Beruflich Dokumente
Kultur Dokumente
(for 2SBI)
March 7, 2018
Contents
4 Transport of heat 24
4.1 transport of heat by conduction . . . . . . . . . . . . . . . . . . . . . . 24
4.2 transport of heat by convection . . . . . . . . . . . . . . . . . . . . . . 26
ii
CONTENTS
iii
CONTENTS
iv
CONTENTS
12 Appendices 227
12.1 Appendix: the King Hubbert method . . . . . . . . . . . . . . . . . . . 227
12.1.1 The Verhulst equation . . . . . . . . . . . . . . . . . . . . . . . 227
12.1.2 Verhulst and consumption . . . . . . . . . . . . . . . . . . . . . 228
12.1.3 Hubbard linearization . . . . . . . . . . . . . . . . . . . . . . . 229
12.2 LIST OF SYMBOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
v
CONTENTS
vi
Chapter 1
Energy: units and orders of
magnitude
1
CHAPTER 1
to 1 kg of gas and thus one expects an energy content of about 40 MJ kg In fact, for
the Groningen gas it is 35 MJ m3 (because it contains quite some nitrogen), while for
Algerian gas it is 42 MJ m3 . Units that are often used are MWh (mega watt hour)
and toe (tonne of oil equivalent). 1 MWh is 106 W × 3600 s = 3 6 × 109 GJ while 1 toe
corresponds to 41.868 GJ or 11.630 MWh.
2
Chapter 2
The Climate and Energy crisis
2.1 PALEOCLIMATOLOGY
To try and predict the future, it can be very profitable to study the past. One can try to
predict the future climate based on the long climate history that is logged in the earth.
There is a large number of data that has logged local weather: (1) tree rings (2) corals
(3) stomatites (4) erosion patterns etc. The science of paleoclimatology tries to extract
the temperature, humidity, prevailing wind etc. from such data. Here we only briefly
mention some results. Temperature is usually deduced from isotope ratios. For example
the average isotopic composition of water is H2 16 O : HD16 O : H2 18 O = 997680 : 320
: 2000 ppm. The more heavy isotopes have a higher boiling point and have a smaller
diffusion constant. As a consequence, in the net transport through the atmosphere
(driven by solar heating) of water, heavier isotopes tend to stay at the equator, while
lighter ones are driven to the poles. If earth is warmer, this isotope separation is of
course stronger. Empirically, a roughly linear relation was found between 18 O, defined
as µ ¶ µ ¶
[18 O] [18 O]
[16 O]
− [16 O]
18 sample standard
O= ³ 18 ´ (2.1)
[ O]
[16 O]
standard
and local temperature (at high latitude). Therefore such calibrations are also used for
reconstructing paleoclimates. An example of such reconstruction is shown in Fig. 2.1.
Clearly, the CO2 concentration in the past has been much higher that is is now, and
the same holds for the average global temperature. From the figure we also see that we
now live in an epoch with ice ages.
Lets zoom in to more recent times, see Fig. 2.2. Here we see a certain
periodicity, with temperature and CO2 moving in parallel up and down. Unfortunately,
the data cannot resolve whether one precedes the other. All of this plot corresponds to
3
CHAPTER 2
zoom
in
now
Car Per Tria Jur Cr e
bon mia ss ass tass
ifer n ic ic eou
ho minids
ous s hominids
dinosaurs
Figure 2.1: Past CO2 concentration and indication of temperature from amount of glaciation.
the ice age epoch at the right hand side of Fig. 2.1, but the peaks correspond to period
where there are few glaciers. Note that we are exactly living at such moment and from
the plot it seems that we may soon see a decrease in temperature!
The variability in temperature etc. is now believed to be due to the so called
Milankovich cycles. This is a variability in the insolation (the amount of sunlight
arriving at earth), due to celestial mechanics. In particular, the earth is a spinning
top with precession and nutation, and earth experiences forces by the other planets,
mainly Jupiter and Saturn. Due to all these mechanisms, the ellipticity or eccentricity
of the orbit changes, the obliquity (angle of the axis of earth with respect to the plane
of orbit) changes and the axial precession changes, leading to the north pole or south
pole having summer at the moment of closest approach between earth and sun. In fact,
a Fourier transform (or rather power spectrum) of Fig. 2.2 clearly shows peaks at the
frequencies corresponding to the effects just mentioned. Since the mechanism behind
the variability of Fig 2.2 is now known, it can be used to predict the future. According
to the IPCC-4 scientists, the next ice age is not to be expected before 30000 y (FAQ
6.1). Of course, the climate can be influenced by other mechanisms, in particular the
CO2 concentration (see below) and albedo. Both of these are presently changed rather
dramatically by mankind.
4
CHAPTER 2
Figure 2.2: The past climate as recontructed from the Vostok ice core data (from Antarctica).
5
CHAPTER 2
400
CO2 (ppm) [75 years smoothed]
300
250
1000 1200 1400 1600 1800 2000
Date http://cdiac.ornl.gov/ftp/trends/co2/lawdome.combined.dat
of sea ice by 2050. If the ice of Greenland would melt completely, global sea level would
rise by about 7 meter. The effect on northern Europe, however, will be very limited,
because the ice on Greenland gravitationally attracts ocean water towards the Arctic.
If the ice on Greenland melts, this effect disappears leading to a reduction in sea level
in northern Europe. In addition, the mantle of earth experiences a reduced pressure
and will move upwards. The total of these three effects could be a small reduction
in sea level. Of course, for meting of land ice on Antarctica the opposite holds: the
three effects there all contribute to an increase of sea level in Europe. Global average
sea level has been observed to increase over the last century and currently increases by
about 3 cm per decade. Part of this increase is due to thermal expansion of the oceans
as a consequence of increasing global temperature.
The burning of fuels is consuming oxygen and indeed the oxygen concentration
in the atmosphere is decreasing at a rate of about 20 ppm/y. We now try to understand
this number. The current CO2 emission is 25×1012 kg y−1 . The oxygen in that CO2 was
taken from the atmosphere and hence about 16 × 1012 kg O2 is consumed each year.
We now calculate the amount of oxygen in the atmosphere. Its volume is 88 km ×
4 (6370 km)2 = 4 487 2 × 1018 m3 the weight of 1 m3 air is about 12 kg and 21% of
that is oxygen. Hence there is 12 × 4 523 9 × 1018 × 021 kg = 1 14 × 1018 kg O2 in the
6
CHAPTER 2
This is a bit smaller than the observed 20 ×10−6 y−1 but for such a crude
calculation, the result is not bad!
2.3 SOLUTIONS
Both problems, the effects of CO2 on climate and the increasing scarcity of fossil fuels,
can be solved by (1) changing to nuclear or renewable energy ’sources’ and (2) by
energy conservation. These topics are subject of the remaining chapters. In particular
the amount of solar energy arriving at earth is so large that even with current technology
only 156 m2 of photovoltaic cells would be needed per person. This would require a
total area for 1010 persons, that is much smaller than the Sahara. In view of the
intermittency of solar radiation (day-night, summer-winter, clouds) a long term storage
or long distance transport system is needed.
7
Chapter 3
Earth’s climate and the Sun
3.2 INTRODUCTION
The average solar power incident on the Earth is approx. 1000 W/m2 or about 100000
TW. This power is far larger than the current world power consumption of ~15 TW.
Currently, ~12 % of the world’s power is supplied by biomass and renewables, while
85% is derived from fossil fuels. Both are the consequence of photosynthesis, in which
plants use solar energy to convert water and carbon dioxide into carbohydrates. While
biomass is not necessarily a net producer of CO2 , the burning of fossil fuels definitely
is. However, biomass is not a good converter of solar energy as the efficiency of biomass
production is low (~0.2 to 2%).
8
CHAPTER 3
Figure 3.1: The contribution of renewable energy sources has increased from
(1.8%+10.6%+0.1%=12.5%) in 1973 to (2.2%+10%+0.5%=12.7%) in 2005. In percentage
this is not impressive. One should however keep in mind that the total energy consumption
doubled between 1973 and 2005.
9
CHAPTER 3
Figure 3.2: The Sun is a star with a diameter of approximately 1390000 km, about 109 times
the diameter of Earth.
10
CHAPTER 3
1
H 1 H → 2 H e e
e e− → 2 (1.02 MeV)
2
H 1 H → 3 He (5.49 MeV)
3
He 3 He → 4 He 1 H 1 H 12.86 MeV
Figure 3.3: The proton-proton chain reaction is the main source of energy production in the
Sun.
energy) of the protons is high enough to overcome their mutual Coulomb repulsion.
The theory that proton-proton reactions were the basic principle by which the Sun and
other stars burn was advocated by Arthur Stanley Eddington in the 1920s. At the time,
the temperature of the Sun was considered too low to allow for protons to overcome
their Coulomb barrier. After the development of quantum mechanics, it was discovered
that tunneling of the protons through the repulsive barrier allows for fusion at a lower
temperature than the classical prediction.
1. The first step in the proton-proton chain reaction involves the fusion of
two hydrogen nuclei 11 (1 proton) into deuterium21 (the lower index says 1 proton;
the upper index indicates the number of nucleons, in this case 1 proton and 1 neutron),
releasing a positron and a neutrino as one proton changes into a neutron.
1
1 + 11 → 21 + + + + 042 MeV
This first step is extremely slow, because both protons have to tunnel through their
Coulomb barrier and because it depends on weak interactions.
2. The positron immediately annihilates with an electron, and their mass
energy is carried off by two gamma ray photons.
− + + → 2 + 102 MeV
3. After this, the deuterium produced in the first stage can fuse with another hydrogen
to produce a light isotope of helium, 32 , i.e. 2 protons and 3 nucleons, in this case 2
protons and 1 neutron),:
11
CHAPTER 3
2
1 + 11 → 32 + + 549 MeV
4. From here there are three possible paths to generate helium isotope 4He. The most
important is
3
2 + 32 → 42 + 211 + 1286 MeV
The complete chain reaction releases a net energy of 26.7 MeV. Important is to note
that this energy cannot be used in totality to heat up the Sun. Only the photons can
couple to ions and shake them. This happens because photons are light and light is an
electromagnetic wave. The electric field couples to the charges of the ions.
12
CHAPTER 3
Figure 3.4: Spectral irradiance of incident solar radiation outside the atmosphere (yellow)
and at sea level (red). The visible region of the spectrum is indicated with UV (Ultra Violet)
on the left and Infrared on the right. Major absorption bands of some of the important
atmospheric gases are indicated. The emission curve of a black body at 5523 K is shown for
comparison, with its peak adjusted to fit the actual curve at the top of the atmosphere.
A similar dip, a little to the right, at 420 nm is also due to Ca atoms in the outer solar
atmosphere.
The red curve in Fig. 3.4 is the solar irradiation curve at sea level. The fact
that it is lower is due to absorption by the atmosphere and the scattering of Sunlight
by the atmosphere back into space. Only about 70 percent of the incoming Sunlight
reaches sea level. At sea level the solar spectrum exhibits much more structure than
at the top of the atmosphere as a result of absorption by molecules such as H2 O and
CO2 , which absorb over a broad region of wavelengths and particularly in the regions
which are indicated. Note that H2 O and CO2 molecules do not absorb in the visible
region, but in many regions in the Infrared.
Finally, we draw attention to the arrows indicated as O3 ozone. Under natural
circumstances, there is not much ozone at low altitudes, but there is a thin ozone layer
at an altitude of 20 to 30 km. There it does no harm but, on the contrary, protects
living organisms on the Earth from harmful solar UV radiation, as it absorbs Sunlight
with a wavelength shorter than 295 nm. This can be seen on the very left in Fig.
3.4. A decrease in the ozone layer in the upper atmosphere does not only increase
the total amount of UV light of a particular wavelength reaching the Earth, but it
also allows the transmission of increasingly shorter UV radiation. This has important
implications for bio-molecules such as DNA proteins, which are essential for life. They
do absorb Sunlight with wavelengths 300 nm if not blocked by the ozone layer,
and, as a consequence, they are destroyed or malfunctioning. With the thinning of the
13
CHAPTER 3
Figure 3.5: Spectral irradiance spectra of the Sun measured at the top of the atmosphere The
corresponding temperature is then 5777 K. This shows that the temperature of the Sun top
layer is not exactly known but for all practical purposes, we will take it as 5800 K in this
course.
protecting ozone layer, the bio-molecules will become increasingly prone to UV damage
in the future.
14
CHAPTER 3
= (3.3)
2 3 1
= 3 2
(3.5)
−1
where T is the absolute temperature of the black body [in degrees Kelvin]
and k is Boltzmann’s constant
k =1.38 × 10−23 J/K
The radiation is also called the radiation flux or briefly, the flux, as it
refers to the radiation (with energy E) passing a square meter per second.
By integrating Eq. 3.5 over all energies, one finds another well-known equa-
tion, the Stefan-Boltzmann law. This law expresses how the total amount of energy I
[W/ m2 ] emitted by a black body depends on its temperature T and is given by:
15
CHAPTER 3
Figure 3.6: Radiation of a man with glasses holding a match. False colours are used to
visualize the temperature of the emitted radiation. Blue is cold and red is hot. White is very
hot (the flame of the match).
16
CHAPTER 3
Figure 3.7: Solar radiation is entering the atmosphere from the left with [W/m2 ]. A
fraction , called the albedo, is scattered or radiated back. The Earth radiates thermally in
all directions while the Sunlight comes only from one side.
Figure 3.8: About 30% of the incoming solar light is reflected or scattered by the surface of
the Earth.
17
CHAPTER 3
Figure 3.9: Improved model of the Earth with an atmosphere that absorbs all the outgoing
radiation of the Earth. This is of course an extreme case
4
(1 − ) = 1366 (1 − 03) = 4 = 4 × 567 × 10−8
4
(3.10)
which leads to = 255 K. Without atmosphere the Earth would thus be
at an average minus18 degree Celsius. There would be no liquid water and probably
no life.
18
CHAPTER 3
80
5800 K 288 K
60
40
20
0
1 10
Wavelength [m]
Figure 3.10: Top panel:The Sun being much hotter than the Earth emits radiation at a much
lower wavelength (typically 500 nm = 0.5 m)) than the Earth (typically around 10 m
(micrometer). The curves are calculated by means of Eq.III.4. Bottom panel: Absorption of
radiation by various molecules in the atmosphere.
indicated in grey. Note that a greater quantity of outgoing radiation is absorbed, which
contributes to the greenhouse effect.
3.5.3 Intermezzo
Quantum mechanics provides the basis for computing the interactions between mole-
cules and electromagnetic radiation. Most of this interaction occurs when the frequency
of the radiation closely matches that of the spectral lines of the molecule, determined
by the quantization of the modes of vibration and rotation of the molecule. The mole-
cules/atoms that constitute the bulk of the atmosphere: oxygen (O2 ), nitrogen (N2 )
and argon (Ar) do not interact with infrared radiation significantly. While the oxygen
and nitrogen molecules can vibrate, because of their symmetry these vibrations do not
19
CHAPTER 3
create any momentary charge separation. Without such a charge separation they can
neither absorb nor emit infrared radiation. In the Earth’s atmosphere, the dominant in-
frared absorbing gases are water vapor H2 O, carbon dioxide CO2 , and ozone (O3 ). The
same molecules are also the dominant infrared emitting molecules. CO2 and O3 have
“floppy” vibration motions whose quantum states can be excited by collisions at ener-
gies encountered in the atmosphere. For example, carbon dioxide is a linear molecule,
but it has an important vibrational mode in which the molecule bends with the carbon
in the middle moving one way and the oxygens on the ends moving the other way,
creating some charge separation, a dipole moment, thus carbon dioxide molecules can
absorb long wave length infrared (IR) radiation. Collisions will immediately transfer
this energy to heating the surrounding gas.
A substantial part of the greenhouse effect due to carbon dioxide exists because
this vibration is easily excited by infrared radiation. Water vapor has a bent shape.
It has a permanent dipole moment (the O atom end is electron rich and the H atoms
electron poor) which means that IR radiation can be emitted and absorbed during
rotational transitions and collisions. Clouds are also very important infrared absorbers.
Therefore, water has multiple effects on infrared radiation, through its vapor phase and
through its condensed phases. Other absorbers of significance include methane, nitrous
oxide and the chlorofluorocarbons.
From Fig. 3.10 follows that direct Sunlight is much less absorbed than the
thermal radiation of the Earth. This means that we have to refine our model and take
the atmosphere into consideration. The simplest model is given in Fig. 3.9. We assume
that the atmosphere absorbs all the outgoing thermal radiation of the Earth. Such an
extreme case could be reached if the amount of greenhouse gases is allowed to reach
very high values.
We proceed as before. An overall amount (1 − ) is reaching the surface
of the Earth per m2 . The Earth receives thus an amount 2 (1 − ) where R
is the radius of the Earth. The total outgoing radiation from the Earth’s surface
is 42 , but the amount 42 is radiated back. Here is the downward
radiation of the atmosphere. In steady state we must have
20
CHAPTER 3
Figure 3.11: Atmospheric CO2 at Mauna Loa Observatory (Hawaii). The yearly seasonal
oscillations are due to growing vegetation in Spring and falling leaves in Autumn.
4
outgoing radiation [W/m2 ].
21
CHAPTER 3
400
CO2 (ppm) [75 years smoothed]
300
250
1000 1200 1400 1600 1800 2000
Date http://cdiac.ornl.gov/ftp/trends/co2/lawdome.combined.dat
Figure 3.12: The Mauna Loa (Hawaii) atmospheric CO2 measurements and Ice Core measure-
ments at Law Dome (Antarctica) are consistent with each other and confirm the exceptionally
rapid increase of CO2 during the last century. There is nowadays consensus that this is due
to human activities, especially to the burning of large amounts of fossil fuels.
22
CHAPTER 3
Figure 3.13: Relation between Wealth and Energy Consumption. The GDP is the gross
domestic product at purchasing power parity (PPP) per capita expressed in thousands of US
dollars of 1997.
23
Chapter 4
Transport of heat
Heat energy can be transported from one place to another. This can be used to our
advantage, but it can also represent an important loss mechanism e.g. if we want to heat
our home. In section 3.4 we already encountered one mechanism for heat transport:
(black body) radiation. In this chapter we discuss: transport of heat by conduction
and transport of heat by convection. The last mechanism relevant for our studies is the
rather trivial heat transport due to the transport of mass with a certain temperature.
We will encounter some examples of that later on.
24
CHAPTER 4
Figure 4.1:
If we take the area of the boxes in the direction perpendicular to the -axis to
be , then we can write for the particle current density through the middle separation:
∙ ¸
1 1
= − ( + ∆) + ()
2 2
which can be rewritten as
∙ ¸
(∆)2 1 ( + ∆) ()
= − +
2 ∆ ∆ ∆
∙ ¸
1 ( + ∆) ()
= − + = −
∆ ∆ ∆
here is the density of the heat particles. Since temperature is proprtional to heat, the
last equation is equivalent to eq. 4.2.
