Light and Matter

International Science Camp 2022
Light and Matter
8.-12. August 2022
Dr. Erhard Irmer
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Table of content
1. Organisational ..................................................................................................................... 1
1.1 Course plan .................................................................................................................. 1
1.1.1 Overview............................................................................................................... 1
1.1.2 Timetable.............................................................................................................. 3
1.2 The online platform Stud.IP ......................................................................................... 5
2. Basics of colour.................................................................................................................... 6
2.1 What is light? ............................................................................................................... 7
2.2 Why do things appear coloured? ................................................................................ 9
3. Organic dyes ...................................................................................................................... 13
3.1 Theory: Organic dyes ................................................................................................. 13
3.1.1 Structural foundations of colourfulness ............................................................ 13
3.1.2 Azo dyes.............................................................................................................. 15
3.1.3 Triphenylmethane dyes...................................................................................... 18
3.1.4 Carbonyl dyes and vat dyeing ............................................................................ 20
3.1.5 The Spectrophotometer ..................................................................................... 21
3.2 Experiments on organic dyes..................................................................................... 24
3.2.1 Synthesis of methyl orange ................................................................................ 25
3.2.2 Synthesis of orange II ......................................................................................... 27
3.2.3 Photometric analysis of the azo dye .................................................................. 29
3.2.4 Dyeing with methyl orange or orange II ............................................................ 32
3.2.5 Preparation and properties of thymolphthalein ................................................ 33
3.2.6 Photometric analysis of thymolphthalein .......................................................... 35
3.2.7 Synthesis of and dyeing with indigo ................................................................... 38
4. Inorganic dyes ................................................................................................................... 40
4.1 Theory: Inorganic dyes .............................................................................................. 40
4.1.1 The characteristics of coordination compounds ................................................ 40
4.1.2 The three-dimensional structure of complexes ................................................. 41
4.1.3 Colour and electron configuration of complex compounds .............................. 42
4.1.4 Magnetic properties of coordination compounds ............................................. 47
4.1.5 Advanced: high-spin complexes and low-spin complexes ................................. 48
4.1.6 Advanced: The spectrochemical series .............................................................. 51
4.2 Experiments on inorganic dyes.................................................................................. 52
4.2.1 The characteristics of coordination compounds ................................................ 53
4.2.2 Photometric determination of the complex composition ................................. 55
III
4.2.3 Magnetic properties of coordination compounds ............................................. 59
4.2.4 Stain dyeing with alizarin ................................................................................... 61
4.2.5 Photochemical reaction of the Fe(III) oxalate system ....................................... 63
4.2.6 Template experiment (Blue print)...................................................................... 65
4.2.7 The colours of copper and iron complexes ....................................................... 66
4.2.7.1 The colour of copper complexes................................................................. 66
4.2.7.2 The colour of iron complexes ..................................................................... 67
5. Photocatalysis ................................................................................................................... 69
5.1 Theory: Photocatalysis............................................................................................... 70
5.1.1 Catalysis .............................................................................................................. 70
5.1.2 Photocatalysis..................................................................................................... 71
5.1.3 The Photo Blue Bottle system ............................................................................ 72
5.1.4 Photocatalytically active nanoparticles.............................................................. 74
5.1.5 The electronic band structure model ................................................................. 75
5.1.6 Organic solar cells............................................................................................... 76
5.1.7 Elementary steps in the conversion of light energy into electrical energy ....... 77
5.2 Experiments on photocatalysis.................................................................................. 79
5.2.1 Catalysis: The decomposition of hydrogen peroxide ......................................... 80
5.2.2 The Photo Blue Bottle – a photocatalytical system ........................................... 82
5.2.2.1 The Photo Blue Bottle experiment ............................................................. 82
5.2.2.2 Energy participation in the Photo-Blue-Bottle experiment ........................ 84
5.2.2.3 The photocatalytically driven concentration element ............................... 86
5.2.3 Photocatalysis using zinc oxide nanoparticles ................................................... 88
5.2.3.1 Preparation of fluorescent zinc oxide nanoparticles .................................. 88
5.2.3.2 Photocatalysis with zinc oxide nanoparticles ............................................. 90
5.2.4 The organic photovoltaic cell (plastic solar cell) ................................................ 91
5.2.5 Construction of an OPV (organic photovoltaic cell) ........................................... 91
5.2.5.1 Preparing the FTO glass (anode) ................................................................. 92
5.2.5.2 Application of the hole extraction layer (PEDOT/PSS)................................ 92
5.2.5.3 Spincoating of the absorber layer (P3HT/PCBM) ....................................... 93
5.2.5.4 Preparation of the Galinstan Electrode (Cathode) ..................................... 94
5.2.5.5 Assembling the organic solar cell................................................................ 94
5.2.6 Measurements on the OPV (organic photovoltaic cell) ..................................... 95
5.2.6.1 Measurement of the open circuit voltage VOC .......................................... 95
5.2.6.2 Measurement of the short-circuit current ISC............................................ 95
6. Luminescence .................................................................................................................... 97
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6.1 Theory: Luminescence ............................................................................................... 98
6.1.1 Fluorescence....................................................................................................... 98
6.1.2 Phosphorescence ............................................................................................... 99
6.1.3 Chemiluminescence ......................................................................................... 100
6.1.4 The electronic band model .............................................................................. 101
6.1.5 Organic light emitting diodes (OLED) ............................................................... 102
6.1.5.1 Structure of an OLED................................................................................. 102
6.1.5.2 Elementary steps of electroluminescence ................................................ 103
6.1.6 Fluorescence and decomposition of B vitamins .............................................. 105
6.2 Experiments on luminescence ................................................................................. 108
6.2.1 Cold glow under UV light (fluorescence).......................................................... 109
6.2.1.1 Fluorescence of quinine ............................................................................ 109
6.2.1.2 The "bleeding" chestnut branch ............................................................... 109
6.2.1.3 Preparation and fluorescence of a chlorophyll solution .......................... 110
6.2.2 Fluorescence of fluoresceine ........................................................................... 111
6.2.3 Phosphorescence ............................................................................................. 113
6.2.4 Chemiluminescence of luminol ........................................................................ 114
6.2.5 Construction of an organic light emitting diode (OLED) .................................. 115
6.2.5.1 Preparing the FTO glass (anode) ............................................................... 116
6.2.5.2 Application of the hole injection layer (PEDOT/PSS) ................................ 116
6.2.5.3 Spincoating of Superyellow® (emitter) ..................................................... 117
6.2.5.4 Preparation of the Galinstan electrode (Cathode) ................................... 118
6.2.5.5 Assembling the organic light emitting diode ............................................ 118
6.2.6 Luminous custard powder – experiments with B vitamins .............................. 120
6.2.6.1 Detection of vitamin B1 via fluorescence.................................................. 120
6.2.6.2 Detection of vitamin B2 via fluorescence.................................................. 121
6.2.6.3 Separation of food colourants in custard powder .................................... 122
6.2.6.4 Redox reaction of riboflavin...................................................................... 124
6.2.6.5 Complexation of riboflavin........................................................................ 125
6.2.6.6 Photodegradation of riboflavin................................................................. 126
7. Molecular switches ......................................................................................................... 129
7.1 Theory: Molecular switches..................................................................................... 130
7.1.1 Introduction: Molecular switches .................................................................... 130
7.1.2 The molecular switch system spiropyran / merocyanine ................................ 131
7.1.3 The chemistry of the Prussian blue system ..................................................... 132
7.2 Experiments on molecular switches ........................................................................ 135
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7.2.1 The molecular switch system spiropyran und merocyanine ........................... 136
7.2.2 Construction of an electrochromic mirror ....................................................... 139
7.2.2.1 Coating an FTO glass with Prussian blue................................................... 139
7.2.2.2 Switching the colour of the coated glass .................................................. 140
7.2.2.3 Production of an FTO glass with silver mirror .......................................... 142
7.2.2.4 Production of an electrochromic mirror ................................................... 143
7.2.2.5 An electrically dimmable mirror ............................................................... 144
7.2.3 Thermoluminescence ....................................................................................... 145
7.2.3.1 Synthesis of a trispyridine copper(I)-iodide complex and examination of its
luminescence at low temperatures ........................................................................... 145
7.2.3.2 Synthesis of bispyridine copper(I)-iodide and investigaton of luminescent
properties ................................................................................................................... 146
7.2.4 Titanium dioxide coatings by anodic oxidation................................................ 147
7.2.4.1 Preparation of nano titanium dioxide coatings by anodic oxidation ....... 147
7.2.4.2 Production of two-colour appearing motifs by anodic oxidation ............ 148
7.2.5 A switchable iron(II) complex ........................................................................... 149
7.2.5.1 Preparation of the switchable iron(II) complex [Fe(H2B(pz)2)2(4-Me-Phen)] .
................................................................................................................... 149
7.2.5.2 Switching the colour of [Fe(H2B(pz)2)2(4-Me-Phen)] ................................ 150
7.2.5.3 Switching the magnetic properties of [Fe(H2B(pz)2)2(4-Me-Phen)].......... 151
8. Tasks for the excursions to the departments in the faculty of Chemistry...................... 153
9. Literature ......................................................................................................................... 155
10. Space for notes and photos ............................................................................................ 157
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1. Organisational
1.1 Course plan
1.1.1 Overview
This course deals with the topics of light and colour, or more generally with the interaction of
light and matter. At first glance, this topic might seem to be more in the field of physics, but in
fact there are numerous links to chemistry, be it the question of how colourfulness can be ex-
plained at the molecular level or the major role of the interaction of light and chemical com-
pounds for current research. One example is the 2014 Nobel Prize in Chemistry for the Göttingen
researcher Stefan Hell, a physicist, and the STED microscopy he developed.
The course "Light and Matter" has a modular structure and attempts to give a rudimentary idea
of the process of scientific work. First, we will get to know the phenomenon of light and colour
in plenary and you will carry out experiments on organic and inorganic dyes on Monday and
Tuesday. This corresponds to the study phase in the scientific process with attendance of lec-
tures, seminars and practical courses.
On the two following days, you will deal with one of the specialisation topics (photocatalysis,
luminescence or molecular switches) and explore these experimentally. On the fourth day, you
will also visit a research group at the university to gain an insight into the laboratory work there.
This phase of the course tries to reflect a little bit the work in the first scientific research (Master's
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thesis or doctorate): Here, specialisation takes place, and you work together with other research-
ers in a detailed area.
The highlight of the research process is when the results of the research are presented to other
researchers at a scientific conference or congress. Therefore, on the last day of the course, a
"science symposium" will take place, in which you will present your specialisation topic to the
other course participants in the form of a Powerpoint presentation, so that all course participants
can gain an insight into each of the three specialisation areas. You are free to choose the focus
of your presentation. The presentation should not exceed a period of 5 to 10 minutes.
To be able to create a lively presentation, during the course you should take photos of your ex-
perimental results and observations so that you can use them in your presentation.
The experiments of this script are assigned to the four topics (Basics including organic and inor-
ganic dyes, photocatalysis, luminescence, molecular switches). Some of the experiments are as-
signed to several areas, which you can recognise by the circles highlighted in the logo (top right).
At the beginning of each chapter, you will find the theoretical background to the experiments.
This is followed by the instructions for the experiments.
The original course script in German was written by Konrad Spickermann as part of his master’s
thesis, modified by Dr. Erhard Irmer and Vivian Keune (as part of his bachelor's thesis), translated
into English and slightly modified for this International Science Camp course.
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1.1.2 Timetable
Monday, 8.8.2022
9:00 - 10:30 Welcome and introduction, theory: Organic dyes
 Welcome and safety briefing, organisational matters
 Introduction to the phenomenon of light and colour
 Introduction to the structural requirements for colourfulness in
organic compounds
10:30 – 13:00 Experiments on organic dyes
 Preparation of an azo dye (methyl orange or orange II)
 Dyeing with methyl orange or orange II
14:00 - 17:00 Experiments on organic dyes (cont.)
 Preparation, indicator properties of thymolphthalein
 Preparation of and dyeing with indigo
 Photometric investigation of azo dyes or thymolphthalein
 Evaluation of the experiments
Tuesday, 9.8.2022
9:00 - 10:30 Theory: Inorganic dyes
 Introduction to the structural requirements for colourfulness
in coordination compounds
 Magnetic properties of coordination compounds
11:00 - 13:00 Experiments on inorganic dyes
 Introduction to coordination compounds
 Photometric determination of the complex composition
 Magnetic properties of coordination compounds
 Stain dyeing with alizarin
 Photochemical reaction of the Fe(III) oxalate system
 Template experiment
14:00 - 17:00 Experiments on inorganic dyes (cont.)
 Continuation of the experiments
 Evaluation of the experiments
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Wednesday,
10.8.2022
9:00 - 10:30 Theory: Topics for specialisation
 Working out the theory on one of the main topics
11:00 - 13:00 Experiments on the specialisation topics
 - Photocatalysis or
 - Luminescence or
 - Molecular switches
14:00 - 18:00 Experiments on the specialisation topics (cont.)
Thursday, 11.8.2022
9:00 - 12:00 Visits to research groups at the Faculty of Chemistry
 Dep. Jun.-Prof‘ Dr. Nadja A. Simeth (Institute of Organic and
Biomolecular Chemistry):
Molecular Labeling Chemistry (Luminescence)
 Dep. Prof. Dr. Dietmar Stalke (Daniel Lüert):
Synthesis of single molecule magnets
(Molecular switches)
 Dep. Prof. Dr. Alec Wodtke (Dr. Oliver Bünermann, Kerstin
Krüger)
Laser Applications in Basic Research: Surface Science
(Photocatalysis)
13:00 - 14:00  Evaluation of the visits to research groups
14:00 - 16:00 Experiments on the specialisation topics (cont.)
16:00 - 17:00 Preparing the „Science Symposium“
Friday
12.8.2022
9:00 - 11:30 Preparing the „Science Symposium“
12:30 - 14:00 Science Symposium „How do chemists use the interaction of light
and matter?“ (plenary)
14:00 – 17:00 Preparing presentation for closing symposium
17:00 - 18:00 Closing session
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1.2 The online platform Stud.IP
In the course, we use the online platform Stud.IP of the Georg-August-University of Göttingen to
provide and exchange digital materials. Stud.IP is the central component of the e-learning infra-
structure at Göttingen University for teachers and students. Stud.IP provides access to content
and numerous supporting tools for teaching and learning. Stud.IP is roughly equivalent to learn-
ing platforms such as Moodle, IServ, HPI-Bildungscloud etc.
When you sign the list of participants, you will receive a Stud.IP user ID and the corresponding
password. Please log in to Stud.IP via "studip.uni-goettingen.de". Confirm that you have read and
understood the terms of use.
Select the practical course "ISC 2022 Light and Matter" via the "Courses" button.
You can share files with other participants via the "Files" tab.
Access to Stud.IP is scheduled until 31.09.2022. Remember to back up your data before this time
expires.
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2. Basics of colour
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2.1 What is light?
Light is electromagnetic radiation visible to the human eye. Electromagnetic radiation consists of
photons, in simple terms "light particles" or "light quanta". However, photons (like electrons)
have the properties of both particles and waves. This is called wave-particle duality. Historically,
when describing the properties of particles, we speak of photons, when describing the properties
of waves, we speak of light waves.
The wave character of photons can be seen, for example, in diffraction at the double slit, where
the interference of "light waves" can be observed. Albert Einstein demonstrated the particle
character in 1905 with his interpretation of the photoelectric effect. He was awarded the Nobel
Prize in Physics for this in 1921.
Figure 1 Waves with different wavelengths (and frequencies)
Like all waves, light waves (or photons) also have a wavelength λ, a frequency ν and a propagation
speed (Figure 1). The propagation speed is the same for all types of electromagnetic radiation; it
corresponds to the speed of light c. Mathematically, the following relationship results for the
description of electromagnetic waves:
c
c=𝜆∙𝜈  𝜆=𝜈
The speed of light is known to be a natural constant. It follows that light with a long wavelength
has a low frequency. Logically, the higher the frequency of light, the shorter its wavelength.
The energy of a photon can also be easily calculated. The following relationship applies:
𝐸 =h∙𝜈
Here E is the energy, ν is already known to us as the frequency and h is another natural constant,
the so-called Planck's quantum of action. In 1918, Max Planck was awarded the Nobel Prize in
Physics for his theory of quantisation (and thus, in a broader sense, for the discovery of h).
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The energy of a photon can also be calculated directly from the wavelength by substituting the
formula ν=c/λ into the above formula for calculating the energy. It follows:
ℎ∙c
𝐸 =ℎ∙𝜈 =
𝜆
Since c and h are constants, they can also be directly multiplied by each other. From this follows:
ℎ∙𝑐 1,986 ∙ 10−25 J ∙ m

𝐸= =
𝜆 𝜆
The shorter the wavelength of a photon, the greater its energy.
Particularly high-energy electromagnetic radiation therefore has very short wavelengths, and
particularly low-energy radiation therefore has long wavelengths.
The so-called electromagnetic spectrum ranges from particularly high-energy gamma radiation
(wavelengths in the femtometer (10-15 m) or picometer (10-12 m) range) to long waves with
wavelengths in the meter to kilometer range.
Figure 2 The electromagnetic spectrum with the visible spectrum highlighted.

source: EM_spectrum.svg: User:Zedh derivative work: Matt (talk) - EM_spectrum.svg CC BY-SA 3.0 (Verfügbar un-
ter: https://commons.wikimedia.org/w/index.php?search=elektromagnetisches+spektrum&title=Spe-
cial%3ASearch&go=Go&ns0=1&ns6=1&ns12=1&ns14=1&ns100=1&ns106=1#/media/File:EM-Spektrum.svg)
Visible light makes up only a small part of the electromagnetic spectrum, more precisely the
wavelength range from about 400 nm to about 700 nm. In the shorter wavelength range, the
energy-rich ultraviolet radiation borders on the visible range, and in the longer wavelength range,
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infrared radiation (thermal radiation). White light is the combination of photons of all wave-
lengths of visible light, which is why it is sometimes called rainbow light (as it contains all the
colours of the rainbow) (Figure 2).
2.2 Why do things appear coloured?

