrary way, but the energy balance of a mass
particle moving in a linear way - with a speed w parallel to the x-axis. Furthermore the exceptional
case of a frictionless fluid is assumed. We will also assume that the field force Ffield force operates in the
direction of the x-axis as shown in Figure 2.4.3.
For the duration dt - the time in which the particle moves over a distance dx - the energy balance for
the mass particle is [Link]:

energy supplied to the system =

increase of the energy in the system + energy given off by the system
Thermodynamics for energy systems 16 J.J.C. van Lier, N. Woudstra

Dividing by [Link] gives the following result for a mass particle with a mass of 1 kg:

(2.4.1)

Note: in this equation du, d½w2 and dv are increases in space and time!

If the observer is in the mass particle (and therefore moves together with the mass particle!) then in
this case the observer also sees the surrounding systems exert forces on the particle. However, the
observer does not see the particle change its place and for him the forces then also do not cover any
distance as a result of a movement. He or she does see the boundary surfaces move as a consequence
of the expansion of the particle. So for the observer the forces only give off work to the surrounding
particles as a consequence of the expansion.
Because to the observer the particle has no speed, for the observer there is no question of an increase
in kinetic energy either. He or she also does not see the particle move in a force field and therefore
does not notice any possible change to the potential energy of the system.

The following is to illustrate the potential energy of the particle: if the particle were only subject
to forces that cancel out the force field, and if the particle only moves in the force field, then an
observer in the particle does not see these forces travel any distance. For the observer no
increase in energy can be seen as a consequence of a change in the force field and therefore also
no increase of the potential energy in the system.

However, the observer is able to perceive a temperature difference and therefore a heat energy flow on
the boundary line. In addition the observer will perceive a change in the properties of the system itself,
in other words of the internal energy.
The energy balance of a moving mass particle [Link], that forms part of a frictionless flow comes
out as follows for an observer in the mass particle:

For a mass standard particle with a mass of 1 kg this makes:

(2.4.2)

Equation 2.4.1 and equation 2.4.2 are energy balances for the same mass particle. Are they completely
different? In order to find out we can now also set out the impulse balance for the mass particle:

Dividing by [Link] gives:

With w = dx/dt this leads to the equation:

(2.4.3)

Note: in equation (2.4.3) d½w2 is an increase in the kinetic energy in space and time!

With this last equation the equation 2.4.1 can be simplified and leads to equation 2.4.2.
The equation:
(2.4.4)
Thermodynamics for energy systems 17 J.J.C. van Lier, N. Woudstra

is therefore the general energy balance for a mass particle in a frictionless flow. One can also say that
it is the energy balance of a mass particle whether in motion or not that only gives off work to the
surrounding systems via the pressure force on the boundary surfaces. This equation may not be seen -
as is sometimes done - as "the first law in the form of a formula". It remains an application of the first
law to an extraordinary, theoretical ,case!
If there is no temperature difference with the surrounding systems, then equation 2.4.4 becomes:

If the energy balance is set up for an open system, then when setting up the balance one must take into
account the energy that together with the mass is supplied to the system or given off by the system
respectively. Furthermore we must realise that work is also necessary to bring mass into the system or
to obtain mass from the system respectively.
In order to obtain a picture of the way in which these last two amounts of work must be calculated, the
energy balance of an open system will be set up in two different ways. We will assume an open system
with a stationary flow, because the energy expert regularly deals with such a system. One can think of
the situation that often arises that an energy balance must be set up for an apparatus that forms part of
a collection of equipment.

The first method of approach for the setting up of the energy balance is normal approach used in this
technology: see Figure 2.4.4. The system with stationary flow is hereby certainly considered as an
open system: a system in which, as a result of the stationary flow, no energy can be accumulated. The
energy balance is therefore:

energy supplied via the boundary line = energy given off via the boundary line

If one chooses as a time period the length of time that 1 kg is supplied to the system while at the same
time 1 kg is given off by the system, then the equation for the energy balance is:

(2.4.5)

In this balance by W is meant the work that is given off via a rotating shaft, an electric wire or
something similar and which can therefore be used for any arbitrary purpose (this in contrast to the
work that is necessary for the giving off of 1 kg mass and the supply of 1 kg mass).
Thermodynamics for energy systems 18 J.J.C. van Lier, N. Woudstra

useful work
W

1 kg mass

internal energy = u 1
1 open system
kinetic energy = 2 w 12 1 kg mass
potential energy = E p,1
internal energy = u 2
1
kinetic energy = 2 w 22
potential energy = E p,2
Q=
energy transfer due to a temperature
difference at the system boundary

Figure 2.4.4
Open system with stationary flow for the time that 1 kg is supplied and
at the same time 1 kg is given off.
The boundary line does not move!

In the second method of approach the open system is transformed into a closed system by, at the start
of the length of time being considered, considering the 1 kg that will be supplied to the open system
together with the open system as a single closed system (see Figure 2.4.5). During the time being
considered, the 1 kg of mass moves as it were from the inlet side to the outlet side and in the originally
open part of the closed system nothing changes: the change of the dashed boundary line in Figure
2.4.5 to the dotted and dashed boundary line.

This means that the increase in the energy in the closed system amounts to:

The boundary line of the closed system moves at the original position of the supply and discharge: the
work thus given off to the surrounding systems is:

The energy balance is now:

(2.4.6)

From the energy balances 2.4.5 and 2.4.6 from both methods of approach it follows that in the energy
balance of the open system (equation 2.4.5) the last term:

representing the total work given off by the system to the surrounding systems as a result of the
giving off of 1 kg mass and the simultaneous supply of 1 kg mass

is equal to (p2.v2 - p1.v1).

p1.v1 is therefore the work that is supplied by the surrounding systems to the open system in order to
bring 1 kg mass into the open system, and p2.v2 is the work that the open system supplies to the
surrounding systems when it gives off 1 kg mass.
Thermodynamics for energy systems 19 J.J.C. van Lier, N. Woudstra

1
closed system 2

part of inlet pipe

with 1 kg mass
part of outlet pipe
Q with 1 kg mass

= boundary at the start of the considered period

= boundary at the end of the considered period

Figure 2.4.5
Transformation of the open system in Figure 2.4.4 into a
closed system. The boundary lines move to the original
inlet side and outlet side

By regrouping, the energy balance of an open system with stationary through-flow can be written in
the following form:
(2.4.7)

The value (u + p.v) appearing in the above equation is made up of the properties of the mass flowing
through and thereby this in itself is also a property. The number of calculations for the application of
the above equation for the energy balance of an open system can be limited if one has available
property tables which together with the usual properties such as pressure, temperature, specific volume
and entropy include the combined property (u + pv). Under normal conditions this does indeed happen
and this combined property is referred to by the name enthalpy:
(2.4.8)
With the introduction of the property enthalpy the following general energy balance exists for an open
system with stationary flow for the time period in which 1 kg mass is supplied to the system and 1 kg
mass given off by the system at the same time:
(2.4.9)

If we are dealing with processes whereby the increase in the kinetic energy and the increase in the
potential energy of a fluid flowing through an open system is to be neglected and whereby also no
technical work is given off, then the energy balance is very much simplified:
(2.4.10)

This balance can be applied e.g., if, for a heat exchanger with stationary flow, we define the area
through which the hot or cold fluid flows as an open system.
If the entire heat exchanger is chosen as a system, then no heat flows over the boundary line of the
system and the energy balance for the duration of 1 second is (the subscript H refers to the hot fluid,
the subscript C to the cold fluid):
(2.4.11)
Thermodynamics for energy systems 20 J.J.C. van Lier, N. Woudstra

In the literature this balance is often referred to as "heat balance". Actually this is not a correct name
since nowhere in this balance is the heat flow Q included. It is therefore more correct to talk of
"enthalpy balance".