Now we apply this equation to calculate the heat loss from the surface of
the earth by conduction. At the surface of the earth, the temperature gradient in the
atmosphere is about 10 K km−1 using the heat conductivity of air at 0024 W K−1 m−1
we find from eq. 4.2
289 K − 279 K
= 0024 W K−1 m−1 × = 24 × 10−4 W m−2 (4.3)
1000 m
this may be compared with the heat radiated by the surface of the earth
= 567 × 10−8 W m−2 K−4 4 = 567 × 10−8 (289 K)4 = 396 W m−2 (4.4)
25
CHAPTER 4
J(x,t)
J(x+dx,t)
dx
If the temperature of the volume is changed by ∆ then its amount of heat changes
by
= (4.6)
this change of heat is of course due to the flow of heat . Hene by combining the last
two equations
( () − ( + )) = (4.7)
hence
26
CHAPTER 4
1.0
0.8 t=0.1
Temperature
0.6
0.4
t=1
0.2 t=10
0.0
-10 -8 -6 -4 -2 0 2 4 6 8 10
X-axis
T1
T2
0 L
27
CHAPTER 4
L
Tatmosphere
d Tbubble
Q
Figure 4.5: An air bubble is heated by the soil and aquires a higher temperature than the
surrounding air.
heated. Heated air rises upwards and thus transports heat to higher altitudes. This
mechanism is called convection and can also take place in a home where the heaters set
up an air flow. Here we calculate the amount of heat transport in the lower atmosphere
due to this mechanism.
Consider the situation of Fig. 4.5. We solve this problem in 3 steps:
First we calculate the Archimedes force on the heated air bubble, then we
calculate its velocity and finally the resulting transport of heat.
The Archimedes force on the heated air bubble is given by the difference
beteen its mass and that of the displaced air. is the volume of the bubble.
Hence:
2
∆ = ∆ = ∆ = ∆ (4.17)
For the last equality we used
= 2 (4.18)
see fig. 4.5, where is the linear dimension in the horizontal plane of the air bubble
and is its thickness. With this we find for the total amount of heat in the bubble
2
= ∆ = ∆ = ∆ (4.19)
where is the molar volume of an ideal gas (about 22.4 liter per mole) and
is its molar specific heat at constant pressure (we assume that the bubble rises over
a modest distance such that the change in pressure with height is unimportant).
The power per area of the soil that is transported by the air air bubble is
given by
1
= = (4.20)
∆
where ∆ is time it takes for the bubble to rise to a height .
Substitution of 4.18 in eq. 4.15 and the resulting and of 4.19 in 4.20 yields
with = 2 r
2
2 ∆
2
∆ 2
= (4.21)
2
which can be simplified to
r
32 (∆ )32 2
= (4.22)
12
Lets now calculate an example. For ∆ = 20 K = 100 m and = 1 m we
find
29
CHAPTER 4
r
(1 m)32 29 J mol−1 K−1 (20 K)32 2 · 98 m s−2
= = 296 W m−2 (4.23)
224 × 10−3 m3 mol−1 (300 K)12 100 m 1
which may be compared to the heat radiated by the soil: if we take ambient =
300 K + 20 K
however, usually
µ ¶ µ ¶
' 01 (4.26)
Note that Newtons Law of Cooling
= − · · ∆ (4.27)
gives
= −∆ (4.28)
which is linear in ∆ while in our convection equation, eq. 4.22, ∼ (∆ )32 . Newtons
Law of Cooling is applicable to the cooling of an object due to a smooth air flow, but is
no longer valid if large scale convection due to the cooling takes place. By the way, the
proportionality constant in eq. 4.27 takes a wide range of values in the literature: for
gasses in free convection ranges from 2 − 25 W m−2 K−1 while for forced convection it
ranges from 25 − 250 W m−2 K−1 This might already be an indication of the inaccuracy
of Newtons Law of Cooling for convection.
30
Chapter 5
Thermal energy and
thermodynamics
31
CHAPTER 5
the analysis of reversible engines, maintains a higher position because of its universality.
The Law of entropy is the Supreme Manager of all natural processes as it tells in which
direction processes occur spontaneously.
The direction of a spontaneous process is not governed by the energy change,
since in many cases the energy of a system does not change during a process. Think for
example of a book falling down from a table. Its potential energy is first transformed
during the fall into kinetic energy, which in turn is transformed into heat and defor-
mation energy when the book hits the ground. However, you never will see that the
molecules in the floor are able in a concerted action to propel the book back onto the
table!!
And this is where the second law comes into play. It says that entropy cannot
decrease in a closed system or that the entropy of the whole universe only increases
and never decreases. This is one of the most profound laws of nature, and should be a
part of every educated person’s world view. It is unfortunate that this law is so widely
misrepresented as simply implying the increase in "disorder".
In this course, we follow a phenomenological approach starting from well es-
tablished experimental results such as the ideal gas law and the conservation of energy
(related to the notion of internal energy of a system). Then, in a careful analysis of a
reversible engine, the Carnot machine, we arrive at the notion of efficiency and show
that heat can never be transformed 100% into mechanical work. By doing so we will
discover a new fundamental characteristic of a thermodynamic state, which is the en-
tropy mentioned above. After introduction of the Van der Waals law for non-ideal
gases, we are in a position to describe (qualitatively) any engine that transforms heat
into work. We will also discover that there are engines (such as the heat pump) that
have an efficiency much larger than 100% and that fuel cells, which generate electricity
from a chemical reaction, are not subject to the limitation of the Carnot cycle.
32
CHAPTER 5
under normal conditions 1 cm3 of air contains about 2.7 × 1019 particles. It is simply
impossible to know the initial position and velocity of each individual molecule; and
even if we had, the calculation of the simultaneous motions of such an enormous number
of molecules is far beyond the capabilities of even the fastest conceivable computer.
Under such conditions we need thus to look for a macroscopic description of a
gas using parameters that are easily accessible to measurements. Such parameters are
for example, the temperature T, the volume V, the pressure exerted by the gas on the
walls of the container, the density of the gas and the number of molecules.
In this chapter we describe the macroscopic properties of gases, and we see
how these macroscopic properties are related to the average microscopic properties
of the molecules of the gas.
= (5.2)
33
CHAPTER 5
12
In 1971, a mole was defined as the number of atoms in 12 grams of C. This
number is approximately
34
CHAPTER 5
The Ideal-Gas Law in Eq. 5.2 is a simple relation between the macroscopic
parameters that characterize a gas. At normal densities and pressures, real gases obey
this law quite well; but if a real gas is compressed to a very high density, then its
behavior will deviate from this law. The ideal gas is thus a limiting case of a real gas
when the density and the pressure of the latter tend to zero. The ideal gas may be
thought of as consisting of atoms of infinitesimal size, exerting no forces on each other
or on the walls of the container, except for instantaneous impact forces exerted during
collisions.
The conditions of a temperature of 273 K and a pressure of 1 atmosphere (1
atm pressure = 1.01325 bar = 1.01325 × 105 Pa = 1.01325 × 105 N/m2 ) are called
standard temperature and pressure, abbreviated STP.
The volume of one mole of gas at STP is a useful quantity that is easily
evaluated from Eq. 5.2
8.31 × 273
= = m3 = 224 × 10−3 m3 = 22.4 liters (5.5)
1.01325 × 105
In the last equality, we have used 1 liter = 1000 cm3 = 10−3 m3 . Note that it
makes no difference whether the gas in this calculation is air or any other gas.
The Ideal-Gas Law can also be written in terms of the number of molecules,
instead of the number of moles. The number of molecules per mole is Avogadro’s
number NA. Thus, if the number of moles is n, the number of molecules N is
= (5.6)
= (5.7)
35
CHAPTER 5
vx -v x
Figure 5.1: A given particle in the gas flies first to the right, hits the container wall and
bounces back with the same velocity (same magnitude but, of course, opposite direction).
motion of the molecules of a gas contained in a cube of side L. We assume that the gas
molecules collide only with the walls but not with each other, and that the collisions
are elastic. The motion of each molecule can be resolved into x, y, and z components.
Consider now the motion of one molecule in the x- direction.
The component of the velocity in the x-direction is vx and its magnitude
remains constant, since the collisions with the wall are elastic. The time that the
molecule needs to move from one face of the cube to the opposite face is
= (5.8)
This means that the molecule hits a given face of the cube every = 2
seconds.
When the molecule hits the face, its x-velocity is reversed from + to −. The
momentum of the molecule changes from + to − a and, consequently the net
momentum change is −2 where is the mass of the molecule. Thus, each collision
transfers a momentum +2 to the face of the cube. The average rate at which the
molecule transfers momentum to the face of the cube is thus:
2
Total force = (5.10)
36
CHAPTER 5
2
= (5.12)
As all three terms on the left hand side of equation are equal, each of them
must be equal to 13 2 . For the pressure we can write
2 2
= = (5.14)
3
We compare now this result for the pressure with the equation of state of the
Ideal-Gas
= (5.15)
to conclude that the average of the square of the speed of a molecule is pro-
portional to the absolute temperature T. We see also that
1 2 1 2 1 2 3
+ + = (5.16)
2 2 2 2
We say that in the average every molecule carries an energy 12 per transla-
tional degree of freedom. A molecule has three translational degrees of freedom.
37
CHAPTER 5
T
Figure 5.2: Addition of heat to a body raises its temperature. The temperature raise ∆T
depends on the experimental conditions imposed on the body.
38
CHAPTER 5
Figure 5.3: A gas kept at constant volume during heating. The added heat raises the tem-
perature and increases the pressure .
Substance [J/kg K]
Aluminum 902
Brass 390
Copper 390
Iron, steel 445
Lead 130
Tin 230
Silver 240
Mercury 140
Water 4187
Seawater 3900
Ice at -10 C 2230
Ethyl alcohol 2430
Glycol 2390
Mineral oil 2000
Glass, thermometer 840
Marble 880
Granite 800
Specific heat of an ideal gas at constant volume For a gas it makes a great
difference whether heat is added at constant volume or at constant pressure.
The molar specific heat at constant volume is designated by ; it is the
amount of heat needed to raise the temperature of 1 mole of gas by 1◦ C. The amount
of heat ∆Q required to increase the temperature of n moles by ∆T is given by
= ∆ (5.17)
39
CHAPTER 5
Figure 5.4: A gas kept at constant pressure during heating. The added heat raises the
temperature and increases the volume V as the piston is assumed to move completely freely
in the cylinder.
Specific heat of an ideal gas at constant pressure The molar specific heat at
constant pressure is designated by c p . The amount of heat ∆Q required to increase
the temperature of n moles by ∆T is given by
= ∆ (5.18)
We expect to be larger than because, at constant pressure only part of
this heat will go into a temperature increase of the gas ; the rest will be converted into
mechanical work as the expanding gas lifts the piston. We will return to the specific
heat of a gas in Section 5.3.2.
40
CHAPTER 5
Potential
energy
mgz
Figure 5.5: The traditional method for the measurement of the mechanical equivalent of heat
is Joule’s experiment.
41
CHAPTER 5
Figure 5.6: Body to which heat Q is added and mechanical work is performed by applying a
pressure p.
state () in many ways. For example, we may first compress the gas and then cool
it. Or else, we may first cool it and then compress it. On the other hand, we may go
through small alternating steps of compressing and cooling. In order to compress the
gas, we must do work on it; and in order to cool the gas, we must remove heat from it.
The work done on the gas (or body, in general) and the heat transferred to
the gas (or body) result in a change ∆ of the internal energy of the gas (body) given
by
∆ = . + . (5.20)
where . is the amount of heat transferred to the gas and . is the amount
of work done on the gas. In many textbooks one writes Eq. 5.20 as
∆ = − (5.21)
with the sign conventions that Q is positive if we add heat to the gas and
negative if we remove heat; W is positive if the gas does work on the surrounding
and negative if the surrounding does work on the gas. As this is sometimes a source
of confusion we have added arrows to indicate whether energy is received (.) by the
system or produced (%) by the system. With this convention we could also write Eq.
5.20 as ∆ = . − %
This is the First Law of Thermodynamics:
When several alternative processes involving heat and work are available to
change a system from an initial state characterized by given values of the macroscopic
42
CHAPTER 5
Pressure
Initial
state
Final
state
Volume
Figure 5.7: The fact that the change in internal energy U of a system does not depend on
the process (red or blue paths) chosen to bring the system from a given “initial state” to a
given “final state” means that U is a thermodynamic potential. It depends only on the
parameters characterizing the state of the system and not on the history bringing a system
into a particular state.
43
CHAPTER 5
Figure 5.8: At constant pressure, the gas does work by moving the piston loaded with a
weight that generates the pressure p. The added heat raises the temperature and increases
the volume.
Relation between and By means of the first law we can derive an explicit
relation between and . For this, consider again moles of a gas in a cylinder
with a freely moving piston of area . The heat absorbed by the gas increases the
internal energy of the gas and provides the expansion work % = ∆ . Note that
∆ = ∆ where ∆ is the vertical displacement of the piston.
Thus the increase in internal energy is
∆ = . + . = . − % = . − ∆ (5.23)
With = ∆ this leads to
44
CHAPTER 5
= + (5.28)
Calculation of for an ideal gas In Section 5.2.3 we have seen that the average
kinetic energy of a particle in an ideal gas is given by
1 2 1 2 1 2 3
+ + = (5.29)
2 2 2 2
The internal energy of a gas of N molecules is
3
= (5.30)
2
Thus, an increase ∆ of the temperature, increases the internal energy by
∆ = 32 ∆ . At constant volume, from the first law, we have = ∆ and thus
3
= ∆ (5.31)
2
which implies, by comparison with Eq. 5.17 that
3
= (5.32)
2
Note that the specific heat of an ideal gas is thus not depending on tem-
perature. From Eqs. 5.32 and 5.28 follows then that
5
= (5.33)
2
Diatomic gases All the relations derived above are valid for monatomic gases for
which the atoms are treated as point like particles. A point-like particle has 3 degrees
of freedom, the kinetic energies associated with the movement in x, y and z directions.
This is clearly showing up in the relation
1 2 1 2 1 2 3
+ + =
2 2 2 2
45
CHAPTER 5
Figure 5.9: Left: The two rotations of a diatomic molecules that carry kinetic energy. Right:
The vibrational motion of a diatomic molecule carries potential as well as kinetic energy
1
= 2 × 2 (5.36)
2
46
CHAPTER 5
In analogy with Eq.5.34 we expect that each of the rotation degrees of freedom and
each of the vibrational degrees of freedom will, in average, carry the same energy.
This expectation turns out to be true and is the basis of the so-called equipartition
theorem.
The equipartition theorem states that:
Each translational, rotational or vibrational component of the random thermal
motion of a molecule has an average kinetic energy of 12 .
According to this theorem, the total average energy of one molecule is
1 2 1 2 1 2 7
+ + + + + + = (5.37)
2 2 2 2
This is true at high temperatures, typically 400◦ C or more. At usual temperatures,
however, only the 3 translational kinetic terms and the 2 rotational terms are “excited”.
The vibrational terms are “dormant” and do not obey the equipartition theorem. This
is not too surprising, as the equipartition theorem does not consider quantum effects.
For practical situations, we will therefore take the total average energy of one molecule
as
1 2 1 2 1 2 5
+ + + + = (5.38)
2 2 2 2
The energy of all the molecules of the diatomic gas taken together is then
5
= (5.39)
2
Thus, an increase ∆ of the temperature increases the internal energy by ∆ =
5
2
∆ . At constant volume, from the first law, we have = ∆ and thus
5
= ∆ (5.40)
2
which implies that
5
= (5.41)
2
and
7
= (5.42)
2
47
CHAPTER 5
Figure 5.10: A steam power plant in Iceland. On the bottom I indicate a somewhat more
realistic diagram of a closed cycle power plant than in the book (top right). Bottom right: a
Siemens steam turbine.
¡ . ¢ ³ % ´
∆ = .
+.
+ .
+ .
=
− %
−
− .
=0
(5.43)
The efficiency of the process is
48
CHAPTER 5
T1 T2
(2) adiabatic (4) adiabatic
expansion to T2 compression
to T1
Figure 5.11: The four steps in a Carnot cycle. Isothermal means that the temperature is kept
constant. Adiabatic means that no heat is exchanged with the surrounding.
% .
− .
− %
%
= = = 1 − 1 (5.44)
.
.
.
The fact that the efficiency is smaller than 100% is a consequence of the
Second law of thermodynamics. We will discover this second law after having
considered the simplest possible reversible thermal engine, the Carnot engine.
49
CHAPTER 5
Figure 5.12: The four steps of the Carnot cycle represented in a temperature versus volume
diagram. The two adiabatic steps are calculated in Section VIII.4.3.
Figure 5.13: The four steps of the Carnot cycle represented in a pressure versus volume
diagram
50
CHAPTER 5
pa T1
Q1
pd d
c
Q2
T2
VaVd Vb Vc
Figure 5.14: The total mechanical work performed during a cycle is equal to the green area. In
order to calculate this work we need to evaluate the integrals of pdV along the two isothermal
and the two adiabatic branches of the cycle.
4 arrows) is equal to the work done by the gas. The difference in shape between
the isothermal steps a-b and c-d on one hand and the adiabatic steps b-c and d-a is,
however, not as evident as in a temperature versus volume graph.
We show below that the total mechanical work produced during one Carnot
cycle is
R R R R
+ ³
´ + ³+ ´ = (5.45)
= 1 ln + 2 ln
= − (5.46)
51
CHAPTER 5
a
pa T1
pb b
Va Vb
= + (5.47)
= = (5.49)
The total amount of heat supplied between state a and b at constant tem-
perature (i.e. = 0) is the integral
Z µ ¶
.
1 = = 1 ln (5.50)
R
with . 1 =
Nota bene: Along the isotherm, we change the pressure and volume in a
series of infinitesimal steps. For each step an infinitesimal amount of heat is required to
maintain the temperature constant. There is also an infinitesimal amount of mechanical
work involved. The reason for using a round- instead of simply a d is that the amount
of heat involved depends on how heat is transferred to the gas. The volume V and the
internal energy U are on the contrary state characteristics that do not depend on how
a given state has been reached.
52
CHAPTER 5
pb b
pc c
Vb Vc
Figure 5.16: This is the second step in the Carnot cycle. By definition Q=0 during an
adiabatic process.