Coloured materials absorb a part of the visible white light and appear in the complementary col-
our of the absorbed light, as all other wavelengths are reflected or pass through the object. This
is called subtractive colour mixing because a certain part of the visible light is absorbed from the
white light and thus "subtracted". The remaining colours "mix" to form the visible complemen-
tary colour. A well-known example from everyday life is the plant pigment chlorophyll. Chloro-
phyll absorbs red and blue light and therefore appears green. Table 1 lists wavelength ranges
with the associated colour and the complementary colour resulting from absorption.
Table 1: Absorbed light with wavelength and colour as well as the resulting complementary colour. Taken from
course script "Dyestuffs and Dyeing" of the XLAB Göttingen Experimental Laboratory for Young People.
wavelength λ of absorbed light

colour of light Complementary colour
in nm
380 – 435 purple yellow green
435 – 480 blue yellow
480 – 490 greenish blue orange
490 – 500 bluish green red
500 – 560 green purple
560 – 580 yellow green violet
580 – 595 yellow blue
595 – 650 orange greenish blue
650 - 780 red bluish green
But why do some substances absorb light of a very specific wavelength and not light of other
wavelengths, and why do other substances, such as table salt or sugar, not absorb any (visible)
light at all?
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The explanation can be found at the molecular level. The simplest way to illustrate this is to take
organic dyes as an example. When a dye molecule absorbs light, it absorbs the energy of the
light, because energy cannot be lost or destroyed. This energy is absorbed by electrons of the
dye molecules. In the process, electrons are raised from the highest occupied energy level (HBE,
from german: Höchste besetzte Energiestufe) to the lowest unoccupied energy level (NUE, from
german: Niedrigste unbesetzte Energiestufe). Put simply, an electron can be lifted from the va-
lence shell to a higher unoccupied shell. These two energy levels are separated by a defined
amount of energy. Figure 3 shows an example energy diagram to illustrate this.
Figure 3 Simplified energy diagram with two valence electrons. The highest occupied energy level (HOE) and the
lowest unoccupied ener-gy level (LUE) are shown. These two are separated from each other by a defined energy
amount ΔE.
Thus, a very specific amount of energy is needed to lift an electron from the HBE to the NUE. For
coloured substances, this energy difference corresponds to the energy of a photon in the wave-
length range of visible light. If a photon, whose energy corresponds to the energy difference be-
tween the HBE and the NUE of a dye molecule, hits such a dye molecule, it is absorbed. In the
process, the energy is transferred to an electron as described above.
Due to the "swallowing" of the light particle, the molecule has more energy and a different elec-
tron configuration than before. This is called an electronically excited state (compared to the
unexcited ground state) or simply an excited state. The excited state is usually indicated with an
asterisk, for example for the excitation of particle A:
h∙𝜈
A → A∗
This excited state A* is not permanently stable and the molecule must release the excess energy
again. This is called deactivation of the excited state. Usually, this energy is converted into rota-
tions and oscillations of the molecule and released in collisions with other molecules (in which
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energy is transferred). This is referred to as non-radiative deactivation. Figure 4 schematically
shows the excitation of a dye molecule by a photon with sufficient energy and the deactivation
of the excited state and thus the return to the ground state.
Figure 4 Electronic excitation by absorption of a photon and return to the electronic ground state.
If an atom does not occur in isolation, there is not a clearly defined energy level, but the energy
levels are broadened by atomic vibrations. This means that several electron transitions with
slightly different energy levels are possible. You do not get a line spectrum, as for example in the
gas phase, but a signal that is broader the more vibrational modes exist (Figure 5).
Figure 5 The excitation of an electron leads to a line spectrum, in the case of a molecule you get a broader peak due
to the different modes of vibration.
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In summary, the highest occupied energy level and the lowest unoccupied energy level in col-
oured substances have an energy difference that corresponds to the energy of light in the visible
range. Substances for which this energy difference is greater appear colourless because the visi-
ble light does not have sufficient energy to lift an electron from the HBE into the NUE.
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3. Organic dyes
3.1 Theory: Organic dyes
3.1.1 Structural foundations of colourfulness
Figure 6 shows the structural formulae of some organic dyes and the objects and creatures in
which they occur or are used.
Figure 6 Some organic dye molecules and living beings or objects in which colourfulness occurs. Chemistry 2000+
(Tausch & Wachtendonk, 2007).
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All dye molecules shown in Figure 6 have extended conjugated double bond systems, i.e., se-
quences of carbon-carbon double bonds (or carbon-oxygen double bonds or carbon-nitrogen
double bonds), alternating with carbon-carbon single bonds. The more extensive such a conju-
gated double bond system is, the smaller the difference between the highest occupied energy
level and the lowest unoccupied energy level.
Table 2 clearly shows, using the example of polyenes, how the absorption wavelength increases
with increasing length of the conjugated double bond system.
Table 2: Absorption wavelength of electromagnetic radiation of polyenes and cyanines depending on the number of
conjugated double bonds. Modified according to Chemie 2000+ (Tausch & Wachtendonk, 2007).
Wavelength of absorbed light λ in nm
Number of
double bonds n
2 225 420 (violet)
3 257 519 (green)
4 300 620 (red)
6 344 848
8 386
10 430 (violet)
12 460 (blue)
14 485 (blue green)
Table 2 shows not only polyenes but also cyanines, which absorb in the visible wavelength range
even with significantly shorter double bond systems. Two conjugated double bonds are already
sufficient. This is explained by the +M effect of the amino group (donor group) and the -M effect
of the quaternary ammonium group (acceptor group). This leads to the fact that the electrons
are almost completely delocalised over the length of the molecule compared to the polyene and
the highest occupied and the lowest unoccupied energy level are consequently very close to each
other (Tausch & Wachtendonk, 2007) (Figure 7).
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one conjugated two conjugated four conjugated many conjugated
double bond double bonds double bonds double bonds
Figure 7 Comparison of conjugated double bond systems in the energy level model (Teacher's book organic photo
electronics 2020)
In dye molecules, such donor groups (with +M effect) are also called auxochromic groups,
acceptor groups (with -M effect) are called antiauxochromic groups (Tausch & Wachtendonk,
2007). Auxochromic groups increase the electron density in the double bond system and thus
reduce the distance between HBE and NUE. They thus shift the absorbed wavelength into the
longer wavelength range. This is also called a bathochromic shift. Antiauxochromic groups at the
other end of the double bond system further enhance the effect of auxochromic groups through
their ability to act as electron acceptors.
In general, the groups and structural elements that give rise to the chromaticity of compounds
are called chromophores or chromophoric groups (Acker & Bartels, 2008).
3.1.2 Azo dyes

Organic dyes can be divided into many different dye classes on the basis of their chemical struc-
ture. The Encyclopaedia of Chemistry, for example, lists at least eleven different dye classes or
groups (Acker & Bartels, 2008). Examples of dye classes are the carbonyl dyes, which include the
well-known indigo, methine dyes (e.g., β-carotene), sulphur dyes and many others. A particularly
important class of dyes is the so-called azo dyes. You will also synthesise and examine an azo dye
during the first day of the experiment.
The azo group -N=N- (also known as azo bridge) gives the azo dyes their name. Azo dyes contain
one or more such azo groups, which is/are involved in the conjugated double bond system of the
dye.
The synthesis of azo dyes takes place in two steps, diazotisation, and azo coupling. This synthesis
is illustrated below using the example of the preparation of methyl orange from the reactants
sulphanilic acid and N,N-dimethylaniline.
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sulphanilic acid N,N-dimethylaniline
First, the nitrosyl cation (NO+) necessary for the reaction is generated.
Then follows the first actual step, the diazotisation of the sulphanilic acid to the diazonium ion.
The diazonium ion produced is not stable and decays at temperatures above 5°C, which is why it
must be cooled during the synthesis.
This is followed by azo coupling. The diazonium ion reacts with N,N-dimethylaniline. The azo
group that gives it its name is formed.
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Finally, the solution is neutralised with sodium hydroxide solution and the following compound
is present as a product:
The description of the synthesis of azo dyes is based on the description in the course script "Dyes and Dyeing" of the
XLAB Göttingen Experimental Laboratory for Young People.
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3.1.3 Triphenylmethane dyes
The best-known representative of the triphenylmethane dye class is probably phenolphthalein.
The name of this dye class is explained by the structural elements of the compound (Figure 8).
Figure 8 In the formula of phenolphthalein, there are three phenyl groups (benzene rings, blue) and a four-bonded-
carbon atom (red), i.e., in a similar bond state as in methane.
You probably know phenolphthalein from school as an acid/base indicator that changes colour
from colourless in acidic and neutral to reddish violet (pink) in alkaline. In the acid/neutral form
(left), the delocalised double bond system is interrupted by the four-bond carbon atom in the
middle (Figure 9).
colourless red violet

0 < pH < 8 8 < pH < 12
Figure 9 Formula representation of phenolphthalein in the acidic and neutral range (left) and in the alkaline range
(right).
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Thymolphthalein and fluorescein are also indicator dyes. In their case, the delocalised double
bond system can be extended in the same way by splitting off the H+ ions at the hydroxyl groups
(Figure 10).
Figure 10 Formula representation of phenolphthalein in the acidic and neutral range (left) and in the alkaline range
(right).
The synthesis of thymolphthalein follows the reaction type of a Friedel-Crafts acylation, a con-
densation reaction (Figure 11).
Figure 11 Synthesis of thymolphthalein
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3.1.4 Carbonyl dyes and vat dyeing
In this section you will get to know indigo, a representative of the carbonyl dyes.
As you can see from the structural formula (Figure 12), the dye indigo is relatively poorly soluble
in water. This is not unproblematic for the dyeing process: A dye should be highly soluble in water
to dissolve well in the solvent water. This is the only way to ensure that the dye is evenly applied
to the fibre. In addition, most natural materials, such as cotton or wool, have rather polar groups
to which dyes with polar groups adhere better.
On the other hand, good water solubility also means that the dye easily detaches from the fibre
again during the washing process, the colour is not sufficiently washfast.
Figure 12 Formula of indigo. There are polar groups (red) in the molecule, but the relatively large non-polar parts of
the structure (blue) cause quite poor solubility in water.
The trick to getting around the problem of poor solubility in water is to convert the indigo mole-
cule into a water-soluble form with the help of the reducing agent sodium dithionite (Na2S2O4).
Unfortunately, however, the resulting leucoindigo also loses the intense blue colour of indigo.
Therefore, after the leucoindigo has been applied to the fibre, it must be oxidised back to the
original indigo. The oxygen contained in the air serves as the oxidising agent for this (Figure 13).
S2O42- ⇌ 2 SO2 + 2 e-
Figure 13 In a redox reaction, indigo (left) and its leuco form are in equilibrium with each other.
You will get to know another dyeing technique on the second day of the practical course, the
stain dyeing using the example of alizarin.
20
3.1.5 The Spectrophotometer
The following explanations on the functioning of the photometer have been taken from the course script "Dyes and
colouring" of the XLAB Göttingen experimental laboratory for young people and slightly modified.
The most common method for examining coloured substances is spectrometry. It is based on the
phenomenon that when a light beam passes through a dye solution, a decrease in light intensity
is observed because the dye particles absorb light quanta (photons) in a characteristic way. The
extent of the light attenuation depends on the type and number of dye particles that are in the
light path (beam path). By measuring the light intensity attenuation, one can therefore draw
conclusions about the concentration of the dye in the solution.
A spectrophotometer is used for the measurement, the set-up of which is shown in Figure 14. A
filter is used to filter out a small wavelength range of light from the broad spectrum of an incan-
descent lamp, which is then sent through the sample with an intensity of I0. The coloured sample
reduces the light intensity to the value I. With the help of a detector, this light intensity can be
displayed on a measuring device.
Figure 14 Schematic design of a photometer.
The ratio of transmitted light intensity I to irradiated light intensity I0 indicates the transmittance
of the sample, which is also called transmission T.
𝐼
𝑇=
𝐼0
21
In most cases, however, spectrophotometers provide not only the transmission, but also its log-
arithmic quantity, the extinction E. The relationship between transmission ("transmittance") and
extinction ("absorption") is E = -lg T and can be illustrated by the following sketch (Figure 15).
Figure 15 The relationship between extinction and transmission and to the dye concentration.
There is a simple proportionality relationship between the extinction E and the concentration c
of the dissolved dye, expressed by the so-called LAMBERT-BEER law:
𝐸 = ε∙𝑐∙𝑑
E is the extinction (E = -lg T), ε is the so-called molar extinction coefficient (this is characteristic
for every type of dye), c is the concentration of the dye (do not confuse with the speed of light!)
and d is the layer thickness of the sample in the cuvette (here 1 cm).
A high dye concentration therefore causes a high extinction, a lot of light is "swallowed" by the
dye solution. The lower the dye concentration, the lower the measured absorbance.
With a layer thickness of the sample of d = 1 cm, one therefore only must calculate the concen-
tration c in mol/L. However, it is often easier and more accurate to measure a series of dye solu-
tions of known concentrations and thus create a calibration line. Then you only must read the
obtained absorbances of the unknown concentration from the calibration line by interpolation.
The concentration determination should take place at the wavelength at which the dye solution
absorbs the light most strongly, i.e., the wavelength at which the dye has its absorption maxi-
mum. To determine this maximum, one must determine the absorbance at different wavelength
ranges. For example, the absorption spectrum of a dye shown here (Figure 16) has its absorption
maximum in the range of visible light at approx. 580 and at approx. 650 nm. This means that
yellow and orange light is absorbed. The complementary colour (the residual light impression)
perceived by our eye is blue to green blue. Especially in conjugated double bond systems, large
22
areas are involved in the absorption of light. The bands obtained in the spectrum are often broad
and overlap.
Figure 16: Absorption spectrum of a blue dye.
Devices that record an absorption spectrum in the visible wavelength range are called UV/VIS
spectrometers. Basically, they function very similarly to a spectrophotometer, they also measure
the transmission or the extinction. For this purpose, they record measured values in a wavelength
range in which they measure the absorbance of the sample in, for example, 1 nm steps. However,
this can also be done manually with a photometer, as in this course, by measuring the absorbance
for different wavelengths and plotting it graphically against the wavelength.
23
3.2 Experiments on organic dyes
In this block of experiments, you will learn about different classes of dyes and their properties.
First, the participants produce an azo dye. You will either make methyl orange or orange II. The
dye produced is used for the other experiments of the day.
Afterward you can syntesise a triphenylmethane dye and a carbonyl dye and examine them.
24
3.2.1 Synthesis of methyl orange
Equipment: Chemicals:
1 laboratory balance (central) sulphanilic acid (4-amino benzene sulphonic acid)
1 magnetic stirrer with stirring rod N,N-dimethyl aniline
1 glass dish Semi-conc. sulfuric acid H2SO4
1 round-bottomed flask 100 mL sodium nitrite solution(c(NaNO2) = 2.5 mol/L))
2 Erlenmeyer flasks 50 mL diluted sodium hydroxide solution (c(NaOH) = 2 mol/L)
1 Buechner funnel sodium chloride NaCl
1 vacuum flask with tubing ice
round filter paper pH indicator paper
1 thermometer
2 graduated pipets 5 mL with pipet aid
1 Pasteur pipet with rubber nipple
1 spatula
1 beaker 100 mL
Procedure:
Set up the experiment as shown in Figure 17.
The experiment must be carried out under the

fume cupboard!
Wear protective gloves!
Preparation of the diazonium salt:
In a 100 mL round bottom flask add:
- 1.6 g sulphanilic acid
- 3 mL semi-concentrated sulfuric acid
Figure 17 Experimental setup for the synthesis of methyl

Under constant cooling and stirring (the tem- orange.
perature must not rise above 5 °C and must

therefore be controlled constantly!) add 4 mL sodium nitrite solution. (Pre-cool the solution first
and then only add in small portions!)
25
Azo coupling:
After further cooling, 1.3 mL of N, N-dimethylaniline is added.
When the reaction has subsided, the mixture is neutralised with diluted sodium hydroxide solu-
tion. The neutralisation can be recognised by a colour change from cherry red to orange. The dye
is isolated by filtration in a Büchner funnel.
Task: Test the colour of a very diluted methyl orange solution in alkaline and acidic solution.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Complete the indicator equilibria below by adding the structural formula of orange II in
acidic solution and the structural formula of methyl orange in basic solution.
Disposal: The dye is needed for later experiments.
Experiment instructions modified according to the course script Dyes and Colouring of the XLAB Göttingen Experi-
mental Laboratory for Young People.
26
3.2.2 Synthesis of orange II
1 laboratory balance (central) sulphanilic acid (4-amino benzene sulphonic acid)
1 magnetic stirrer with stirring rod 2-naphtol
1 glass dish hydrochloric acid solution (c(HCl) = 4 mol/L)
1 round-bottomed flask 100 mL Sodium nitrite solution (c(NaNO2) = 2.5 mol/L)
2 Erlenmeyer flasks 50 mL dil. sodium hydroxide solution (c(NaOH) = 2 mol/L)
1 Buechner funnel sodium chloride NaCl
1 vacuum flask with tubing urea
round filter paper ice
1 thermometer pH indicator paper
2 graduated pipets 5 mL with pipet aid iodide-starch paper
1 graduated pipet 10 mL with pipet aid
1 spatula
1 beaker 100 mL
Procedure:
Set up the experiment as shown in Figure 18.
The experiment must be carried out under the

fume cupboard!
Wear protective gloves!
Preparation of the diazonium salt:
In a 100 mL round bottom flask, dissolve 1 g

sulphanilic acid in 5 mL sodium hydroxide so-
lution (c = 2 mol/L). Under constant stirring
and cooling in an ice bath (the temperature
Figure 18 Experimental set-up for the production of
must not rise above 5 °C and is therefore to be orange II.
controlled constantly!) 3 mL sodium nitrite so-
lution is added.
Then slowly add 10 mL of cooled hydrochloric acid solution (c = 4 mol/L), whereby the solution
must not warm up above 5 °C even now. Check with pH paper that the solution is acidic.
Use iodide-starch paper to check that there is no excess of nitrite ions (if the blue colour is strong,
add urea for such a long time that the iodide-starch paper turns only very faintly blue).
↳ a
spatulas
27
Dissolve the coupling component and coupling:
Suspend 0.5 g 2-naphthol in 25 mL sodium hydroxide solution (c = 2 mol/L). This mixture is slowly
stirred into the diazonium salt, whereby the pH value should become alkaline (check with pH
indicator paper; add some sodium hydroxide solution if necessary).
The dye is salted out with sodium chloride and separated by filtration in a Büchner funnel.
↳ 3
spatulas
Task: Test the colour of a very strongly diluted orange II solution in alkaline and in acidic solution.
Alkaline Orange / Acidic

:
:
Red
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Complete the indicator equilibrium formula below by adding the structural formula of or-
ange II in acidic solution and the structural formula of methyl orange in basic solution.
as
-
-
Tss - -
Ñ=N_ -
Disposal: The dye is needed for later experiments.
Experiment instructions modified according to course script Dyes and colouring of the XLAB Göttingen experimental
laboratory for young people.
28
Hce NaOH
2m01 / L
4 Me
3.2.3 Photometric analysis of the azo dye
in acidic and alkaline milieu
3 cuvettes dye from former experiment
2 Erlenmeyer flasks
1 cuvette holder
1 spectrophotometer
For the measurements with the spectrophotometers, each working group must bring the follow-
ing with them into the seminar room:
 1 small Erlenmeyer flask with methyl orange / orange II solution in acidic medium
 1 small Erlenmeyer flask with methyl orange / orange II solution in basic medium
The solutions must be strongly diluted!

=
Procedure:
Record an absorbance spectrum of the methyl orange or orange II solution in an acidic and alka-
line environment by measuring the absorbance of the solution in wavelengths steps of 10 nm.
Enter the values in a spreadsheet program (e.g., Excel) or alternatively use the following table of
values. Create a graph of the absorption curves using the spreadsheet program.
Determine the maximum absorption of the dye.
methyl orange acidic: .......................... nm
alkaline: .......................... nm
4851s
orange II acidic: .......................... nm
alkaline: .......................... nm
The experiment instructions have been modified according to the course script Dyes and Colouring of the XLAB Göt-
ting Experimental Laboratory for Young People.
29
Table of measured values
aline .
wavelength λ extinction E of dye
in nm acidic alkaline
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
30
580
590
600
610
620
630
640
650
660
670
680
690
700
710
720
730
✗ Alkaline .
31
II
orange
dead H
+
II
+
orange
Read It
3.2.4 Dyeing with methyl orange or orange II
1 beaker 250 mL
aqueous solution of methyl orange
1 magnetic stirrer with stirring rod
aqueous solution of orange II
1 spatula
1 glass rod
cotton cloth
wool
Procedure:
Place a woollen thread and a piece of cotton fabric in an aqueous solution of self-prepared or-
ange II or methyl orange and heat for about half an hour while stirring. Then allow the dye sam-
ples to dry.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
After 20 minutes, wash the staining samples under running water and dry them again.
Compare the two dyeing results:
The wool took darker shade of

a
orange
......................................................................................................................................................
than the cotton

......................................................................................................................................................
.
......................................................................................................................................................
Disposal: Disposal is via the sink.
tingen Experimental Laboratory for Young People.
32
3.2.5 Preparation and properties of thymolphthalein
3 test tubes with rack und stopper
thymol
1 test tube holder
1 spatula phthalic anhydride
2 Pasteur pipets with rubber nipple
1 funnel with filter paper zinc dichloride ZnCl2, anhydrous
1 gas burner ethanol
graduated pipet 5 mL with pipet aid
sodium hydroxide solution (w(NaOH) = 25 %)
diluted hydrochloric acid (c(HCl) = 2 mol/L)
Procedure:
Place 1 spatula tip of thymol, 2 spatula tips of phthalic anhydride and a few crystals of zinc chlo-
ride in a test tube. Heat this mixture carefully in the burner flame until a violet-red melt is formed
(not longer).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
After cooling, add approx. 5 mL of 50% ethanol and shake vigorously. Filter off the almost colour-
less solution.
Put a few drops of the thymolphthalein solution into a test tube with sodium hydroxide solution
(pH ≈ 14)
dark blue
It produces a
......................................................................................................................................................
solution
......................................................................................................................................................
.
......................................................................................................................................................
33
Put a few drops of the thymolphthalein solution into a test tube with hydrochloric acid (pH ≈ 0).
The solution remained colorless