Fexternal = force that will cause

a displacement
of object 1
object 1
Ffriction,2 1

Ffriction,1 2
object 2

molecular interaction due to direct

contact between the objects

Figure 2.4.6
Molecular interaction at the boudary surface of two inflexible
objects that in respect to each other

2.4.2 Friction

When setting up an energy balance it is of great importance to have a good picture of the phenomenon
"friction" in a process and of the consequences of this phenomenon for the process. In order to
determine this we can consider two solid objects that are in contact with each other (Figure 2.4.6). If a
force Fexternal is exerted on object 1, which tries to move object 1 in relation to object 2, then because of
the molecular interaction at the boundary surface of both objects a force will be exerted by object 2 on
object 1 to try to prevent this movement: Ffriction, 261. This is referred to as the force of friction and the
size of it depends on the intensity of the contact between the two substances (or in other words the
force with which the two objects are pressed against each other!). According to the law "action =
reaction" object 1 will exert an equal but opposing force on object 2: Ffriction, 162.

If the external force Fexternal is only a fraction greater than the maximum value of the opposing force as
a result of the molecular interaction Ffriction, 261 then object 1 will begin to move across object 2. For
further explanation we assume that object 1 has a constant speed w compared to object 2.

An observer in object 2 sees the force Fexternal in the time dt cover the distance dx and therefore sees
that work (Fexternal . dx) is transferred to object 1.

From the rise of the property temperature of both objects the observer also perceives that as a
consequence of the molecular interaction at the boundary surfaces of the two objects, the internal
energy of both objects increases. Thus, according to the law of conservation of energy, at the point
where the two boundary surfaces meet the work transferred is transformed into an energy flow,
whereby the part absorbed by object 1 has the effect of a heat flow dQfriction, object 1 with a temperature T1
and the part absorbed by object 2 has the effect of a heat flow dQfriction, object 2 with a temperature T2. The
total energy absorbed by both the objects is therefore described as frictional heat. So for the
transformation can be written:

However, for an observer in object 2 the energy flow dQfriction, object 1 cannot be seen. Such an observer
only sees the energy flow "work supplied [Link]" and the energy flow dQfriction, object 2 to object 2
Thermodynamics for energy systems 21 J.J.C. van Lier, N. Woudstra

caused by the molecular interaction. The observer also sees the internal energy of object1 and of
object 2 increase and possibly both objects expanding. The observer concerned in this way arrives at
the following energy balance for object l:

The observer moving together with object 1does not see the external force Fexternal cover any distance.
But this observer does perceive that the molecular interaction at the boundary surface creates an
energy flow dQfriction, object 1 to be “absorbed” by object 1. This observer has the following energy
balance for object 1:

The conclusion from all this is that the frictional forces between two objects 1 and 2 in the energy
balance of object 1, for the observer in object 2, has as a consequence an extra energy flow frictional
heat from object 1 to object 2 (= dQfriction, object 2). The observer in object 1 when setting up the energy
balance for object 1, takes into account the frictional forces by including an extra amount of energy
"frictional heat" (= dQfriction, object 1) in the supplied energy.

δτ
τ+ δy
dy

deformation due
to shear forces

τ
Figure 2.4.7
Deformation of a mass particle as a
result of the shear forces on the
boundary surfaces exerted by the
surrounding particles

The movement of two stiff objects in respect to each other by sliding can play an important role
in a technical process. Just think of journal bearings and thrust bearings! Limiting the frictional
heat in these cases (or in other words reducing the friction) can be done by supplying a lubricant
between the moving surfaces of both objects. For this a completely separate field of study exists
called "tribology".

In the above example we have of course assumed that neither of the objects deforms as a result of the
frictional forces and that there is a speed difference at the boundary surface between the two objects
(the objects slide across each other!). What happens now if, as a result of molecular interaction,
frictional forces come into play between two objects that easily deform? For example this is the case
for a flowing gaseous or liquid medium.
If we consider a mass particle of this medium, then the surrounding particles will exert frictional
forces on this mass particle as a result of the molecular interaction, which in fluid dynamics are known
as shear forces: see Figure 2.2.3 and Figure 2.4.7. These shear forces will deform the particle. With the
deformation the shear forces move. This means that with the deformation the shear forces supply work
to the particle. This work serves to overcome the resistance of the particle against deformation.
Because when the shear forces are no longer present the particle will not “rebound”, the energy is
therefore completely absorbed by the particle. This means that the energy is absorbed by the molecules
and in just the same way as a heat flow.
Thermodynamics for energy systems 22 J.J.C. van Lier, N. Woudstra

The identical character of the deformation work and a heat flow also becomes clear from the energy
balance of the mass particle, as set up by an observer moving with the particle. This observer does not
only see the pressure forces themselves move on the boundary surfaces during the expansion and give
off work to the surrounding particles, but also sees the shear forces move and the particle deform. For
this observer this means an extra supply of energy by the surrounding particles to the particle
concerned. It would be going too far to work out the energy balance completely here. For this the
reader is directed to handbooks on hydrodynamics, including literature 2.1.

In completing our consideration of friction we must very quickly take a look at the consequences of
"resistance", which occurs in the electrons in an electric wire. Because of this resistance, during the
flow of the electrons the internal energy of the wire increases and in most cases this increase is
simultaneously given off to the surroundings as a heat flow. This is known as "heat of resistance" that
is given off.

In this section we have seen that in all the cases described a flow of work or electric energy
respectively is transformed into an energy flow with the same characteristic properties as a heat flow.
Because, according to the second law of thermodynamics, it is not possible to transform heat
completely into work or energy respectively, the occurrence of friction or resistance respectively is
therefore a process with a definitely irreversible character.

2.5 ELABORATION OF THE CONVENTIONS ARISING FROM THE SECOND LAW OF

THERMODYNAMICS. INTRODUCTION TO THE THERMODYNAMIC TEMPERATURE

There are many formulations for the second law of thermodynamics. However, they are all equivalent
to each other. The four most important formulations for those concerned with energy conversion are:

- work can be transformed completely into heat but heat can never be transformed completely
into work (Carnot)

- it is not possible to build a machine that takes heat from a body such as the sea for example and
turns this heat completely into work (Max Planck)

- heat - withdrawn from a body with a certain temperature - can only be transformed into work if
at the same time a certain amount of this heat is given off to a body at a lower temperature
(Thomson)

- heat can not by itself flow from a body with a lower temperature to a body with a higher
temperature (Clausius).
Thermodynamics for energy systems 23 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q1

W
system
converting
heat into work

Q2

cold reservoir at temp. T2

Figure 2.5.1
System between two heat reservoirs
that has the task to convert as much of
the heat from the hot reservoir into
work

These formulations were made in the time when people could not completely get away from the old
conception that heat was a sort of fluid present in matter. However, this does not affect the validity of
these formulations. After the introduction of the exergy concept in Section 4.2 we will summarise
these formulations into one formulation that is more suitable for the present day.