= − (5.56)
= − (5.57)
53
CHAPTER 5
Vb Va Vb Vc
a
Vc Vd Va Vd
pa
T V
cV ln 1 R ln d b T V
T2 Va cV ln 2 R ln b
T1 Vc
pd d
c
VaVd Vb Vc
Relation between volumes in a Carnot cycle The 4 volumes taken by the gas
at points a, b, c and d are related to each other. From Eq. 5.58 and the corresponding
relation µ ¶ µ ¶
2
ln = − ln (5.59)
1
follows directly that
µ ¶ µ ¶
= (5.60)
Relations between
³ the ³ ´cycle From Eq. 5.50 we
´ heats involved in a Carnot
. .
have 1 = 1 ln and similarly 2 = 2 ln . Note that because is
smaller than the heat .2 0 , which means that heat is actually leaving the gas
involved in the Carnot cycle. ³ ´ ³ ´
Combining these relations with = leads to the remarkable relation
54
CHAPTER 5
Vb Vc
a
V Va Vd
pa Q1 nRT1 ln b
Va
b Q1 Q Q
2 2
T1 T2 T2
pd d
c
V
Q2 nRT2 ln d
Vc
VaVd Vb Vc
.
1 %
= 2 (5.61)
1 2
which can be written
.
1 .
+ 2 =0 (5.62)
1 2
This means that the combined quantity (Heat/Temperature) when summed
over a whole Carnot cycle does not change. This observation has a profound implication
and leads to the concept of entropy developed later in this chapter. First, however,
we focus our attention on a technologically essential parameter, the efficiency.
55
CHAPTER 5
³ ´
and you “pay” the heat .
1 = 1 ln
. The efficiency is thus given
by
³ ³ ´´
(1 − 2 ) ln 2
= ³ ´ =1− (5.64)
1 ln 1
The efficiency of the Carnot engine depends only on the temperatures of the
two thermal baths. The fact that the efficiency is smaller than 1 (i.e. smaller than
100%) is at first sight not surprising. No machine is perfect: there are always heat
losses, friction, etc. Note, however, that we have not considered any of these loss
processes. Carnot’s machine is ideal and nevertheless it does not have 100 % efficiency.
This is related to a fundamental law, the Second Law of Thermodynamics.
56
CHAPTER 5
T1
Carnot Super
engine Carnot
engine
T2
Figure 5.19: Arrangement used to prove that the efficiency of any engine is never greater than
that of a Carnot engine
.1 .
+ 2 =0 (5.65)
1 2
Is it possible to generalize this relation for any cycle ? To demonstrate that this
is possible we consider the arbitrary cycle in Fig. 5.20 Any cycle of a reversible engine
can be approximated by a set of infinitesimal Carnot cycles. For each infinitesimal
Carnot cycle we have
57
CHAPTER 5
Pressure
Pressure
V olu m e V o lu m e
Figure 5.20: Any reversible cycle can be represented as the sum of infinitesimal Carnot
processes. One specific “infinitesimal” Carnot cycle is indicated in blue in the right panel.
.
1 .
2
+ =0 (5.66)
1 2
Thus, for the whole cycle
I
.
=0 (5.67)
Let us now pick a given initial state and a final state and go from the initial
state to the final state along two different paths in the p-V diagram as indicated in
H .
Fig. 5.21. From = 0 follows that
I Z Z
. .
.
= − =0 (5.68)
1 2
and consequently,
Z Z
.
.
= =0 (5.69)
1 2
One defines the change ∆ in entropy as follows:
Z
.
∆ = − = (5.70)
The change in entropy ∆ does not depend on the way a system is brought
58
CHAPTER 5
Initial state i
Pressure
Path 1
Path 2
Final state f
Volume
Figure 5.21: Two paths in a p-V diagram to bring a system from initial state i to final state
f.
from an initial state to a given final state. One says that the entropy is a thermody-
namic potential.
• The internal energy U is uniquely determined for a state with given p, V and T
• The entropy S is also uniquely determined for a state with given p, V and T
One can construct other thermodynamic potentials. For example U-TS, U+pV,
U-TS+pV... They are uniquely determined for a state with p, V and T. There
is in fact an infinite number of ways to construct thermodynamic potentials. Most of
them are, however, of no use. Can you discover, for example, why U+pV is much more
useful than U-pV or U+3pV.....?
The thermodynamic potential U+pV is called the enthalpy and is designated
by the letter H.
59
CHAPTER 5
Q
Figure 5.22: When the heat . is supplied to the gas under constant pressure its volume
increases by the small amount dV
This is for example what happens in boilers in which heat is fed at constant pressure.
To see that, we consider first a gas that is free to expand at constant pressure
60
CHAPTER 5
Q 0
p1 constant p2 constant
Wturbine
Q 0
p1 constant p2 constant
the right after having rotating the blades of a turbine. The pressure of the gas is kept
constant on both sides during the expansion.
From the first law we have since there is no heat involved (i.e. adiabatic process)
.
∆ = 2 − 1 = −2 ∆2 − (−1 ∆ )1 + (5.75)
.
= 2 + 2 2 − (1 + 1 ) = 2 − 1 (5.76)
In this case the difference in enthalpy is equal to the work produced by the turbine.
Note that 2 − 1 0.
If there is no turbine but, for example, only a capillary, then no work is extracted and
the change in enthalpy is zero.
We have then
2 − 1 = 0 (5.77)
61
CHAPTER 5
62
CHAPTER 5
Carnot
T1 T1 engine
To
T2 Carnot Q1
T2 engine
Figure 5.25: left panel: When a hot reservoir is coupled to a cold reservoir heat flows spon-
taneously from hot to cold. Everyday experience that this process is irreversible.
right panel: the same amount of heat can be reversibly transferred between hot and cold
by using two Carnot engines so that ∆1 = ∆. Note that the change of entropy of the
intermediate heat bath at temperature is zero.
where . is the reversibly added heat to the system at temperature T .
One of the Carnot engines operates between the hot bath and an auxiliary
bath at a temperature 0 . The second one is coupled between the baths at 0 and
2 . The change of entropy is then −100 J400 K + 100 J300 K = 008 J K. Note that
the entropy of the system has increased although no heat has been exchanged with the
surrounding. One finds in general that entropy is always increasing in an irreversible
process such as heat conduction.
For reversible processes the entropy remains constant as ∆ = 0 because
∆ = 0. For irreversible processes the entropy of a closed system (i.e. without heat
exchange with the surrounding) is always increasing. This led to new formulations of
the Second Law.
63
CHAPTER 5
64
CHAPTER 5
Figure 5.26: Some of the dishes of Stirling Energy Systems that Southern California Edison
is planning to use for a 500 MW, 19 km2 , solar power plant to open some time after 2009.
(sandia.gov)
Figure 5.27: Small Stirling engine demonstrated in the lecture. The hot plate is at the bottom
of the engine. The cold plate is the top blue plate. The Stirling engine is a closed system
engine. There is no exchange of air with the atmosphere. In the practicum we have set up
Stirling engines for you to explore the efficiency of this type of engine.
65
CHAPTER 5
hot cold
displacer
66
CHAPTER 5
67
CHAPTER 5
Turboprop turbine The turboprop is similar to the turbojet, except that most
of the nozzle gas pressure drives the turbine shaft — by the time the gas gets past the
turbine, there’s very little pressure left
to create thrust. Instead, the shaft is geared to a propeller which creates the
majority of the thrust. ’Jet’ helicopters work the same way, except that their engines
are connected to the main rotor shaft instead of a propeller.
Turboprops are more fuel efficient than turbojets at low altitudes, where the
thicker air gives a propeller a lot more ’traction.’ This makes them popular on planes
used for short flights, where the time spent at low altitudes represents a greater per-
centage of the overall flight time.
68
CHAPTER 5
Tc c
Q1
Td d
Tb b Q2
Ta a
V1 V2
Figure 5.31: Otto cycle in a Temperature-versus-Volume graph. Note that between d and
a the hot gas is dumped into the atmosphere and replaced by fresh and cold gas. This is
modeled as a cooling of the gas at constant volume.
69
CHAPTER 5
70
CHAPTER 5
b c
a d
a b c d c
d
a
Figure 5.34: Joule cycle: During this cycle heat is added to the compressed gas via the
combustion of fuel in the combustion chambers between (b) and (c). Heat is removed between
(d) and (a) by the atmosphere. Although it is an open cycle the atmosphere can be considered
as a huge heat exchanger that cools the air before it is entering the compressor.
71
CHAPTER 5
1 = − (5.82)
Defining the efficiency as
% .
−
= (5.83)
.
1
we obtain finally
( − ) − ( − )
= (5.84)
( − )
This expression for the efficiency of a gas turbine is not really useful as the
values of the various temperatures in the engine are generally not known. A much
more useful expression would be in terms of the compression ratio . This ratio is
typically 15.
For this we need to know how pressure and temperature are related to each
other for an ideal gas under adiabatic compression. From Section 5.3.4 and the ideal
gas law we can write that
µ ¶ µ ¶ µ ¶
ln = ln = ln (5.85)
and
µ ¶ µ ¶ µ ¶
ln = ln = ln (5.86)
which implies that
µ ¶ µ ¶( −1
)
= (5.87)
as = − . In Eq. 5.87 we have introduced
= (5.88)
The efficiency of the gas turbine is then
72
CHAPTER 5
turbine
compressor
Figure 5.35: World’s largest and most efficient gas turbine (60%) with a capacity of 340
megawatts The SGT5-8000H gas turbine, newly developed by Siemens, is the world’s largest
and most efficient gas turbine (60%) with a capacity of 340 megawatts.
µ ¶ 1−
( − ) − ( − )
= =1− (5.89)
( − )
For a monatomic ideal gas = (52)(32) = 53. For a diatomic gas =
(72)(52) = 14. With a compression ratio = 15 we find that the maximum
efficiency of a gas turbine in air (air is a diatomic gas) is 54%. The temperature in the
combustion chamber is typically 1300 K and the exhaust gas temperature is ˜600 K.
Carnot’s equation for efficiency gives then also 54% (as it should !)
Gas turbines for electric generation Gas turbines for electricity generation orig-
inally evolved from jet turbine engines. In a jet engine, the thrust arises from the
combustion of gaseous fuel and the expansion of the exhaust gases that deliver most of
their energy to the turbine
73
CHAPTER 5
a
pa T1
Q1
pd d
Q2 c
T2
Va Vd Vb Vc
Figure 5.36: Heat pumps are used to heat houses. T 1 is the temperature of the house, which
is higehr than that of the outer world. The house plays thus the role of the warm heat bath
and the surrounding (garden, air, river,....) is the cold bath.
reservoir to a hot one. The efficiency of the reverse Carnot engine depends also only on
the temperatures of the two reservoir but note that the efficiency is defined differently
than for an “engine” that produces mechanical work. For the reverse Carnot cycle we
use mechanical work to extract heat from the cold reservoir in order to add it to the
hot reservoir. Such a device is called a heat pump. The efficiency of heat pump is
larger than 100 % as shown below. How is this possible ?
To answer this question we need to go back to the definition of efficiency. As
said earlier efficiency is defined as
= (5.90)
For a heat pump “What you get” is the heating of your house and “What you
pay” is the mechanical work needed to operate the heat pump.
%
heat pump = 1. (5.91)
and thus
74
CHAPTER 5
Q
1
Q2 W 0
Q
a h.p. 1
pa W
Q1 1
h.p.
Q1 Q2 Q2
1
b Q1
Q1 Q2
pd
d T1 T2
c
1
h.p. 1
T2
1
VaVd Vb Vc T1
Figure 5.37: This figure summarizes the various steps used to derive Eq.V.12
1
heat pump = 1 (5.92)
1 − 21
as 1 2 . The various steps of the derivation of Eq.5.92 are indicated in
Fig. 5.37. From Eq.5.92 we see that the efficiency of a heat pump is indeed higher than
100%. It is thus much more efficient to heat your house with a heat pump than with
electricity.
75
CHAPTER 5
Figure 5.38: A heat pump heating system consists of the heat source system, the heat pump
itself and a heat distribution and storage system. Note that the heat source (i.e. the environ-
ment) is at a lower temperature than inside the house.
76
CHAPTER 5
increases significantly, thus also increasing the temperature of the refrigerant. The
heated refrigerant then flows on to the liquefier - a heat exchanger in which the heat is
transferred to the heating system in the house. In this cooling process, the refrigerant
returns to liquid form at high pressure. After the expansion valve the refrigerant is still
liquid but now at a lower pressure and temperature: in this state it is again able to
absorb heat from the environment. The next cycle can again take place and so on.
77
CHAPTER 5
R: Interaction
range
d: average
distance
between
molecules
Figure 5.40: A molecule at the surface of a gas is attracted inward by all the molecules within
a distance R. The forces are indicated by red arrows.
We have then
23
≈ 3
∝ (5.95)
as the radius R is a characteristic interaction radius that is the same for all molecules.
The preceding reasoning needs to be extended to all the molecules that still feel the
surface. We call these molecules “subsurface molecules” (see Fig. 5.41).
The number of “subsurface” molecules is also proportional to , since
23
≈ 3
∝ (5.96)
3
The total inward force on “subsurface” moleculesµ is thus
¶2
× ∝ (5.97)
This force acts on the area 2 . The corresponding additional pressure ( = )
is: µ ¶2
× 4
= 2
∝ 6 ∝ (5.98)
This additional pressure should be taken into account in the equation of state of the gas.
In a first approximation one would then be tempted to write for n moles of non-ideal
gas that
78
CHAPTER 5
R: Interaction
range
Figure 5.41: A molecule within a distance D from the surface of a gas is also attracted inward
by all the molecules within a distance R. The forces are indicated by red arrows. There are
more arrows with an inward component than arrows with an outward component. This is
true as long as . As long as a molecule is at a distance shorter than the interaction
range it feels a net force directed inwards. This applies to all the molecules contained in
the green half-sphere. The number of these molecules is also proportional to
µ ³ ´2 ¶
+ = (5.99)
We need, however, to take another ingredient into account. In an ideal gas molecules are
treated as point-like objects. In reality, a molecule has a finite size. As a consequence
the free volume available to molecules in a gas contained in a vessel of volume V is
smaller than V. Denoting by b the volume of n moles of molecules we conclude that
the free available volume is (V-nb) and write the Equation of States of a non-ideal gas
as µ ³ ´2 ¶
+ ( − ) = (5.100)
where a and b depend on the gas under consideration. Typical values are given in the ta-
ble below of the van der Waals Coefficients for typical gases (from http://en.wikipedia.org/wiki/Van
der Waals constants)
79
CHAPTER 5
120 F1
F3
100 400 K
F4
F2
80 350 K
Pressure [105 Pa]
F5
60 300 K
40
20
0 250 K
-20
200 K
-40
0.0 0.2 0.4 0.6 0.8 1.0
Volume [liter]
Figure 5.42: Pressure-volume isotherms for carbondioxide (CO2 ) calculated with the values
given in the table of Van der Waals coefficients by means of Eq. 5.100
80
CHAPTER 5
120
100 400 K a)
80 350 K
Pressure [105 Pa]
60 300 K
40
20
0 250 K
-20
200 K
-40
0.0 0.2 0.4 0.6 0.8 1.0
Volume [liter]
240
220 673 K
200
180
b)
573 K
Pressure [105 Pa]
160
140
120 473 K
100
80
60
40
20 373 K
0
-20 283 K
-40
0.0 0.2 0.4 0.6 0.8 1.0
Volume [liter]
Figure 5.43: a) The Maxwell construction replaces the unphysical region of the Van der
Waals isotherms by a flat plateau along which gaseous CO2 coexists with liquid CO2 . The
blue “bubbly” area represents the region in the p-V diagram where liquid and gaseous CO2
coexist.
b) the same for water. The critical point is at a temperature of 647 K and at a pressure of
218 ×105 Pa.
81
CHAPTER 5
Q S
T T T
cp cp
Temperature [K]
Temperature [K]
Figure 5.44: Left panel : Variation of the temperature during heating of water at constant
pressure. At the boiling point the temperature remains constant until all the water has been
converted to vapour. Instead of plotting the added heat Q one can also choose the entropy
(green curve). One obtains then the green curve in the right panel.
the temperature remains constant. The heat is used to break the molecular attraction
between water molecules in liquid water. After all the water has been vaporized, the
temperature increases again linearly with increasing Q. The amount of heat necessary
to transform all the water into vapour is called the latent heat. On the right of Fig.
5.44 we have replotted the measurements on the left in a temperature versus entropy
graph. The green curve is obtained from measurements at constant pressure. It is
called an isobar. In the plateau region there is coexistence of water and water vapour.
A whole collection of such isobars is given in Fig. 5.45.
82
CHAPTER 5
700
600
[ C]
o
T e m p e ratu re
500
400
300
200
100
0
0 1 2 3 4 5 6 7 8 9 10
Entropy S [kJ/kg/K]
Figure 5.45: left panel: Selected isotherms of water up to high temperatures and pressures.
Right panel: copy of the corresponding schematic figure of the book.
of such a plant. The most convenient thermodynamic variables for describing thermal
power plants are temperature T and entropy S. The T -S diagram for water and steam
is shown in Fig. 5.45.
There are three distinct regions of interest:
• Region I: water
• Region II: two-phase mixture of water and steam
• Region III: dry steam.
The bell-shaped curve represents the phase boundary. The solid lines are isobars (con-
stant pressure) and the dashed lines in region II are lines of constant steam quality x,
i.e. the fraction by mass of steam in the two-phase mixture.
To illustrate how to interpret the T -S diagram, consider the process of boiling water
in a kettle. Since the fluid remains at atmospheric pressure throughout the heating
process, we follow the isobar ABCD (at a pressure of 1 bar). Along AB water is heated
from cold to the boiling point of 100◦ C. Water starts to boil at point B but the temper-
ature remains at 100◦ C along BC as the fluid absorbs the latent heat of evaporation.
At point C all the water has converted to dry steam. (This is an idealization of what
happens in practice, since some water droplets may still exist for a while beyond point
C.) The line CD represents superheated fluid (i.e. the temperature of the steam is above
the boiling point), and the temperature of the dry steam rises at constant pressure as
more heat is supplied.
83
CHAPTER 5
Figure 5.46: (top) Coal-fired steam turbine power plant installed by Siemens in Cityplace-
Shanghai, with a capacity of 2 × 900 MW. Thanks to advanced power plant technology based
on high steam temperatures and pressures, the CO2 emissions are reduced by 2.1 million tons
a year. (right) SST-800 industrial steam turbine with a capacity up to 150 MW.
c
Wturbine
b
d
a Qout
Wpump
Qin
f c
e
Qin
a
b Wturbine
Wpump e d
Qout
Figure 5.47: Physical layout of the four main devices used in the Rankine cycle
http://en.wikipedia.org/wiki/Rankine_cycle
84
CHAPTER 5
The Rankine cycle used in steam turbines involves four main devices, each changing
the state of the working fluid. These states are identified by letters in Fig. 5.47.
Process a-b: The high pressure liquid enters a boiler where it is heated at constant
pressure by an external heat source to become a vapor.
Process c-d: The vapor expands through a turbine, generating power. This decreases
the temperature and pressure of the vapor.