......................................................................................................................................................
.
......................................................................................................................................................
......................................................................................................................................................
34
3.2.6 Photometric analysis of thymolphthalein
in acidic and alkaline milieu
3 cuvettes dye from previous experiment
2 Erlenmeyer flasks
1 cuvette holder
1 photometer
For the measurements with the spectrophotometers, each working group must bring the follow-
ing with them:
 1 small Erlenmeyer flask with thymolphthalein solution in acidic medium
 1 small Erlenmeyer flask with thymolphthalein solution in a basic medium.
The solutions must be strongly diluted!
Procedure:
Record an absorbance curve of the thymolphthalein solution in an acidic and alkaline environ-
ment by measuring the absorbance of the solution in wavelength-dependent steps of 10 nm.
Enter the values in a spreadsheet program (e.g., Excel) or alternatively use the following table of
values. Create a graph of the absorption curves using the spreadsheet program.
Determine the maximum absorption of the dye.
Thymolphthalein acidic: .......................... nm
alkaline: .......................... nm
35
Table of measured values
wavelength λ extinction E of dye
in nm acidic alkaline
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
36
580
590
600
610
620
630
640
650
660
670
680
690
700
710
720
730
37
3.2.7 Synthesis of and dyeing with indigo
2 beakers 400 mL
2-nitrobenzaldehyde
2 magnetic stirrers
2 glass rods sodium dithionite Na2S2O4
1 thermometer
1 spatula ethanol
2 pieces of cotton cloth acetone
1 Erlenmeyer flask 100 mL sodium hydroxide solution
1 graduated cylinder 50 mL
1 graduated pipet 10 mL with pipet aid (c(NaOH) = 2 mol/L)
paper towels
1 vacuum flask with Buechner funnel und Rundfilter
1 laboratory balance (central)
Procedure:
In a 100 mL conical flask, dissolve 1 g 2-nitrobenzaldehyde in 13 mL acetone. Then 8 mL demin.
water is added. Add sodium hydroxide solution (c = 2 mol/L) while shaking until a blue precipitate
is formed.
The resulting blue precipitate is slipped off with the Buechner funnel and washed out with etha-
nol. The quantity obtained is divided between two 400 mL beakers.
......................................................................................................................................................
......................................................................................................................................................
38
Dyeing with indigo
Experiment 1: Experiment 2:
Put 50 mL water into the beaker with your in- Put 4 mL sodium hydroxide solution (c = 2
digo and heat the mixture to 70 °C on the hot mol/L) into the beaker with your indigo. Add
plate. Stir the mixture thoroughly with the glass 0.5 g sodium dithionite and 50 mL water
rod. and heat the mixture to 70 °C on the hot
plate. Stir slowly with the glass rod.
After 10 minutes, add a piece of cotton to

After 10 minutes, add a piece of cotton to the
the liquid.
liquid.
Leave the cotton in the liquid for 15
The cotton remains in the liquid for 15 minutes
minutes, turning it slowly with the glass rod
and is occasionally turned slowly with the glass
from time to time.
rod.
Then dry the piece of cotton on paper.
Then dry the piece of cotton on paper.
After 20 minutes, both cotton pieces are rinsed under running

water, dried again and compared.
................................................................................ ............................................................................
................................................................................ ............................................................................
................................................................................ ............................................................................
................................................................................ ...........................................................................
39
4. Inorganic dyes
4.1 Theory: Inorganic dyes
4.1.1 The characteristics of coordination compounds
Not all coloured substances are organic compounds. The classic example of coloured inorganic
compounds are the so-called coordination compounds. They are also known as complex com-
pounds.
All complexes, i.e., the individual particles that form coloured complex compounds, consist of a
central atom - usually a metal cation - to which a certain number of other molecules or ions are
coordinately bound. These bonded molecules are called ligands. Ligands are usually anions or
molecules. Figure 19 shows the semi-structural formula of such a complex. In this one, a cop-
per(II) ion is the central atom to which four ammonia molecules are coordinately bound (via their
free electron pairs).
Figure 19 Exemplary semi-structural formula of a complex compound, here of the tetraammine copper(II) complex.
In coloured coordination compounds, the central atom is a metal ion or atom from the third to
twelfth group of the periodic table of the elements. These metals are also called transition met-
als, subgroup elements or d-block elements. For example, if sufficient hydrochloric acid solution
is added to a solution containing copper(II) ions, a water-soluble green complex compound forms
with the copper(II) ion as the central atom and coordinated chloride ions as ligands.
However, complex compounds do not only occur in solutions, but also in solid salt crystals. An
example is the light blue copper(II) sulphate pentahydrate. In fact, four water molecules are co-
ordinately bound to each copper(II) ion in this salt. For each tetraaqua copper(II) complex, an-
other water molecule and a sulphate ion also occur in the crystal. The name of the compound,
which correctly reflects these bonding ratios, is tetraaquacopper(II) sulphate monohydrate (Bee
et al., 2019). Aqua stands for the coordinately bound water molecules, the prefix "tetra" for the
number of these ligands (four). The anion and the additional water occurring in the crystal are
then listed. The corresponding formula notation of the compound is [Cu(H2O)4]SO4∙H2O.
40
The following rules for naming are modified after "Elemente Chemie Oberstufe" (Bee et al.,
2019):
Writing formulas of complex compounds follows some simple rules.
 In the formulas of complexes, the central atom is written first.
 Then the ligands are noted in alphabetical order.
 The complex is written in square brackets. Its charge is the sum of the charges of the
central atom and the ligands.
 In the formulae, the cation is named first, then the anion, regardless of which is the com-
plex.
 The names of the ligands are prefixed, with a prefix for the number of ligands if necessary.
When naming complexes, the ligands are named first with their preceding number, followed by
the central atom. Here, too, the cations are always named first, then the anions. For anionic
complexes there are own names for the central atom, e.g., ferrate.
Table 3: Examples of naming complex compounds.
[Cr(H2O)6]Cl3 Hexaaquachromium(III) chloride
[Co(NH3)6]Cl2 Hexaamminecobalt(II) chloride
[CuCl2(H2O)2] Diaquadichloridocopper(II)
K2[HgI4] Potassium tetraiodidomercurate(II)
4.1.2 The three-dimensional structure of complexes

As already mentioned, complex compounds always have a defined number of ligands coordi-
nated to the central particle. As the previous examples show, there are often four or six ligands,
but there are also complexes with, for example, two ligands. The number of ligands bound to a
central atom is called the coordination number. The spatial structure of a complex compound
depends on the number of ligands bound, their space requirements and the nature (radius, elec-
tron configuration, etc.) of the central atom (Bee et al., 2019).
As described above, the most common coordination numbers (and thus the number of co-ordi-
nated ligands) are four and six. The logical (and most common) arrangement of six ligands around
41
a central atom is the octahedral arrangement (Figure 20). By arranging the ligands at the corners
of an (imaginary) octahedron, the distance between the ligands is maximised with identical dis-
tances to the central atom.
Figure 20 Octahedron and exemplary structure of an octahedral complex with ligands in blue and the central atom
in red. Modified after "Octahedron." by Stannered CC BY-SA 3.0. Available at: https://commons.wiki-
media.org/wiki/File:Octahedron.svg#/media/File:Octahedron.svg.
In complexes with the coordination number four, the most common arrangement is the square-
planar geometry. An example is the tetrachloridocuprate(II) ion. The central atom and the ligands
lie in one plane (the complex is thus planar) and the ligands lie at the four corners of an (imagi-
nary) square. This structure is shown in Figure 21.
Figure 21 Square and exemplary structure of a square planar complex with ligands in blue and central atom in red.
4.1.3 Colour and electron configuration of complex compounds

Like organic dyes, coloured cooordination compounds absorb parts of the visible light of a certain
energy and appear in the complementary colour of the absorbed light. Analogous to organic dyes,
the energy of the absorbed photon lifts an electron from a lower energy level to a higher. When
looking at the structural formula of complex compounds, as for example in Figure 19, it is notice-
able that complexes, as inorganic compounds, do not have extended conjugated double bond
systems. In coordination compounds, there must therefore be another reason why the energy
difference between the energy levels is sufficiently small to overcome them with the energy of
visible light. The explanation can be found in a common model for bonding in complex com-
pounds - the ligand field theory; however, this first requires a look at the electron shell of the
transition metals.
42
To understand the ligand field theory, the model of electron shells or energy levels commonly
used in schools is not sufficient. Therefore, a very simplified orbital model is introduced here.
Just like photons, electrons have the properties of both waves and particles. This wave-particle
duality is considered in the orbital model. Compared to the electron shell model, this results in a
highly simplified way that the "shells" consist of orbitals in which the electrons are very likely to
reside. Each orbital offers "space" for two electrons. The first shell - analogous to the shell model
- holds only two electrons and thus consists of only one single orbital, the so-called 1s orbital. Its
shape is strongly reminiscent of a spherical shell (similar to the shell model).
The valence shell (the outermost shell) of the elements from the second period onwards contains
a total of eight electrons. Accordingly, this shell consists of four orbitals. In the example of an
element of the second period, the 1s orbital (and thus the first shell) is completely occupied. In
the second shell, there is also a spherical shell-shaped orbital, the 2s orbital. This is followed by
three p-orbitals, which resemble dumbbells in their shape. They are called 2px, 2py and 2pz after
their orientation in an imaginary coordinate system with x, y and z axes (the orbital lies more or
less exactly on the spatial axis that gives it its name, see Figure 22).
43
Figure 22 Shape of the orbitals up to and including the second period of the periodic system of the elements and
their energetic position relative to each other. Modified from "Overview of Orbitals, Chemistry." By Tim Kaluza CC
BY-SA 3.0. Available at: https://commons.wikimedia.org/wiki/File:Chemie_Orbitale.svg?uselang=de#/me-
dia/File:Chemie_Orbitale.svg.
This means that the energetically most favourable orbitals are filled first (i.e., the s orbital is filled
before the p orbitals). The energetically equivalent p orbitals are first filled with one electron
each. Only when each of the p-orbitals is single occupied they are filled with a second electron
(Hund’s rule; named after the Göttingen physicist Friedrich Hund 1896-1997). In the case of ele-
ments of the third period, the 3s orbital and the three 3p orbitals are filled one after the other,
and so on.
In the transition metals, which play a prominent role in coloured coordination compounds, the s
or p orbitals are not in the focus, but the d orbitals. These are filled up one after the other in the
transition metals. Therefore, these elements are sometimes also called d-block elements. Figure
23 shows the shape of the d-orbitals. Without ligands in the vicinity of the d-orbitals, these are
also energetically equivalent, so they are all at the same energy level.
44
Figure 23 Spatial shape of the d orbitals. Modified from "Overview of Orbitals, Chemistry." by Tim Kaluza CC BY-SA
3.0. Available at: https://commons.wikimedia.org/wiki/File:Chemie_Orbitale.svg?uselang=de#/me-
dia/File:Chemie_Orbitale.svg
The simplest way to explain the colourfulness is to use the example of octahedral complexes.
Here, the d orbitals interact with six ligands. Figure 24 shows the approach of the six ligands along
the three spatial axes.
45
Figure 24 d orbitals with ligands as point charges (blue) in the octahedral ligand field. Modified after "Overview of
Orbitals, Che-mie." By Tim Kaluza CC BY-SA 3.0. Available at: https://commons.wikimedia.org/wiki/File:Chemie_Or-
bitale.svg?uselang=de#/media/File:Chemie_Orbitale.svg.
As can be seen in Figure 24, the ligands reach closer to the dz2 orbital and the dx2-y2 orbital because
they meet them head-on, whereas the ligands lie quasi "between" the other three d orbitals (dxz,
dxy and dyz).
The ligands are simplified here as negative point charges. Since the orbitals are also negatively
charged due to the electrons in them, an electrostatic repulsion occurs between ligands and or-
bitals. This is higher for the orbitals that the ligands meet head-on than for the other three orbit-
als since the charges of the same name are closer than for the other three orbitals. Therefore, in
octahedral complex compounds, the dz2 and the dx2-y2 orbitals are energetically higher than the
other three d orbitals. Compared to the energetically equivalent, hypothetical spherically sym-
metrical ligand field, three orbitals are thus energetically lowered and two energetically raised.
Figure 25 shows a schematic energy diagram for the splitting in the octahedral ligand field.
46
Figure 25 Energy diagram of the d-orbitals in the spherically symmetrical ligand field (left) and the energetic split-
ting of the d-orbitals in the octahedral ligand field (right). A horizontal line corresponds to an orbital.
In coloured complex compounds, the d-orbitals of the central ion are not fully occupied, and the
energy of the ligand field splitting (ΔE in Figure 25) corresponds to the energy of light in the visible
wavelength range. If a photon with the appropriate energy hits a complex, an electron can be
lifted from one of the energetically lower d orbitals (dxz, dxy and dyz) into one of the energetically
higher orbitals (dz2 and dx2-y2)). Just as with organic dyes, the wavelength of light corresponding
to the energy difference ΔE is absorbed and the coordination compound appears in the comple-
mentary colour.
4.1.4 Magnetic properties of coordination compounds

Magnetism is an omnipresent phenomenon, be it magnet buttons, compasses, or electromag-
nets. However, the magnetic properties that are relevant in everyday life are (almost) always
ferromagnetism or electromagnetism.
There are other forms of magnetism, such as paramagnetism and diamagnetism. Paramagnetic
substances are attracted to an external magnetic field in a similar way to ferromagnetic sub-
stances; diamagnetic substances, on the other hand, are repelled by an external magnetic field.
These forms of magnetism are determined by the electron configuration (and thus the occupa-
tion of the orbitals) of the atoms, molecules, or ions of the substance under consideration.
Paramagnetic substances have at least one unpaired electron (i.e., an orbital that is not fully oc-
cupied), whereas diamagnetic substances have only paired electrons. In complexes, therefore,
either only paired electrons or (partially) unpaired electrons are found in the energetically split
d-orbitals.
47
In energy diagrams, electrons are usually represented as arrows pointing either upwards or
downwards. The direction of the arrow represents the so-called "spin" of the electrons. The spin
describes the intrinsic rotation of the electrons, simplified, whether they rotate clockwise or
counterclockwise (sometimes we also talk about spin up or spin down).
Only electrons with opposite spin can be in an orbital. The electrons together with their spins are
what are usually called "elementary magnets" in school. In the magnetic field, the unpaired elec-
trons (or their spins) of a paramagnetic substance all align themselves parallel to each other. This
ensures that the substance is deflected into the magnetic field. If the external magnetic field is
removed, this parallel alignment of the spins disappears again. In a ferromagnetic substance, the
elementary magnets, i.e., the electrons with spin, are also aligned in parallel by an external mag-
netic field; in their case, this parallel alignment is maintained even after the external magnetic
field is removed (example: magnetisable iron nail).
Diamagnetic substances have exclusively paired electrons and thus no unpaired electrons that
can align themselves parallel to each other. It is therefore not drawn into the external magnetic
field but is even repelled by it.
Most substances are diamagnetic ((Riedel & Janiak, 2015), p. 691). The phenomenon of paramag-
netism can be observed in complex compounds in particular (but not only). Figure 26 shows an
example of the electron configuration of a diamagnetic iron (III) complex salt and a paramagnetic
iron (II) complex salt.
Figure 26 Examplary energy diagrams of two iron complex compounds. On the left the paramagnetic iron(III) chlo-
ride hexahydrate and on the right the diamagnetic potassium hexacyanidoferrate(II).
4.1.5 Advanced: high-spin complexes and low-spin complexes

As mentioned before, the orbitals are filled according to Hund's rule, i.e., the orbitals are first all
filled with one electron and only then the electrons in the orbitals are paired. This is because
48
energy must be expended when the electrons are paired. This energy is called spin pairing en-
ergy.
As an example, let us consider a complex with an iron(III) ion as the central atom (
Figure 27) An Fe3+ ion has the electron configuration d5. In the octahedral ligand field, the five d
orbitals split into three lower t2g and two higher eg orbitals.
Figure 27 An iron(III) ion in high and low spin form.
If the splitting by the ligands is low (small ΔE), all five d-orbitals will be single occupied according
to Hund's rule. Such a complex with a maximum number of unpaired electrons is called a high
spin complex. High-spin complexes have the largest possible number of unpaired electrons and
therefore always show paramagnetism. The iron(III) chloride hexahydrate in Figure 26 is such a
high-spin complex.
However, if the ligands cause a strong splitting, it is energetically more favourable to apply the
spin-pairing energy and place all five electrons in the lower t2g orbitals. In this case, we have two
orbitals with paired electrons and only one orbital with unpaired electrons. This is a low spin
49
complex. Low-spin complexes have the smallest possible number of unpaired electrons. The po-
tassium hexacyanidoferrate(II) in Figure 26 is such a low-spin complex. It will show now mag-
netism at all.
50
4.1.6 Advanced: The spectrochemical series
The strength of the splitting of the ligand field, i.e., how large the amount of ΔE is, depends on
the ligands and the central atom. Ligands can be ordered according to how strongly they split the
ligand field energetically. This results in the so-called spectrochemical series for ligands. The fol-
lowing is an exemplary list for some ligands, sorted according to their strength of ligand field
splitting (modified after: (Riedel & Janiak, 2015), p. 723):
I- < Cl- < F- < OH- < NH3 < CN- ≈ CO ≈ NO+
The more the ligand field is split, the more energy is needed to lift an electron from an energeti-
cally lower d-orbital into an energetically higher, unoccupied d-orbital. Therefore, complexes
with ligands located further to the right in the spectrochemical series absorb more energetic light
than complexes with ligands located further to the left in the spectrochemical series.
Analogous to the ligands, a spectrochemical series can also be established for the central atoms.
For identical ligands, the strength of the ligand field splitting by the central atoms can be ordered
as follows (modified after: (Riedel & Janiak, 2015), p. 723):
Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ < Co3+ < Mn4+< Mo3+< Rh3+< Pd4+< Ir3+< Re4+< Pt4+
A complex compound with iron(II) ions as central atoms therefore absorbs lower-energy (longer-
wavelength) light than a complex compound with the same ligands, but iron(III) ions as central
atoms.
51
.¥÷¥¥¥*☒☆
¥
;:÷;¥¥ai☒
1
4.2 Experiments on inorganic dyes
In the experiments on inorganic dyes, you will learn about the phenomenon of coordination com-
pounds, investigate the composition of a complex and dye with the help of a complex compound.
You will also carry out a photochemical reaction with coordination compounds.
52
4.2.1 The characteristics of coordination compounds
6 test tubes
copper sulphate solution (c(CuSO4) = 0.1 mol/L)
test tube rack

diluted ammonia solution (c(NH3) = 2 mol/L)
1 beaker 50 mL diluted sodium hydroxide solution
(c(NaOH) = 2 mol/L)
sandpaper diluted barium chloride solution BaCl2(aq)
graduated pipet 10 mL with pipet aid 2 iron nails
graduated cylinder 100 mL
Pasteur pipet with rubber nipple
tweezers
Procedure
Add diluted ammonia solution to about 30 mL of copper sulphate solution in a beaker until a
deep blue solution without turbidity is obtained.
One test tube is filled to a height of about 2-3 cm with the deep blue solution, another test tube
is filled to a height of about 2-3 cm with copper sulphate solution. Place a sanded iron nail in both
solutions and observe it after a few minutes.
when Nitz is added
we
form a chord .
compound .
There a re n o free
......................................................................................................................................................
copper ions , they
as
bend to NH 3
ful NUDE
.
es
Cnsoq £ No
Rusted
change
...................................................................................................................................................... .
solid
C coat of
copper )
......................................................................................................................................................
Ceitcagg 1- Fees ) -
left aggt Gcs)
Fill another test tube to a height of about 2-3 cm with the deep blue solution and another test
tube to a height of about 2-3 cm with copper sulphate solution. Add some diluted sodium hy-
droxide solution to both.
......................................................................................................................................................
......................................................................................................................................................
53
lnsoq i
L b
CHCNU De .
stats
Small e .
Sky Blue ,
precipitation .
Gelatinous consistence
......................................................................................................................................................
Task: Based on the observations, what conclusions can be drawn about the presence of copper
ions in the solutions?
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Two further test tubes are filled with a little deep blue solution and copper sulphate solution
respectively. Diluted barium chloride solution is added to both solutions.
(Note: Barium chloride solution is used to detect dissolved sulphate ions, as water-insoluble bar-
ium sulphate is formed from barium ions and sulphate ions).
......................................................................................................................................................
......................................................................................................................................................
& ↳
......................................................................................................................................................
Ansa :
Chants)4
Whitestone,
:
white
ppe White
Darker blue
ppt
.
Task: Based on the observations, what conclusions can be drawn about the presence of sulphate
ions in the solutions?
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solutions are disposed of via the sink.
Experiment instructions based on (Bee et al., 2019) and Praktikumsskript LAK-F-Praktikum (University of Göttingen).
54
4.2.2 Photometric determination of the complex composition
11 test tubes
copper sulphate solution (c(CuSO4) = 0.1 mol/L)
test tube rack

ammonia solution (c(NH3) = 0.1 mol/L)
1 spatula
ammonium nitrate NH4NO3
1 glass rod
2 beakers 100 mL
graduated cylinder
stopper
Procedure:
Preparation of the sample solutions:
Put about 80 mL of the copper sulphate solution into one of the beakers and 80 mL of the am-
monia solution into the other beaker.
Fill the test tubes with copper sulphate solution according to the table below.
Then dissolve about 2 g of ammonium nitrate in each of the test tubes filled with copper sulphate
solution. Make sure the ammonia nitrate is dissolved completely, by shaking the test tubes thor-
oughly.
Only after the ammonium nitrate has been added, ammonia solution is filled into the test tubes
according to the table.
Probe 0 1 2 3 4 5 6 7 8 9 10 X
V(copper sulphate so-