We agree on the convention that by a heat reservoir we understand a system of dimensions and
construction such that - when during a process a finite amount of energy is supplied as heat to another
system or withdrawn from another system respectively - the temperature of this system during the
process can be considered to be a constant.
If, as a consequence of a temperature difference, energy flows from a heat reservoir with a higher
temperature to a heat reservoir with a lower temperature, then according to the second law a part of
this energy (= heat) can be converted into work. However, this does not happen by itself. For this a
system must be placed between the two heat reservoirs that only has the task of transforming as much
of the heat into work as possible. The system may not itself accumulate energy, in other words it will
not undergo a state change. This will be the case if:
a) the whole system undergoes a cyclic process or
b) apparatus is available in the system, wherein some sort of medium with a stationary flow
performs a cyclic process.

If the process between the two heat reservoirs (Figure 2.5.1) that is performed in or by the system
respectively is reversible, then - we do not want to come into conflict with the second law - the amount
of the "heat to be converted into work" will be independent of both the process performed in or by the
system respectively and of the construction of the system itself. This means that the ratio of the work
obtained to the heat supplied, the so-called thermal efficiency:

(2.5.1)

is independent of the process between the two heat reservoirs and is only dependent on the
temperature of each heat reservoir separately.
Thermodynamics for energy systems 24 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q A1 Q B1

system system
A B

Q A2 Q B2

cold reservoir at temp. T2

Figure 2.5.2
Two systems A en B between two heat reservoirs,
each with its own configuration and its own
reversible process, and whereby it is supposed that
the thermal efficiency of the two systems is not the
same.

Supposing that this is not the case, then two systems A and B with differing efficiency for the
work processes involved can be placed between the two heat reservoirs (Figure 2.5.2). Both
systems perform a reversible process: that means that next to each system another system can be
placed that must be in a position to recover the original starting state (Figure 2.5.3). Because the
systems A and B themselves have not undergone any state change at the end of the work
process, systems A' and B' only have to perform a cooling process.
If we tune the duration of process A and the duration of process B together so that ultimately
QA1 is still equal to QB1 then if 0A is greater than 0B then this results in WA > WB and |QA2| <
|QB2|.
Now we combine the systems A and B' with each other (Figure 2.5.4). Because |QA2| < QB'2 and
WA > |WB'| with this combination heat will be completely converted into work. This conflicts
with the second law of thermodynamics. So the assumption that 0A and 0B differ from each
other also conflicts with the second law.
Thermodynamics for energy systems 25 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q A1 Q A1 Q B1 Q B1

system system system system

A' A B B'

W A' = W A W B = WB'

QA'2 QA2 QB2 QB'2

Q A'2 = QA2 Q B2 = Q B'2
cold reservoir at temp. T2

Figure 2.5.3
The addition of two systems A’ and B’ between the heat
reservoirs of figure 2.5.2, with the task to recover the initial
state after the processes performed by the systems A and B

hot reservoir at temp. T1

Q A1 Q A1 = Q B'1 Q B'1

system system
WA W A - W B'
A B'

WB'

net extracted: Q B'2 - Q A2

cold reservoir at temp. T2

Figure 2.5.4
Combination of the processes taking place in the systems A and
B’ in figure 2.5.3 such that net no heat is transferred to or from
the hot heat reservoir

If the power process performed between the two heat reservoirs by or in the system respectively is
irreversible, then - we still do not want to come into conflict with the second law - the thermal
efficiency 0 of the irreversible process must be less than that of the reversible process.

Suppose that this is not the case. We now consider a system A with an irreversible power
process and a system B with a reversible power process (Figure 2.5.5). Because the process
carried out by system B is reversible we can next to system B imagine another system - system
B' - that performs a reversible process with the aim of returning all systems that have taken part
in the process of the system B back to their initial state. We again adjust the duration of process
A and process B with each other such that QA1 is still equal to QB1.
Thermodynamics for energy systems 26 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q A1 Q B1 Q B'1

system system system

A B B'
irrev. rev.
process process

Q A2 Q B2 Q B'2
Q B2 = QB'2

cold reservoir at temp. T2

Figure 2.5.5
Two systems A and B for the carrying out of power
processes between two heat reservoirs. System A
performs an irreversible process and system B a
reversible process. System B’ now has the task, at the
end of the process performed by system B, to restore
the original state

hot reservoir at temp. T1

Q A1 Q A1 = Q B'1 Q B'1

system system
WA W A - W B'
A B'
irrev. rev.
process WB' process

net extracted: Q B'2 - Q A2

cold reservoir at temp. T2

Figure 2.5.6
Systems A and B’ from Figure 2.5.5 adjusted to each other such
that net no heat is transferred to or from the hot heat reservoir

If we combine the systems A and B' with each other, then we obtain the situation shown in
Figure 2.5.6. If now 0A > 0B then QB'2 > |QA2| en WA > |WB'|. This means that with this
combination heat is completely converted into work. This conflicts with the second law of
thermodynamics.
If 0A and 0B are equal to each other, then QA2 and |QB'2| are also equal to each other. System B'
has now completely undone the changes caused by system A. This means that at the completion
Thermodynamics for energy systems 27 J.J.C. van Lier, N. Woudstra

of the process of system A all the systems that have taken place can be brought back to their
original starting state. In other words system A has now demonstrated not an irreversible
process, but a reversible one.
The only possibility left now is that 0A is less than 0B; which means that more work must be
supplied to system B' than system A generates and that this extra work is with the combination
A-B' completely absorbed as heat by the heat reservoir met temperature T2.

If a system placed between two heat reservoirs has the task of extracting heat from the reservoir with
the lower temperature and supplying this heat to the reservoir with the higher temperature, then the
second law states that this system will have to make a certain "effort" to do this. In other words work
is necessary for this (Figure 2.5.7).

hot reservoir at temp. T1

Q1

system extracting
heat from the cold W
reservoir and
delivering heat to
the hot reservoir

Q2

cold reservoir at temp. T2

Figure 2.5.7
System between two heat reservoirs, that
has the task of transporting heat from the
cold heat reservoir to the hot heat
reservoir

The good working of such a cooling process is assessed with the aid of the following evaluation
factor:

(2.5.2)

The minus sign in this evaluation factor is necessary to prevent a negative value for the evaluation
factor because according to the drawing convention W is negative and Q2 is positive in a cooling
process.
Thermodynamics for energy systems 28 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q A1 Q B1

system system
A B
WA WB

Q A1 Q B1

cold reservoir at temp. T2

Figure 2.5.8
Two systems between two heat reservoirs. Each
has its own structure and its own reversible
cooling process. It is assumed that the evaluation
factors of the cooling processes do not have the
same values: aA < aB

hot reservoir at temp. T1

Q B1 = Q B'1
Q A1 Q B1 Q B'1

system system system

A B B'
irrev. rev.
process process

Q A2 Q B2 Q B'2

cold reservoir at temp. T2

Figure 2.5.9
Systems A and B from Figure 2.5.8 adjusted to
each other such that both systems transfer an
equal amount of heat from the cold heat reservoir.
System B’ has the task of recovering the original
state at the end of the process represented by
system B