Process d-e: The wet vapor then enters a condenser where it is cooled at a constant
pressure and temperature to become a liquid. The pressure and temperature of the
condenser is fixed by the temperature of the cooling coils as the fluid is undergoing a
phase-change.
Process e-f: The working fluid is pumped from low to high pressure. As the fluid is
a liquid at this stage, the pump requires little input energy.
In an ideal Rankine cycle the pump and turbine would be isentropic (this means con-
serving entropy, which is equivalent with saying that the process is adiabatic), i.e., the
pump and turbine would generate no entropy and hence maximize the net work output.
Processes c-d and e-f would be represented by vertical lines on the − diagram and
more closely resemble that of the Carnot cycle. The Rankine cycle shown here prevents
the vapor ending up in the superheat region after the expansion in the turbine, which
reduces the energy removed by the condensers. In the book you can read why it is
necessary to operate a steam turbine in a Rankine cycle rather than a Carnot cycle.
85
CHAPTER 5
1 km
2 km
This follows directly from the First Law that says that
= − (5.102)
thus
86
CHAPTER 5
303 K
Pressure [105 Pa]
298 K
60 293 K
283 K
273 K
40
Figure 5.49: Van der Waals isotherms for CO2 . The critical point is 7.38 MPa at 31.1 C.
The isotherms shown are relevant for CO2 sequestration
+ = (5.103)
but, at constant pressure
87
CHAPTER 5
Figure 5.50: Fuel cell. Hydrogen enters the fuel cell on the left and in contact with a catalyst
is separated in electrons and protons. The PEM membrane has the very special property to
conduct protons but no electrons. The electrons are thus forced to flow externally towards
the cathode where they are needed to recombine with the protons and ultimately to form
water molecules. The theoretical efficiency of a fuel cell is much higher than that of a Carnot
cycle as the step producing heat from chemical energy is bypassed. Note that there are no
mechanically moving parts.
Figure 5.51: One of the 3 hydrogen busses in Amsterdam. They are powered by fuel cells
produced by the Canadian Ballard Company.
88
CHAPTER 5
= − + (5.109)
= . (5.111)
This shows that the non-mechanical work performed on the system is simply
equal to the increase in its Gibbs free energy. This is why G plays an important role
in thermodynamics. Note, of course that the non-mechanical work performed by the
system is
89
CHAPTER 5
90
CHAPTER 5
100
80
Gas &
Steam
Efficiency [%]
turbines
60
Fuel cells
40
Stirling
20 Diesel
Otto
0
1E-3 0.01 0.1 1 10 100
Power [MW]
Figure 5.52: Efficiency of various engines as a function of the nominal engine output power.
91
Chapter 6
Introduction to fluiddynamics for
energy
6.1 INTRODUCTION
After introducing the basic concepts of fluid dynamics, in a first part we use essentially
no more than Newton’s mechanics to derive useful relations for the efficiency of wind
turbines and aircraft. In a second part we develop the basic concepts of fluid mechanics
to understand what makes wind turbines turn in the wind.
92
CHAPTER 6
Figure 6.1: Force equilium on a cylinder of fluid, submerged in the same fluid.
fluid and we cannot have a spontaneous continuous motion of fluid (or else we would
have a perpetuum mobile). Hence, from this force equilibrium,
2 − 1 = (2 − 1 ) (6.4)
or
∆ = ∆ (6.5)
Incompressible fluids
If 6= (r) (i.e. the fluid in incompressible, which most fluids approximately are) then
pressure increases linearly with depth. For water the pressure increases 1 bar for each
10 m of depth.
Using this effect, one can make a pressure measuring device, or barometer, as
shown in Fig. 6.2.
93
CHAPTER 6
Figure 6.2: Principle of a barometer. The ambient pressure is related to the height as =
The top of the tube is connected to a vacuum pump and hence there the
pressure is = 0. Hence the pressure at the surface of the liquid in the container on
the left is
= (6.6)
Knowing the density of the liquid and measuring the height , allows one
to determine the pressure using eq. 6.6. If the liquid is mercury, at atmospheric
pressure the height is approximately 760 mm. By definition, 1 atm = 760 mmHg. Note
that 1 bar = 105 Pa ' 1 atm.
= () (6.7)
A relevant example is the pressure in the atmosphere, where the ’barometric’
pressure must be obtained from integration:
Z Z ∞
= = () (6.8)
0
To find (), we use for the air in the atmosphere the ideal gas law
= (6.9)
94
CHAPTER 6
95
CHAPTER 6
Figure 6.3: The pressure at the Thorong-La pass in Nepal is only 0.51 atm Still after proper
accimatisation, humans and animals are able to cope.
Equation of Bernoulli
To derive an extremely useful equation for fluid flow, consider streamlines in the fluid.
These are the trajectories that particles with the same density as the fluid (or parts of
the fluid itself!) would follow due to the motion of the fluid. In the Fig. 6.4 these are
indicated by dashed lines.
Also indicated in Fig Fig. 6.4 is what happens as the fluid moves trough the
right with the fluid between the two blue lines. Initially there is a part of the fluid
bounded by the blue lines and 1 and 2 . A time ∆ later, the fluid has move to the
right. At the left side over a distance ∆1 and at the right side over ∆2 which are
unequal because the width between the blue lines is changing. The mass that moved
on the left hand side
∆1 = 1 ∆1 (6.18)
should be equal to the mass that moved on the right hand side,
96
CHAPTER 6
Figure 6.4: A fluid in motion. The dashed lines are streamlines. A particle in the fluid with
the same density as the fluid would follow a streamline.
97
CHAPTER 6
∆ = 1 1 1 ∆ − 2 2 2 ∆ (6.27)
On the other hand, due to energy conservation, the work done on this piece
of fluid must equal the change in total energy of this piece of fluid:
∆ = ∆ + ∆ (6.28)
where the potential energy is just due to gravity. Hence we have
1 1
∆ = ∆ 22 + ∆ 2 − ∆ 12 − ∆ 1 (6.29)
2 2
with
∆ = 1 1 1 ∆ (6.30)
which can be written as
∆
1 1 ∆ = (6.31)
1
Substituting the last expression and its equivalent at position 2 in eq. 6.27 gives
∆ ∆
∆ = 1 − 2 (6.32)
1 2
and combination with eq. 6.29 gives
1 2 1 1
− = 22 + 2 − 12 − 1 (6.33)
1 2 2 2
where we divided the left and right hand sides by ∆. Rearranging gives
1 1 2 2 1 2
+ 1 + 1 = + + 2 (6.34)
1 2 2 2 2
which should hold for all positions 1 and 2 and hence we have finally
1 2
+ + = const (6.35)
2
which is the "Bernoulli equation".
98
CHAPTER 6
Figure 6.5: The flowlines around the wing of an airplane. The longer flowlines above the
plane imply a larger velocity of the air.
It is illustrative to look briefly back at the static case: if the fluid is not
moving, = 0 and we find that
Flow meters
Using the same principles as above, we can easily design instruments for the measure-
ment of fluid velocity. First consider an incompressible fluid flowing trough a tube, see
Fig. 6.6.
For this geometry, again the gravity terms cancel, leading to eq. 6.37. Using
the incompressibility property we thus find
1 ¡ ¢
1 − 2 = 22 − 12 (6.38)
2
99
CHAPTER 6
Figure 6.6: A Venturi. The pressure gauge measures the pressure difference in the fluid
between the constriction and a wider part of the tube.
100
CHAPTER 6
v v1 v0
p P1 p P2
p P1
Figure 6.7: Two tubes used together of the mesaurement of the velocity of a gas.
p1
p2
101
CHAPTER 6
Figure 6.9: Laminar flow of a fluid above a static plate (bottom). Flowlines are indicated
dashed, velocity vectors are blue.
102
CHAPTER 6
Within this tube, we consider the surface of tube within the fluid with radius
, indicated in blue in the figure. The fluid is flowing from the left to the right under
influence of a pressure difference as indicated in the figure. The net force due to the
pressure is
103
CHAPTER 6
Figure 6.12: Within the tube we consider an annular tube of fluid (blue),
104
CHAPTER 6
Figure 6.13: Streamlines for a turbulent flow. Note that these are not static, but cahnge as
a function of time.
or the flowrate is 2 ∆ The total flow through the whole tube is thus given by
Z Z
1 ¡ 2 ¢ 4
= 2 = 2 − 2 = (6.48)
0 0 4 8
where we used eq. 6.46 to substitute for (). Finally, we have for the mass
transport through a tube
4 2 − 1
= (6.49)
8
which is called "Poiseuille’s Law".
Turbulence
For larger flow velocities the laminar flow of Fig. 6.9 breaks down and an erratic,
time-dependent flow occurs, shown schematically in Fig. 6.13.
The occurrence of turbulence is governed by the ratio of inertial forces (due
to the mass density of the fluid) and shear forces (due to the viscosity). An important
parameter is the Rayleigh number Re defined as
inertial force
Re = (6.50)
viscous force
for small Re the flow is laminar, for large Re, the flow is turbulent.
105
CHAPTER 6
F lift
F drag
Figure 6.14: Lift is the force perpendicular to the fluid stream direction on an object in a
flow of fluid, while drag is the force along the direction of flow.
106
Chapter 7
Water energy: rivers, reservoirs and
tides
107
CHAPTER 7
rotating
2
1
in out
static
Figure 7.1: A simple turbine. Fluid enters at the centre and leaves at the periphery. The
central part is static, the part outside the dashed circle can rotate. Note the change of sign
of tangential flow direction between entry and exit.
108
CHAPTER 7
Figure 7.2: Schematic of a reservoir with dam and generator. The head of water above the
generator is .
Figure 7.3: Optimal turbine types as a function of head and volume flow ≡ .
109
CHAPTER 7
Figure 7.4: Geometry of Earth and moon. The tides are indicated, largely exaggerated, in
blue.
catastrophic (this is the other side of the coin of the capability to store large amounts
of energy) and expensive decommissioning. As a result of the net positive economics,
such hydroelectric schemes have been mostly carried out where possible. The installed
capacity in 2005 was for the World 700 GW (USA 80 GW, China 65 GW, Norway 28
GW).
Tides
For a brief discussion of the tides we use Fig. 7.4. For simplicity of argument we first
discuss how the earth rotates around the sun, and "moon" in the figure can be read
as "sun". At the center of gravity of earth, the gravitational and centrifugal force are
in equilibrium. Since ∼ 12 and ∼ this equilibrium does not at any other
position. Closer to the sun, the gravitational force wins, leading to an extra attraction
(and bump) of the surface of the oceans towards the sun. At the farthest point from
the sun, the centrifugal force wins, leading to a bump in the oceans away from the sun.
Hence there is simultaneously a bump at two sides of earth. Due to the rotation of
earth in 24h, the leads roughly to high tide every 12h. The argument above also holds
for the rotation of earth around the center of mass of the earth-moon system. It turns
out that the tides created by the moon are larger than those by the sun.
We now proceed to estimate the height of the tides. The important point is
that the surface of a liquid (water) adjusts itself such that there is no force along the
110
CHAPTER 7
surface (otherwise the water would flow in the direction of the force). Hence the water
surface is an equipotential surface. The gravitational force is given by
= (7.3)
2
and hence the gravitational potential by
= − (7.4)
We now need to find at any position of the earth’s surface. From Fig. 7.4.
we obtain using the cosine rule
1 1 1
=√ = q ¡ ¢ (7.5)
2 + 2 − 2 cos 2
1 + 2 − 2 cos
using the Taylor expansion
1 1 3
√ = 1 − + 2 (7.6)
1+ 2 8
this can be written as
à µ ¶ µ ¶2 !
1 1 1 2 3 2
= 1− − 2 cos + − 2 cos (7.7)
2 2 8 2
3
and ignoring terms that or of order 3
or higher
µ µ ¶ ´2 ¶ 1 ∙ µ ¶¸
1 1 1 2 3³ 2 3 2 1
= 1− − 2 cos + 2 cos = 1 + cos + 2 cos −
2 2 8 2 2
(7.8)
Substitution of Eq 7.8 in Eq. 7.4 yields
∙ µ ¶¸
2 3 2 1
= − 1 + cos + 2 cos − (7.9)
2 2
The centrifugal force is
= 2 (7.10)
and hence the centrifugal potential is
1
= − 2 2 (7.11)
2
111
CHAPTER 7
For the geometry of Fig. 7.4 we thus find with = and using again the cosine rule:
1 ¡ ¢
= − 2 2 + 2 − 2 cos (7.12)
2
or
µ ¶
1 ¡ ¢ 1 2
= − 2 2 − 2 cos + 2 = − 2 2 − cos + 2 (7.13)
2 2 2
At the COM
= = 2 = (7.14)
2
and thus
2 2 = (7.15)
substitution of eq 7.15 in 7.13 yields
µ ¶
1 2
=− − cos + 2 (7.16)
2 2
The total potential is due to the sum of the gravitational and centrifugal forces, that
is the sum of eq 7.16 and 7.9:
∙ ¸
3 2 2
= − 1 + 2 cos (7.17)
2
The constant term does not contribute to any force and should be omitted.
Since the surface of a liquid (i.e. the surface of the oceans) is an equipotential
surface (see discussion above), we must have that at the surface of the oceans
∙ ¸
3 2 2
= − cos = (7.18)
2 2
where is of course equal to the gravitational potential, which can also be expressed
as (since the potential energy is ) hence
3 2
2
cos2 = () (7.19)
2
hence
3 2
() = cos2 (7.20)
2 2
112
CHAPTER 7
3 4
() = 2
cos2 (7.22)
2
the tidal difference is thus:
34
max = ' 054 m (7.23)
23
where we used the numerical values for the earth-moon system. For the earth-sun
system, the effect is about 22× smaller. Although the mass of the sun is larger, the
gradient of the gravitational force due to the sun is smaller than that due to the moon.
That is because the moon is much closer to the earth. The gradient determines the
strength of the mismatch between and at the points B and D in Fig. 7.4. To
continue the discussion of tidal power we must now consider the flow of water in the
oceans due to the tides.
113
CHAPTER 7
p0
∂p
p p ∂x
dx
Figure 7.5: Geometry for deriving the shallow water equation. is pressure and and are
vertical and horizontal velocities.
= − (7.27)
To continue, we need another ingredient: since water is (practically) incom-
pressible, if there is a different horizontal flux at and + , then the height of the
water must change. To work with volumes, we use a thickness of the water perpen-
dicular to the plane of Fig. 7.5. This is of course constant. So we have that the total
outflux from this ’piece’ of water must be zero:
or
− + ( + ) ( + ) + = 0 (7.29)
substituting
=
=
(7.30)
=
in eq. 7.29 yields
µ ¶µ ¶
− + + + + = 0 (7.31)
and after simplification and ignoring terms of order ()2
114
CHAPTER 7
+ + = 0 (7.32)
or
+ + =0 (7.33)
Because ln is small (the waves are much smaller than the water depth), while
fluctuates round zero
(7.34)
hence
(7.35)
and thus the first term in eq. 7.33 can be neglected with respect to the second. So
from eq. 7.33 we have
+ =0 (7.36)
or
1
'− (7.37)
0
To obtain from this a wave equation we take
to find
2 1
2
=− (7.38)
0
substitution of eq 7.27 finally gives
2 1 2
2
= 0 2
(7.39)
which is the wave equation for shallow water waves. The velocity of the shallow water
waves thus is
p
= 0 (7.40)
For an ocean of 2000 m depth we obtain
p √
0 = 98 m s−2 × 2000 m = 140 m s−1 = 500 km h (7.41)
which is a remarkable velocity, but a velocity that is indeed observed. In Fig we show
the arrival time of the 26 December 2004 tsunami expressed in hours after the moment
of the earthquake.
115
CHAPTER 7
Figure 7.6: Arrival time of the 26 December 2004 tsunami expressed in hours after the moment
of the earthquake.
The distance from the centre of origin to Africa is about 6000 km, and the
tsunami used 8 h to traverse that distance, thus it had a velocity of about 750 km/h,
roughly in agreement with the calculation above (eq. 7.41).
What we just calculated has important consequences for the tides. For in-
stance, the tides at the equator should move roughly with the velocity of rotation of
earth at the equator, which is
2 × 6371 × 106 m
= 463 m s−1 = 1666 8 km h (7.42)
24 × 3600 s
about four times faster than the water wave can move according to eq. 7.41. As a
consequence, the wave velocity cannot keep up with the tidal forces and a lag arises.
On the other hand, the fact that the wave velocity is determined by eq. 7.40, implies
that resonances might occur. The distance between Europe and America in the Atlantic
ocean is 4000 km and its average depth is 4000 m. From eq. 7.40 we find
p √
= 0 = 98 m s−2 × 4000 m = 200 m s−1 = 720 km h (7.43)
and thus the time the wave needs for one period is
2 × 4000 km
→ → = = 11 1 h (7.44)
720 km h
which is very close to the drive frequency of 11.5 h. Hence a tidal resonance occurs
that increases the height of the tides somewhat above that calculated above (eq. 7.23).
More spectacular increases in tidal height are found in the Bay of Fundy in Nova Scotia
and in the Channel and in the Severn Bay in England. In all these cases tidal resonance
116
CHAPTER 7
Figure 7.7: Schematic and photograph of the La Rance barrage tidal power station.
and the funnel shape of the water plays a role. Due to the funnel shape, the tidal wave
becomes higher and higher as it approaches the narrow part of the funnel. In the Severn,
the height difference is up to 10m, in the Bay of Fundy it may be 15 m. Clearly such
height differences can be used in a similar way as with reservoirs to generate power.
The earliest large scale station is that of La Rance in Brittany, France with a capacity
of 250 MW, see Fig. 7.7. Power is generated both at the influx and outflux parts of
the cycle.
We can calculate the power that can be generated from La Rance as follows.
The mass difference between high and low tide of the water in the reservoir is
= (7.45)
and the potential energy stored is thus
1
= (7.46)
2
(the COM is at 12 ). Substitution of eq 7.45 in eq 7.46 gives the total work that the
station can deliver in one cycle of length :
1
= 2 (7.47)
2
and the power is thus
2
= = (7.48)
2
117
CHAPTER 7
118
CHAPTER 7
uc c
2 r c
c
2 r
ut c
Figure 7.8: The (local) velocities of water in a water wave, from the perspective of an observer
moving with the wave.
Consider a wave moving at velocity . For an observer moving with the wave,
the water (which is static on a large scale) moves with velocity − but there is also
the local rotary motion discussed above, see Fig. 7.8.