0 1 2 3 4 5 6 7 8 9 10 2
lution) in mL
V(ammonia
10 9 8 7 6 5 4 3 2 1 0 10
solution) in mL
Photometric measurement:
First, the wavelength of light that the deep blue complex absorbs most strongly is determined.
This value is also called λmax. For this purpose, an absorption spectrum of sample X (2 mL copper
sulphate solution + 2 g ammonium nitrate + 10mL ammonia solution) and determine the value
of λmax.
55
𝝀𝐦𝐚𝐱 = ………………
602 nm
Subsequently, the absorbances of samples 1 to 10 are determined in a photometric measure-

ment and the measured absorbances are recorded. The measurement is carried out at the pre-
Ref value
viously determined wavelength λmax.
01323%62
Sample 0 1 2 3 4 5 6 7 8 9 10
Extinction 0 O' 462 01756 0160701429 i' 035 01434 01268 01177 01138 01121
b
This sample
was not deal The sample
had a precipitated
solid at the bottom
sample ×
56
Evaluation
Plot the absorbance against the respective volume of the copper sulphate solution and deter-
mine the optimum molar ratio of copper(II) ions to ammonia to form the complex. Alternatively,
you can use Excel to create the plot.
57
Determine the ideal molar ratio of ammonia to copper ions and give the formula for the complex
formed.
......................................................................................................................................................
O
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solutions are disposed of in the collection container for inorganic salt solutions.
Experimental instructions modified according to the LAK-F practical course script (University of Göttingen).
58
↳ nu ratio
4.2.3 Magnetic properties of coordination compounds
3 Eppendorf cups
iron (III) chloride hexahydrate FeCl3 ∙ 6 H2O
1 support stand with support rod potassium hexacyanidoferrate(II) K4[Fe(CN)6]
(ferrocyanide)
thread potassium hexacyanidoferrate(III) K3[Fe(CN)6]
(ferricyanide)
neodymium magnet
(or other strong magnet)
Procedure:
The experiment is set up as shown in the illustration
on the right.
The Eppendorf cups are each filled with one of the

salts. The vessels are then each suspended with a
thread from the crossbar of the stand (Figure 28).
A strong magnet, for example a neodymium magnet,

is brought close to one of the samples. To detect a Figure 28 Set-up for investigating the mag-
netic properties of various salts.
deflection, the Eppendorf cups must hang as still as
possible. we cringle oec .
↑ orbitals =
nomen
Fells 64-0 > Ks [Fecal ,]
.
kq-LE.CC/Ds ] ≈0
......................................................................................................................................................
,
↓
small C-
gaps high spin
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Cosby 5420
F-
"
C.
[ a Cltzoy ] 1-11-20 t so
→ It has colour
C complex compound )
[ Fec H2O> 61ˢᵗ t 3cL

_
AT
splitting
small
↑↑↑↑↑ ↑ At
↑↓ ↑↓ ↑ large
59
splitting
Task: Based on the observations, what conclusions can be drawn about the magnetic properties
of the respective salts and their electron configurations?
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Additional task: Make a reasoned hypothesis as to why the iron (III) chloride hexahydrate is more
strongly attracted to the magnet than the potassium hexacyanidoferrate(II).
(Hint: Look at the spectrochemical series)
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The salts remain in the Eppendorf cups and can be reused.
Experiment instructions modified according to (Hoffmann, Mika, Herbst-Irmer, Irmer & Waitz, 61).
60
↳
only paired e
4.2.4 Stain dyeing with alizarin
3 beakers 250 mL aluminium acetate
iron(III) chloride hexahydrate FeCl3 ∙ 6 H2O
2 glass rods sodium acetate
2 stirring hot plates alizarin S
3 cotton strips
spatula
tweezers
Procedure '
1:49
Staining
1 spatula of aluminium acetate is given in 50 mL of water. One of the cotton strips is placed in
this solution and is boiled for about 5 minutes.
In parallel, another piece of fabric is boiled for 5 minutes in a solution of one spatula tip of iron(III)
chloride in 50 mL of water.
Dyeing
Put 1 spatula tip of alizarin S, one spatula of sodium acetate and about 150 mL tap water into the
third beaker. Then the cotton strips stained in the first part of the experiment and a non-stained
cotton strip are also added to the beaker. The solution is boiled on the hot plate for 5 minutes.
The cotton strips are then removed and washed with warm water.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Explain why stain dyeing with alizarin can be seen as a combination of the course topic
"Organic dyes" and the “Inorganic dyes”.
(Note: Aluminium ions are coordinatively bound to the cotton fibre by the pickling process).
61
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Additional information:
Known important biological compounds are also organic molecules in which metal ions are coor-
dinately bound. A first example are the green plant dyes, the chlorophylls. In these, a magnesium
ion is coordinately bound as the central particle. A second prominent example is the red blood
pigment hemoglobin, in which an iron ion is coordinately bound as a central particle within a large
organic molecule.
Disposal The iron solution is given into the collection container “Inorganic waste”, the other so-
lutions are disposed via the sink.
Experimental instructions modified according to the LAK-F practical course script (University of Göttingen).
62
a
§ 8
:&} .
B
83 ☒
§
4.2.5 Photochemical reaction of the Fe(III) oxalate system
1 Erlenmeyer flask 250 mL iron(III) nitrate nonahydrate
Fe(NO3)3 ∙ 9 H2O
1 stopper für Erlenmeyer flask
sodium oxalate Na2C2O4
4 small Petri dishes potassium hexacyanidoferrate(III) K3[Fe(CN)6]
(ferricyanide)
1 test tube
1 glass rod
1 beaker 50 mL
1 graduated cylinder 100mL
spatula
lamp
Pasteur pipet
aluminium foil
° -6
Procedure
Dissolve 0.6 g iron(III) nitrate nonahydrate in 100 mL demineralised water in an Erlenmeyer flask.
Add 0.4 g sodium oxalate and wrap the Erlenmeyer flask in aluminium foil to protect the solution
from light.
The Petri dishes are each filled with 10 mL of the prepared solution. One of the filled Petri dishes
is kept in the dark. The other three Petri dishes are irradiated with the lamp in a darkened room
for 2, 4 and 6 minutes respectively.
Then an aqueous potassium hexacyanidoferrate(III) solution is added to all 4 samples (2-3 Pas-
teur pipets). To prepare this, dissolve a spatula tip of the salt in approx. 20 mL water in a beaker.
Observation
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
63
Note: The solution of the ferricyanide (potassium hexacyanidoferrate(III) solution) is used for
detecting free iron(II) ions. If iron(II) ions are present, a blue colouration is visible.
In the unexposed shell, iron(III) ions are present bound in a complex. Exposure triggers a reaction
in which the complex is destroyed and the iron(III) ions are reduced to iron(II) ions by oxalate.
Oxalate is oxidised to carbon dioxide. The iron(II) ions can then be detected after the exposure.
[Fe(H2O)6]3+(aq) + 3 C2O42-(aq)  [Fe(C2O4)3]3-(aq) + 6 H2O(l)


12 H2O(l) + 2 [Fe(C2O4)3]3-(aq) h 2 [Fe(H2O)6]2+(aq) + 2 CO2(g) + 5 C2O42-(aq)
K+(aq) + [Fe(H2O)6]2+(aq) + [Fe(CN)6]3-(aq)  K[Fe(III)Fe(II)(CN)6](s) + 6 H2O(l)

Prussian Blue
Disposal: The unexposed Petri dish and the potassium hexacyanidoferrate(III) solution are
needed for the next experiment. Everything else can be disposed of via the sink.
Experimental instructions modified according to the LAK-F practical course script (University of Göttingen) based on
(Roesky, Möckel & Hoffmann, 1996).
this was appeared to
be the darkest colour
64
4.2.6 Template experiment (Blue print)
1 graduated pipet 10 mL unexposed Petri dish from the previous experiment
1 beaker 50 mL Cabosil M-5 (silicic acid, highly dispersed)
graduated cylinder
spatula
Lamp
glass rod
Procedure
Cabosil is added to the solution in the unexposed Petri dish from the previous experiment and
stirred until a thick paste is obtained. Cut a simple geometric figure (like a circle or triangle) from
the cardboard. This should be smaller than the diameter of the Petri dish.
In the darkened room, cover the Petri dish with the cardboard template and shine the lamp on it
for a few minutes.
Observation:
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: All solutions and suspensions used in the experiment are disposed of via the sink.
Experimental instructions modified according to the LAK-F practical course script (University of Göttingen) based on
(Roesky et al., 1996).
65
4.2.7 The colours of copper and iron complexes
12 test tubes, 1 stopper and test tube rack copper sulphate pentahydrate CuSO4  5 H2O
4 Pasteur pipets with rubber nipple

hydrochloric acid (c(HCl) = 2 mol/L)
spatula
ammonia solution (c(NH3) = 2 mol/L)
gas burner potassium hexacyanidoferrate(II) K4[Fe(CN)6]
Potassium hexacyanidoferrate(III) K3[Fe(CN)6]
iron(III) nitrate Fe(NO3)3  9H2O
iron(II) sulphate FeSO4  7 H2O
ammonium thiocyanate NH4SCN
4.2.7.1 The colour of copper complexes
Procedure
A spatula tip of hydrous copper sulphate pentahydrate is placed in a dry test tube and heated
over the gas burner until no more water vapour escapes (care is taken that no condensed water
rinses back). After cooling, demin. water is carefully added up to half of the test tube and shaken.
The solution is divided between two test tubes
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Add hydrochloric acid to the solution in the first test tube until a colour change is observed.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Then try to reverse the colour change by adding demin. water to reverse the colour change.
66
......................................................................................................................................................
......................................................................................................................................................
Add ammonia solution to the solution in the second test tube until a distinct colour change is
observed.
......................................................................................................................................................
......................................................................................................................................................
Here, too, an attempt is made to reverse the change.
......................................................................................................................................................
......................................................................................................................................................
4.2.7.2 The colour of iron complexes
Three test tubes are filled to one quarter with demin. water.
A few crystals of iron(III) nitrate are dissolved in the first test tube. Then a few crystals of ferro-
cyanide K4[Fe(CN)6] are added. Mix thoroughly. If the colour should be very intense, a few drops
of the solution can be added to a half-full test tube with water.
......................................................................................................................................................
......................................................................................................................................................
In the second test tube, dissolve a few crystals of iron(II) sulphate. Then add a few crystals of
ferricyanide K3[Fe(CN)6]. Mix thoroughly. If the colour should be very intense, a few drops can be
added to a half-full test tube of water.
......................................................................................................................................................
......................................................................................................................................................
67
In the third test tube, dissolve a few crystals of iron(III) nitrate. Then add a few crystals of ammo-
nium thiocyanate NH4SCN. Mix thoroughly. If the colour should be very intense, a few drops of
the solution can be added to a half-full test tube of water.
......................................................................................................................................................
......................................................................................................................................................
Disposal: All solutions and suspensions used in the experiment are given into the collection con-
tainer “inorganic waste”
Experimental instructions modified according to the LAK-F practical course script
68
5. Photocatalysis
69
5.1 Theory: Photocatalysis
5.1.1 Catalysis
Catalysts are substances that increase the speed of a chemical reaction by changing the mecha-
nism of the reaction. This has the effect of reducing the activation energy (EA), i.e., the energy
barrier that must be overcome for the reaction to take place. The position of the chemical equi-
librium is not changed by catalysts. Catalysts are not consumed during the reaction, i.e., after the
reaction they are present again exactly as before the reaction. Figure 29 shows a diagram for
both an exothermic and an endothermic reaction, in each case with and without a catalyst.
Figure 29 Schematic representation of the energy ratios of the reaction of substances A and B to the product AB,
without catalyst (black) and with catalyst (red). The potential energy is plotted against the reaction coordinate (the
path of the reaction). The left graph shows an exothermic reaction, the right graph an endothermic reaction. A and
B stand for the reactants, K for the catalyst, AB for the product and KA for the transition stage formed as an inter-
mediate step from complex and reactant A. EA stands for the activation energy.
Many substances have catalytic activity; for example, platinum and iron are metals that are used
as catalysts. However, there are also organic compounds or ions with catalytic properties. Often
catalysts are quite unspecific and catalyse a variety of reactions - frequently also undesirable
ones.
Enzymes are biological macromolecules and particularly powerful catalysts. Without them, many
reactions in organisms would only take place at extremely low speeds - or not at all. Enzymes are
also highly specific, i.e., they catalyse only very specific chemical reactions. Other biological mac-
romolecules such as RNA can also catalyse reactions. Together, these biological catalysts are
called biocatalysts.
Classically, catalytic reactions are divided into two classes, heterogeneous and homogeneous ca-
talysis. Heterogeneous catalysis describes catalytic reactions in which the reacting substances
and the catalyst are not present in the same phase. A familiar example from everyday life is the
purification of gaseous combustion gases in the internal combustion engine at the solid catalyst
in the exhaust system of a car.
70
In homogeneous catalysis, on the other hand, the reactants and the catalyst are present in the
same phase. An example is the acid-catalysed esterification of an alcohol and a carboxylic acid,
in which both reactants and catalyst are present in solution and thus in the same (liquid) phase.
5.1.2 Photocatalysis
Photocatalysis describes catalytic processes in which light is involved. Photocatalytic processes
can also be assigned to the known categories of heterogeneous and homogeneous. Likewise,
there are biocatalysts that are only active under the influence of light. The probably most im-
portant biochemical process, photosynthesis, is such a biological photocatalytic process.
Simplified, a distinction can be made between two types of photocatalysis (cf. (Acker & Bartels,
2008)). In the first type, the catalyst particle is brought into the excited state by light of a suitable
wavelength, analogous to the absorption of visible light in coloured substances. Only this excited
catalyst particle has the property to catalyse the reaction in question. Often, another substance
must react as a "sacrifice" to regenerate the catalyst. Figure 30 schematically shows such a pho-
tocatalytic reaction.
Figure 30 Example of a photocatalytic reaction in which the catalyst must first be excited by light in order to cata-
lyse the reaction from the substrate to the product. Without excitation by light of suitable wavelengths, the reac-
tion cannot be catalysed.
Photosynthesis is an example of such photocatalysis. Simplified, in photosynthesis a part of the

so-called photosystem is excited by light of the appropriate wavelength. This excited molecule
transfers its electron, which is now energetically higher, to another protein and starts a whole
series of redox reactions, at the end of which glucose is formed from carbon dioxide and water.
To regenerate the catalyst particle, another electron must be transferred to it. This happens
through the oxidation of water. The by-product is oxygen, which is vital for us. By taking up elec-
trons, the catalyst particle is again in its original form and can (under the influence of light) cata-
lyse the reaction again. Water serves as a sacrifice for the regeneration of the catalyst (Figure
34).
71
In the second type of photocatalytic reactions, it is not the catalyst that is converted into the
excited state by light, but one of the reactants. This excited particle is then converted with the
help of the catalyst (Figure 31). Without prior excitation of the substrate particle, the catalyst
cannot catalyse the reaction.
Figure 31 Example of a photocatalytic reaction in which the substrate must first be excited by light in order to be
catalytically converted by the catalyst to the product. Without excitation by light of suitable wavelengths, the reac-
tion cannot be catalysed (left); with prior excitation of the substrate, the reaction can be catalysed to the product
(right).
Photocatalytic processes are not only of great importance in nature but are also gaining more
and more significance in our engineered world, for example in the form of solar cells in which
photocatalytic processes take place. Research into photocatalysts can make a major contribution
to the energy transition and the fight against climate change, for example through photocatalytic
production of "green hydrogen" (Bundesministerium für Umwelt, Naturschutz und nukleare
Sicherheit, 2020; Tausch, 2019).
5.1.3 The Photo Blue Bottle system

The elementary steps of a typical photocatalytic reaction can be demonstrated on the Photo-
Blue-Bottle (PBB) system developed by Prof. M. Tausch (Figure 32). At the beginning, the photo-
catalyst particle, the proflavine monocation PF+, is raised to the excited state PF+* by absorbing a
photon of blue light and is then able to reduce the ethylviologen dication EV 2+ to the monocation
EV+ (Figure 33). This causes a blue colouration of the solution, which makes the reaction process
easy to follow visually. The proflavine monocation PF+ is regenerated from the dication PF2+ by
transferring an electron from the sacrificial donor particle EDTA to PF 2+. By introducing atmos-
pheric oxygen (e.g., by shaking), the reduced substrate monocation EV+ is oxidised back to the
original substrate dication EV2+, which is accompanied by the recolouration of the solution from
blue to yellow (Heffen & Tausch, 2015).
72
E
Figure 32 Schematic representation of the Photo-Blue-Bottle system (Heffen & Tausch, 2015).
Figure 33 Formulas of the chemicals used in the Photo-Blue-Bottle system. Ethylviologen serves as a substrate,
proflavin as a photocatalyst (Heffen & Tausch, 2015).
The photo blue bottle experiment can be seen as a model experiment for photosynthesis. The
substrate of photosynthesis is, in simplified terms, carbon dioxide, which is reduced by the pho-
tocatalyst (the chlorophylls) and converted to sugar.
In the model, the ethyl viologen as substrate is therefore the analogue of carbon dioxide. The
reduced blue ethylviologen represents the product (the sugar) in the model, while the proflavin
is representative of the photocatalysts (chlorophylls) in the plant. EDTA takes the role of water
in the model experiment as a "sacrifice" to regenerate the catalyst (Figure 34).
73
Figure 34 Comparison of model experiment Photo-Blue-Bottle-System with the system photosynthesis - cellular res-
piration in nature (Heffen & Tausch, 2015).
5.1.4 Photocatalytically active nanoparticles

Nanoparticles, i.e., particles on the scale of nanometres (one nanometre corresponds to
0.000 000 001 m or 10-9 m), have special properties. For example, certain nanoparticles fluoresce
under UV light, while larger particles of the same substance do not fluoresce (see also focus on
luminescence). Nanoparticles can also have special catalytic properties. The classic example is
titanium dioxide nanoparticles: They can absorb UV light and then serve as catalysts for various
reactions.
The special properties of nanoparticles can be explained by the extraordinarily high number of
atoms on the particle surface compared to the volume of the particle. The larger the particles
become, the more the volume gains the upper hand in this ratio and the special properties of the
nanoparticles disappear (Riedel & Janiak, 2015).
74
5.1.5 The electronic band structure model
To understand the processes within organic photovoltaic cells (OPVs), the so-called energy band
model is used. This model is mainly used to explain the electrical conductivity of conductors, non-
conductors, and semiconductors.
The energy band model does not describe the electron shell and the energy levels of individual
atoms or molecules but serves to describe associations (crystals) of very many atoms (or ions or
molecules). In such crystals, all atoms - and thus their electron shells - interact with each other.
While in a vapour of single, isolated metal atoms all atoms have identical electron shells with
identical energy levels, the interaction in a metal crystal blurs these into a so-called energy band.
An energy band consists of many energy levels that are energetically extremely close together.
The number of energy levels in the energy band is proportional to the number of atoms in the
crystal (Riedel & Janiak, 2015). Figure 35 shows the formation of a metal crystal from a metal
vapour as a model and the resulting energy band schematically.
Figure 35 Formation of a metal crystal from isolated metal atoms in the metal vapour (a). (b) shows the equivalent
energy levels of the individual atoms of the metal vapour (left); when the metal vapour solidifies, the electron shells
of the individual atoms interact with each other and the energy levels "smear" to form an energy band with very
closely spaced energy levels (right). Figure modified after "Inorganic Chemistry" (Riedel & Janiak, 2015, p. 183).
Above the energy bands occupied by the electrons of the atoms lie further unoccupied energy
bands. The highest-energy occupied energy band (analogous to the valence shell of atoms) is
called the valence band. The lowest-energy unoccupied energy band is called the conduction
band.
75
Electrons can only move freely (and a crystal can thus conduct the electric current) if the elec-
trons of the valence band (the valence electrons) have sufficient free energy levels available. In
all metals, the energy levels of the valence band (i.e., the highest occupied energy band) and the
conduction band (i.e., the lowest unoccupied energy band) overlap. Electrons can thus easily
change from the valence band to the conduction band and thus move freely when an electric
current is applied. In non-conductors (insulators), the conduction band is energetically far above
the valence band. The energy difference between the two energy bands is also called the forbid-
den zone.
In semiconductors, the conduction band and valence band do not overlap either, but the forbid-
den zone is very narrow. By adding energy (in the form of heat or light), electrons can be lifted
from the valence band into the conduction band. The lifting causes an electron to be missing in
the valence band, creating a so-called defect electron (also known as an electron hole or electron
defect). Virtually, there is a positive charge in the valence band. Both the electrons in the con-
duction band and the defect electrons in the valence band are freely movable and can therefore
conduct the electric current. Figure 36shows the energy band models for an alkali metal and an
alkaline earth metal as well as a non-conductor and a semiconductor.
Figure 36 Energy band model for alkali metals (for which half of the valence band is occupied), alkaline earth met-
als (for which the valence band is fully occupied) and non-conductors and semiconductors. Modified according to
"Chemistry in Context" (Demuth & Baur, 2009, p. 250).
5.1.6 Organic solar cells