From the second law it follows that in the case of a reversible process the evaluation factor a is
independent of the process performed by or in the system respectively and of the construction of the
system.
Thermodynamics for energy systems 29 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

net extracted: Q B'1 - Q A1
Q A1 Q B'1

system system
WA WB'
A B'
W B' - W A

Q A2 = Q B'2

cold reservoir at temp. T2

Figure 2.5.10
Combination of systems A and B’ shown in Figure 2.5.9
such that net no heat is transferred from the cold
reservoir

Suppose that the reversible cooling process described by system A in Figure 2.5.8 has a better a
(and thus a lower value) than the reversible cooling process shown by system B. We now
choose the duration of each process such that QA2 = QB2. In addition we include system B’ in
our considerations, which will undo all the changes that have been caused by system B (Figure
2.5.9).
If we combine system B' with system A then we obtain the situation as shown in Figure 2.5.10.
Because aA < aB it is also the case that |WA| < WB' and |QA1| < QB'1. This means that using this
combination - thanks to the fact that aA < aB - heat can be completely converted into work. This
can’t be true because it is in conflict with the second law of thermodynamics.
Thermodynamics for energy systems 30 J.J.C. van Lier, N. Woudstra

hot reservoir at temp. T1

Q A1 Q B1

system system
A WA WB B
irrev. rev.
process process

Q A2 Q B2

cold reservoir at temp. T2

Figure 2.5.11
Two systems A and B with cooling process between
two heat reservoirs. System A represents an
irreversible cooling process and system B a
reversible cooling process. The processes
represented by both systems are tuned to each
other such that both systems withdraw the same
amount of heat from the cold heat reservoir.

It also follows from the second law that in the case of a cooling process being irreversible, the a-
values must be greater than in the case where the cooling process is reversible.

hot reservoir at temp. T1

Q A1 Q B'1

system system
A WA W B' B'
irrev. rev.
process process

Q A2 Q B'2
Q A2 = Q B'2

cold reservoir at temp. T2

Figure 2.5.12
System A from Figure 2.5.11 combined with system
B’, which, at the end of the process represented by
system B from Figure 2.5.11 can restore the
original state.
Thermodynamics for energy systems 31 J.J.C. van Lier, N. Woudstra

Suppose that in Figure 2.5.11 system A represents an irreversible cooling process and system B
a reversible process and that the duration for each process is such that QA2 = QB2. The
combination of system A with system B' - the system that can restore the original state for the
process with system B - is shown in Figure 2.5.12.
If the values of a in system A and that of system B are equal to each other, then also |QA1| and
QB1 are equal to each other: that means that system B' has completely restored the original state
for the process performed by system A. System A has then shown not an irreversible process
but a reversible one.
If aA < aB then is |WA| < WB’ and |QA1| < QB’1 : in other words heat is completely converted into
work. This conflicts with the second law. The only possibility left is aA > aB.

hot reservoir at temp. T1

Q P1 Q C1

rev. WP WC rev.
power cooling
process process

Q P2 Q C2

cold reservoir at temp. T2

Figure 2.5.13
Power process P and cooling process C tuned to
each other such that net no heat is transferred to
or from the cold heat reservoir.

Of course the question now arises whether a direct connection exists between the evaluation factor 0
of a reversible work process and the evaluation factor a of a reversible cooling process performed
between two heat reservoirs. In order to find out, we will look at an arbitrary system that performs a
reversible process between two heat reservoirs and an arbitrary system that performs a reversible
cooling process between the same heat reservoirs (Figure 2.5.13). We will choose the duration of the
process of each system separately such that |QP2| = QC2 still holds true. If we do not want to conflict
with the second law, then WP = |WC| and QP1 = |QC1| will be the case. Taking into account the drawing
convention that Q is positive if the heat is supplied and W is positive if the work is given off, then the
energy balance for each of the two systems is:

The equation for the thermal efficiency 0 can be worked out further as follows:

With a = - WC /QC2 this then gives the following relationship between the thermal efficiency 0 and the
evaluation factor a of both reversible processes :
Thermodynamics for energy systems 32 J.J.C. van Lier, N. Woudstra

(2.5.3)

For calculating the power processes and cooling processes between two heat reservoirs with
temperatures T1 and T2 respectively (T1 > T2) it is necessary to know the relationship between 0rev and
arev and the temperatures T1 en T2 respectively.

hotter reservoir at T'1

Q 1 + ∆Q

rev. power
W2 (= ∆Q)
process

hot reservoir at T1
Q1

rev. power
W1
process

Q1
cold reservoir at T2

Figure 2.5.14
System with a reversible power
process between two heat
reservoirs with T1 > T2. The
amount of heat extracted from the
hot reservoir is replenished via a
system with a reversible power
process from a reservoir with a
higher temperature with T’ > T1.

Before determining this relationship we will first consider a heat reservoir with a temperature T1, that
via a system with a reversible work process transfers heat to a heat reservoir with a temperature T2. We
can now imagine that the heat Q1 extracted from the hot heat reservoir is replenished from a heat
reservoir with a still higher temperature (T1' > T1) and that this also happens with the aid of a system
with a reversible power process: Figure 2.5.14. Seen as a whole, both systems withdraw a certain
amount of heat (Q1 + )Q) from the heat reservoir at temperature T1', convert the part (W1' + W1) of
this into work and transfer the remaining part Q2 to the heat reservoir with temperature T2. For the
efficiency of this work process we can write:

This means that the efficiency of the power process between the heat reservoirs with temperatures T1'
and T2 has a higher value than the efficiency of the power process between the heat reservoirs with
temperatures T1 en T2. This higher value is only the consequence of the greater temperature difference
between the two heat reservoirs.
Thermodynamics for energy systems 33 J.J.C. van Lier, N. Woudstra

If we repeat this game of the replenishment of the heat withdrawn with the help of a heat reservoir
with a still higher temperature, then it appears that the higher the temperature difference, the more the
efficiency approaches the value of 1:

Because 0 is dimensionless, the temperature difference in the equation that shows the relationship
between 0 and the temperature difference must also be dimensionless. This can be achieved by
dividing the temperature difference )T by the temperature T2 of the medium absorbing the heat.

Table 2.5.1 Possible relationships between 0 and )T

)T = 0 )T 6 4
)T dividing by the cold reservoir
temperature

)T dividing by the temperature of the

hot reservoir

However it is also possible to divide the temperature difference )T by the temperature T1 of the
medium giving off the heat. From Table 2.5.1 one can see that dividing the temperature difference by
the temperature of the medium giving off the heat shows a more logical relationship between the
efficiency and the dimensionless temperature difference.

constant
level
rise of mercury
h
level during a
measurement

U-tube filled
with mercury
low
density
gas

Figure 2.5.15
Gas thermometer filled with a low density gas. The
gas volume be kept constant during measurements.