If the radius of a wave is and the time of rotation , then for the co-moving
observer, the velocity at the crest and at the trough are:
= − + 2
(7.52)
= − − 2
From the Bernoulli equation, eq. 6.35,
1 1
+ + 2 = + + 2 (7.53)
2 2
since = (they are both in contact with the atmosphere) and = 2 + we find
after substitution of eq 7.52
µ ¶2 µ ¶2
1 2 1 2
2 + − − = − + (7.54)
2 2
and thus after some simplification,
1 4 1 4
2 − = (7.55)
2 2
from which
2 22
=
= (7.56)
where for the second equality the usual relation between wavelength and period of
oscillation was used: = . From eq. 7.56 one find the velocity of wind-driven
119
CHAPTER 7
= (7.59)
and the total potential energy in the wave is the integral of this (1) over the local height
of the wave and (2) over the whole wave. For (2) we take 2 × the integral over the
crest. Hence for the whole wave
Z = Z = sin 2
2 1
=2 = 2 (7.60)
=0 =0 4
Here, we analyzed the wave at moment of maximum height, where all the energy of
that wave is potential energy. Hence at any moment in time the total energy of the
wave per area is:
1
¤ = 2 (7.61)
4
120
CHAPTER 7
TAPered CHANnel
Figure 7.10: Oscillating water column and tapered channel scheme for extracting energy from
surface waves of the sea.
Let us now investigate how realistic this is. As discussed in chapter 3, the energy from
the sun reaching the surface of earth is about 1000 W m−2 However, this is effectively
2
falling on a surface equal to which means that on average over the whole earth
and day and night, about 250 W m−2 reaches the surface. Clearly eq. 7.63 cannot hold
as average over the whole earth and eq. 7.64 must be an over-estimate. Actually, one
estimates that about 1% of the incident solar radiation is converted to wind, it seems
reasonable that at most about the same amount is converted into water waves.
If we place a buoy of 11 m diameter in water with the kind of waves assumed
above, then such buoy would have a power of about
such values are indeed measured at suitable locations at sea. Potential problems for the
conversion of wave energy into electric energy are fouling, mechanical stress of enormous
varying range etc.
To solve the issues, various schemes are used, such as an oscillating water
column (the turbine is in air, not in water) or a tapered channel (creating a small
121
CHAPTER 7
Salter Duck
Archimedes Wave Swing
Pelamis
Figure 7.11: Various mechanisms for extracting energy from surface waves of the sea.
reservoir), see Fig 7.10 and structures with moving links that couple to generators,
such as the Pelamis, Archimedes wave swing and Salter Duck, see Fig 7.11.
122
Chapter 8
Wind energy
123
CHAPTER 8
v u
Figure 8.1: A vertical slab striven forward at velocity by a wind with velocity .
( = ) = 0 (no force). In other words: one can only extract work from the wind at
intermediate velocities: 0 .
We now show that the maximum power that can be extracted from the wind
by a wind turbine can be calculated from simple energy and momentum considerations.
In this treatment we do not look at the details of the air flow. We just assume that the
turbine is transforming some kinetic energy of the wind into mechanical work and that
consequently some momentum is lost by the wind. The effect of the blades is smeared
out on a disk of radius equal to that of the turbine.
= (8.4)
The mass of the air contained in this volume is
= (8.5)
where is the density of the air.
The kinetic energy of the air in the tube shown in Fig. 8.3 is
1 1
= 2 = 3 (8.6)
2 2
The corresponding kinetic energy density (i.e. the kinetic energy per volume) is
124
CHAPTER 8
u1
u2
uo
Ao A1 A2
Figure 8.2: Overall air flow passing a wind turbine. The area of the air tube well ahead of
the turbine is smaller than that behind the turbine as the wind velocity uo is larger than 2 .
dx
Figure 8.3: Air tube defined by the movement of the air molecules passing the area A during
the short time dt.
125
CHAPTER 8
u1
u2
uo
Thrust
Ao A1 A2
Figure 8.4: Wind power before and behind a wind turbine. Before (left) it is = 12 ××3
while after the turbine (right) it is 2 = 12 2 × × 32 .
1
2 1
= 2
= 2 (8.7)
2
and using eq. 8.6, the power of the wind is
1
= = 3 (8.8)
2
Note that the wind power is proportional to the third power of the wind velocity. A
wind of 20 m/s has thus 8 times more power than a wind at 10 m/s. The power of
wind of 20 m/s in a tube of 10m diameter is
1 1 ¡ ¢3
3 = 10 m2 × 12 kg m−3 × 20 m s−1 = 37 kW (8.9)
2 24
note that we cannot extract all of that power, because if we did, the wind would stop
and we would have an accumulation of air. Hence the flow tube must expand at a wind
mill and the question is how to do this optimally.
As such this expression is not very useful as it contains two unknown areas and one
unknown velocity 2 . We assume here that the wind velocity far from the turbine is
known. As the amount of air is conserved (we assume that air is incompressible) we
must have
= 1 1 = 2 2 (8.11)
(see eq 6.24) and we can re-write Eq.8.10 as
1 ¡ ¢
= − 2 = 1 1 2 − 22 (8.12)
2
To proceed we consider the thrust, i.e. the force acting horizontally on the turbine
8.2.3 Thrust
From Newton’s second law, the thrust on the wind turbine is equal to the change in
momentum of the air in the time .
= = (8.13)
By definition the momentum is the product of the mass and the velocity: = . For
the air tube this means
= 2 (8.14)
Substituting eq. 8.14 in eq. 8.13, it follows that
− 2 ¡ ¢
= = 2 − 2 22 = 1 1 ( − 2 ) (8.15)
where for the third equality eq. 8.11 was used. Since power is force times velocity, the
power delivered by the wind is
= 1 = 1 21 ( − 2 ) (8.16)
We have now two expressions for the extracted power, eq 8.12 and eq. 8.16. These two
expressions must be equal and thus
1 ¡ ¢
1 1 2 − 22 = 1 21 ( − 2 ) (8.17)
2
or
1¡ 2 ¢
− 22 = 1 ( − 2 ) (8.18)
2
which implies that
1
( + 2 ) = 1 (8.19)
2
or
127
CHAPTER 8
2 = 21 − (8.20)
Thus from 8.16
= 21 21 ( − 1 ) (8.21)
Note that the only parameters that are assumed to be known are 1 , the area of the
wind turbine, and the wind velocity measured far from the turbine. We still need to
calculate 1 .
µ ¶
Power extracted 21 21 (0 − 1 ) 421 (0 − 1 ) 21 0 1
:= = 1 = = 4 −
Power in the wind 2
1 30 30 20 0 0
(8.24)
if we define the induction factor as
1
:= 1 − (8.25)
0
then eq 8.24 can be written as
Hence (combining eq. 8.23 and eq. 8.26), the power generated is
1
= = 1 3 4 (1 − )2 (8.27)
2
The function 4 (1 − )2 is shown in Fig. 8.5. From eq 8.26 we find that the
maximum occurs for
1
max = (8.28)
3
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CHAPTER 8
1.0
0.8
Power coefficient CP
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Induction factor
1
Figure 8.5: Power coefficient as a function of induction factor = 1 − 0
µ ¶2 µ ¶
2 2 8
= 21 21 (0 − 1 ) = 21 0 0 − 0 = 1 30 (8.32)
3 3 27
Combining eq 8.31 and eq 8.20,
2 1
2 = 21 − = 2 − = (8.33)
3 3
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CHAPTER 8
Clearly, at maximum power the velocity behind the turbine has dropped to one third
of the undisturbed wind velocity.
In the argument above, we assumed that the incident power of the wind was
1 3
2
1 0 However, due to the expansion of the wind streamlines in front of the turbine,
one can also argue that the incident power should be taken only from those streamlines
that will finally hit the turbine. In that case = 12 0 30 . We do not need to redo
the whole calculation. We still require that the poweroutput (and not: the effciency)
is maximized: only the numerator of Eq. 8.24 must be maximized, which still requires
= 13 and thus the output power remains the same. Only input power is changed.
Combining eq. 8.31 and eq. 8.11 we find 0
1
= 23 and changing = 12 1 30 to
= 12 0 30 thus reduces by a factor 23 as a consequence (see eq 8.24, is
increased by a factor 32 and we have (from eq 8.29) that
µ ¶
1 16 3 8
= × = = 89% (8.34)
3 27 2 9
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CHAPTER 8
= = 2̇ ( − ) (8.36)
1
which is maximal for = 2
hence
1 1
max = 2̇ 2 = ̇2 (8.37)
4 2
and since the power in the waterjet is
1
= ̇2 (8.38)
2
the efficiency is 1:
max
= = 100% (8.39)
Note, however, that in a single fluid, the flow reversal is impossible: then Betz is valid.
131
CHAPTER 8
L lift
D drag
l w U
Figure 8.7: The drag and lift force components on a wing blade of width and length in
an airflow of velocity
investigate how to design the turbine blades optimally. On a structure in a fluid flow,
there is a drag force component in the direction of the incident flow and a lift force
component in the perpendicular direction. As discussed in the section on general fluid
flow, eq 6.51 and eq 6.52, these components are given by
1
D := = 2 (8.40)
2
and analogously
1
L := = 2 (8.41)
2
where we have substituted = considering the geometry of Fig 8.7
It is illustrative to consider aver simple case where molecules impinge perpen-
dicular on a plate and are reflected back without interaction with the other molecules,
see Fig. 8.8.
The force due to a single molcule is
∆ 2
= = (8.42)
∆ ∆
and using the mass density =
where is the number of molecules impinging on
the plate in the time ∆ we have = ∆ and hence = ∆
thus we find for the
total force on an area due to all molecules
132
CHAPTER 8
Figure 8.8: Molecules impinging on a plate and reflecting straight backwards without inter-
acting with each other.
and
1
tan = (8.45)
Also
1 = sin (8.46)
and
1
= (8.47)
sin
We define the angle of attack as the angle between the flat part of the
blade and the direction of the relative air speed . In Fig 8.10 the resulting drag and
lift forces are shown for three different incident wind velocities. Also the components
in the direction of the blade rotation are shown. It is clear that for large wind speeds,
133
CHAPTER 8
Air speed u 1
Blade speed v
the drag force can become (almost) equal to the lift force, leading to reduced drive or
even a stall of the turbine. Some turbines are even designed to stall at high winds to
prevent damage.
Before proceeding we note that the coefficients and in eqns 8.41 and
8.40 not only depend on the shape of the object, but also on the angle of attack (Fig
8.9). The dependence on of the lift coefficient for a typical blade is shown in Fig.
8.11
As already stipulated in Fig 8.10, both lift and drag depend on the angle
of attack and a plot showing the dependence of both is given in Fig 8.12. The ratio
occurs for the steepest line through both the origin and a point on the blue
line. Clearly this occurs for ' 6◦ . It also clear that above approximately 10◦ the
drag increases rapidly while the lift is essentially constant. At higher angles there is
even a sharp drop in the lift. Under such conditions stall occurs.
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CHAPTER 8
Weak wind
u1
u u
u u1
u1
Optimal wind
Figure 8.11: Dependence of the coefficient in the lift force = 12 2 on the angle
of attack
135
CHAPTER 8
14o
7o
6o
Lift coefficient CL
0o
-2o
10o
Drag coefficient C D
Figure 8.12: Lift and drag coefficients for various angles of attack as indicated along the
blue curve.
where
= L (sin ) (8.49)
is the component of L in the direction of blade velocity. Here we ignore drag, because
it is typically much smaller than lift (see Fig 8.12). The second equality holds because
of eq. 8.45. Since L cos is the component of L in the direction of 1 L cos must be
equal to the thrust which is by definition in the direction of the incident velocity.
So we may also write
= 1 (8.50)
As we will now see, the above implies that we need to make the blade twisted. For
optimal performance, we need to be in the Betz situation, eq 8.31. Hence
2
1 = 0 (8.51)
3
also from eq. 8.45
1
tan = (8.52)
and thus
2
1 0
tan = = 3 (8.53)
136
CHAPTER 8
137
CHAPTER 8
where for the first equality we used that the turbine effectively can be considered as a
disk. For the second equality we used that from eq. 8.31 and 8.33 follows 0 − 2 = 1 .
On the other hand, from eq. 8.41
1
L = 2 (8.58)
2
If we still ignore drag, then we must have that
1
= L cos = 2 cos (8.59)
2
where is the number of blades. Our two equations for must give the same result
and hence
1
21 2 = 2 cos (8.60)
2
and with eq 8.47
1
= (8.61)
sin
this can be simplified to
2 4
= ³ ´2 = sin tan (8.62)
1 1
2
sin
cos
() is a decreasing function of : according to this equation, the width of the blade
should decrease in the direction away from the axis. Note that we have used again
the Betz velocity ratio’s and that this () thus follows from the requirement that we
want to be optimal everywhere along the blade. Note also that we have ignored the
(small) drag force in this derivation. For a typical turbine of = 24 m and = 8 one
has values for () and () as shown below
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CHAPTER 8
[ m] [ m] [◦ ]
6 2.6 18.4
12 1.4 9.5
18 0.9 6.3
24 0.7 4.8
8.4 Losses
We now discuss various loss mechanisms that were ignored so far:
2. Drag
We now discuss the losses in turn, except stall, which we discussed already
above.
139
CHAPTER 8
Betz+wake
(see next)
Figure 8.14: Losses due to drag (red line) and rotation of the air (dashed curve) as a function
of tip-speed ratio .
140
CHAPTER 8
= + (8.74)
2 1
Ω = (−) Ω = Ω =Ω (8.76)
where is the (total) angular momentum of the air. We used the general law =
and = 2 . Hence eq. 8.75 becomes
1 2 2
= Ω2 1 + 1 (8.77)
2
where
= 1 1 (8.78)
is the mass flow rate of the air and hence
1
= 1 1 2 Ω 1 + 1 1 2 21 (8.79)
2
with the definition
1
0 := (8.80)
2Ω
141
CHAPTER 8
hence
= (8.82)
1 + 0
in words: due to the rotation of the air, the output power of the turbine is reduced by
a factor 1(1 + 0 ).
step 2: calculate : the output power
Since we already calculated the power that can be obtained in the absence of
this rotational loss in eq. 8.27, we find that with rotational loss, the generated power
is
1 4 (1 − )2
= 1 3 (8.83)
2 1 + 0
step 3: calculate 0 in terms of
To optimize the output power, we need a relation between and 0 . We note
that was found above in eq. 8.12. Substitution in the left part of eq. 8.81 yields
1 ¡ ¢
1 1 2 − 22 = 1 1 2 Ω 1 (1 + 0 ) (8.84)
2
the left hand side can be rewritten. From eq. 8.66
2 = (1 − 2) 0 (8.85)
hence ¡ 2 ¢
0 − 22 = 20 − ((1 − 2) 0 )2 = 420 (1 − ) (8.86)
and substitution in eq. 8.84 gives
1
1 1 420 (1 − ) = 1 1 2 Ω1 (1 + 0 ) (8.87)
2
or
220 (1 − ) = 2 Ω 1 (1 + 0 ) (8.88)
defining
Ω
:= (8.89)
0
we have
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CHAPTER 8
Ω
0 = (8.90)
and substituting in eq. 8.88 yields
Ω
2 (1 − ) = 1 (1 + 0 ) (8.91)
2
1 4 (1 − )2
= 1 3 (8.94)
2 1 + 0
To proceed, we note that 0 should be small, because it is a loss term. In
other words, we should optimize the turbine such that 0 is small. Assuming that we
have succeeded, 0 1 and from eq. 8.93
1 0
2 (1 − ) = (8.95)
so
2
1 3 4 (1 − ) 1 3 4 (1 − )2
= 1 ' 1 (8.96)
2 1 + 0 2 1 + 12 (1 − )
0
this can be optimized in terms of Since is small, the optimization of this equation,
is practically equivalent to optimizing eq. 8.27. Hence we obtain here
1
' (8.97)
3
and substituting in eq. 8.95 we find
2 1
0 = (8.98)
9 2
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CHAPTER 8
1
0 = (8.99)
22
and substituting in eq. 8.82
= (8.100)
1 + 212
The resulting loss in efficiency is plotted as the dashed line in Fig. 8.14. Note
that there is only a significant loss for small tip-speed ratio’s.
144
CHAPTER 8
Figure 8.15: Turbine control and operation. For low wind speeds, the load is adjusted for
optimal rotational speed, above the ’rated’ wind speed, the maximum output power is reached
and the input power must be reduced by changing the pitch. At very high wind speeds, to
prevent damage, the turbine should either stall by design, or the control system should feather
the blades (turn them to have no torque on the axis).
The turbine must be controlled for optimum output, see Fig 8.15. For low
wind speeds, the load is adjusted for optimal rotational speed, above the ’rated’ wind
speed, the maximum output power is reached and the input power must be reduced by
changing the pitch. At very high wind speeds, to prevent damage, the turbine should
either stall by design, or the control system should feather the blades (turn them to
have no torque on the axis).
145
CHAPTER 8
Figure 8.16: Example for Rayleigh wind speed distribution, in this case with a mean speed
op 8 m s−1 .
1 ®
= 3 ' hi3 (8.104)
2
where the last approximate equality holds because
Z µ ¶3
1 3® 1 ∞
2 2 3 √ 3 2 hi √
= 3 2 −() = 3 = √ = 0954 95 hi3 ' hi3
2 2 0 8 8
(8.105)
A turbine of diameter the area = 4 2 thus would capture
2
' hi3 = hi3 (8.106)
4
The power output of the turbine is about 3× lower due the Betz limit and the other
losses discussed. One important factor reducing the efficiency is that sometimes the
wind velocity is too low for the turbine to be able to operate in the Betz limit, increasing
the loss significantly. Hence we find roughly
1 2
' hi3 ' 0262 hi3 (8.107)
3 4
the power goes as the square of the blades diameter (big is beautiful) and with the third
power of wind speed. Since wind speed increases with height, again, big is beautiful.
146
CHAPTER 8
147
CHAPTER 8
50 kW 1 MW 100 MW
Figure 8.17: Left: traditional Dutch mill with typically 50 kW output. Middle: modern 1 MW
turbine. Right: kite-ladder scheme of Wubbo Ockels generating 100 MW
148
CHAPTER 8
Figure 8.18: The KiteGen scheme. A ground based generator is driven by high flying con-
trollable kites.
149
Chapter 9
Quantum mechanics
9.2 WAVES
9.2.1 Introduction
A typical example of a circular wave at the surface of a pond is shown in Fig. 9.1
Although this example triggers naturally an association with a wave it involves also
the complex phenomena near the place where the drop felt in the water that is not
describable as a wave.
To introduce the concept of a wave we consider thus a much simpler example:
that of a propagating disturbance along a stretched rope. It is characterized by a
wavelength and a propagation velocity . For an observer at a fixed place along the
x -axis the rope is moving up and down with a frequency f.
150
CHAPTER 9
Figure 9.1: Circular wave produced by the impact of a water drop on a pond.
151
CHAPTER 9
u u x, t
xo
Figure 9.3: For an observer sitting at a fixed position in space the rope moves up and down at
a certain frequency . If the top picture corresponds to time = 0, then the bottom picture
corresponds to = 2 where is the period of the oscillation.