Semiconducting organic polymers are used in an organic photovoltaic cell. In the photoactive
polymer, light of the appropriate wavelength excites electrons in the valence band and raises
them into the conduction band. A defect electron remains in the valence band. These charge
76
carriers - electron and defect electron - are separated and conducted via semiconductors to the
two poles (+/-) of the photovoltaic cell. These semiconductors are organic molecules that serve
as electron acceptors (for the transport of the excited electrons) or as so-called "hole conductors"
(transport of the defect electrons). By separating and passing the charge carriers to the two poles
of the cell, a usable electric current can be derived (Scherf, 2015; Zepp & Tausch, 2015).
The photoactive layer, usually a mixture of an electron-conducting and a hole-conducting semi-

conductor, is embedded between a transparent anode (e.g., FTO, fluorine doped tin oxide) and
a metallic cathode (e.g., aluminium). To improve the contact, a hole transport layer made of PE-
DOT/PSS is applied between the anode and the photoactive layer (Figure 37).
Figure 37 Setup of a photovoltaic cell (from teaching material on organic photo electronics 2020)
5.1.7 Elementary steps in the conversion of light energy into electrical energy
As soon as the organic solar cell is irradiated with light of suitable energy and connected to a
consumer (e.g., a small motor), it converts light energy into electrical energy. The conversion of
light energy into electrical energy can be divided into four elementary steps (Fig. 10 a) and b).
If a photon of suitable energy hits a P3HT molecule (electron donor), this photon is absorbed and
an electron from the highest occupied energy level (HBE) is excited to the lowest unoccupied
energy level (NUE). An electron vacancy (positive hole) remains in the HBE. The excited electron
and the positive hole attract each other relatively strongly due to their opposite charge and an
electron-hole pair (exciton) is formed.
The electron-hole pair is an outwardly electrically neutral "quasi-particle" and has a very short
lifetime. During its lifetime, however, it can move over a very short distance of approx. 10 nm
77
within the donor molecules (diffuse). Ideally, it reaches the interface between P3HT molecules
and PCBM molecules (donor/acceptor interface) within this distance.
At the donor/acceptor interface, the electron-hole pair separates, and free charge carriers are
formed. In the process, the electron is transferred from the NUE of the donor to the NUE of the
acceptor. The positive hole remains in the HBE of the donor.
The free charge carriers created in this way can now migrate via the respective components to
the corresponding electrodes and be transferred via these into an external circuit.
The electrons move within the NUE of the acceptor molecules (PCBM molecules) in the direction
of the Galinstan cathode. Electron transfer takes place between two acceptor molecules by
means of hopping processes (electro hopping). The holes move indirectly via the HBE of the do-
nor molecules (P3HT molecules) in the direction of the FTO anode. The charge transport between
two donor molecules also takes place here via hopping processes (hole hopping). The respective
charges are extracted at the electrodes (Figure 38).
a) Structural model of an organic solar cell in operation
b) Energy model of an organic solar cell in operation
Figure 38 Elementary steps in the organic solar cell (according to teacher's manual organic photo electronics 2020).
78
5.2 Experiments on photocatalysis
In the specialisation topic on photocatalysis, you first carry out a general experiment on catalysis
before you deal with the phenomenon of photocatalysis. Within the framework of this topic, you
can, for example, deal with the Photo Blue Bottle experiment, which can be regarded as a model
experiment on photosynthesis or construct an organic solar cell. The experiments on zinc oxide
nanoparticles overlap in content with the topic on luminescence. If you would like to learn more
about the phenomenon of fluorescence, you can do so in the theoretical texts of the topic on
luminescence.
79
5.2.1 Catalysis: The decomposition of hydrogen peroxide
2 test tubes
manganese dioxide MNO2
1 test tube rack
hydrogen peroxide solution (w(H2O2) = 10%)
1 spatula iron (III) chloride solution
(c(FeCl3) = 0.1 mol/L)
wooden stick (glow splint) potato
petri dish
knife
Procedure
Add about 1 mL of hydrogen peroxide solution to each of the two test tubes. Prepare everything
for the glowing splint test. Add a spatula tip (not more!) of manganese dioxide to the first test
tube and swirl gently if necessary. The glowing splint test is carried out.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Add about 1 mL of the iron(III) chloride solution to the second test tube. It is also swirled, and
the glowing splint test is carried out.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Cut a thin slice from a potato and place it in a Petri dish. A few drops of the hydrogen peroxide
solution are placed on the potato.
80
Optional:
Heat some pieces of potato carefully over the flame of a gas burner. Add hydrogen peroxide
solution and compare with the previous experiment.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Explain what type of catalysis is present in each of the experiments
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Explain how the manganese dioxide or the iron(III) ions are present after the reaction.
......................................................................................................................................................
......................................................................................................................................................
Task: Write the reaction equation for the decomposition of hydrogen peroxide.
......................................................................................................................................................
Disposal: The reacted hydrogen peroxide solutions can be disposed via the sink. If necessary, the
manganese dioxide is filtered off beforehand.
81
5.2.2 The Photo Blue Bottle – a photocatalytical system
5.2.2.1 The Photo Blue Bottle experiment
Screw-cap vial 5 mL PBB solution (contains the following chemicals:)
proflavin (3,6‐Diaminoacridin hemisulphate),
LED torch
ethylviologen (1,1′-Diethyl-4,4′-bipyridinium dibro-
mide),
EDTA disodium salt (Ethylenediamine tetraacetic acid
disodium salt)
cooking oil
Procedure
If no PBB solution is available, it is first prepared. For this purpose, 1 g EDTA disodium salt, 561
mg ethylviologen and 12 mg proflavin are dissolved in 500 mL demineralised water. This solution
is transferred into an amber glass bottle and can be stored for a longer period.
For the actual experiment, 4 mL of the PBB solution is transferred into the screw-cap vial. The
sealed vial is irradiated with white light using the LED torch and observed. After irradiation, the
jar is observed unirradiated for approx. 30 seconds.
………………………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………………………
The vessel is then shaken vigorously and observed. The vessel can be irradiated again and then
shaken. This procedure is repeated several times.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
82
Place 4 mL of PBB solution in each of two screw cap jars. In one, the PBB solution is carefully
coated with cooking oil. The two screw-cap jars are each irradiated for approx. 5 minutes with
the UV torch. Afterwards, the screw cap of both vials is removed, and the solutions are left to
stand in the air. The time until decolourisation is compared.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Further suggestions:
You can also pass through your sample various gases that are present in the air, e.g., nitrogen,
oxygen, carbon dioxide.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solution is used in the following experiment.
Experiment instructions modified according to (Heffen & Tausch, 2015) and (Tausch, 2019).
83
5.2.2.2 Energy participation in the Photo-Blue-Bottle experiment
screw-cap vial 5 mL PBB solution from the previous experiment
LED torch
magnetic stirrer
boiling stones
Procedure
Light
The screw cap vial with PBB solution from the previous experiment is used again. The experiment
is carried out analogously to the previous experiment, this time different light colours of the LED
torch are used.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Heat
To check whether the reaction can also be driven by heat energy, a small boiling stone is placed
in the screw-top vial filled with the yellow PBB solution. The opened screw cap vial with boiling
stone is heated on the hot plate and left to boil for about 2 to 3 minutes.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
84
Kinetic energy
A screw-top vial (the vial from the heat experiment can be used after cooling) is filled as com-
pletely as possible with PBB solution and sealed (there should be no air left in the screw-top vial).
The vessel is illuminated with the blue LED torch and then shaken.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Explain which form of energy is required for the reaction of the solution of yellow to blue.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Hypothesise what is needed for the back reaction of the solution from blue to yellow. What
kind of reaction is involved?
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Experimental instructions prepared on the basis of Photocatalysis - homogeneous and heterogeneous (Heffen &
Tausch, 2015), (Tausch, 2019) and Photo-Cat script (Korn et al., 2019).
85
5.2.2.3 The photocatalytically driven concentration element
2 snap-lid vials PBB solution from the previous experiment
LED torch (blue)
cardboard
2 nails or screws (as electrodes)
cable with alligator clips
multimeter
sandpaper
electrolyt salt bridge (tubing with filter
paper)
Procedure
Fill 2 snap-lid vials each with about 4 mL of the PBB
solution (filling level about halfway). They are closed
with the prepared, pierced snap-on lids.
As a salt bridge, the plastic tube is filled with a match-

ing filter paper strip and inserted into the matching
Figure 39 Experimental set-up for the photocata-
holes of the snap-on lids. The ends must be immersed lytically operated concentration cell.
in the solutions.
The nails are sanded, connected to the multimeter and inserted into the solutions through the
remaining holes in the snap-on covers (Figure 39).
One of the half cells is illuminated with the LED torch. Make sure not to irradiate the solution in
the other snap-on lid glass as much as possible (cardboard separation or use aluminium foil). The
measured voltage is observed and recorded.
If the voltage no longer increases, the torch is switched off and continued to be observed for a
few minutes and the voltage tracked. By moving the vessels slightly, an attempt can be made to
introduce air into the solution.
......................................................................................................................................................
......................................................................................................................................................
86
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Further suggestions
Test out other electrode materials: e.g., copper, platinum, graphite. Try also to repeat the exper-
iment on a larger scale, e.g., in two small beakers
Based on (Heffen & Tausch, 2015) and Photo-Cat script (Korn et al., 2019).
87
5.2.3 Photocatalysis using zinc oxide nanoparticles
5.2.3.1 Preparation of fluorescent zinc oxide nanoparticles
1 beaker 50 mL
ethanol
1 beaker 250 mL
zinc acetate dihydrate
1 Erlenmeyer flask 250 mL
sodium hydroxide NaOH
1 graduated cylinder 100 mL ice
UV lamp
thermometer
ice bath
magnetic stirrer with stirring magnet
Procedure
In the 50 mL beaker, dissolve 0.3 g sodium hydroxide in 30 mL ethanol by longer stirring with the
magnet on the magnetic stirrer. In the 250 mL beaker, 2.2 g of zinc acetate dihydrate are dis-
solved in 110 mL of ethanol at 60°C with stirring. As soon as both solutions are clear, they are
cooled to about 0°C in an ice bath. Meanwhile, the hot plate of the magnetic stirrer is preheated
to 150°C in a darkened room.
The two cooled solutions are combined in the Erlenmeyer flask, which contains a magnetic stir-
ring rod, and this is placed on the preheated hot plate (in the darkened room). The solution is
stirred slowly and irradiated from above with the UV lamp. The solution is irradiated for 20
minutes and observed. A photo of the solution is taken every 2 minutes.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The suspension of the zinc oxide nanoparticles is needed for the following experiment.
Experimental instructions based on (Wilke, Waitz, von Hoff & Waitz, 2018)..
88
Insert your photos here:
89
5.2.3.2 Photocatalysis with zinc oxide nanoparticles
glass dish
suspension of zinc oxide nanoparticles in ethanol
(from previous experiment)
2 beakers 100 mL
coumarin or other colourants
1 beaker 250 mL
zinc oxide ZnO
1 graduated cylinder 100 mL
2 magnetic stirrers with stirring magnet
funnel with folded filter
UV lamp
Procedure
First, a powder is prepared from the suspension of zinc oxide nanoparticles by evaporating about
100 mL of the ethanolic suspension in the glass dish on the hot plate (alternatively, commercial
zinc oxide powder can be used).
Dissolve 0.5 g coumarin in 100 mL warm demineralised water and divide the solution equally
between the two 100 mL beakers.
Add three spatula tips of the zinc oxide powder to one of the two beakers. Both beakers with
coumarin solution (with and without zinc oxide) are irradiated from above with the UV lamp for
30 minutes. The solutions are stirred with the magnetic stirrer.
Then the powder is filtered out of the solution (filter several times if necessary) and the two
solutions are observed under irradiation with UV light.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Test out if other coloured substances are also decoloured.
Disposal: The solid is disposed of in the solid waste. The solutions are disposed of in the collection
container for inorganic salt solutions.
Experimental instructions prepared based on (Wilke et al., 2018).
90
5.2.4 The organic photovoltaic cell (plastic solar cell)
5.2.5 Construction of an OPV (organic photovoltaic cell)

box kit, additionally needed are: box kit
adhesive tape (tesafilm)
1 multimeter
1 hairdryer
1 microscope slide
1 splash protection from a PET bottle neck
1 magnetic stirrer
Procedure
To build the organic photovoltaic cell, follow the instructions from the organic photo electronics
kit on the following pages.
The individual steps in the construction of the OPV can also be followed in the video series of the
University of Cologne under the following link:
https://chemiedidaktik.uni-koeln.de/das-team-1/prof-dr-amitabh-banerji/or-
ganische-elektronik/videos/videoanleitung-zum-opv-bau
Safety information
Safety goggles!
Fume cupboard!
Take special care when handling syringes
Galinstan is harmless to health and can be used in student experiments. The alloy can leave black,
greasy stains, but these can be washed off with soap solution.
Working with the P3HT/PCBM solution (in 1,2-dichlorobenzene) must be done in a fume cup-
board!
Galinstan can leave black stains, but these can easily be washed off with soap and water!
91
5.2.5.1 Preparing the FTO glass (anode)
a. First measure the electrical resistance of both sides of the glass by pressing the cable ends
of the multimeter onto the glass surface at a distance of 1 cm. The conductive side should
show a value of approx. 20-40 Ω.
Note: The video shows an example of how to operate the multimeter.
b. Wet the conductive side with some acetone and rub the surface clean (with strong pres-
sure) with the cellulose cloth. From here on, avoid touching the glass in the middle with
your fingers.
c. Now tape the upper third of the conductive side flush with a strip of adhesive tape (Figure
40). Make sure that the tape does not stick out on any side.
Figure 40 Preparing the FTO glass
5.2.5.2 Application of the hole extraction layer (PEDOT/PSS)
a. Place the prepared FTO jar on a paper towel and place three small drops of the PEDOT/PSS
solution on the edge of the tape strip. You can use one of the enclosed plastic pipettes
(with blue dot) for this.
b. Now place a clean slide on the edge and slowly tip the slide onto the FTO glass so that the
solution is evenly distributed between the glass slides (Figure 41). Alternatively, you can
proceed as in the video.
c. Pull the slide firmly and briskly away over the FTO glass towards the side that is not taped.
This technique is also called squeegeeing. A very thin layer of PEDOT/PSS solution should
remain on the FTO glass.
Note: Repeat step c if the layer seems too thick.
92
d. Dry the applied PEDOT/PSS layer with the help of a hair dryer for about 1 minute. Make
sure that the PEDOT/PSS layer is not touched.
Figure 41 Coating of the FTO glass with PEDOT/PSS
5.2.5.3 Spincoating of the absorber layer (P3HT/PCBM)
Important: When spincoating, an exact and clean procedure is of high importance.
a. Fix the FTO glass on the top tape of the spincoater (PC fan) so that the conductive side is
facing up.
b. Put the splash guard over it.
c. Connect the spincoater to the 4.5 V battery using the crocodile cables (pay attention to
the polarity of the PC fan). The spincoater should now rotate.
d. Now draw up approx. 0.1 mL of P3HT/PCBM solution with the empty syringe (purple dot)
and hold the syringe centrally just above the FTO glass. Inject the solution in a steady
stream (not dropwise and not too fast) onto the rotating glass.
e. Allow the glass to rotate for a further 10-20 sec. You should then get a thin, continuous
layer of P3HT/PCBM on your FTO glass (Figure 42).
f. Then remove the adhesive film from step 1 and place the glass, coated side up, on a hot
plate for 10 min at 140°C.
g. Remove the glass from the hot plate with tweezers or gripping tongs and let it cool on a
piece of paper for 5 min.
Figure 42 Spincoating of the P3HT/PCBM layer
93
5.2.5.4 Preparation of the Galinstan Electrode (Cathode)
Place the Galinstan socket in front of you so that the black rubber strips face upwards (see Figure
43). These serve as spacers. Now create a Galinstan drop on each copper strip the size of a small
pinhead (at least as high as the spacers). The drops can be wider than the copper strips but should
not run into each other.
Figure 43 Preparation of the Galinstan electrode
5.2.5.5 Assembling the organic solar cell
Important: A common mistake in this step is that the coated glass is placed on the galinstan
mount the wrong way round. Please follow the instructions exactly or look at the pictures care-
fully!
a. Take the coated FTO glass and place it with the coated side down on the Galinstan mount
so that there is close contact between the P3HT/PCBM layer and the Galinstan (Figure
44). Place the glasses slightly offset on top of each other so that the copper strips can be
contacted with a crocodile clip.
b. Carefully take the "sandwich" in your hand and fix it in place using the two foldback
clamps (Figure 45). Place the clamps so that the pressure is on the rubber strip.
c. Your solar cell is now ready. Do not move it too much, otherwise the Galinstan could leak!
Figure 44 Assembling the OPV.
94
Figure 45 The complete OPV.
5.2.6 Measurements on the OPV (organic photovoltaic cell)

Two important parameters of solar cells are the open circuit voltage (VOC) and the short circuit
current (ISC). The open circuit voltage is the voltage that is measured without a load. It is the
maximum voltage that the solar cell can build up. The short-circuit current is measured when
both poles are connected to each other without any resistance. It is therefore the maximum cur-
rent that the solar cell can deliver under a given irradiation.
5.2.6.1 Measurement of the open circuit voltage VOC
Connect a photoactive area of the solar cell with a multimeter. Measure the voltage generated
with room lighting.
 -Examine the other two photoactive areas of the solar cell in the same way and note down
all measurement results in the table below.
 Now connect all three copper leads with the copper clamp and measure the voltage gen-
erated by the enlarged photoactive surface.
 Repeat this series of measurements each time the cell is irradiated with sunlight, with the
white torch and by the blue, green and red LEDs of the flashlight.
 Vary the distance of the lamp and observe the effect on the measured values. Agree on a
constant distance and note down the values.
5.2.6.2 Measurement of the short-circuit current ISC
 Now switch the multimeter to current measurement and repeat all the series of meas-
urements from experiment 1. Again, note down all the values in the table.
95
Room light Sun light White Light
VOC in mV ISC in mA VOC in mV ISC in mA VOC in mV ISC in mA
1
1-3
Blue light Green light Red Light