For the determining of the relationship between 0rev and )T/T1 there only remains the question of
which temperature scale to use.
In Section 2.1 we have already mentioned the "liquid temperature scale". The disadvantage of this
scale is that it is completely dependent on the type of liquid in the thermometer and the material from
which the thermometer itself is made.
For the temperature measurement it is also possible to use a vessel with a constant volume and filled
with a low density gas (Figure 2.5.15). If the gas in the vessel receives energy (= heat) because of a
temperature difference, then the temperature of the gas increases and thus also the pressure of the gas.
This pressure can be precisely measured by means of the height h of the column of mercury:
Thermodynamics for energy systems 34 J.J.C. van Lier, N. Woudstra

For the measurement we work as follows. First we determine the pressure in the vessel when it is in
contact with a liquid of which the state can be very accurately established and of which also the
temperature 2 - according to our new gas temperature scale! - is very precisely known (for example
water at the triple point). The value measured here for the pressure in the vessel and the value of the
temperature of the liquid we will refer to as pref and 2ref. Next we bring the vessel into contact with the
object of which we want to determine the temperature 2. We measure the pressure p of the gas and
then by definition state that the temperature 2, that is measured in this way with the gas thermometer,
amounts to:

However, it seems that the value 2 the temperature scale introduced in this way is both dependent on
the working pressure of the gas and on the type of gas in the vessel. If we carry out the measurement
at a decreasing pressure of the gas and if in the end we extrapolate to the limit value of pactual60 then
we see that the measured value 2 is independent of the operating pressure of the gas and of the type of
gas. As a result in the gas thermometer the temperature is determined with the aid of the equation:

(2.5.4)

In building the liquid temperature scale as well as the gas temperature scale it becomes clear that for
the fixing of a temperature scale we are completely free in the choice of the system (= the instrument)
with which we want to take measurements and the allocation of the numerical values for the
temperature scale concerned.
Because with a reversible power cycle 0 is independent of the nature of the system that performs the
cycle and considering the logical coherence between 0rev and )T/T1 we can also introduce a
temperature scale by stating by definition:

(2.5.5)

The temperature scale that is introduced in this way has a great advantage in that it is completely
independent of the nature of the measuring system.
With the help of equation 2.5.3 and with the thermodynamic temperature scale introduced above, the
evaluation factor a of a reversible cooling process can be written:

(2.5.6)

This last equation is now the generally used definition for the thermodynamics temperature scale and
because the thermodynamic temperature scale was first proposed by Lord Kelvin, it is called the
Kelvin scale.
If we look more closely at equation 2.5.6 then we can see that when fixing the numerical value for T
we again have a certain freedom. According to the second law, with a temperature measurement the
left-hand side of the equation is completely fixed. If for the numeric value of T2 we choose a value that
is n times as large as we had originally planned, then all the numeric values T of the temperature scale
will be n times as large. So which numeric value should we choose?

Although the choice has absolutely no influence on the further building up of classical
thermodynamics, it will however give us a more satisfactory feeling if we now also turn to a
choice of the numeric values for the thermodynamic temperature scale. We can do this without
Thermodynamics for energy systems 35 J.J.C. van Lier, N. Woudstra

any difficulty. We will for a moment, however, have to anticipate the further build-up of
thermodynamics. For in Chapter 3 the relationship fixed between the different properties of a
substance will be described. With the use of this relationship (see section 3.4) it is possible to
show that the thermodynamic temperature scale and in physics the introduced ideal gas
temperature scale - with the aid of the gas thermometer in Figure 2.5.15 - are proportional to
each other.
In order to limit the number of temperature scales as much as possible in practice and because
we are free to choose the numeric values of the thermodynamic temperature scale, it is sensible
to make use of the proportionality of both scales just mentioned and to set the numeric values of
the thermodynamic temperature scale equal to those of the ideal gas temperature scale.
As regards the numeric values of the gas temperature scale we must remind ourselves that this
gas temperature scale was preceded by the liquid temperature scale. In the 18th century for the
liquid temperature scale - which is still in use - Celsius set the boiling point of water at
atmospheric pressure at "100" and the melting point of ice at atmospheric pressure at "0"
degrees. With the introduction of the gas temperature scale, in order to assign the same
“weighting” as possible to 1 degree on the Celsius scale and 1 degree on the gas temperature
scale, the numeric values for the gas temperature scale were chosen such that the difference
between the boiling point of water and the melting point of ice is also 100 degrees.
Because it is not simple to reproduce these two characteristic points during a calibration with
very high accuracy every time, it has been internationally agreed to fix the triple point of water -
that can be very accurately reproduced in a laboratory - at 273,16 K, which then leads to the
desired temperature difference of precisely 100 K between the starting points just mentioned for
the creation of the liquid thermometer scale.
It must be mentioned here that the liquid thermometer scale (= the Celsius scale) is not only
determined by the temperatures in question 0 °C and 100 °C. A number of other points on this
scale have been fixed likewise - in international collaboration - as the melting point and boiling
point of particular substances. The exact values of these melting points and boiling points are
determined with the aid of gas thermometers and the Celsius values are calculated with the
following fixed relationship between the thermodynamic temperature scale (T in K) and the
Celsius scale (t in °C):

It also goes without saying that the gas thermometer can only be used next to the
thermodynamic temperature measuring device if the gas in the gas thermometer indeed can be
approximated to an ideal gas (as described in physics). This means that extremely low
temperatures can only be determined with a thermodynamic temperature meter, based on
equation 2.5.6.

With the aid of the temperature scale that is based on the second law of thermodynamics we can arrive
at a very important statement regarding the possible temperatures here on earth and in the universe
(where the second main law also applies!).
Namely, if we cool a specific amount of a substance to the zero point of the thermodynamic
temperature scale, then - according to the definition of the thermodynamic temperature scale - the
amount of work needed for the giving off of the last quantity of heat to reach the zero point amounts
to:

However, as T2 approaches zero, this amount of work needed becomes infinitely large. Cooling to
extremely low temperatures also involves an extremely big problem. The lowest temperature that has
been achieved currently is 0,000016 K. Whether the zero point will ever be reached is still open to
Thermodynamics for energy systems 36 J.J.C. van Lier, N. Woudstra

question. In general people also refer to this as "the point of absolute zero". Reaching a temperature
below the absolute zero point is in any case impossible because then we would arrive at a situation
where the right-hand side of the above equation is negative and the numeric value "-W" on the left-
hand side is consequently positive. This would mean that heat and work would be given off
simultaneously - an absurd idea!
The statement that on the thermodynamic temperature scale there is an absolute zero point means that
the value for the temperature in an arbitrary equation will always be always positive! In the further
building up of thermodynamics we will thankfully make use of this fact more than once.

One can ask oneself if there is also a maximum temperature value. Several scientists have been
occupied with this, but no-one has (yet) come up with a definite theory.

After this introduction to the temperature scale that we will use for our further considerations, we will,
with the aid of this temperature scale, look further at a cyclic process performed by a system. For this
we begin with a system that performs a cyclic process between two heat reservoirs. In the case of a
reversible power cycle the following is true:

and in the case of a reversible cooling cycle:

According to the drawing convention, the energy balance for both is:

whereby for both processes, if they are reversible, we can write:

(2.5.7a)

If we are dealing with irreversible processes then for the power cycle we can write:

and for the cooling cycle:

According to the first law of thermodynamics the following is also valid for both of these processes:

whereby for both of these processes if they are irreversible we must write:

(2.5.7b)

The equations 2.5.7a and 2.5.7b are normally combined into one equation:
Thermodynamics for energy systems 37 J.J.C. van Lier, N. Woudstra

(2.5.8)

whereby the "equals " sign is valid for a reversible process and the "less than" sign for an irreversible
process.

hot reservoir at T0
T0 > T1 max

system with variable T0

temperature at the heat
T temperature of
supply and the heat T1 max the heat
discharge
transferred to
and from the
system

T2 min
T3

property of state
T3 < T2 min
cold reservoir at T3

Figure 2.5.16
System with variable temperature during heat supply (= T1) and
heat discharge (= T2). The temperature development is shown
in a state diagram in which the temperature is plotted on the y-
axis.
T1 max is the maximum temperature during heat supply,
T3 min is the minimum temperature during heat discharge.