152
CHAPTER 9
It takes a certain time T for the fixed observer to see locally the rope to go
up, pass through a maximum deflection, move down, pass through a minimum and to
come back to the original position. This time T is called the period of an oscillation.
During the time T the wave has moved by exactly one wavelength . We have therefore
the fundamental relation
= (9.1)
The displacement = ( ) of the rope can mathematically be described
with
µ ¶
2 2
= ( ) = sin − (9.2)
In this form and are readily identifiable as
→ wavelength [m]
→ period [s]
For an observer at position x0 the displacement varies sinusoidaly with a period
µ ¶
2 2
= ( ) = sin − (9.3)
The following physical quantities are introduced for a more elegant notation
153
CHAPTER 9
F
Figure 9.4: Detail of the disturbance of a stretched rope. The force used to stretch the
rope is indicated by red arrows. The displacement at position is ( ) and at position
+ ∆ it is ( + ∆ ). Both displacements are strongly exaggerated for clarity. In reality
they are much smaller than the length of the rope. Note that we do not assume that ( )
is a sine function of and .
154
CHAPTER 9
¯
¯
¯
¯
2 +∆
−
= (9.9)
2 ∆
we obtain that
¯ ¯ ¯
¯¯ ¯¯ 2 ¯¯
= + ∆ (9.10)
¯+∆ ¯ 2 ¯
and consequently
2
∆∆ = (9.11)
2
From Newton’s law we know, however, that Force = mass × acceleration. For
the rope element this implies that
2
∆ = ∆ (9.12)
2
Equating Eqs. 9.11 and 9.12 we obtain
2 2
= (9.13)
2 2
Intermezzo:
2
At this point we must be very careful with our notation.. When we write 2
2
we mean in fact a derivative with respect to at constant and when we write 2
we mean in fact a derivative with respect to at constant . To make this clear we
2 2
use the notation 2 and 2 For a function depending on two variables, for example
( ) we mean that
= ()
= partial derivative with respect to while is kept constant
and
= ()
= partial derivative with respect to while is kept constant
with this notational convention, Eq. 9.13 can be re-written as
2 2
= 2 (9.14)
2
End of intermezzo
In fact, as explained in the intermezzo, we should have written
2 2
= (9.15)
2 2
[ ] N
¡ m ¢2
Since []
= kg/m
= s
has the dimension of a velocity squared we write
155
CHAPTER 9
2 2
2 2 = 2
(9.16)
This equation is called the wave equation. It is a partial differential equation.
All solutions of this equation are called waves. We discuss now some interesting features.
A special solution
You can for example check that = ( ) = sin ( − ) is indeed a solution of
Eq. 9.16 since
= − cos( − ) (9.17)
2
= −2 sin( − ) (9.18)
2
= cos( − ) (9.19)
2
= −2 sin( − ) (9.20)
2
and thus
156
CHAPTER 9
General solution
Not only sine- and cosine-functions are solutions of the wave equation. In fact all
functions of the form
( ) = 1 ( − ) + 2 ( + ) (9.26)
are solutions, where 1 and 2 are arbitrary functions. Simply substitute this
expression into Eq. 9.16 to verify.
2
∆ = ∆ (9.27)
2
For = sin( − ) this means
157
CHAPTER 9
Z
2
∝ (force) ∝ (9.30)
0 2
The energy of the string element of length ∆ is thus
1
∆ = 2 2 ∆ (9.31)
2
and the energy in one wavelength is
1
= 2 2 (9.32)
2
Since it takes a time = for one wavelength to pass by an observer one
defines the power carried by a wave as
1
:= = 2 2 (9.33)
2
However, we know that
= = . Thus
= 12 2 2 (9.34)
or
1
= 2 2 (9.35)
2
since = and 2 = . Here it is important that you remember that
power is proportional to the square of the amplitude. The intensity is defined as
“power/m2 ”
158
CHAPTER 9
Figure 9.5: Fig. VI.5: The sum of two sinusoidal waves with slightly different frequencies
leads to a single wave with modulated amplitude. This effect is called beating.
¡ ¢
( ) = (−) (∆−∆) + −(∆−∆)
(9.37)
= (−) 2 cos [∆ − ∆]
Since ∆ and ∆ we obtain a wave with wavenumber and
angular frequency slowly modulated in amplitude as shown in Fig. 9.5.
159
CHAPTER 9
∆
= ∆
(9.40)
This is called the group velocity, as it originates from the interaction of a
“group” (here only 2) of waves. The group velocity is fundamentally different from the
phase velocity
=
(9.41)
Assume now that we add many waves with = 1 2 3 and =
1 2 3 then the result still remains that the amplitude modulation moves with
a velocity = if all the (and ) are close to each other. The notion of group
velocity will play an essential role the description of a particle in quantum mechanics.
It will also play a crucial role in discussing metals, semiconductors and insulators.
160
CHAPTER 9
u( x, t )
amplitude
frequency f
Figure 9.6: Fourier synthesis of periodic functions. (top panel): with two periodic functions
with similar frequencies one obtains an amplitude modulated wave; (middle panel): with
11 frequencies with amplitudes distributed like a Gaussian function one obtains also a mod-
ulation. However, now the resulting periodic function has a very small amplitude over a
substantial interval of the -axis. (bottom panel): this effect is even more apparent when a
wider range of frequencies is used.
161
CHAPTER 9
162
CHAPTER 9
Figure 9.7: Circular wave produced by a pulsating point source. The intensity of the colours
indicates the amplitude of the wave. This picture is somewhat similar to that shown in Fig.
9.1
Figure 9.8:
163
CHAPTER 9
9.2.5 Summary
In these additional lecture notes I gave all the ingredients necessary to describe the
propagation of classical waves. The basic characteristics of a wave such as wavelength,
frequency, wave number, wave vector, angular frequency, intensity and power have
164
CHAPTER 9
Figure 9.11: Diffraction pattern of a plane wave when it passes two narrow slits
165
CHAPTER 9
been defined. The wave equation has been derived for the case of a stretched rope and
the wave equations for sound and electromagnetic waves in 3D have been indicated.
Furthermore you have “seen” that localized waves can be generated by adding several
waves: the localisation is strongest when the spread in frequency is largest. Finally,
you can explore with two applets the propagation of 2D waves through obstacles such
as slits. You are now ready for Quantum Physics!
2 2 1
= 2
(9.49)
−1
In this equation
166
CHAPTER 9
200
Spectral energy density dE/df
150
5800 K
100
50
0
0 1 2 3 4 5 6 7
Photon energy [eV]
167
CHAPTER 9
_
+
Large Zero
negative current
voltage 0
Figure 9.13: Light falls on a metallic plate. Electrons start to be ejected from the metallic
plate. By applying a suitable electric voltage one can reduce the velocity of the ejected
electrons in such a way that they are just reaching the negative electrode. In this way one
can measure their kinetic energy when they leave the electrode on the right.
minimum amount of energy, with any surplus energy becoming the freed electron’s
kinetic energy. The amount of energy required to free an electron, the work function
, is a characteristic of the metal.
If light were “only”a classical wave, several definite things should be observed.
• First, if light of one wavelength is able to eject electrons, then light of any wave-
length should be able to do so; independent of the wavelength, the rate at which
energy arrives (i.e., the intensity), and thus the rate at which electrons are ejected,
could be increased to any arbitrarily large value simply by increasing the intensity
of the light.
• Secondly, if the intensity is low, although electrons might still be ejected, a mea-
surable time delay should occur; a wave being diffuse, considerable time may be
required for enough energy to accumulate in the electron’s vicinity.
• Finally, at any given frequency, if the intensity is increased, the departing elec-
trons should be more energetic; a stronger electric field should produce a larger
acceleration.
Imagine the surprise of the experimenter whose weak light of 520-nm wave-
length ejects electrons from sodium, with no time lag, while light of 550 nm cannot, even
at many times the intensity, and the energy of the electrons liberated by the 520-nm
light is completely independent of the intensity. Classically, this cannot be explained!
168
CHAPTER 9
Albert Einstein in 1905 proposed the following explanation: The light is be-
having as a collection of particles, called photons, each with energy given by
= (9.50)
where h is Planck’s constant,663 × 10−34 J s, and is the frequency. The
ejection of a given electron is accomplished by a single photon, the photon transferring
all its energy to the electron then disappearing. If the frequency of the incoming light
is too low, so that the photon energy is less than the work function , there is simply
not enough energy in any given photon to liberate an electron. Thus, no electron can
be ejected, no matter what the intensity of the incoming light is, or in a “light particle”
language, no matter how abundant the photons. However, if the frequency of the light
is high enough, so that the photon energy is greater than the work function ,
an electron can be ejected. The kinetic energy given to the electron is then be
the difference between the photon’s energy and the energy required to free the electron
from the metal.
= − (9.51)
Einstein’s interpretation of the photoelectric effect explains not only the ob-
servation that a certain minimum frequency is required, but the other classically unex-
pected results as well. If a single photon, i.e. a particle of concentrated energy rather
than a diffuse wave, does have enough energy, electron ejection should be immediate,
with no time lag. Then too, the electron’s kinetic energy should depend only on the
energy of the single photon (i.e., the frequency), not on how many strike the metal
per unit time (the intensity). In all respects, Einstein’s explanation agrees with the
experimental evidence. This accomplishment won Einstein the 1921 Nobel prize in
physics.
The central point in Einstein’s explanation of the photoelectric effect is that
electromagnetic radiation appears to be behaving as a collection of particles, each with
a discrete energy. Something that is discrete (as opposed to continuous) is said to be
quantized. In the photoelectric effect, the energy in light is quantized.
169
CHAPTER 9
Figure 9.14: Schematic representation of an X-ray tube. Electrons “evaporate” from the hot
filament on the left of the tube. They are accelerated by a potential of the order of several
keV towards the metallic plate on the right, where they are abruptly slowed down. In this
process they emit very short wavelength light, the so-called X-rays.
electromagnetic radiation.
As shown in Fig. 9.14, X-rays may be produced by smashing high-speed elec-
trons into a metal target. Any charged particle radiates electromagnetic energy when
it accelerates, and smashing electrons into a target is an unusually violent acceleration,
so much radiation is produced. The radiation associated with the abrupt stopping
of a charged particle is called Bremsstrahlung, a German word meaning “braking ra-
diation.” Physicists were not surprised that rapid deceleration of electrons produced
electromagnetic radiation, but they expected to see radiation covering the entire spec-
trum of wavelengths. Although the total energy is, of course, limited by the number
of electrons arriving per unit time, physicists saw no reason that there should not be
some amplitude of waves produced at all frequencies, from the very low to the very
high.
Physicists did indeed find a broad range of frequencies but there was a clear
maximum called the cutoff frequency. There is no classical explanation for such a sharp
termination of the spectrum.
A non-classical explanation is that at a given frequency, electromagnetic ra-
diation cannot be of arbitrarily small amplitude. If the radiation is quantized, the
minimum energy that can be produced at frequency is , which is the energy of a
single photon. We cannot produce a half of a photon. In this picture we have also to
assume that it is not possible for several electrons to combine their effort to produce a
single photon.
170
CHAPTER 9
x
Figure 9.15: A short wavelength photon (violet) is scattered by an electron (green). The
scattered photon (blue) has a longer wavelength than the incoming one. This implies that
it has lost some energy during the scattering process. The equation is derived by assuming
that the photon has a momentum = and an energy = . where = 299792458 ×
108 m s−1 is the speed of light. The importance of the Compton effect is that it demonstrates
that the photon carries a momentum.
171
CHAPTER 9
= (9.52)
Where c is the speed of light. From = and = follows then
= (9.53)
But this idea had to be verified experimentally. Compton provided the first
experimental evidence that a photon does carry this momentum, and the phenomenon
now bears his name. It is not the purpose of this lecture to give a detailed theory of the
Compton experiment. For us it is only important to conclude that the experimental
data could be well described by assuming that the momentum of a photon is indeed
given by
=
(9.54)
On the basis of the experimental results described above and of other experi-
mental data on
One can conclude that light behaves sometime like a wave with frequency ,
wave length and velocity = 2998 × 108 m s−1 and sometimes like a beam of particles
with energy = and momentum = .
172
CHAPTER 9
wave
Particle
!!
173
CHAPTER 9
174
CHAPTER 9
the sense that the individual slits are much narrower than the wavelength of the light
under investigation. In this case the wave emerges from a narrow slit as if it came from
a line source. It spreads essentially uniformly in all directions and there are essentially
no diffraction minima.
At high intensities, we would observe a typical interference pattern: the in-
tensity varying from a maximum (constructive interference) at the center of the film,
to zero (destructive), then back to a maximum (constructive again), and so on. The
light is exhibiting the wave nature we attribute to it in classical physics. Particles don’t
interfere, or “cancel”; waves do.
Now suppose the intensity is greatly reduced, to the point that the unaided
eye can no longer see light on the screen. The film still registers the arrival of light, but
sporadically at scattered locations. Evidently, the light is being detected one photon
(one particle) at a time. Fig. 9.18 shows what would be found if the film were to register
the arrival of light by producing a visible spot. Although the locations at which spots
are recorded seem at first almost completely unpredictable, there soon appears a regular
pattern to the density of spots. Understanding the link between wave and particle rests
on two key observations:
• First, the exact location where the next photon will be found clearly cannot be
known, but the probability of detecting the next photon in a given region is
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Figure 9.18: The same experiment as in Fig. 9.17, but now with very low intensity light: so
low that only one photon is present in the apparatus at a given time. Photons producing a
double-slit interference pattern one particle at a time.
surely proportional to the density of spots-high where density is high, low where
density is low. Therefore, if the density of spots assumes a pattern, the probability
assumes a pattern.
• Secondly, careful study reveals that the density of spots in a region is directly
proportional to what wave theory (physical optics) predicts for the intensity of the
wave in that region, which is in turn proportional to the square of the amplitude
of the wave. In particular, no photons are ever detected at the locations where
there should be points of destructive interference. Although the light is being
detected one particle at a time, its wave nature is still apparent.
Combining these two observations, we conclude that since both are propor-
tional to the density of spots, there is a proportionality between the probability of de-
tecting the photon and the square of the amplitude of the electromagnetic wave. This
connection between particle and wave natures is a cornerstone of quantum mechanics,
crucial to its understanding:
Observation:
When a phenomenon in an experiment is detected as particles it is not pos-
sible to predict where the particles will be found. The only prediction is that of the
probability to find the particles in a given region of space. The probability is thus a
product of a probability density × volume of the chosen region of space. The probabil-
ity density is proportional to the square of the amplitude of the electromagnetic wave
in that region.
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End of observation
In the case of electromagnetic radiation, the “associated wave” is the usual
oscillating electromagnetic field. Electromagnetic fields, then, have multiple traits to
their personality. We learn in electricity and magnetism that they exert forces on
charges, and we now see that for an electromagnetic wave they also measure the prob-
ability of finding the “associated particle” (i. e., the photon). We point this out partly
to prepare the reader for a possible shock in the next chapter. The wave associated
with massive objects is a measure of the probability of finding a massive particle, but
it does not appear to have any readily observable “other side” to its personality!
Before leaving the double slit, we address a point central to wave-particle du-
ality. In the double slit, it is not proper to ask, “Through which slit did the 17th photon
pass?” This cannot be determined in the specific experiment assumed, and by altering
the experiment so as to “observe” a particle passing through a slit-an experiment in
itself, requiring some interaction with light in one slit alone: we would alter the very
behavior we wish to observe. Since interference requires two coherent waves, the pat-
tern would be disturbed. We can’t have it both ways! Wavelike interference can only
be observed by allowing each “particle” to behave as a wave-passing through
both slits simultaneously.
9.3.8 Summary
A series of key experiments shows that electromagnetic radiation behaves in some sit-
uations as a collection of particles, the photons. A summary is given below:
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x
y
Figure 9.19: Single-slit diffraction: Better knowledge of particle position along (a narrower
slit) implies decreased knowledge of -component of momentum (a wider pattern), and vice
versa.
= (9.55)
and
=
(9.56)
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Figure 9.20: Electrons passing one by one through one narrow slit hit the screen everywhere.
This might to some extent be understood classically as a simple bouncing of the electron at
the sharp edges of the slit.
matter’s wave nature more convincingly than the following double slit experiment with
particles instead of photons.
Imagine a beam of mono-energetic electrons striking a barrier in which there
is a slit. Beyond the slit is a phosphorescent screen that registers each electron’s arrival
by producing a flash. With a “wide” slit, as shown in Fig. 9.20, the beam passes
straight through and produces, electron by electron, a stripe on the screen the same
width as the slit.
With a narrow slit, however, we find electrons registering sporadically over
the entire screen.
Suppose, then, that we add a second narrow slit, see Fig 9.21. Again, with
either slit open alone, electrons are detected sooner or later at all points on the screen.
But when both are open at the same time, at certain locations, locations where electrons
had been detected with either slit open separately, electrons are never detected. Opening
a second “door” decreases to zero the number arriving per unit time at specific, regularly
spaced locations on the screen! This is impossible to explain if electrons are simply
“classical”particles passing through one slit or the other; a particle passing through
one slit would not suddenly have reason to avoid specific locations on the screen just
because a slit had been opened elsewhere. In a “wave” picture this behaviour is however
simply understood as a destructive interference of a wave passing through both slits.
This destructive interference requires multiple coherent waves, so that each electron
must be behaving as a wave passing through both slits at once. Fig. 9.21 shows how
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Figure 9.21: In presence of two slits the electron hit the screen only in certain regions. This is
a clear indication of interference effects of a wave, but the question is: what sort of “wave”?
the electron flashes accumulate with both slits open. It should ring a bell to you: it is
very similar to the double-slit photon detection pattern of Fig. 9.17.
The point is that both light and massive objects exhibit the same kind of wave-
particle duality. Associated with the particle of light (photon) is a wave of oscillating
electromagnetic field; we must now accept that there is also a sort of wave associated
with a massive particle. Certainly it is different, and it is natural to wonder what is
analogous to the electromagnetic fields-that is, what is oscillating.
To identify at least one property of this wave, we note that the same two
observations we made about electromagnetic waves also apply here:
• Although it is obviously impossible to know where the next electron will be de-
tected, it is surely true that the density of spots in a given region is proportional
to the probability that it will be found in that region.