VOC in mV ISC in mA VOC in mV ISC in mA VOC in mV ISC in mA
1
1-3
96
6. Luminescence
97
6.1 Theory: Luminescence
We are all familiar with luminescence from everyday life, be it light bulbs, the sun, fireflies or
modern smartphone displays with OLED technology. Light bulbs and flames glow, i.e., they emit
light, but they also emit heat at the same time. The glow of smartphone screens and fireflies, on
the other hand, occurs (almost) without the emission of thermal energy. This "cold" glow is the
focus of this specialisation topic.
6.1.1 Fluorescence
Fluorescence is "cold" glow, excited by the absorption of electromagnetic radiation. The excita-
tion of fluorescent molecules is analogous to the absorption of photons in dye molecules. In con-
trast, the deactivation of the resulting excited state does not only occur through the emission of
heat, but also through the emission of light. One therefore speaks of radiative deactivation. The
emitted radiation is always lower in energy than the absorbed radiation. This can be explained
by the fact that when a photon is absorbed, there is never only an electronic excitation (i.e., the
lifting of an electron from the HBE (HOMO) into the NUE (LUMO)), but also an excitation of vi-
brations of the molecule. Also, the oscillation of molecules can only take place in certain "al-
lowed" levels. Strictly speaking, the energy of the absorbed photon does not correspond to the
energy difference between HBE and NUE, but to the difference between the basic oscillation
state in the HBE and an excited oscillation state in the NUE. During the relaxation of the excited
state, the molecule first releases energy in the form of heat and thus reaches the vibrational
ground level of the electronically excited state. Only then does the excited electron fall from the
higher energy level back to the ground level. There, too, the molecule is first in a higher vibra-
tional level and then emits the excess energy in the form of heat. The energy of the emitted
photon thus corresponds to the energy difference between the basic vibrational level of the NUE
and the vibrationally excited state of the HBE. This energy difference is smaller than that between
the vibration base level of the HBE and the vibrationally excited state of the NUE. Figure 46 shows
the processes of fluorescence - absorption and emission - schematically.
98
Figure 46 Schematic representation of fluorescence. On the left, excitation by (UV) light, on the right, return to the
ground state by emitting a photon.
Fluorescence vanishes after a few nanoseconds after the radiation source that provides the ex-
citation has been switched off. This is therefore a very fast process (Atkins & Paula, 2012).
6.1.2 Phosphorescence
Phosphorescence is also a "cold" luminous phenomenon. Compared to fluorescence, phospho-
rescence can last for a long time after the exciting radiation source is switched off. Usually, phos-
phorescence goes out after seconds or fractions of seconds, but can also last for up to several
hours (Atkins & Paula, 2012).
Excitation is analogous to fluorescence, but during deactivation, the excited electron can be
transferred to an intermediate state through so-called intersystem crossing. In this process, the
spin - the intrinsic direction of rotation of the electron - is reversed. The intermediate state is
energetically below the NUE. From the intermediate state, the electron can return to the HBE by
emitting a photon. The energy of the emitted photon corresponds to the energy difference be-
tween the oscillation ground state of the intermediate state and the (oscillation excited) ground
state. For the electron to fall back to the ground level (HBE), its spin must be reversed, since only
electrons with opposite spin can occupy an energy level (orbital). This spin reversal can only take
place very slowly, which is why phosphorescence can last for a very long time. Figure 47 shows a
schematic of the processes involved in phosphorescence.
99
Figure 47 Schematic representation of phosphorescence. ISC stands for inter system crossing.
Substances that phosphoresce also show fluorescence. Logically, the wavelength of phosphores-
cence is always longer than that of fluorescence. Thus, the energy of the light emitted by phos-
phorescence is lower.
6.1.3 Chemiluminescence
The previously described types of luminescence - fluorescence and phosphorescence - are both
triggered by excitation with UV light or visible light. One therefore speaks of photoluminescence.
However, luminescence can also be triggered by other processes, for example, by electric fields
(electroluminescence), an increase in temperature (thermoluminescence) or X-rays (X-ray lumi-
nescence).
A special phenomenon is chemiluminescence, in which the luminescence is triggered by chemical

processes. In such a reaction, energy is thus not (only) released in the form of heat, but (also) in
the form of light (Spektrum Akademischer Verlag, 1998). The reaction of luminol, which is used
in criminal technology to examine traces of blood, is probably the best-known example of such a
reaction with chemiluminescence.
A special form of chemiluminescence is bioluminescence, i.e., the "glow" of, for example, fireflies
or luminescent bacteria. This is particularly efficient, i.e., almost all energy is emitted in the form
of light. The "losses" in the form of heat emission are significantly lower than with classical chem-
iluminescence (Acker & Bartels, 2008).
100
6.1.4 The electronic band model
To understand the processes within organic light-emitting diodes (OLEDs), the so-called elec-
tronic band model is used. This model is mainly used to explain the electrical conductivity of
conductors, non-conductors, and semiconductors.
The energy band model does not describe the electron shell and the energy levels of individual
atoms or molecules but serves to describe associations (crystals) of very many atoms (or ions or
molecules). In such crystals, all atoms - and thus their electron shells - interact with each other.
While in a vapour of single, isolated metal atoms all atoms have identical electron shells with
identical energy levels, the interaction in a metal crystal blurs these into a so-called energy band.
An energy band consists of many energy levels that are energetically extremely close together.
The number of energy levels in the energy band is proportional to the number of atoms in the
crystal (Riedel & Janiak, 2015) Figure 48 shows the formation of a metal crystal from a metal
vapour as a model and the resulting energy band schematically.
Figure 48 Model representation of the formation of a metal crystal from isolated metal atoms in metal vapour (a).
(b) shows the equi-valent energy levels of the individual atoms of the metal vapour (left); when the metal vapour
solidifies, the electrode shells of the individual atoms interact with each other and the energy levels "smear" to
form an energy band with very closely spaced energy levels (right). Figure modified after "Inorganic Chemistry"
(Riedel & Janiak, 2015, p. 183).
Above the energy bands occupied by the electrons of the atoms lie further unoccupied energy
bands. The highest-energy occupied energy band (analogous to the valence shell of atoms) is
called the valence band. The lowest-energy unoccupied energy band is called the conduction
band.
101
Electrons can only move freely (and a crystal can thus conduct the electric current) if the elec-
trons of the valence band (the valence electrons) have sufficient free energy levels available. In
all metals, the energy levels of the valence band (i.e., the highest occupied energy band) and the
conduction band (i.e., the lowest unoccupied energy band) overlap. Electrons can thus easily
change from the valence band to the conduction band and thus move freely when an electric
current is applied. In non-conductors (insulators), the conduction band is energetically far above
the valence band. The energy difference between the two energy bands is also called the forbid-
den zone.
In semiconductors, the conduction band and valence band do not overlap either, but the forbid-
den zone is very narrow. By adding energy (in the form of heat or light), electrons can be lifted
from the valence band into the conduction band. The lifting causes an electron to be missing in
the valence band, creating a so-called defect electron (also known as an electron hole or electron
defect). Virtually, there is a positive charge in the valence band. Both the electrons in the con-
duction band and the defect electrons in the valence band are freely movable and can therefore
conduct the electric current. Figure 49 shows the energy band models for an alkali metal and an
alkaline earth metal as well as a non-conductor and a semiconductor.
Figure 49 Electronic band model for alkali metals (for which half of the valence band is occupied), alkaline earth
metals (for which the valence band is fully occupied) and non-conductors and semiconductors. Modified according
to "Chemistry in Context" (Demuth & Baur, 2009, p. 250).
6.1.5 Organic light emitting diodes (OLED)

6.1.5.1 Structure of an OLED
In organic light-emitting diodes, there is a layer of organic molecules with semiconductor prop-
erties between the positive and negative poles. In the case of the course, this is on the one hand
the hole conductor PEDOT:PPS, a semiconductor that can conduct defect electrons, i.e. positive
102
charges, very well. On the other hand, "superyellow" is also present in the cell, which serves to
transport electrons (Banerji, Dörschelln & Schwarz, 2018b) (Figure 50).
Figure 50 Structure and functional principle of an organic light-emitting diode (OLED, from teaching material on
organic photo electronics 2020).
By applying a sufficiently large voltage to the cell, electrons are "pumped" (injected) into the cell
at the negative pole, while electrons are removed at the positive pole. The injected electrons are
in the conduction band and thus energetically above the valence band. They move through the
electric field in the direction of the positive pole of the cell, the defect electrons created at the
positive pole move - in the valence band - in the opposite direction. The positive and negative
charge carriers thus move towards each other. They can recombine. To do this, however, the
electron must move from the conduction band into the valence band. The excess energy, i.e. the
difference between the conduction band and the valence band (or NUE and HBE), is emitted in
the form of visible light. The OLED glows.
6.1.5.2 Elementary steps of electroluminescence
As soon as the OLED is connected to a voltage source, it begins to glow. This process is called
electroluminescence, which is divided into five elementary steps (Figure 51).
Electrons are transferred from the cathode (galinstane) to the adjacent polymer molecules. In
terms of energy, the electrons are injected into the lowest unoccupied energy level (NUE)* of
the molecules (electron injection). Due to the electric field, the electrons within the NUE move
along the molecules towards the FTO anode. Electron transfer between the polymer molecules
takes place via so-called electron hopping.
In parallel, electrons are removed from the adjacent polymer molecules at the positively charged
anode (FTO), resulting in electron defects, so-called holes, in the polymer molecules. From an
103
energy point of view, electrons are extracted from or holes are injected into the highest occupied
energy level (HBE)* of the polymer molecules. The holes migrate indirectly along the molecules
on the HBE towards the cathode due to the electric field. Here, too, hopping processes take place
between the molecules (hole hopping).
If a hole (on the HBE) within a molecule meets an electron (in the NUE), a recombination (union)
of electron and hole takes place, releasing energy in the form of light. The electron takes the
position of the hole. In this way, electrical energy is efficiently converted into light energy in the
OLED.
a) Structural model of an OLED in operation
b) Energy model of an OLED in operation
Figure 51 Elementary steps of electroluminescence (according to teacher's manual organic photo electronics 2020).
104
6.1.6 Fluorescence and decomposition of B vitamins
The occurrence or change of fluorescence can be used, for example, to detect and separate sub-
stances, but also to detect chemical reaction processes. Using the reactions of two B vitamins as
an example, you will learn more about the possible applications of fluorescence phenomena.
Vitamin B1 (thiamine) and vitamin B2 (riboflavin) are water-soluble vitamins of great importance
for the human metabolism and the function of the nervous system (Figure 52). These vitamins
are found in larger quantities in wheat and yeast, but also in animal products. Riboflavin is also
added to many foods as a colouring agent due to its orange yellow colour.
Figure 52 Thiamine and riboflavin.
Riboflavin (vitamin B2), in contrast to thiamine, has an extended conjugated double-bond system
and therefore shows colourfulness and fluorescence when irradiated with UV light. However, this
fluorescence is pH-dependent, as only the neutral form fluoresces strongly, whereas the cationic
form (at low pH due to the addition of H+ to the aromatically bound nitrogen atoms) or the ani-
onic form (at high pH due to the splitting off H+ from the secondary amine group) does not or
hardly fluoresce.
A disturbance of the double-bond system (which causes the fluorescence to go out) can also be
caused by the addition of a reducing agent (such as sodium dithionite), since the leucoform of
riboflavin is formed by the reduction (Figure 53).
105
Figure 53 Formation of the leucoform of riboflavin by addition of a reducing agent.
Thiamine (vitamin B1) does not have a conjugated double-binding system; however, through a
ring closure reaction (by adding potassium hexacyanidoferrate(III) in a basic environment), thia-
mine can react to form thiochrome, which shows fluorescence due to its conjugated double-
binding system (Figure 54).
Figure 54 Ring closure reaction of thiamine.
Many organic substances are not resistant to heat, light or other environmental factors, including
vitamin B1 and vitamin B2: thiamine is sensitive to heat, whereas riboflavin decomposes when
exposed to light (especially UV light).
Vitamin B1 is decomposed by high temperatures into individual molecular fragments (e.g., hy-
drogen sulphide), vitamin B2 splits off the side chain when exposed to light and reacts to form
lumichrome (Figure 55).
106
Figure 55 Photodegradation of vitamin B2.
Since riboflavin fluoresces yellowish, but lumichrome green blue, the degree of riboflavin degra-
dation can be determined by the colour of the fluorescence.
To protect medicines, chemicals or food ingredients from decomposition, stabilisers (such as eth-
ylenediaminetetraacetic acid, EDTA) are added, solvents and pH values are changed, or brown
glass bottles are used for storage and transport. Notes such as "store in a cool place away from
light" also serve to avoid unwanted decomposition products.
107
6.2 Experiments on luminescence
In this specialisation topic, you will first carry out some "classic experiments" from XLAB courses
on luminescence (fluorescence, phosphorescence, chemiluminescence). However, this topic also
offers the opportunity to construct an organic light-emitting diode (OLED), for example. You will
also investigate the luminescent behaviour of the two important vitamins, B1 and B2. In addition
to the experiments on luminescence listed in the following chapter, the experiments on zinc ox-
ide nanoparticles (topic on photocatalysis) and the experiments on luminescence thermochrom-
ism (topic on molecular switches) can also be carried out in this topic. You will find the experi-
ments in the respective section. There you will also find additional theoretical background infor-
mation on these experiments.
108
6.2.1 Cold glow under UV light (fluorescence)
1 test tube tonic water or bitter lemon (containing quinine)
1 test tube rack green leaves
1 spatula
ethanol
UV lamp sea sand
1 mortar with pestle Calcium carbonate CaCO3
1 beaker 600 mL
1 scissor
1 funnel with folded filter
The fluorescence experiments are best visible when the room is dark or at least somewhat darke-
ned. You can use the UV torches provided. However, in the dark rooms you will also find UV
lamps with two different wavelengths of UV light. Feel free to try out the different possibilities.
6.2.1.1 Fluorescence of quinine
A bottle (do not open the bottle) of tonic water (containing quinine) is irradiated with the light
of an UV lamp.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
6.2.1.2 The "bleeding" chestnut branch
A large beaker is filled with tap water and irradiated with UV light in a darkened room. Then a
freshly cut horse chestnut branch is dipped into the water with the cut surface.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
109
6.2.1.3 Preparation and fluorescence of a chlorophyll solution
Some green leaves are cut into small pieces (about 3 g) and ground in a mortar with some ethanol
(solvent for chlorophyll, should be about 1 finger width in the mortar) with the addition of about
two spatulas of sea sand and about two spatulas of calcium carbonate (serves to neutralise the
acidic cell sap). The resulting raw chlorophyll solution (it also contains carotenoids and xantho-
phylls) is filtered into a test tube. The raw chlorophyll solution is irradiated with UV light (366
nm) in the dark (get as close as possible to the UV source).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal Disposal is via the sink or wastepaper bin.
Experiment instructions modified according to the course script How to Teach Fireflies to Glow (Chemistry of Lumi-
nous Phenomena) of the XLAB Göttingen Experimental Laboratory for Young People.
110
6.2.2 Fluorescence of fluoresceine
1 beaker 400 mL
phthalic anhydride
1 spatula
resorcinol
3 test tubes diluted sodium hydroxide solution
(c(NaOH) = 2 mol/L)
1 test tube rack
zinc chloride ZnCl2, anhydrous
1 gas burner
bromine water Br2(aq)
1 test tube holder
1 UV lamp pH paper
Procedure
Mix one spatula tip of phthalic anhydride and of resorcinol in a test tube and add a few crystals
of zinc chloride.
The mixture is heated briefly until the melt turns dark red. The melt is then cooled and allowed
to solidify. Then the test tube is half filled with diluted sodium hydroxide solution and the solid
is dissolved in it.
A large beaker is filled with water and irradiated with UV light in a darkened room. Now slowly
drop the fluorescein solution into the beaker with water.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Three test tubes are filled to about one quarter with the fluorescein solution from the beaker.
The pH value of the solution in the first test tube is checked with pH paper for an alkaline pH
value and sodium hydroxide solution is added if necessary.
Hydrochloric acid is then added to the solution in the second test tube until acidic (check with pH
paper).
The fluorescence of the alkaline and acidic fluorescein solutions is observed under UV irradiation.
After the acidic solution has been made alkaline again, the fluorescence is checked again.
111
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Add bromine water drop by drop to the fluorescein solution in the third test tube until the colour
changes. It is irradiated again with the UV lamp.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
The pH value of the solution with bromine water is checked with pH paper. If necessary, sodium
hydroxide solution is added to the solution until the alkaline reaction is reached. The solution is
irradiated again with the UV lamp.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solution mixed with bromine water is disposed of in the collection container for
halogens.
Experimental instructions modified according to the course script How to Teach Fireflies to Glow (Chemistry of Lumi-
nous Phenomena) of the XLAB Göttingen Experimental Laboratory for Young People. Information on fluorescence
from: (Slyusareva & Gerasimova, 2014).
112
6.2.3 Phosphorescence
1 porcelain dish
fluorescein-tartaric acid mixture
1 gas burner with tripod and wire gauze
ice
1 crucible tongs
1 scoop
1 UV lamp (central)
Procedure:
A porcelain dish is filled with approx. 1 spoonful of the fluorescein-tartaric acid mixture and
briefly heated with the burner flame until the mixture forms a glassy melt. The still hot dish is
irradiated with UV light. Investigate whether and how long the fluorescence lasts after the UV
lamp has been turned off.
......................................................................................................................................................
......................................................................................................................................................
After the dish has cooled down somewhat, it is carefully placed in an ice bath for at least 10
minutes. The content of the cooled dish is tested again for phosphorescence under the UV lamp.
......................................................................................................................................................
......................................................................................................................................................
Disposal: dissolved in water in the sink
113
6.2.4 Chemiluminescence of luminol
2 beakers 600 mL (central) diluted sodium hydroxide solution
(c(NaOH) = 2 mol/L)
2 graduated cylinders 100 mL (central)
hydrogen peroxide solution (w(H2O2) = 10 %)
1 beaker 1000 mL (central) luminol (5-Amino-2,3-dihydrophthalazin-1,4-dion)
1 coil distillate condenser (central) potassium hexacyanidoferrate(III) K3[Fe(CN)6]
1 spatula (central)
2 glass rods (central)
Procedure
First, two solutions are prepared.
Solution 1: Dissolve 100 mg luminol in 5 mL sodium hydroxide solution (c = 2 mol/L). The solution
is made up to 500 mL with water.
Solution 2: Dissolve 0.3 g potassium hexacyanidoferrate(III) (ferricyanide) in 500 mL water. Add