For the further building up of thermodynamics we shall often return to equation 2.5.8. We must
always bear in mind that the temperatures T1 and T2 in this equation are the temperatures of the heat
flows Q1 and Q2 on the border line of the system (see Section 2.2). These temperatures may therefore
not simply be set equal to the temperatures in the system. Only when there is no temperature
difference between the transferred heat and the medium absorbing heat and the medium giving off in
the system respectively, these temperatures can be considered as temperatures of the system.

In the cycle worked out above, the heat is supplied and given off at a constant temperature on the
border line. As a rule this will not be the case for a cyclic process and the heat will be supplied and
given off with a variable temperature on the border line. For a closer look at this process we can by
means of a little trick still base our observations on two heat reservoirs, with temperatures T0 and T3
respectively. The temperature T0 is higher than the highest temperature at the heat supply to the system
and the temperature T3 is lower than the lowest temperature at the heat exhaust of the system: see
Figure 2.5.16.
We imagine that the heat being input to and the heat being given off by the system placed between
both heat reservoirs take place in an infinite number of infinitely small steps. In other words in steps
whereby at each step the temperature of the heat at the border line has a constant value.
The heat supply to the system being observed for each little step is made from the heat reservoir at
temperature T0 via an auxiliary system, that performs a reversible cyclic process: Figure 2.5.17. For
each cyclic process performed by the auxiliary system the following applies:
Thermodynamics for energy systems 38 J.J.C. van Lier, N. Woudstra

hot reservoir at T0
dQ 0

auxiliary system 1 that

enables heat transfer to
the system at the right
temperature
(= reversible cycle)
dQ 1 system

dQ 2
auxiliary system 2 that
enables heat transfer from
the system at the right
temperature
(= reversible cycle)

dQ 3

cold reservoir at T3

Figure 2.5.17
Use of two auxiliary systems with a reversible cycle for a
system with variable temperatures during heat supply and heat
discharge if for the heat transfer of this system two heat
reservoirs are required.

Because dQ1 hulpsystem = - dQ1 system we obtain the following relationship between the heat supply from
the heat reservoir with T = T0 and the heat taken up by the system:

(2.5.9)

The transfer of heat from the system - in an infinite number of infinitely small steps with at each step
a constant temperature for the heat on the border line - is supposed to take place by means of an
auxiliary system which now performs a reversible cyclic process between the system and the heat
reservoir with temperature T3: Figure 2.5.17. In the same way as for the step by step heat supply we
can then write:

(2.5.10)

If we consider the system from which we started and the auxiliary systems that take care of the supply
and removal of heat as one system - as shown in Figure 2.5.18 - then for this"large" system heat is
supplied at a constant temperature T0 and heat is given off at constant temperature T3. Of this "large"
process we know that:
Thermodynamics for energy systems 39 J.J.C. van Lier, N. Woudstra

The equals sign is valid if the system with variable temperatures during heat transfer to and from the
cycle is reversible.

hot reservoir at T0
dQ 0

dQ3

cold reservoir at T3

Figure 2.5.18
Combination of the original system
and the auxiliary systems in Figure
2.5.17 into one large system,
where the heat is transferred to
and from the system at constant
temperatures

We can also write:

With equation 2.5.9 and equation 2.5.10 this can be worked out into the following equation:

or:

(2.5.11)

The equals sign is valid if we are dealing with a reversible process and the temperature T is the
temperature that the heat flow dQ has on the border line of the system, and will thus in the first
instance be equal to the temperature of the bordering system that performs the heat supply or heat
removal dQ.

2.6 THE PROPERTY ENTROPY

Thermodynamics for energy systems 40 J.J.C. van Lier, N. Woudstra

In the previous section we have seen that the following equation applies to an arbitrary closed system,
by or in which a cyclic process is performed:

1
property

b a c

property

Figure 2.6.1
Reversible cyclic processes with the states 1
and 2 as intermediate phases.

We must thereby be well aware that the temperature T in this equation in the first instance is not a
property of the system. Only under particular circumstances is this the case, among others if the
system is formed by a particular amount of a substance and the heat transfer process takes place in a
reversible way. There is then no difference in temperature during the heat transfer and the temperature
T, that belongs to the heat flow dQ on the border line of the system, is therefore equal to the
temperature T of the substance.

We now consider two arbitrary states 1 and 2 of an arbitrary closed system. These two states can be
intermediate phases in a reversible cyclic process performed by the system. Such a cyclic process is
shown in Figure 2.6.1 and we can imagine that it is built up from two state change lines a and b.
In general the following is true for any reversible cyclic process:

This means that for the cyclic process with the state change lines a and b we can write:

If in the cyclic process with states 1 and 2 as intermediate states we do not follow path a but path c
from state 1 to state 2, we can write:
Thermodynamics for energy systems 41 J.J.C. van Lier, N. Woudstra

From this it can be concluded that:

This leads to the following proposition:

If a closed system goes from state 1 to state 2 in a reversible way, then the summation of dQ/T
during the state change has a value that is independent of the state change path followed. It is
only dependent on the starting state 1 and the end state 2.

This indicates that every system has a property of which at a transition of one state of equilibrium to
another is determined by the related summation. This property is called "entropy" and is denoted by
the symbol S. For the state change from state 1 to state 2 the following then applies:

(2.6.1)

and for an infinitesimal state change:

(2.6.2)

If the closed system is formed by a particular amount of mass of some substance and if this mass only
gives off work to the surrounding systems via the pressure forces and shearing forces on the boundary
surfaces, then in the case of a reversible process we can write:

Because according to "action = reaction" pboundary is equal to the property p of the mass involved, we
can also write:

In the equation for the entropy increase

as for a reversible process no jump in temperature can occur at the boundary surfaces, Tboundary will be
equal to the temperature T of the mass particle, which results in the following equation for the increase
of entropy of the mass concerned:

For 1 kg of the mass, the equation is:

Thermodynamics for energy systems 42 J.J.C. van Lier, N. Woudstra

(2.6.3)

Equation 2.6.3 was derived by using the relationships for reversible processes. However, the result is
an equation that only consists of properties, thus quantities that are only determined by the state of the
substance concerned. After all, p and T are also properties. Because the mutual relationship between
the properties is independent of the way in which the state change is achieved, equation 2.6.3 may be
used for both reversible and irreversible processes. However, the condition must be fulfilled that
during the process the substance concerned exclusively gives off work to the surrounding mass
through forces on the boundary surfaces.