• As coherent waves of equal amplitude are emanating from the two slits, it is
natural to expect an interference pattern. In particular, we would expect the
amplitude at the center of the screen (constructive interference) to be twice what
it would be if only one slit were open. Note that the square of the amplitude,
which is proportional to an intensity, should be 4 times as large. Conspicuously,
the density of spots is indeed 4 times larger at the center with both slits open
than with either slit alone. In fact, at all points on the screen we find that the
density of spots is proportional to the square of the total wave obtained in a
standard classical analysis of the double slit. Combining these observations (that
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Figure 9.22: Analogy between the pattern of the registered electrons hitting a screen after
having passed one-by-one two narrow slits and the interference pattern observed when an
intense beam of coherent light is directed towards the double slit.
the square of the wave’s amplitude and the probability of finding the particle are
proportional to the same thing i.e., the density of spots), we arrive at the same
conclusion as for light:
Observation
When a phenomenon in an experiment is detected as particles it is not pos-
sible to predict where the particles will be found. The only prediction is that of the
probability to find the particles in a given region of space. The probability is thus a
product of a probability density × volume of the chosen region of space. The probabil-
ity density is proportional to the square of the amplitude of the electromagnetic wave
in that region.
End observation
Although the wave-particle relationship for light (electromagnetic radiation)
and massive objects is the same, matter waves differ in an important way: They cannot
be directly detected! Electric and magnetic fields can be isolated and caused to exert
forces on objects; they may be directly detected. But we have not found any analogous
way of directly detecting matter waves; no one has ever “seen” one. What then is
the answer to the question: What is oscillating? We have no other readily identifiable
property than guessing that probability is oscillating.
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s cr e e n scr e e n sc r e en
Amplitude Intensity
Figure 9.23: Plane wave arriving at a narrow double slit (right panel). The amplitude varies
between zero (destructive interference) and 2 × the amplitude observed for a single slit (ei-
ther the right or left one). The intensity is the square of the amplitude. The intensity is
proportional to the probability to find a particle in a certain region on the screen.
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X
d d
Figure 9.24: Constructive (left) and destructive (right) interference of the “wave” associated
with electrons scattered at the surface of a Nickel crystal in the Davisson-Germer experiment.
electrons are to be found. The experimentally observed electron detection rate versus
angle is in perfect agreement with the theoretical prediction based upon the assumption
of wave interference.
In the Davisson-Germer experiment, the electrons are accelerated by a fairly
low potential: Only 54 V was used. This means that the energy of the electrons was 54
eV. At higher energies, electrons and their associated matter wave are able to penetrate
to atomic planes beneath the surface, and a different experimental setup is preferred.
The same is true for neutrons.
2 cos = (9.57)
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2 D cos n
Figure 9.25: Constructive interference for neutrons scattered by atoms in the bulk of a crystal.
Figure 9.26: Constructive interference for neutrons scattered by atoms in the bulk of a crystal.
This is an enlarged view of the crystal as compared to Fig. 9.25. The path difference (in red)
must be equal to an integer number of wave lengths in order to have constructive interference.
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Figure 9.27: Cartoon illustrating the scattering of neutrons passing through a crystal. Under
certain well defined directions there is constructive interference and a large fraction of neutrons
are registered on the detector. This is the origin of the bright spots on the photograph. From
the pattern of bright spot one can reconstruct the structure of the crystal under investigation.
with an integer number. Significantly, the same equation gives the interfer-
ence maxima when X-rays scatter from a crystal. (It is known as the Bragg law, for
father and son W. H. and W. L. Bragg, who were awarded the 1915 Nobel prize for
their X-ray diffraction work.) We saw previously that X-rays may behave as particles
where visible light (of longer wavelength) would behave as waves. The spacing in a
crystal is so small that even X-rays behave as waves.
Crystal diffraction is an indispensable tool in the study of solids; the details
of the diffraction patterns provide much information about the crystal’s microscopic
geometry. An example of the type of data that can be generated by scattering neutrons
on a crystal is shown in Fig. 9.27.
1. • have a wavelength,
• a frequency,
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• a speed,
• an amplitude that varies with position and time. The generic term for a
mathematical function giving the amplitude is the name wave function.
Since what actually oscillates depends on the kind of wave, we use different
symbols for the wave functions of different kinds of waves: For transverse waves on a
string, we used the symbol ( ); the string’s transverse displacement varies as a
function of the position along the string and time . For an electromagnetic plane
wave moving along the -axis, we have two wave functions, ( ) and ( ), which
describe how the oscillating electric () and magnetic () fields vary with position and
time.
For the wave function for matter waves, we choose the symbol Ψ( ). In the
following part of this lecture we shall simply call it “the wave function.” We will see
that the wave function Ψ( ) is determined by Schrödinger’s equation. But for the
time being we concentrate on important matter wave behaviors that can be understood
without having an explicit formula for the wave function Ψ( ).
Wavelength
Louis de Broglie submitted the following hypothesis: The wavelength of the matter
wave associated with a massive particle of momentum is given by
=
(9.58)
At first sight this looks completely trivial as Eq. 9.58 can be obtained by a
simple algebraic manipulation of Eq. 9.54. The implication of Eq. 9.58 is however very
deep as it says that a wavelength can be associated to a particle. This relationship
has been indisputably confirmed, even for relativistic speeds, by experiments such as
crystal diffraction. The momentum of the electrons in a beam is known, analysis of the
diffraction pattern establishes the wavelength, and together the relationship is verified.
The discovery won de Broglie the 1929 Nobel prize. In recognition, we often refer to
the wavelength of a matter wave as the de Broglie wavelength (pronounce de Broil).
In ordinary situations, the wavelength of matter waves is short enough to
ensure that matter behaves as particles. This is true because Planck’s constant, the
fundamental constant of quantum mechanics, is so small. Even so, as an object’s
momentum approaches zero, its wavelength would become arbitrarily large. We might
draw the unsettling conclusion that a stationary particle, with an infinite wavelength,
should certainly behave as a wave. As we shall see in an exercise the way out of this
predicament rests upon the fact that it is difficult to guarantee that a particle is indeed
stationary.
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Frequency
Matter waves, of course, have a frequency. The evidence is not quite so direct as the
interference pattern evidence that clearly demonstrates a wavelength. But once again,
the relationship is the same as for electromagnetic radiation:
=
(9.59)
The wave property of frequency is related to the particle property of discrete
energy. Think about the discrete absorption lines of atoms.
A useful notation
In many cases it is more convenient to use the wave number and angular frequency,
instead of the wavelength and the frequency. With:
2
= (9.60)
for the wave number, and
2
= = 2 (9.61)
for angular frequency and the very convenient definition
~= (9.62)
2
we can write the wave-particle relationships in a very compact way
= ~ (9.63)
and
= ~ (9.64)
These are the fundamental relationships between wave and particle
properties for all phenomena. Their importance cannot be overstated.
For a classical free particle we have
1 ()2 2
= 2 = = (9.65)
2 2 2
For a free quantum mechanical particle one expects thus
2 ~2 2
= ~ = = (9.66)
2 2
Which implies that the angular frequency should be proportional to the square
of the wave number.
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the fact that many phenomena in physics, such diffusion of particles, heat conduction,
sound waves, light, water waves, etc, are described by partial differential equations.
The quantum wave equation we are looking for might thus look like
Ψ 2Ψ Ψ 2Ψ
+ 2 = + 2 (9.68)
But what are the parameters and ? At this point we note that we
can expand any wave in a series of sine-waves using Fourier analysis. In Section 9.2.2
we showed that it practical/efficient/advantageous to use a complex notation for waves.
Hence let’s take now as a supposed solution
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~2 2
= ~ (9.73)
2
for a free particle. Comparing Eqs. 9.72 and 9.73, we conclude that
~2
=− = ~ (9.74)
2
and
= ~ (9.75)
would be a good choice. In fact, it turns out to be “the“ good choice. The
result of substituting Eqns 9.66,9.74 and 9.75 in 9.68 is that the wave equation obeyed
by matter waves is the Schrödinger equation,
~2 2 Ψ Ψ
− 2
= ~ (9.76)
2
So far we considered only the special case of “free particles”. In presence of
external forces, the Schrödinger equation becomes
~2 2 Ψ Ψ
− 2
+ ()Ψ = ~ (9.77)
2
Where () is the potential energy experienced by the particle. For example,
for a particle attached to a spring () = 12 2 where is the spring constant. A
large means a stiff spring.
The Schrödinger equation often troubles beginning students of quantum me-
chanics on three accounts:
• First, its form is certainly not intuitively obvious, so it is natural to hope for a
derivation from first principles. However, the Schrödinger equation is the first
principle. Classical wave equations rest upon a fundamental assumption or phys-
ical law, but there simply is no underlying, more basic principle upon which the
Schrödinger equation is built. Its acceptance as, in essence, a “law” arises from
the fact that it renders correct predictions about the behavior of matter (proba-
bilities of finding particles, for instance). By analogy, Maxwell’s equations, which
cannot be derived or proved, will remain accepted laws only so long as we dis-
cover no situation in which they are violated. Although the Schrödinger equation
cannot be derived, we have shown that it is at least plausible.
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• The
√ second concern is that the Schrödinger equation is complex (involving =
−1). This distresses and alienates some students of quantum mechanics. It
might be incorrectly concluded that a matter wave is not “real.” Unfortunately,
this would also seem to fit perfectly with the point we made earlier-that the wave
function is not directly observable. (Why should it be, since it isn’t real anyway?)
• The third difficulty is that even if we could calculate Ψ( )it is not clear what
we can do with it. In our interpretation of the one- and two-slit experiments the
square of the amplitude of matter wave was found to be related to the probability
to find a particle in a certain region of space. A probability is by definition a
positive number between 0 and 1. The square of a complex number is however in
general also complex. Therefore, we must invent something else. This something
else is the square of the norm of Ψ( )i.e. |Ψ( )|2 . This is always positive as
We are now all set to explore predictions of the Schrödinger equation in simple
cases.
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Chapter 10
Photovoltaic energy
~2 2 Ψ Ψ
− 2
+ ()Ψ = ~ (10.1)
2
In presence of a constant potential the Schrödinger equation becomes
~2 2 Ψ Ψ
− + Ψ = ~ (10.2)
2 2
The solution of this equation is exp [ ( − )] as can be verified by subsi-
tution in eq. 10.1. The result is
~2 2 2
+ = ~ = + = (10.3)
2 2
In other words the two terms on the left hand side of Eq. 10.1 represent the
kinetic and potential energy of a particle of total energy .
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~2 2 Ψ Ψ
− 2
= ~ (10.4)
2
and outside the box
~2 2 Ψ Ψ
− 2
+ ∞ ∗ Ψ = ~ (10.5)
2
Outside the box the only possibility is Ψ = 0. Inside the box, the solution is
[(−)]
, introduction of this expression in Eq. 10.1 gives
~2 2
= ~ = (10.6)
2
Note that [(−−)] is also a solution. Any linear combination of these two
solutions is also a solution of the problem. Thus
= (10.11)
where is an integer i.e. = 1 2 3. . . .. Note that = 0 is no option as it
would imply that the particle is nowhere. The solution is thus finally
³ ´
Ψ( ) = 2 sin − ~ (10.12)
in which we have replaced by ~. Going back to Eq. 10.6 we find from
10.12,
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~2 2 ~2 2 2
= = (10.13)
2 22
This result is very important as it shows that the energy of the particle is
quantized. It can only assume discrete values. A practical way of representing energy
levels and the corresponding quantum states is indicated in Fig. 10.1. In order to draw
the wave functions and the probability densities we needed to know the value of the
amplitude A. The value of A is determined by physics! If the square of the norm of
the wave function is to represent a probability then it is obvious that
Z
|Ψ ( )|2 = 1 (10.14)
0
Since the probability to find the particle in the box must be 1. Inserting Eq.
10.6 into Eq.10.14 we obtain that
Z Z ³ ´ ³ ´
2 2
|Ψ ( )| = 1 = 4 sin − ~ sin + ~ (10.15)
0 0
and
Z h ³ ´i2
2
4 sin = 22 = 1 (10.16)
0
And finally
r
³ ´
2
Ψ ( ) = sin − (10.17)
Although the wave function does depend on time, the probability density
2 h ³ ´i2
|Ψ ( )|2 = sin (10.18)
depends only on position, see Fig. 10.1.
Where there are nodes in the standing waves, the probability density is zero.
But how, we might ask, can the particle get from one place in the well to another if there
is no possibility of it ever being found at a point in between? The answer is simple: It
is a wave, not a particle. As we know from a study of classical waves, standing waves
may be thought of as two waves passing one another in opposite directions. Although
they bounce back and forth, there are nodes where the displacement is always zero.
We cannot demand that the “particle” behave as a classical particle. For one thing, it
cannot be “watched”; the photons that would have to be bounced off the particle would
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n n
2
Figure 10.1: The six lowest energy states of a particle in a super hard box. For this example
we have chosen ~2 = 1 and = 2. The problem is treated in one dimension. The black
curve represents the potential seen by the particle: it is taken to be zero between = −
and = . Outside this range it is infinitely high. These funny values are just chosen for
numerical simplicity. The ground state energy is then 0.125. The energy of the first excited
state ( = 2) is then 0.500, that of the second excited state 1.125, etc. The ground state
corresponds to the red curve. It is plotted in such a way that the −axis is placed at position
0.125. The first excited state, which corresponds to the green curve, is similarly plotted with
its −axis at 0.500, and so on. All the wave functions have zero amplitude at the boundary
of the well. The probability density to find the particle at the well edge is thus zero. The
increasing number of oscillations, or what is equivalent, the decreasing wave length of the
wave function (for increasing ), reflects the increasing of the kinetic energy.
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introduce potential energies () that have not been taken into account in our solution
of the Schrödinger equation. The assumed simplicity of the situation forbids our having
detailed knowledge of the particle’s activities. On the other hand, lack of knowledge
of precise whereabouts is a fact in all the real situations to which quantum mechanics
is applied. We cannot, for example, say exactly what an electron orbiting a nucleus
is doing. But despite these limitations, in microscopic applications, the predictions of
quantum mechanics have succeeded, while those of classical physics have failed.
The standing wave of lowest energy is known as the ground state and its
energy as the ground-state energy (or zero-point energy). It is in the ground state
that quantum-mechanical behavior deviates most from the classical expectation. Most
importantly, the kinetic energy is not zero: a bound particle cannot be stationary. This
is a direct consequence of the uncertainty principle of Heisenberg; to have a position
uncertainty comparable to and a certain momentum of zero is impossible. Another
deviation from the classical is that in its ground state the particle is most likely to be
found near the center. Classically, if we were to “turn on the lights” suddenly and catch
the particle somewhere in the course of its constant-speed back-and-forth motion, it is
equally likely to be found anywhere within the well. As we see in Fig. 10.1, the larger
the , the more evenly the probability of finding the particle is spread over the well in
agreement with the classical expectation.
1. The wave function must be continuous everywhere and thus also at = 0 and
=
2. The first derivative of the wave function must be continuous everywhere, i.e. also
at = 0 and =
3. The wave function must be normalized to guarantee that the probability to find
the particle between −∞ and ∞ is 1.
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Uo
Ce ax De ax
It is not the purpose of this course to give more mathematical details. It is,
however, very important to remember the effect of the finiteness of the potential barrier
on the wave function of the particle.
~2 2 Ψ()
− + () Ψ () = Ψ () (10.19)
2 2
The potential () seen by the electron is obviously periodic as a result of
the assumed regular arrangement of the atoms along the chain.
At this point it is useful to give some simple examples of the ideas described
so far. For this we consider the simple case of a 2-square well “molecule”. We see that
the ground state of the 1-well leads to 2 groups of 2 states. For a 3-square well “solid”
we obtain two groups of 3 states. For a solid consisting of N -square wells there will be
2 groups of N states. Each of these groups is called an energy band, see Fig. 10.4
and 10.5.
The lower band (often called the valence band) is relatively narrow since the
wave functions do not overlap very much. The upper band (often called the conduction
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n n
2
Figure 10.3: The six lowest energy states of a particle in a box with “soft”walls. By soft we
mean walls characterized by a finite potential energy. For this example we have again chosen
~2 = 1 and = 2. The problem is treated in one dimension. The black curve represents
the potential seen by the particle: it is taken to be zero between = − and = . All
the wave functions have non-zero amplitude at the boundary of the well. This is completely
different from the situation encountered in classical mechanics. It means that in quantum
mechanics a particle is allowed to be in a region of space that is classically forbidden.
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Figure 10.4: Energy levels for one (left) and two square potential wells (right). Note that
there are two groups of bonding and antibonding states (red+blue and green+yellow), which
correspond roughly to the energy levels of the single well.
Conduction band
N levels
Valence band
N levels
Figure 10.5: (upper panel): Energy levels for one and three square potential wells. There are
still two groups of levels, but now each group contains 3 states. (lower panel): for a linear
chain of atoms there are levels in the lower band called Valence band and levels in
the upper band called Conduction band. We shall see later, that each level can accommodate
at most 2 electrons.
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band) is significantly broadened. For a real solid, which contains 1029 atoms per m3 ,
each atomic level leads to a band with 1029 levels !
10.3 Semiconductors
A completely different behaviour is observed for materials such as Silicon (Si) and Ger-
manium (Ge). For them the electrical resistivity is very high at low temperatures but
it decreases rapidly with increasing temperature. Closer inspection of the experimental
data in Fig. 10.10 reveals that there is a characteristic temperature dependence. This
is clearly shown by replotting the data as a function of the inverse temperature rather
than simply . One obtains then the graph in Fig. 10.11.
The temperature dependence of the resistivity shown in Fig. 10.11 implies
the following relation between resistivity and the absolute temperature
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3
Energy
0
0.0 0.2 0.4 0.6 0.8 1.0
Fermi-Dirac distribution
Figure 10.6: The ground state of a linear chain of 12 hydrogen atoms (left panel). The degree
of occupation of states (per spin) is given by the Fermi-Dirac function () in the right panel.
The Fermi energy is set equal to 1.75 in this example. The occupied states are indicated
as red filled circles. The states below the Fermi energy are all filled and those above the Fermi
energy are all empty.
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Energy
2
0
0.0 0.2 0.4 0.6 0.8 1.0
Fermi-Dirac distribution
Figure 10.7: The occupation of electronic states of a linear chain of 12 hydrogen atoms at
high temperature (left panel). The degree of occupation of states (per spin) is given by the
Fermi-Dirac function () in the right panel. The Fermi energy is set equal to 1.75 in this
example. The occupied states are indicated as red filled circles. The states below the Fermi
energy are mostly filled and those above the Fermi energy are mostly empty.
−
= 2
(10.20)
where is the energy gap between the valence band and the conduction
band in Fig. 10.12.
As seen in Fig. 10.13, the states below the Fermi energy are mostly filled (but
there are clearly unoccupied states, called holes) and those above the Fermi energy are
mostly empty. There is, however, a non-negligible number of electrons at the bottom of
the conduction band. It is these electrons in the upper band and the holes in the lower
band that can carry electrical current. The number of these charge carriers depends
clearly on temperature. The higher the temperature the more carriers there are and
the lower the resistivity.