8 mL of hydrogen peroxide solution (w = 10 %).
Solution 1 and 2 are shared by all participants.
Add 50 mL of each of the two solutions simultaneously in the dark through a coil condenser into
a large beaker. Try out whether the luminescence can be refreshed several times by adding more
solid potassium hexacyanidoferrate(III).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Experiment instructions modified according to the course script How to Teach Fireflies to Glow (Chemistry of Lumi-
nous Phenomena) of the XLAB Göttingen Experimental Laboratory for Young People.
114
6.2.5 Construction of an organic light emitting diode (OLED)
OLED box kit, additionally needed are: OLED box kit
adhesive tape
tissues
1 multimeter
1 hairdryer
1 microscope slide
1 splash protection from PET bottle neck
Procedure
To build the organic light-emitting diode, follow the instructions from the organic photo elec-
tronics kit on the following pages. See also Supporting Information for the article "Organic light-
emitting diodes in chemistry lessons" (Banerji, Dörschelln & Schwarz, 2018a, 2018b).
The individual steps of OLED construction can also be viewed in this video series from the Uni-
versity of Cologne:
https://chemiedidaktik.uni-koeln.de/das-team-1/prof-dr-amitabh-
banerji/organische-elektronik/videos/videoanleitung-zum-oled-bau
Safety information
Safety goggles!
Fume cupboard!
Take special care when handling syringes
Galinstan is harmless to health and can be used in student experiments. The alloy can leave black,
greasy stains, but these can be washed off with soap solution.
Superyellow is dissolved in toluene and must be handled with gloves under the fume cupboard!
Be sure to wear safety goggles when spin-coating!
115
6.2.5.1 Preparing the FTO glass (anode)
a. First measure the electrical resistance of both sides of the glass by pressing the cable ends
of the multimeter onto the glass surface at a distance of 1 cm. The conductive side should
show a value of approx. 20-40 Ω.
Note: The video shows an example of how to operate the multimeter.
b. Wet the conductive side with some acetone and rub the surface clean (with strong pres-
sure) with the cellulose cloth. From here on, avoid touching the glass in the middle with
your fingers.
c. Now tape the upper third of the conductive side flush with a strip of adhesive tape (Figure
56). Make sure that the tape does not stick out on any side.
Figure 56 Preparing the FTO glass.
6.2.5.2 Application of the hole injection layer (PEDOT/PSS)
a. Place the prepared FTO jar on a paper towel and place three small drops of the PEDOT/PSS
solution on the edge of the tape strip. You can use one of the enclosed plastic pipettes
(with blue dot) for this.
b. Now place a clean slide on the edge and slowly tip the slide onto the FTO glass so that the
solution is evenly distributed between the glass slides (see Figure 57). Alternatively, you
can proceed as in the video.
c. Pull the slide firmly and briskly away over the FTO glass towards the side that is not taped.
This technique is also called squeegeeing. A very thin layer of PEDOT/PSS solution should
remain on the FTO glass.
Note: Repeat step c if the layer seems too thick.
116
d. Dry the applied PEDOT/PSS layer with the help of a hair dryer for about 1 minute. Make
sure that the PEDOT/PSS layer is not touched.
Figure 57 Coating of the FTO glass with PEDOT/PSS.
6.2.5.3 Spincoating of Superyellow® (emitter)
Important: When spincoating, an exact and clean procedure is of high importance. Please read
the instructions on p. 68!
a. Fix the FTO glass on the top tape of the spincoater (PC fan) so that the conductive side is
facing up.
b. Put the splash guard over it.
c. Connect the spincoater to the 4.5 V battery using the crocodile cables (pay attention to
the polarity of the PC fan). The spincoater should now rotate.
d. Now draw up approx. 0.1 mL of superyellow solution with the empty syringe (yellow dot)
and hold the syringe in the centre just above the FTO glass. Squirt the solution in a steady
stream (not drop by drop and not too fast) onto the rotating glass.
e. Allow the glass to rotate for a further 10-20 sec. You should then get a thin, continuous
layer of Super Yellow on your FTO glass (Figure 58).
f. Remove the adhesive film from step 1.
Figure 58 Spincoating of the Superyellow® layer
117
6.2.5.4 Preparation of the Galinstan electrode (Cathode)
Place the Galinstan socket in front of you so that the black rubber strips face upwards (see fig.
4). These serve as spacers.
At the end of each copper strip (see Figure 59), create a Galinstan drop the size of a small pinhead
(at least as high as the spacers). The drops can be wider than the copper strips, but should not
but should not run into each other.
Figure 59 Preparation of the cathode
6.2.5.5 Assembling the organic light emitting diode
Important: A common mistake in this step is that the coated glass is placed on the galinstan
mount the wrong way round. Please follow the instructions exactly or look at the pictures care-
fully!
a. Take the coated FTO glass and place it with the coated side down on the Galinstan mount
so that there is close contact between the Superyellow® layer and the Galinstan (Figure
60). Place the glasses slightly offset on top of each other so that the copper strips can be
contacted with a crocodile clip.
b. Carefully take the "sandwich" in your hand and fix it with the help of the two foldback
clamps (Figure 61). Place the clamps so that the pressure is on the rubber strips.
c. Your OLED is now ready. Do not move it too much, otherwise the Galinstan could leak!
118
Figure 60 Assembling the OLED.
Figure 61 The complete OLED.
119
6.2.6 Luminous custard powder – experiments with B vitamins
6.2.6.1 Detection of vitamin B1 via fluorescence
2 test tubes und stopper vitamin B1 tablets
1 mortar with pestle sodium hydroxide solution (c(NaOH) = 0.5 mol/L)
1 spatula
1 gas burner
1 Pasteur pipet with rubber nipple potassium hexacyanidoferrate(III)
1 UV lamp
Procedure
Crush two vitamin B1 tablets in a mortar and grind them to a fine powder.
The resulting powder is divided into 2 test tubes, each containing 5 mL (one quarter of the test
tube height) of demineralised water and shaken.
One of the two suspensions is boiled over the gas burner for about 3 minutes. The second sus-
pension serves as a comparison. Both liquids are observed under UV light.
A few crystals of potassium hexacyanidoferrate(III) are added to both suspensions. Then about 5
mL of sodium hydroxide solution is added and the test tubes are shaken well. Wait for about 15
minutes. The suspensions are observed again under UV light.
What effects does the addition of potassium hexacyanidoferrate(III) and sodium hydroxide solu-
tion have?
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
What are the effects of heating (heat stability of vitamin B1)?
......................................................................................................................................................
......................................................................................................................................................
120
6.2.6.2 Detection of vitamin B2 via fluorescence
3 test tubes custard powder
1 beaker 250 mL
stirring hot plate with stirring rod sodium hydroxide solution (c(NaOH) = 2 mol/L)
1 funnel with filter paper
1 UV lamp
Procedure
About 15 g of custard powder are heated in 50 mL of demineralised water for a few minutes and
filtered hot.
The filtrate is divided into 3 test tubes, one with about 5 mL sodium hydroxide solution and one
with about 5 mL hydrochloric acid. All three solutions are observed under UV light.
The solution to which no hydrochloric acid or sodium hydroxide has been added is kept for the
following experiment 6.2.6.3!
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......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal. Disposal is via the sink, or the neutral solution is stored.
121
6.2.6.3 Separation of food colourants in custard powder
TLC plates (cellulose)
1 beaker 100 mL Solution from 6.2.6.2 (extract from custard powder
glass rod dyes)
TLC capillaries TLC eluent (ethanol : ethyl acetate : n-heptane =
pencil 3:1:4)
TLC chamber riboflavin
1 UV lamp
Procedure
A spatula tip of riboflavin is added to 50 mL water. By means of thin-layer chromatography, this
riboflavin solution is to be compared with the solution from 6.2.6.2:
First, a thin pencil line (starting line) is carefully applied to a DC plate at a distance of approx. 1
cm from the lower edge and the two solutions are applied next to each other (as two broad dots)
on this with the help of the capillaries (immerse the capillaries only slightly in the solution). When
applying the solution from 6.2.6.2, it is advisable to apply the solution several times in succession
until a reddish colour is visible.
Place the DC plates in the glass vessel with the eluent, close the lid and wait until the solvent
mixture front has almost reached the upper end of the plate. The plates are then removed, the
solvent front is marked with a pencil, the plates are dried briefly and observed both in room
lighting and under UV light.
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......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Additional information:
Thin-layer chromatography (TLC) is a standard method in the laboratory for obtaining an initial
overview of the constituents of substance samples. It is based on the different solubility of sub-
stances in solvent mixtures (solvent as mobile phase) and on the different adsorption capacity on
carrier substances (cellulose-se-DC plate as stationary phase) (Figure 62)
122
Figure 62 Schematic of a thin-layer chromatography, here with three substances. © Ernst Klett Verlag, Stuttgart.
Disposal: The riboflavin solution can be kept for experiment 6.2.6.4., the TLC plates are added to
the solid waste.
123
6.2.6.4 Redox reaction of riboflavin
2 test tubes riboflavin solution (from 6.2.6.3)
1 UV lamp
sodium dithionite Na2S2O4
Pasteur pipette with rubber nipple
hydrogen peroxide solution (w(H2O2) = 10 %)
1 Erlenmeyer flask 100 mL
Procedure
Dissolve about 2 g of sodium dithionite in 10 mL of water in a test tube.
In a 100 mL Erlenmeyer flask, about 10 mL of the riboflavin solution is added and observed under
UV light. Sodium dithionite solution is added until a clear change can be seen. Be careful not to
use too much sodium dithionite solution.
......................................................................................................................................................
......................................................................................................................................................
Then shake the Erlenmeyer flask (without stopper) for a longer time until you can see a change.
You can also try to accelerate the reaction by adding a few drops of hydrogen peroxide solution.
Then a small amount of sodium dithionite solution is added again.
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Disposal:. The disposal is via the sink.
124
6.2.6.5 Complexation of riboflavin
2 test tubes
spatula riboflavin
1 Pasteur pipet with rubber nipple silver nitrate AgNO3
1 UV lamp
Procedure
Add a small spatula tip of riboflavin to about 10 mL of water, shake well, filtrate the solution and
divide it equally between two test tubes. Add a small spatula tip of silver nitrate to one test tube,
shake and wait briefly.
......................................................................................................................................................
......................................................................................................................................................
Both solutions are observed under UV light.
......................................................................................................................................................
......................................................................................................................................................
You can also record absorption spectra of the different riboflavin solutions (unexposed, exposed,
complexated with silver ions) with the spectrophotometer.
Disposal: The riboflavin solution is stored for photometry. The solution with added silver nitrate
is disposed of in the collection container for inorganic liquids.
Experiments based on (Sheraz, Kazi, Ahmed, Anwar & Ahmad, 2014)
125
6.2.6.6 Photodegradation of riboflavin
test tubes and stopper
terrarium lamp (UV rich) Riboflavin
1 beaker 250 mL Different solvents (e.g., acetone, methanol, ethanol,
spatula
glass rod …)
1 graduated pipet 20 mL with pipet aid stabilisators and complex builders (e.g., ethylenedia-
1 graduated pipet 10 mL with pipet aid mine tetraacetic acid (EDTA) or silver nitrate
1 UV lamp
2 graduated pipettes 10 mL with pipetting )
aid acids, bases, reduction and oxidation agents (e.g.,
1 funnel with filter paper hydrochloric acid (c(HCl) = 2 mol/L ), sodium hydrox-
Optional: ide solution (c(NaOH) = 2 mol/L), sodium dithionite,
torch with different colours hydrogen peroxide solution (w(H2O2) = 10%)
ice bath
2 beakers 50 mL )
stirring hot plate
Procedure
Two spatula tips of riboflavin are added to 150 mL of water, it is stirred well, and the suspension
is filtered.
The yellow fluorescent riboflavin solution produced in this way is not light-stable and decom-
poses into blue fluorescent lumichrome when irradiated. You are to investigate the decomposi-
tion in this experiment.
The riboflavin solution is divided into several test tubes. These are closed with a stopper.
One test tube with the riboflavin solution should be kept in a dark place as a reference solution.
The remaining solutions are further treated according to the possibilities suggested below and
then exposed to light with the aid of the irradiation lamp for about 10 minutes to cause decay.
After irradiation, the test tubes are viewed under UV light and the colours of the fluorescence
are compared. The observations can also be recorded photographically.
You now have to find out which factors can accelerate or slow down this decay! Use the prepared
riboflavin solutions for this.
Possibilities for investigations:
You can investigate the influence of different chemicals and solvents (a large selection of sub-
stances that can be added to the riboflavin solution is available at the places).
......................................................................................................................................................
126
......................................................................................................................................................
......................................................................................................................................................
You can check the temperature dependence by carrying out the exposure in a beaker in an ice
bath or on a hot plate.
......................................................................................................................................................
......................................................................................................................................................
There are various lamps available for irradiation with which you can investigate the influence of
the light colour.
......................................................................................................................................................
......................................................................................................................................................
You can dilute the riboflavin solution to investigate the concentration dependence of the decay.
......................................................................................................................................................
......................................................................................................................................................
The following also applies to all suggested experiments: You can observe the fluorescence of the
samples under UV light after different exposure times. To do this, change the duration of the
exposure time for individual experiments (e.g., observation after 5 min, 10 min, 30 min, ...).
......................................................................................................................................................
......................................................................................................................................................
127
You are also welcome to combine these focal points of investigation or to try out additional de-
pendencies yourself. Be sure to label all samples to prevent confusion.
If possible, try to summarise your results in tabular form.
You can also record absorption spectra of the different riboflavin solutions with the spectropho-
tometer.
Disposal: Disposal is via the sink. Solutions with added silver nitrate are given into the collection
container for inorganic liquids
Experiment developed based on (Keune, Waitz & Irmer, 2022).
128
7. Molecular switches
129
7.1 Theory: Molecular switches
7.1.1 Introduction: Molecular switches
Molecular switches are molecules that can be reversibly transferred from one state to another
by an external stimulus - analogous to a classical switch that can be "on" or "off". Such a stimulus
can be, for example, light, a chemical reaction or electric current (Feringa, 2003). Acid-base indi-
cators (e.g., the azo dyes methyl orange and orange II from the first day of the experiment) are a
very simple example of a molecular switch. A chemical reaction "switches" the light absorption
behaviour of the dye molecules and thus the colour of a solution of the dye.
In this focus, you will mainly learn about molecular switches in which the colour can be switched
by an external stimulus. Depending on the type of stimulus that triggers this colour change, we
talk about photochromism (triggered by light), electrochromism (triggered by electric current) or
thermochromism (triggered by temperature change). In the experiments on the luminescence
thermochromism of copper(I) iodide complexes, not only the colour of the compound but also
the wavelength and thus the colour of the luminescence (i.e., the emitted light in fluorescence
and phosphorescence) of the compound is switched by temperature change. More information
on the phenomenon of luminescence can be found in the specialisation area luminescence.
Azobenzene represents a simple molecular switch. Normally, azobenzene is present as (E)-azo-

benzene (trans-azobenzene), but by irradiation with UV light, an equilibrium with the isomeric
(Z)-azobenzene (cis-azobenzene) is established. The two isomers can be separated by chroma-
tography (Spektrum Akademischer Verlag, 1998). The isomerisation of (E)-azobenzene to (Z)-az-
obenzene, shown in Figure 51, only takes place by means of excitation by UV light; the reverse
reaction can be triggered by both light and heat (Tausch, 2019). Molecular switches are mole-
cules that can be reversibly transferred from one state to another by an external stimulus - anal-
ogous to a classical switch that can be "on" or "off". Such a stimulus can be, for example, light, a
chemical reaction or electric current (Feringa, 2003). Acid-base indicators (e.g. the azo dyes me-
thyl orange and orange II from the first day of the experiment) are a very simple example of a
molecular switch. A chemical reaction "switches" the light absorption behaviour of the dye mol-
ecules and thus the colour of a solution of the dye.
In this focus, you will mainly learn about molecular switches in which the colour can be switched
by an external stimulus. Depending on the type of stimulus that triggers this colour change, we
talk about photochromism (triggered by light), electrochromism (triggered by electric current) or
thermochromism (triggered by temperature change). In the experiments on the luminescence
thermochromism of copper(I) iodide complexes, not only the colour of the compound but also
the wavelength and thus the colour of the luminescence (i.e., the emitted light in fluorescence
130
and phosphorescence) of the compound is switched by temperature change. More information
on the phenomenon of luminescence can be found in the focus area luminescent phenomena.
x
Azobenzene represents a simple molecular switch. Normally, azobenzene is present as (E)-azo-
benzene (trans-azobenzene), but by irradiation with UV light, an equilibrium with the isomeric
(Z)-azobenzene (cis-azobenzene) is established. The two isomers can be separated by chroma-
tography (Spektrum Akademischer Verlag, 1998). The isomerisation of (E)-azobenzene to (Z)-az-
obenzene, shown in Figure 63, only takes place by means of excitation by UV light; the reverse
reaction can be triggered by both light and heat (Tausch, 2019).
Figure 63 Photochemical and thermal isomerisation of (E)-azobenzene and (Z)-azobenzene. Modified according to
"Chemistry with Light" (Tausch, 2019, p. 139).
Isomerisation triggered by light is also the core process of human vision. Photons cause isomeri-
sation from the 11-cis to the all-trans retinal at the protein rhodopsin (Urry, Cain, Wasserman,
Minorsky & Reece, 2019), which is localised in the photoreceptors of the eye. This isomerisation
starts a whole chain of subsequent reactions in which the light stimulus is recoded into an elec-
trical signal that is transmitted via the optic nerve to the brain and processed there.
In addition to colour, other properties of molecular switches can also be switched, for example
the magnetic properties. Also, of interest for research are compounds whose catalytic properties
can be changed virtually at the touch of a button, which can optimise the synthesis of certain
compounds.
7.1.2 The molecular switch system spiropyran / merocyanine

One molecular switch you will learn about in the course is the compound spiropyran. By exciting
it with light of the appropriate wavelength, the spiropyran (dissolved in the solvent xylene, for
example) can be "switched" to the isomer merocyanine (Figure 64).
131
Figure 64 Spiropyran and merocyanine.
Spiropyran is colourless when dissolved in xylene, whereas merocyanine is blue. This reaction is
thus an example of photochromism, the switching of colour by excitation with light. While the
reaction of spiropyran to merocyanine can only be triggered by light of a suitable wavelength,
the reverse reaction can also be driven by heat energy.
Compared to spiropyran, merocyanine shows a much more extended system of conjugated dou-
ble bonds. As can be seen from the structural formulae above, in spiropyran, conjugated double
bond systems are present separately in both halves of the molecule (left and right). In merocya-
nine, these two conjugated double bond systems are connected to each other and thus form a
single, more extensive system of conjugated double bonds.
It is known from the chapter on organic dyes that an extended system of conjugated double
bonds ensures that the highest occupied and the lowest unoccupied energy levels are closer to-
gether. Merocyanine, for example, shows its absorption maximum at 584 nm (i.e. in the wave-
length range of yellow light) and therefore appears blue (Tausch, 2019). Spiropyran, on the other
hand, absorbs mainly in the UV range (and somewhat in the violet range) and therefore appears
colourless.
The switching of spiropyran to merocyanine is a so-called electrocyclic reaction (Tausch, 2019).
7.1.3 The chemistry of the Prussian blue system

Iron ions can be detected, among other things, by characteristic reactions with the ferrocya-
nide/ferricyanide salts (potassium hexacyanidoferrates). In this process, iron(II) ions with the red
ferricyanide K3[Fe(CN)6)] and iron(III) ions with the ferrocyanide K4[Fe(CN)6] each produce an in-
tense blue colouration (Prussian blue). A distinction is made between so-called "soluble"
K[FeIIIFeII(CN)6] and "insoluble" FeIII4[FeII(CN)6]3 Prussian blue. Both compounds are basically
poorly soluble in water, whereas the soluble Prussian blue is colloidal. The structures of "soluble"
and "insoluble" Prussian blue are basically the same.
132
Figure 65 Simplified structural model of Prussian blue
Thin layers of Prussian blue are often obtained by electrochemical reduction of an Fe(III) ion so-
lution and a hexacyanidoferrate(III) solution. When these two aqueous solutions are added to-
gether, a brown soluble complex, the iron tricyanide complex [FeIII(CN)3] or FeIII[FeIII(CN)6],
Prussian brown), is initially formed. The cathodic electrode reaction for the electrochemical dep-
osition of Prussian blue can be formulated as follows:
⊝-Pol: FeIII[FeIII(CN)6] + e-  [FeIIIFeII(CN)6]-
Prussian brown Prussian blue / brown

red
¥
blue
↓ ai
white
/
To balance the charge, potassium ions are intercalated into the lattice.
green
The deposited Prussian blue can now be electrochemically oxidised and reduced.
A partial oxidation of Prussian blue results in the so-called Prussian green:
⨁-Pol: 3 FeIII[FeII(CN)6]-  [FeIII3{FeIII(CN)6}2{FeII(CN)6}]- + 2e-
Prussian blue Prussian green
The fully oxidised form of Prussian Blue has a yellow-brown colour and is achieved by anodic
oxidation of Prussian Blue. The process can be described as follows:
⨁-Pol: FeIII[FeII(CN)6]-  FeIII[FeIII(CN)6] + e-
Prussian blue Prussian brown
133
A cathodic reduction of Prussian blue produces Prussian white (Everitts salt), which appears col-
ourless and transparent as a thin layer.
⊝-Pol: FeIII[FeII(CN)6]- + e-  [FeIIFeII(CN)6]2-
Prussian blue Prussian white
(Wagner & Oetken, 2016a)
134
7.2 Experiments on molecular switches
In this specialisation topic, you can conduct experiments on photochromism, thermochromism,

luminescence thermochromism and electrochromism. In the experiments on electrochromism,
you can construct a small electrically dimmable disc or an electrically dimmable mirror.
If you carry out the experiments on luminescence thermochromics, you will find information on
the phenomenon of luminescence in the specialisation topic on luminescence. In the experi-
ments on luminescence thermochromism, no distinction is made between fluorescence and
phosphorescence, so the term luminescence is used in general.
135
7.2.1 The molecular switch system spiropyran und merocyanine
1 small test tube with screwcap
spiropyran
(1,3,3-Trimethylindolino-6-nitrobenzopyrylospiran)
xylene (mixture of isomers)
1 spatula tap water
stopwatch ice
1 LED torch with violet light
toluene
2 beakers (as ice or water bath)
aceton
magnetic stirrer
ethanol
diethyl ether
Procedure:
A small spatula tip of spiropyran is dissolved in 10 mL of xylene in the small test tube. The sub-
stance is relatively difficult to dissolve, it must be shaken for a longer time. The test tube is closed
with the screwcap. The solution is irradiated with the LED torch (or sunlight) for a few seconds.
Then the time is measured in a darkened room until the solution is colourless again.
201
xylene →
......................................................................................................................................................
.
'
Acetone → comin 53
......................................................................................................................................................
' "
/ 34 lo / 32
' " '
toluene → 33 83
......................................................................................................................................................
The colourless solution of spiropyran in xylene is heated in the sealed test tube in the washing
bath on the hot plate to investigate whether the spiropyran can also be "switched" by heating.
no
change
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
136
xylene
↳ Acetone / Taccone
The spiropyran solution heated to about 60°C in the water bath is "switched" in the darkened
room by shining the violet torch on it and the time taken for the solution to decolourise in the
water bath is measured.
"
Toluene 2 63
' "
/ 2 87
'
/ 272 "
......................................................................................................................................................
" ' " "
/
' '
3 48 3 54 I 4 52
xylene
......................................................................................................................................................
Acetone
......................................................................................................................................................
leg
"
1:15 81
......................................................................................................................................................
......................................................................................................................................................
The colourless spiropyran solution is cooled to about 0°C in the ice bath in a darkened room and
then switched by shining the torch on it. Then the vessel is transferred back to the ice bath and
the time is stopped until the solution appears colourless again (this can take a very long time;
you do not have to watch the solution the whole time). If no discolouration can be observed even
after a long time, transfer the ice bath together with the sample solution to a room with sunlight
(or a lighted room).
Xylene 2m 41
......................................................................................................................................................
T oluene 3m
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
You can partially cover the test tube before exposure or use different light colours for exposure.
White No
change ( Xylitol ) Green No
change
Blue
change
.
No C "
"
t 137
w →
change C" a) Lamp light No

change
Red No change
You can also investigate the behaviour of the spiropyran in other solvents (solvatochromism):
Dissolve a very small spatula tip of spiropyran (just a few small crumbs) in toluene, acetone, di-
ethyl ether or ethanol. Shake well and then check whether the solutions can be coloured and
also decoloured.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solutions can be reused.
This experiment manual was created on the basis of (Meuter, Spinnen, Yurdanur & Tausch, 2020).
138
7.2.2 Construction of an electrochromic mirror
FTO glass graphite foil
2 multimeters iron(III) sulphate solution (c(Fe2(SO4)3) = 0.1 mol/L )
potassium hexacyanidoferrate(III) solution
cable
(c(K3[Fe(CN)6)]) = 0.1 mol/L )
alligator clips acetone
2 beakers 100 mL (high) potassium nitrate solution (c(KNO3) = 1 mol/L)
glass rod silver nitrate solution (c(AgNO3) = 0.1 mol/L)
1 graduated cylinder 100 mL transparent nail varnish
stopwatch ammonia solution (w(NH3) = 10 %)
hairdryer
DC power supply
plastic box (Tic-Tac® 8 cm x 4,5 cm
x 2 cm)
stirring hot plate
Transparent adhesive tape (Tesa® film)
7.2.2.1 Coating an FTO glass with Prussian blue
Procedure:
Preparation of the electrodes
First, the conductive side of the FTO glass is determined. To do this, the resistance on both sides
of the FTO glass is measured with a multi-meter. The conductive side should have a value of
about 20 to 60 Ω. Afterwards, both the FTO glass and the graphite foil are cleaned with acetone.
Coating
To prepare the electrolyte solution, 40 mL of the

potassium hexacyanidoferrate(III) solution is
added to 40 mL of the iron(III) solution in one of
the beakers and stirred well with the glass rod.
The experiment is then set up as inFigure 66.