We can also look at equation 2.6.3 from a purely mathematical point of view. We then see that
the equation indicates the increase of the dependent variable s as a consequence of an increase
of the independent variables u and v. Thus equation 2.6.3 essentially forms the first derivative of
the function:
(2.6.4)
In this function (the state equation) s is only dependent on position, thus on the state of the mass
particle and not on the way in which this position is reached. Thus ds, in the mathematical
sense, is the total differential of this function. If the variables u, v and s gradually change during
the change of position (that is, a change of state) across a specific distance, then also the first
partial differential quotients (and the second partial differential quotients) over this distance also
gradually change and for the total differential ds we can write:

(2.6.5)

The equations 2.6.3 and 2.6.5 together lead to the following statements for the entropy change
under specific conditions:

and:

Normally equation (2.6.3) is written in the form:

(2.6.6)
or in the form (since: dh = du + pdv + vdp) :
(2.6.7)
Is it possible to get a certain feeling for what the entropy of a substance actually is? In Section 2.2 we
already decided that the property temperature should be seen as a measure for the quantity of energy
that a substance can give off because of its molecular structure.
If we now supply to a substance that is in a fixed state energy at a constant pressure, that can be
described as "heat", then either the temperature of the substance increases or the substance starts to
melt and, with a further increase in temperature, evaporate. In the case of a temperature increase of the
fixed substance, the molecules of which the substance is made up will move more strongly, but remain
in their positions. With continuous heat supply at a certain moment the substance will begin to melt. In
the liquid that results form this the molecules can move freely in relation to each other: however the
Thermodynamics for energy systems 43 J.J.C. van Lier, N. Woudstra

mutual force of attraction keeps the molecules next to each other. After a further increase in the
temperature of the liquid and evaporation the molecules move completely freely of each other and
begin to “drift”. Thus under the influence of the heat supply the molecules change from an organised
state to a less organised state. According to equation 2.6.2 the entropy likewise increases. Statistically
seen, we may therefore consider the entropy as a measure of the disorder in a system.

If we lower the temperature of a certain amount of a substance still further, then the movement of each
molecule slows down further. At the absolute zero point the substance attains a crystalline structure
with highest organisation possible. The disorder has disappeared. This supposes that the entropy of a
substance with a crystalline structure at the absolute zero point has the value"zero". In statistical
thermodynamics this is intensively discussed. The observations described here and the conclusions
that follow, and in some cases verified by measurement, give us a basis to use the supposition just
arrived at - as well as the three laws of thermodynamics - as a postulate. In practice people then talk of
the“third law" of thermodynamics (in fact it is then the fourth!), and also often of "Nernst’s law",
named in honour of Walther Nernst, who worked very intensively on the third law.
If we assume the correctness of Nernst’s law, then it is possible to determine the absolute entropy of a
substance at each arbitrary point and to show the entropy value of a substance in the form of a table. It
must be noted that this is not always done and that the entropy value in a book of tables can also be the
increase in entropy in relation to a particular zero point. For example, in an international book of
tables for the properties of water/steam, the entropy is given as the increase in entropy in relation to
the state "liquid water at the triple point".

In the preceding pages we have deduced that in classic thermodynamics the entropy increase S2 - S1 of
a closed system must be seen as the summation of the value dQ/T over the path along which the
system changes in a reversible way from state of equilibrium 1 to state of equilibrium 2. One can ask
oneself what value this summation has when the system changes from state 1 to state 2 in an
irreversible way. To determine this we change a closed system first in an irreversible way from state of
equilibrium 1 to state of equilibrium 2 and then in a reversible way back from state 2 to state 1: Figure
2.6.2. For this irreversible cyclic process the following is true:

from which we can write:

1
property

a (= irrev. process)

b (= rev. process)
2

property

Figure 2.6.2
Irreversible cyclic process with an irreversible
transition from state 1 to state 2 and a reversible
transition from state 2 to state 1.
Thermodynamics for energy systems 44 J.J.C. van Lier, N. Woudstra

As from the previous discussion it already appears that the integral:

gives us the increase of the property entropy with the transition from state 2 to state 1, this eventually
results in the following general equation for the summation of dQ/T for an irreversible transition from
state 1 to state 2:

This statement can also be interpreted as follows:

(2.6.8)

or respectively:

(2.6.9)

In other words the entropy increase with an irreversible transition from state 1 to state 2 has a higher
value than the amount that is obtained by the summation of dQ/T along the state change line
concerned.
In order, via a summation of dQ/T along the state change line, to be able to determine the entropy
increase, a certain amount must still be added to this summation. How much this is depends entirely on
the irreversible character of the process. This amount is always positive and the more irreversible the
process is, the greater the amount. When studying irreversible processes this amount plays an
important role. People talk of it as the “irreversible entropy increase" and represent it with the symbols
)Sirrev and dSirrev respectively:

(2.6.10)

(2.6.11)

As a result we can therefore state that the general equation for the entropy increase of a closed system
is:
Thermodynamics for energy systems 45 J.J.C. van Lier, N. Woudstra

In this equation the irreversible entropy increase dSirrev is always positive and the temperature T is not a
property of the system but the temperature of the heat flow dQ at the point of the boundary surface.

For a reversible process the equation changes to the form:

In closing this section with the introduction of the property entropy it is useful to mention that in
practise careless use is often made of the equations:

and:

However, we must be well aware that these are not general equations, but equations for a particular
case, being the case that we are dealing with a homogenous substance of which the state is completely
fixed by the two properties u and v and h and p respectively, and where as a result of the process work
is only given off to the surrounding fluid by the forces on the boundary surfaces.
From the following, among other things, it appears that one should be careful when applying both
these equations. Suppose that a system undergoes a state change and that - in the case that the state
change occurred via a reversible process - the energy balance is as follows:

The term ydX in this energy balance shows the amount of "energy", that is given off by the system
together with the work of expansion pdV. Taking into consideration the equation for the entropy
increase - equation 2.6.2 - we must now write for the entropy increase:

This equation shows that the closed system is determined by three properties, being the properties U, V
and X and that dS is the total differential of the equation S = S(U,V,X).

2.7 WORK OBTAINED FROM A CYCLIC PROCESS PERFORMED BY A CLOSED SYSTEM

AND BY A MONOTHERM PROCESS

If a closed system performs a cyclic process, then during this process the value of the entropy also
changes according to the equation:

T is thereby the temperature of the heat dQ supplied and given off respectively on the border line of
the system. Because this concerns a cyclic process the entropy finally attains its original value.

For the work obtained we can write:

Thermodynamics for energy systems 46 J.J.C. van Lier, N. Woudstra

If a cyclic process performed by a system must perform such that the state parameters follow a
predefined state change line, then the value Š TdS is fixed.
The value Š TdSirrev depends entirely on whether the process more or less approximates a reversible
process. Because we work with the thermodynamic temperature scale the value for T is always
positive. This is likewise the case with the value for dSirrev. This means that W reaches a maximum
value in the case of a reversible process. The value of W becomes less as the process deviates more
from a reversible process.
In the case of a power cycle W is positive and the work "obtained" is maximum with a reversible
process. In the case of a cooling process W is negative and the "needed" work is minimum with a
reversible process.