As the amount of charge carriers determines the conductivity of a solid it is
now useful to estimate how their number depends on temperature. For this we need
to look at the Fermi-Dirac distribution function () that gives the probability that a
level of energy is occupied by an electron,
1
() = (10.21)
((− ) )
+1
For energies such that − À the Fermi-Dirac function reduces to
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3
Energy
0
0.0 0.2 0.4 0.6 0.8 1.0
Fermi-Dirac distribution
Figure 10.8: The occupation at high temperature of electronic states of a linear chain of 12
atoms with 3 valence electrons per atom at high temperature (left panel). The degree of
occupation of states (per spin) is given by the Fermi-Dirac function () in the right panel.
The Fermi energy is set equal to 4.0 in this example. The occupied states are indicated
as red filled circles. The states below the Fermi energy are mostly filled and those above the
Fermi energy are mostly empty.
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3.0
(cm)
2.5
Electrical resisitivity
2.0
1.5
1.0
0.5
0.0
0 50 100 150 200 250 300 350 400
Temperature (K)
Figure 10.9: Electrical resistivity of a typical metal. At zero Kelvin the resistivity is small
but finite because of imperfections and impurities in the material. Above 100 K it increases
linearly with increasing temperature as a result of scattering of conduction electrons with the
thermally agitated metal atoms. Note that the scale is in micro-Ohm.cm
1E8
1E7 cm
1000000
Electrical resistivity
100000
10000
1000
100
10
1
0.1
0.01
1E-3
0 100 200 300 400 500 600 700 800 9001000
Temperature (K)
Figure 10.10: Electrical resistivity of a typical semiconductor. At zero Kelvin the resistivity
is huge. With increasing temperature it decreases by many orders of magnitude. Note that
the scale is in now in Ohm.cm. At 1000 K the resistivity is still much higher than for a metal.
204
CHAPTER 10
1E8
1E7 cm
1000000
Electrical resistivity
100000
10000
1000
100
10
1
0.1
0.01
1E-3
0.000 0.002 0.004 0.006
-1
1 / Temperature (K )
Figure 10.11: Electrical resistivity of a typical semiconductor plotted now as a function of the
inverse temperature. We obtain essentially a straight line.
3
Energy
Egap
0
0.0 0.2 0.4 0.6 0.8 1.0
Fermi-Dirac distribution
Figure 10.12: The occupation at medium temperature of electronic states of a linear chain of
12 atoms with 2 valence electrons per atom at high temperature (left panel). The degree of
occupation of states (per spin) is given by the Fermi-Dirac function () in the right panel.
The Fermi energy is set equal to 4.0 in this example. The occupied states are indicated
as red filled circles. The states below the Fermi energy are filled and those above the Fermi
energy are empty.
205
CHAPTER 10
Energy 2
0
0.0 0.2 0.4 0.6 0.8 1.0
Fermi-Dirac distribution
Figure 10.13: The occupation at very high temperature of electronic states of a linear chain
of 12 atoms with 2 valence electrons per atom at high temperature (left panel). The degree
of occupation of states (per spin) is given by the Fermi-Dirac function () in the right panel.
The Fermi energy is set equal to 4.0 in this example. The occupied states are indicated
as red filled circles.
f(
1.0
0.5
1000
800
0.0 600
400 )
0.0 0.5 200 T(K
1.0 1.5 re
2.0 2.5 3.0 er atu
Energy eV)
emp
T
Figure 10.14: Fermi-Dirac distribution function for temperatures between 0 and 1000 K. For
this example the Fermi energy, is taken equal to 2 eV.
206
CHAPTER 10
() ∼
= −(− ) (10.22)
It is this exponential dependence that is at the origin of the strong temperature
dependence of the electrical resistivity of semiconductors.
−2
() = (10.23)
40
but the screened potential
−2
() = (10.24)
40
where is the dielectric constant of the material under consideration. This
implies that the extra electron is only very weakly bound to the +1 excess charge of
the phosphorous atom, see Fig. 10.15.
The ionization energy of the electron around a donor impurity (this is the
energy required to free the electron from the donor) is just a few 0.01 eV. This means
that if this energy is provided to the electron it will leave the P atom and travel through
the crystal as a free conduction electron.
In presence of donor impurities we have to modify the representation of elec-
tronic energy levels used so far in previous figures. Look for example at Fig. 10.12:
the left panel has horizontal black lines that represent the energy levels. The length of
207
CHAPTER 10
P
(+5)
Si
(+4)
Figure 10.15: Phosphorous (P; valence 5) impurity in silicon (valence 4). The extra electron
of P is very loosely bound to the +1 effective charge of the Phosphorous. Its effective Bohr
radius is of the order of 10 nm instead of 0.05 nm for the electron in a Hydrogen atom.
these black lines have no physical meaning. Neither does the position of the red dots
indicating which levels are occupied. I could have placed them at any position on the
black lines. Now let us consider a doped semiconductor. Here and there a P atoms has
replaced a Si atom. We want to represent this situation in a combined picture: one in
which we give information both on the allowed quantum mechanical energy levels and
on the position of the impurity levels. In Fig. 10.16 we first show the correspondence
of the new representation with that in Fig. 10.12 at low temperatures (by low we mean
that ¿ ) and that in Fig. 10.17 at high temperatures.
After this presentation we can now move to situations where electron donors
have been added to the semiconductor. We obtain then the situation in p-n junctions.
208
CHAPTER 10
Conduction band
Valence band
x-axis
Figure 10.16: The occupation at low temperature of electronic states of a linear chain of 12
atoms with 2 valence electrons per atom (left panel). On the right panel we indicate the
energy bands that are allowed: in blue the valence band and in gray the conduction band.
We will see later that for example in a p-n junction the position of these bands depends on
position in the doped semiconductor.
Conduction band
Valence band
x-axis
Figure 10.17: Same as in Fig. 10.16 but now at much higher temperatures. The occupied
states are indicated as red filled circles. They correspond to electrons thermally excited
across the energy gap from the valence band to the conduction band of the semiconductor.
The missing electrons in the valence bands are indicated with white dots. They are called
holes.
209
CHAPTER 10
EF EF
Egap
Egap
x-axis x-axis
Figure 10.18: Band structure of a n-type semiconductor, that is a semiconductor doped with
donor impurity atoms. Left panel: At very low temperature all donor electrons are bound
to the impurities. Right panel: At moderate temperatures nearly all the impurities have lost
their electron which are now donated to the conduction band. The temperature is however
too small to excite electrons from the valence band to the conduction band. Note that the
Fermi energy has fallen below the donor levels.
what happens with electrons and holes when the n- and p- sides are brought into contact
with each other. Just after the two separate crystals (one p-type, the other n-type), are
brought in contact with each other, the electrons, which are much more concentrated
on the n-side than on the p-side start to diffuse into the p-region. Similarly the holes
diffuse into the n-region since they are much more concentrated on the p-side. At
equilibrium ( = ∞) the carrier concentration is as indicated in Fig. 10.24 and Fig.
10.26. It exhibits a very sharp drop at = and = − . This can be understood
as follows: The diffusion of electrons from n to p and the diffusion of holes from p to n
cannot last forever because of the resulting space charge of the ionized donors on the
n-side and acceptors on the p-side. This dipole-layer induces an electrical field directed
in such a way as to inhibit a further diffusion of electrons and holes. This electrical field
is proportional to and from charge neutrality = . This explains why
and are finite. The sharp drop at and is a consequence of a law that states
that the product of electron concentration in the conduction band times the hole
concentration in the valence band is constant [this law cannot be derived within
the framework of this lecture]. Typically = 1026 cm−6 . Far from the junction
= and = (−∞) on the n-side and = and = (∞) on the p-side.
For a typical semiconductor with = 1017 cm−3 we have thus (∞) = 109 cm−3 .
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CHAPTER 10
Conduction Conduction
Egap Egap
EF EF
x-axis x-axis
Figure 10.19: Band structure of a p-type semiconductor, that is a semiconductor doped with
acceptor impurity atoms. Left panel: At very low temperature all acceptors are empty. Right
panel: At moderate temperatures all the impurities have captured an electron from the valence
band. The temperature is however too small to excite electrons from the valence band to the
conduction band.
Somewhere between − and + we must therefore have = . This implies
= = 1013 cm−3 at this point. As can be seen by comparing this value with
= 1017 cm−3 the carrier concentration is 104 times smaller in the junction region
than far away from it. This is the reason why this region is called the depletion
region.
We have now all ingredients to understand the rectifying properties of a p-n
junction. The electrical field E set up by the charges in Fig. 10.29 makes it difficult
for electrons to diffuse from the n-side to p-side and for holes to diffuse from p to n. It
is, however, not high enough to prevent every electron to travel from n to p because
electrons can recombine with one of the many holes on the p-side. There is thus always
a certain recombination current from n to p for electrons (similarly from
p to n for holes). At equilibrium, (or ) is, however, exactly compensated by
(or ), the so- called generation current: it is obvious from Fig. 10.30 that
if an electron excited thermally on the p-side reaches the depletion region it will be
accelerated by the electrical field towards the n-region.
The compensation
= (10.25)
is necessary to prevent a piling up of charges on one side of the junction. Let us now
211
CHAPTER 10
Conductio
ban
EF
Egap
Valence
x-axis
Figure 10.20: Same as in Fig. 10.18 but now for a n-type semiconductor at much higher
temperatures. In addition to the electrons donated by the donors there are electrons which
have been excited out of the valence band. They leave behind holes in the valence band.
Both the electrons in the conduction band and the holes in the valence band can conduct
electricity.
212
CHAPTER 10
Conductio
ban
Egap
Valence
x-axis
Figure 10.21: Same as in Fig. 10.19, but now for a p-type semiconductor at high temperatures.
In addition to the electrons captured by the acceptors there are electrons which have been
excited out of the valence band. They leave behind holes in the valence band. There are more
holes than electrons. As in the previous figure both the electrons in the conduction band and
the holes in the valence band can conduct electricity.
213
CHAPTER 10
p- doped n- doped
E gap EF
E gap
x-axis x-axis
Conduction
Conduction
E gap
EF
Eg ap
Valence band
Valence band
x-axis
x-axis
Figure 10.22: Shift of the energy bands when a p-doped and a n-doped semiconductor are
brought into contact. At the end the Fermi energy is constant throughout the p-n-junction.
214
CHAPTER 10
Impurity concentration
Nd
Na
n-type
p-type
Figure 10.23: Concentration of donors and acceptors on both sides of our idealised p-n junc-
tion. On the p-side = 0 and on the n- side = 0. At sufficiently high temperatures
(certainly at 300 K) all the donors are ionised. The electron concentration on the n-side is
equal to . Similarly, the hole concentration on the p-side is equal to
Electron concentration
Nd
Figure 10.24: Electron concentration as a function of time. Far from the junction we assume
that at the temperature of interest all the donors are ionized. Immediately after “gluing”
the p-side with the n-side the electrons close to the junction spill over to the p-side because
of the sharp concentration gradient at = 0. The electric field which is set up leads to
an equilibrium electron concentration profile with a sharp edge at a distance , from the
junction.
215
CHAPTER 10
eNd
+
dn x
Figure 10.25: Total charge density on the n - side. The electrons that have diffused from
the n-side to the p-side leave an overall positive space charge behind (ionized donors) on the
n-side
Hole concentration
Na
t=0
t=
Figure 10.26: Hole concentration. Far from the junction we assume that at the temperature
of interest all the acceptors are ionized. Close to the junction the holes spill over to the
n-side because of the sharp concentration gradient at = 0. The electric field which is set
up leads to an equilibrium hole concentration profile with a sharp edge at a distance from
the junction.
216
CHAPTER 10
dp
_ x
-eNa
Figure 10.27: Total charge density on the p - side. The holes that have diffused from the
p-side to the n - side leave an overall negative space charge behind (ionized acceptors) on the
p-side
eNd
+
dp
_ dn x
-eNa
Figure 10.28: Charge density around the p-n junction obtained by superposition of the charges
in Fig. 10.25 and Fig. 10.27. The resulting dipole layer leads to an electric field so that the
potential energy of an electron on the p-side is higher than on the n-side
217
CHAPTER 10
Jnr
Jng
Jpg
Jpr
real space coordinate
Figure 10.29: Position of the energy bands near a p-n junction. The black dots and the white
dots indicate symbolically the concentration of electrons and holes, respectively. The chemical
potential (red line) is constant as required by general thermodynamical considerations.
apply an external voltage and see what happens to the bands shown in Fig. 10.30.
The generation current remains approximately constant as it is controlled
by the excitation rate of electrons in the bulk of the p-material (far from the junction;
do not forget that + ∼ 10−4 cm, while the diffusion length for holes and electrons
is 10−1 cm). The recombination current, on the other hand, depends critically on the
height of the barrier. We have
= ( ) − ( ) =
= ( ) − ( = 0) ¡ ¢ (10.27)
= ( = 0) − ( = 0) = ( = 0) − 1
The electrical current due to the electrons is
¡ ¢
= − = − ( = 0) − 1 (10.28)
218
CHAPTER 10
Jnr
Jng
Jpg
Jpr
real space coordinate
Figure 10.30: Effect of an external voltage on the energy bands near a p-n junction. The
voltage is such that the p-side becomes less attractive for electrons. In other words the negative
electrode of the battery is connected to the p-side. The generation currents of electrons and
holes is essentially not affected by the voltage. However, the recombination currents decrease
strongly since the charge carriers have now to climb up a higher hill. This is the backward
voltage regime.
219
CHAPTER 10
Figure 10.31: Current () versus voltage( ) characteristics for a germanium p-n junction.
Note the marked asymmetry between the forward regime ( 0) and the backward regime
( 0), which leads to the rectifying property of the p-n junction. Note also the use of
completely different scales for the forward and backward voltage regime.
The total electrical current (electrons + holes) is thus (we do not repeat the
argument for the holes)
¡ ¢
= − 1 (10.29)
where is the sum of the generation electrical currents. This relation is found
to be in good agreement with experimental data in germanium.
The p-n junction is only one of the numerous "solid-state" devices that are
found nowadays in almost any apparatus such as radio, television, computers, etc. It is,
however, a nice example that demonstrates some of the basic phenomena taking place
in the class of semiconducting materials.
220
CHAPTER 10
jlight jp/n j
current p/n
source junction
Figure 10.32: Equivalent cicuit diagram for a photovoltaic (PV) cell. The current source
respresents the light-induced current. The resistor represents the load for the PV-cell.
where is the current in the load, that is: the output current of the photo-
voltaic (PV) cell. This IV-behavior is shown in Fig. 10.33
¡ The open
¢ circuit voltage is found from eq 10.30 with = 0, giving 0 =
− 1 − and hence
µ ¶
= log +1 (10.31)
while the current flowing at short-circuit is = − (from Eq. 10.30 with
= 0). The maximum efficiency of a PV cell is limited by a number of factors:
Hence the total efficiency is about ' 047 × 065 × 09 × 096 ' 26%.
We now discuss a few of these point in more detail.
221
CHAPTER 10
-3
2.0x10
no illumination
illumination
-3
1.0x10
Current (A)
0.0
-3
-1.0x10
-3
-2.0x10
-1.0 -0.5 0.0 0.5 1.0
Voltage (V)
Fill factor
The power ∗ = is an overestimate of the power that can be delivered by the
PV cells, since one cannot have and at the same conditions. The ratio between
the maximum power delivered by the cell and ∗ is called the ’fill factor’ . The
maximum power obtainable from the IV-curves discussed can be calculated as follows.
If the voltage across the cell is then from eq. 10.30 its power is given by
£ ¡ ¢¤
= − = − − 1 (10.32)
the maximum power can be found from
© £ ¡ ¢¤ª
= − − 1 =0 (10.33)
which yields
¡ ¡ ¢¢
− − 1 − = 0 (10.34)
or defining
:= (10.35)
222
CHAPTER 10
which, using =
=
can be written as
2 ( )3 2
() = (10.40)
3 2 − 1
with =
we thus find for the maximum efficiency of a solar cell
R∞ R ∞ 2
()
( ) = R ∞ = R ∞ 3−1 (10.41)
0
() 0 −1
using some mathematics no to be discussed here, one can derive that
R ∞ 2 P∞ − ³ 3 22 2 ´
=1
+ 2 + 2
( ) = R ∞ 3−1 = 4 (10.42)
0 −1
15
223
CHAPTER 10
x
0.4
0.3
0.2
0.1
0 1 2 3 4 5
x
x
Figure 10.34: Efficiency () as a function of =
132 3 eV. The efficiency can thus never be higher than 45% since that is the fraction of
sunlight that can be converted to energy of excited electrons.
There is a way, however, to increase the amount of sunlight captured. One
can use a stack of solar cells that each capture part of the incident radiation, see Fig.
10.35.
Efficiencies of solar cells obtained the laboratory are shown in Fig. 10.36.
224
CHAPTER 10
Figure 10.35: Example of a multi-junction PV cell. The top layer captures radiation above
1.86 eV, the middle captures of the remainder the radiation above 1.4 eV and the bottom cell
captures of the remainder the radiation above 0.65 eV.
225
Chapter 11
Final Remarks
226
Chapter 12
Appendices
227
CHAPTER 12
Figure 12.1: Prediction in 1956 by King Hubbert of the U.S.A.oil production (blue curve)
and the actual oil production (black dots).
= =
−+2+ (−+) 2 + cosh ( − )
Hence the rate of ‘harvesting’ is
= (12.3)
2 + cosh ( − )
228
CHAPTER 12
0.3
0.25
production
0.2
0.15
0.1
0.05
0
0 2 4 6 8 10
x 12 14 16 18 20
time
Figure 12.2: Plot of production rate versus time according to the Verhulst equation.
By analogy to the above, the oil industry can invest a certain percentage of its
current value to new production facilities. That is the growth rate of its production
facilities is given by
=
However, the growth is in fact limited by the amount of oil to be extracted, such that
there is no growth if there is no oil left. This leads to
1
= (1 − ) (12.4)
which is indeed eq. 12.1. Hence the oil production rate (rate of ‘harvesting’)
1
is given by eq. 12.3, a plot of which (actually 2+cosh(−10) ) is given in Fig, 12.2. Note
the symmetric curve and the clear peak.
We note that the area under this curve corresponds to the total harvested
amount, which under the above assumptions equals the total available reserves.
where is the rate of ‘harvesting’, normally called the production (i.e. production
volume per unit of time). From eq. 12.5, we see that
= (1 − )
which means that a linear scaled plot of () versus yields a decreasing straight
line, which hits zero at complete depletion, = 1 In this context one usually uses the
non-rescaled equation µ ¶
= 1−
where is called the ‘ultimately recoverable resource’, is the production and is the
cumulative production.
230
CHAPTER 12
231
CHAPTER 12
232
CHAPTER 12
number density
Stephan Boltzman constant
torque
time interval
potential (energy)
angle
Ψ wave function
angular frequency/angular velocity
Ω angular velocity
233