If we take a critical look at the processes which the energy expert deals with in practise, then we see
that with many of these processes one or more systems change to another state of equilibrium in such a
way that use is only made of one heat reservoir. As a rule this is the large heat reservoir that
completely surrounds us, being the"surroundings".
A process that makes use of only one heat reservoir is described in thermodynamics as a "monotherm
process". The second main law makes a statement about such a process, being:

the work obtainable with a monotherm process is, for a given starting and end state, in the case
of a reversible process independent of the way in which the state change takes place, and in the
case of an irreversible process less than in the case of a reversible process.

state 1 a (reversible)
a' (reversible)

state 2
b (reversible)

heat reservoir
at temperature T

Figure 2.7.1
Two reversible, monotherm processes (a
and b, with use of the heat reservoir at
temperature T) between state 1 and state
2

Suppose that the first part of the statement is not correct and that in Figure 2.7.1 with the reversible
process with state change line a, less work is obtained than with the reversible process with state
change line b. Because process a performs in a reversible way, there must equally well be a reversible
process a' possible, which returns all the systems that take part in process a back to their original state.
A combination of process b and process a' gives a cyclic process whereby more work is generated by
process b than is demanded by process a'. This would mean that ultimately heat is transferred from the
available heat reservoir and this heat would be completely transformed into work, all of which is
contrary to the second law.
Thermodynamics for energy systems 47 J.J.C. van Lier, N. Woudstra

state 1 a (reversible)
a' (reversible)

state 2
b (irreversible)

heat reservoir
at temperature T

Figure 2.7.2
Two monotherm processes (a and b), of
which one with a reversible transition
and the other an irreversible transition
from state 1 to state 2.

In order to demonstrate the correctness of the second part of the statement, Figure 2.7.2 shows the
reversible process a with the state change line a and the irreversible process b with the state change
line b opposite each other. We now also make use of a reversible process a' that can bring all the
systems that have taken part in the reversible process a back to their original starting state. Combining
process b and process a' again gives us a cyclic process. If more work is generated by the irreversible
process than by the reversible process, then with the cyclic process ultimately heat will be completely
converted into work, which is contrary to the second law. If the work obtained by the irreversible
process the same as that obtained by the reversible process, then process a' ensures that all systems that
have taken part in process b, are returned to their original starting state. This means that process b is
not irreversible but has performed in a reversible way. There therefore remains the only possibility left
that the work obtained by the irreversible process is less than that by the reversible process.

The words "obtainable work" in the above paragraphs must not lead one to the conclusion that these
definitions are only valid for a monotherm power generating process. If work has to be supplied to the
monotherm process, then the value of the "obtainable work" is negative: less "obtainable work" will
then mean a smaller negative value. This then also means a higher absolute value, in other words,
more "work needed" for the irreversible process with work supplied.

2.8 GENERAL DEFINITIONS REGARDING ENERGY TRANSFORMATIONS TO BE

OBTAINED WITH THE HELP OF ENTROPY

If a closed system takes part in a process, then the following is true for the entropy increase:

dQ is then the heat that at the temperature T is supplied to the system across the border line. If the
direction of flow of the heat on the border line is actually directed towards the system, then dQ is
positive, and otherwise negative!
Thermodynamics for energy systems 48 J.J.C. van Lier, N. Woudstra

property possible adiabatic

1 changes of state

Figure 2.8.1
Possible state changes by adiabatic
processes with state 1 as the starting state.
The shaded area can not contain
intermediate states and the entropy will
always increase.

Often the state change of the closed system takes place so fast that the system has no time to exchange
energy with the surrounding systems as a consequence of the temperature difference. The system can
also be provided with adiabatic walls. In all these cases dQ = 0 and the equation for the entropy
increase is:

(2.7.1)

Conclusion:
the entropy increase of a closed system, to which no heat is supplied and from which no heat is
given off:
- can never be negative
- will remained unchanged in a reversible process
- will only increase in an irreversible process.

If we work with a state diagram (Figure 2.8.1) in which the property entropy is plotted on the x-axis
and state 1 represents the state of a closed system before the start of a process, then for any process in
which at no time at all during the process heat is supplied to (or given off by) the closed system, the
end state can never lie to the left of the vertical line indicated by state 1. Along the same lines, the
quasi-static state change line of such a process can never cross the marked area in Figure 2.8.1.

Conclusion:
in a diagram with the property entropy on the abscissa, with an adiabatic state change the state
change line can at no point move to the left.

If for a process we consider all the systems involved in the process as one large system, then heat can
not flow over the border line of this one large system at any point. This means that the sum of the
entropy increases of all these systems in the ideal case (the reversible process) is zero and in practice
(the irreversible process) is positive.
Thermodynamics for energy systems 49 J.J.C. van Lier, N. Woudstra

If we look at a closed system with constant volume that is completely isolated from the surrounding
systems then in practice it appears that such a system - if because of some operation it is no longer in
equilibrium with itself - will spontaneously regain its state of equilibrium if it has an opportunity to do
so. Because of the spontaneous action this "transition process" is a process whereby it is impossible at
the end to bring back everything to its original state. This means that it is an irreversible process, and
the entropy of the system increases according to the equation )S = )Sirrev.
Finally we will look into how a system that is not in equilibrium with itself can reach the state of
equilibrium concerned via a reversible process. We renounce the original starting point that the closed
system is "completely" isolated and now we assume that with the same transition to the equilibrium
state an energy exchange may take place between the closed system and the surrounding systems.
Because the system must remain a closed system, there is a limitation as regards the sort of energy that
can be exchanged. This may not be bound to the mass.
Because with the spontaneous transition process the amount of energy in the system does not change,
this must also be the case with the reversible process. For the reversible process this gives the
following energy balance:

energy supplied = energy given off.

With the reversible process the entropy increase is only caused by the heat supply:

Thus for the heat supplied (positive or negative ?) We can write:

In this equation T and dS are always positive (because the reversible increase of entropy equals the
previously supposed irreversible entropy increase). This means that the numeric value for Q is also
positive. From this we can conclude that with the reversible process heat is actually "supplied".
According to the energy balance, energy must also be given off at the same time. Because we are
dealing with a closed system, the energy given off may not be bound to mass. It can therefore only be
concerned with work or a type of energy that is identical to work.
However, in general work can be given off by a system in two ways, as work of expansion and
technical work. With the spontaneous transition process no exchange of energy can take place with -
thus also no giving off of work of expansion to - the surrounding systems. This means that the volume
of the closed system remains constant during the spontaneous process. For the reversible process we
must therefore also base our observations on a constant volume. The giving off of work by the
reversible process in the form of work of expansion is therefore not possible. Thus, as far as giving off
work is concerned, the only form that remains is giving off work in the form of technical work Wtechn.
The energy balance to the reversible process thus becomes:

Because Q is positive, Wtechn must also be positive. This means that with a reversible transition to the
state of equilibrium work is actually "given off".
We should realize that for technical processes we eventually have at our disposal only one large heat
reservoir, being the heat reservoir "the environment" with a surrounding temperature T0. If for the
reversible transition process of the closed system we make use of the heat Q at a variable temperature
T, that is higher than the surrounding temperature T0, then we could have obtained work from this
heat, with the help of the big 'environment' heat reservoir:
Thermodynamics for energy systems 50 J.J.C. van Lier, N. Woudstra

From the viewpoint of the energy expert the net obtainable work is thus smaller for a reversible
transition to the state of equilibrium and amounts to:

Because )S is positive, in this case the net work obtainable is also positive.

Conclusion:
an energetic isolated, closed system will, in the case that it is not with itself in equilibrium,
represent a certain amount of work.