Note whether the meters are connected in series
or parallel. The FTO glass is thus connected as
the negative pole, the graphite foil as the posi-
tive pole. The conductive side of the FTO glass
should face the graphite foil.
Figure 66 Experimental setup for the coating of FTO
glass.
For coating, electrolysis is carried out at a voltage
of about 0.3 V for 90 seconds. A current of approx.
139
5 mA should flow, which drops to approx. 2 mA during the experiment. Try to keep to these
values as closely as possible. Make sure that the voltage and current are not too high. This is
important for the further course of the experiment.
After 90 seconds, the FTO glass is removed from the electrolyte solution and immersed in the
second beaker with demineralised water. The glass is then placed on an absorbent cloth and
dried with a hair dryer for one to two minutes.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solution is disposed of via the sink. The FTO glass is used in the following experi-
ment. The graphite foil can also be reused or disposed of with household waste.
7.2.2.2 Switching the colour of the coated glass
The experiment is set up according to the di-

agram in Figure 67 (analogous to the previ-
ous experiment). The graphite foil is first
cleaned with acetone. The coated FTO glass
is connected as the negative pole, the graph-
ite foil as the positive pole. The beaker is
filled with about 80 mL potassium nitrate so-
lution.
For switching, a voltage of about 1.5 V is ap-

plied.
To switch back, the positive and negative

poles are reversed and a voltage of about Figure 67 Experimental setup for switching the colour of the
0.5 V is applied. Switching back and forth coated glass.
can be repeated as often as desired.
In addition, an attempt can be made to visualise the different oxidation states of the Prussian
blue. For this purpose, starting from the white form, the glass is switched as the plus pole and
140
the graphite foil as the minus pole. A voltage of 0.5 V is applied to switch again to the Prussian
blue.
Then the voltage can be increased to 1.1 V to observe another oxidation stage. Afterwards, the
voltage can be increased to 1.7 V and possibly another oxidation stage can be observed.
Task Explain what kind of reaction takes place when the Prussian blue is switched to the Prussian
white. (Hint: Consider to which pole of the voltage source the coated glass is connected).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Explain what kind of reaction takes place when the Prussian white is switched to Prussian
blue and further to Prussian green or Prussian brown. (Note: Consider to which pole of the volt-
age source the coated glass is connected).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The solution is disposed of in the collection container for inorganic salt solutions. The
FTO glasses can be reused. The same applies to the graphite foil, or it is disposed of in the house-
hold waste.
141
7.2.2.3 Production of an FTO glass with silver mirror
First, the conductive side of the FTO

glass is determined with the help of
the multimeter.
The conductive side is sealed with

transparent adhesive tape (Tesa®
film). The non-conductive side is
cleaned with acetone.
Add about 40 mL of the silver nitrate

solution to the plastic vessel. Then,
while stirring with the glass rod, am-
Figure 68 Experimental setup for the production of the silver mirror.
monia solution is added. At first, a
slight turbidity occurs. Add as much ammonia solution as is necessary to dissolve this turbidity or
precipitate. Then 3 to 4 spatulas of glucose are added while stirring with the glass rod.
The prepared FTO jar is placed in the plastic vessel, and this is then placed in the water bath on
the heating plate (Figure 68). The water bath is then heated to about 70°C. The plastic vessel is
left in the water bath. The plastic vessel remains in the hot water bath for about 15 minutes.
The FTO jar is then removed from the solution and rinsed with distilled water. The adhesive tape
is removed, and the conductive side is completely freed from residues of the adhesive tape with
the help of acetone. Then the silvered side of the FTO glass is sealed with transparent nail varnish.
Task The reaction used for mirroring the FTO glass is also known as the Tollens sample or silver
mirror sample. You may be familiar with this detection reaction from your chemistry lessons.
Name which compounds are detected with this reaction and give a general reaction equation for
the detection reaction.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
142
Disposal: The ammoniacal silver nitrate solution is disposed of in the collection container for salt
solutions containing silver.
7.2.2.4 Production of an electrochromic mirror
Analogous to the first experiment on electrochromy:
To prepare the electrolyte solution, add 40 mL of the

potassium hexacyanidoferrate(III) solution with 40 mL
of the iron(III) solution to one of the beakers and stir
well with the glass rod. The graphite foil is cleaned with
acetone.
The experiment is then set up as inFigure 69. The FTO

glass is thus connected as the negative pole, the graph-
ite foil as the positive pole. The conductive side of the
FTO glass must face the graphite foil.
Figure 69 Experimental setup for the produc-
For coating, electrolysis is carried out at a voltage of tion of an electrochromic mirror.
about 0.3 V for 120 seconds. A current of approx. 5 mA

should flow, which drops to approx. 2 mA in the course of the experiment.
After 90 seconds, the FTO glass is removed from the electrolyte solution and immersed in the
second beaker with demineralised water. The glass is then placed on an absorbent cloth and
dried with a hair dryer for one to two minutes.
Disposal: The solution is disposed of via the sink. The FTO glass is used in the following experi-
ment. The graphite foil can also be reused or disposed of with household waste.
Final Product .
143
7.2.2.5 An electrically dimmable mirror
The experiment is set up according to the (analogous to the previous experiment). The graphite
foil is first cleaned with acetone. The coated FTO glass is
connected as the negative pole, the graphite foil as the pos-
itive pole. The beaker is filled with about 80 mL potassium
nitrate solution (Figure 70).
For switching, a voltage of about 1.5 V is applied.
To switch back, the positive and negative poles are re-

versed and a voltage of approx. 0.5 V is applied. Switching
back and forth can be repeated as often as desired.
During switching, the glass is illuminated with the torch to

Figure 70 Experimental setup for an electrically
illustrate the dimming effect. For the most visible effect, dimmable mirror.
make sure that the side of the FTO glass coated with Prus-
sian Blue faces outwards (instead of towards the graphite foil).
Disposal: The solution is disposed of in the collection container for inorganic salt solutions. The
FTO glasses are reused. The same applies to the graphite foil, or it is disposed of in the household
waste.
Experimental instructions based on (Wagner & Oetken, 2016a).

.
→ dimmed
returned .
144
7.2.3 Thermoluminescence
1 round-bottomed flask with ground joint
(100 mL) pyridine
1 glass stopper copper(I) iodide CuI
1 joint clip liquid nitrogen N2(l)
Dewar vessel
spatula
UV lamp (365 nm)
1 magnetic stirrer with stirring rod
cork ring
heat protecting gloves
7.2.3.1 Synthesis of a trispyridine copper(I)-iodide complex and examination of its

luminescence at low temperatures
The test must be carried out under the fume cupboard! Wear protective gloves!
10 mL pyridine and the stirring magnet are added to the round bottom flask under the fume
hood. Then 20 mg (0.02 g) copper(I) iodide are added, the flask is closed with the stopper and
the ground-glass clamp and stirred for approx. 3 minutes.
In a darkened environment, the flask is irradiated with UV light. The Dewar vessel is filled with
liquid nitrogen. The flask is then immersed in the liquid nitrogen to cool down and continues to
be irradiated with the UV lamp.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
145
7.2.3.2 Synthesis of bispyridine copper(I)-iodide and investigaton of luminescent properties
The test must be carried out under the fume cupboard! Wear protective gloves!
Wet the filter paper with the solution from the previous experiment using the pipette. Fill the
Dewar flask with liquid nitrogen. The filter paper is left to dry in the fume cupboard at room
temperature while being irradiated with the UV lamp.
After complete drying (recognisable by the luminescence of the previously wetted area after ap-
prox. 3 minutes), the filter paper is cooled under UV light by immersion in liquid nitrogen.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The filter paper is disposed of via the collection waste for contaminated filter materials.
Experimental instructions based on (Lanfermann et al., 2020)
146
7.2.4 Titanium dioxide coatings by anodic oxidation
DC power supply titanium sheets (cleaned with acetone)
cable
oxalic acid solution (w = 4 %)
alligator clips
Luster clamp acetone
laboratory jack nail varnish
beaker100 mL demin. water
7.2.4.1 Preparation of nano titanium dioxide coatings by anodic oxidation
Procedure:
An electrolysis apparatus is constructed according
to the scheme (Figure 71). For this purpose, one ti-
tanium sheet is connected as the cathode and one
as the anode. An aqueous 4% oxalic acid solution is
used as the electrolyte and the sheet is anodised at
5 V.
Since the actual anodising process is very fast, care

must be taken to set this voltage before the elec-
trodes are immersed in the solution. After one mi-
Figure 71 Experimental setup for the coating by an-
nute, the anode sheet is removed and rinsed with odic oxidation.
distilled water.
To demonstrate the influence of the anodising voltage on the colour impression, further sheets
can be treated at other voltages. Repeat the experiment with voltages of 10 V, 15 V, 20 V ... 50
V. Use a new titanium sheet each time. The cathode (negative pole) can be used several times.
Alternatively, the different colour impressions can also be displayed on one sheet. For this pur-
pose, the voltage is increased evenly or in small steps, while the electrolyte solution is lowered
accordingly by means of an additional laboratory jack.
Include photos of your coloured titanium sheets.
Disposal: The cathodic titanium sheet is left at the laboratory; the coloured sheets are kept for
documentation. The electrolyte is disposed via the sink.
147
7.2.4.2 Production of two-colour appearing motifs by anodic oxidation
Analogous to the previous experiment, an electrolysis apparatus is set up. The desired motif is
applied to the titanium sheet with nail varnish before it is placed in the electrolyte solution. After
an anodising step with the voltage that provides the desired background colour according to
experiment 4.2.9, the nail varnish is removed with acetone and a second anodising step is carried
out to achieve the second colour. The applied voltage must be lower than in the first step. Finally,
the sheet is rinsed with water and dried.
Disposal: The cathodic titanium sheet is left at the laboratory; the coloured sheets are kept for
documentation. The electrolyte is disposed via the sink.
Include photos of your coloured titanium sheets here.
148
7.2.5 A switchable iron(II) complex
Dewar vessel
iron(II) perchlorate hydrate Fe(ClO4)2 H2O
Crucible tongs
Potassium dihydrobispyrazolyl borate
heat protecting gloves
4-Methyl-1,10-phenantroline
spatula
tert-Butylmethylether (MTBE)
Eppendorf cup
thread
1 support stand with support rod
Neodyme magnet
The experiment is carried out at the chemistry department of the faculty of chemistry at the
university.
7.2.5.1 Preparation of the switchable iron(II) complex [Fe(H2B(pz)2)2(4-Me-Phen)]
Some of the starting materials for this experiment are not stable in an oxygen-containing envi-
ronment - and thus also in air. These starting materials must therefore be stored and handled in
an inert gas atmosphere. The inert gas in this case is nitrogen.
The production of the complex takes place with a PhD student in a laboratory of the department
of Prof. Dr. Stalke. This way, the product can be produced on a larger scale (if desired) and an
insight into working under inert gas can be gained.
Single scale:
For the synthesis, 23.2 mg iron(II) perchlorate hydrate are dissolved in 5 mL MTBE. In another
vessel, 12.9 mg 4-methyl-1,10-phenantroline are also dissolved in 5 mL MTBE. In a third vessel,
24.8 mg of potassium dihydrobispyrazolyl borate is dissolved in 10 mL of MTBE.
To synthesise the intermediate, the solution of potassium dihydrobispyrazolyl borate is dropped

into the solution of iron(II) perchlorate. The formation of the intermediate product, the tetrahe-
dral iron complex [Fe(H2B(pz)2)2], can be recognised by the yellow colour of the solution.
To synthesise the final product, the yellow solution (without precipitate) is added to the solution
of 4-methyl-1,10-phenantroline. This reaction is accompanied by another colour change.
The final product is stable in air and can be filtered off (in the XLAB) using the funnel. (Alterna-
tively, the solvent can be removed using a vacuum membrane pump/water jet pump). For stor-
age, the (dry) product should be transferred to a snap cap jar.
149
The structure of the synthesised complex is shown in Figure 72. The central atom, an iron(II) ion,
is octahedrally coordinated in it. Each of the three ligands binds with the central atom via two
different nitrogen atoms, resulting in the octahedral coordination.
1 :
-
Figure 72 Structure of the switchable iron complex [Fe(H2B(pz)2)2(4-Me-Phen)].
7.2.5.2 Switching the colour of [Fe(H2B(pz)2)2(4-Me-Phen)]
Procedure:
The Dewar vessel is filled with liquid nitrogen. With the help of the crucible tongs and/or a ther-
mal glove, the snap-lid jar filled with the red product is cooled in the liquid nitrogen and the
colour of the product is observed. For heating, the snap lid jar is lifted out of the liquid nitrogen
and observed. Try to repeat the cooling and heating.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Disposal: The product is used again in the next experiment.
150
7.2.5.3 Switching the magnetic properties of [Fe(H2B(pz)2)2(4-Me-Phen)]
Procedure:
The Dewar vessel is filled with liquid nitrogen. The product
from the snap-lid jar is transferred to an Eppendorf cup. A
thread is attached to this so that the vessel can be attached
to the crossbar of a stand as shown in the illustration in Fig-
ure 73.
To investigate the magnetic properties of the product, the

neodymium magnet is brought close to the Eppendorf cup.
Figure 73 Examination of the magnetic
The product is then cooled in liquid nitrogen and the properties.
neodymium magnet is then brought close to the Eppendorf
cup again. The magnetic properties can also be examined during heating. Try to repeat the
experiment several times.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Task: Name the magnetic property exhibited by the complex at room temperature or below -
108°C (cooled down with liquid nitrogen).
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
151
Task: Describe what conclusions can be drawn from the experimental observation about the
electron configuration of the complex at room temperature or below -108°C.
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Explanation for the change in colour and magnetic properties:
During cooling, the distance between the ligands and the central particle becomes smaller, which
increases the repulsion between the ligands and the orbitals of the central particle. The stronger
repulsion increases the energy difference between the energetically split d orbitals. Due to the
stronger splitting, it is energetically more favourable to apply the spin-pairing energy, and the
complex exists as a diamagnetic low-spin complex.
At room temperature, the ligand field splitting is lower, so that it is more favourable to occupy
the energetically higher orbitals instead of applying the spin-pairing energy. This results in a high-
spin complex at room temperature, which is paramagnetic.
Disposal: The product is collected and can be reused.
Experimental instructions based on (Rudnik et al., 2014)
152
8. Tasks for the excursions to the departments in the faculty
of Chemistry
The visits to the three departments are intended to show you how the topics covered in our
course are implemented in real research. In addition, you should get to know how scientists work
and feel something of the enthusiasm with which the researchers are at work.
Please bear in mind that it is not always possible to find a department that absolutely fits your
specialisation topic.
Before you go to the department, you should therefore think about a few questions that will help
you to better understand the applications of your subject area. The following questions can serve
as suggestions. However, you should also think of your own questions.
Possible questions for the visit:
On the content:
 Where does the interaction of light and matter appear in the research shown to you?
 For what purpose do the researchers use this interaction?
 At what points in the research shown to you does your specialisation topic appear?
 How does the equipment in the research group differ from what you learned about in the
XLAB?
My own questions:
"
why do we need this special

......................................................................................................................................................
environment ? How ?
"
......................................................................................................................................................
What are the

apt of the ar t
...................................................................................................................................................... .
blood that
......................................................................................................................................................
why do we were meadow

......................................................................................................................................................
......................................................................................................................................................
153
About the researchers:
 Try to find out something about the researchers' work histories.
 What do the researchers seem to find fascinating about their work?
 What career prospects do the researchers have?
My own questions:
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
......................................................................................................................................................
Please keep in mind that the researchers take extra time for you, even though this is not their
job. Therefore, please always be friendly, polite and show interest. This is the only way the XLAB
can make such an experience possible for other students.
154
9. Literature
Acker, A. & Bartels, S. (Hrsg.). (2008). Lexikon der Chemie. In drei Bänden (Jokers edition, Son-
derausg). Heidelberg, Berlin: Spektrum Akademischer Verlag.
Atkins, P. W. & Paula, J. de. (2012). Physikalische Chemie (4., vollst. überarb. Aufl., 2. Nachdr).
Weinheim: Wiley-VCH.
Banerji, A., Dörschelln, J. & Schwarz, D. (2018a). Organische Leuchtdioden im Chemieunterricht.
Chem. Unserer Zeit, 52(1), 34–41. https://doi.org/10.1002/ciuz.201700795
Banerji, A., Dörschelln, J. & Schwarz, D. (2018b). Organische Leuchtdioden im Chemieunterricht
Supporting Information. Chemie in unserer Zeit, 52(1).
https://doi.org/10.1002/ciuz.201700795
Bee, U., Blauth, O., Gietz, P., Irmer, E. [Erhard], Kirberger, C., Maier, H. et al. (2019). Elemente
Chemie Oberstufe (1. Auflage, [Ausgabe] Niedersachsen). Stuttgart, Leipzig: Ernst Klett Ver-
lag.
Bundesministerium für Umwelt, Naturschutz und nukleare Sicherheit. (2020, Juni). Nationale
Wasserstoffstrategie – ein wichtiger Beitrag zum Klimaschutz und zur Zukunftsfähigkeit unse-
rer Wirtschaft. BMU Infopapier: Nationale Wasserstoffstrategie (Juni 2020). Verfügbar unter:
https://www.bmu.de/fileadmin/Daten_BMU/Download_PDF/Klimaschutz/nationale_was-
serstoffstrategie_infopapier_bf.pdf
Feringa, B. L. (Ed.). (2003). Molecular switches (1. Nachdr). Weinheim: Wiley-VCH.
Heffen, M. & Tausch, M. W. (2015). Photokatalyse - homogen und heterogen. Das Photo-Blue-
Bottle-Experiment runderneuert. Praxis der Naturwissenschaften - Chemie in der Schule,
64(6), 51–55. Zugriff am 06.02.2020.
Hoffmann, C., Mika, S., Herbst-Irmer, R., Irmer, E. [Erhard.] & Waitz, T. (61). Echt anziehend -
Untersuchung des magnetischen Verhaltens von Komplexverbindungen. Praxis der Naturwis-
senschaften - Chemie in der Schule, 2012(6), 31–35.
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ments on Photo Processes in Chemistry Class. New Perspectives in Science Education. Confer-
ence Proceedings, 86–91.
Korn, S., Posalla, F., Nietz, D., Heffen, M., Kremer, R., Yurdanur, Y. et al. (2019). PHOTO-CAT
(Bergische Universität Wuppertal, C., Hrsg.). Wuppertal. Verfügbar unter: https://chemiemit-
licht.uni-wuppertal.de/fileadmin/Chemie/chemiemitlicht/files/kits/photo-cat/photo-cat.pdf
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KON. https://doi.org/10.1002/ckon.202000035
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Boston: De Gruyter.
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10. Space for notes and photos
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International Science Camp 2022

Light and Matter

8.-12. August 2022

Dr. Erhard Irmer

Stud.IP user account: ………………………………..

Stud.IP password: ………………………………………………

Figure 1 Waves with different wavelengths (and frequencies)

ℎ∙𝑐 1,986 ∙ 10−25 J ∙ m

Figure 2 The electromagnetic spectrum with the visible spectrum highlighted.

2.2 Why do things appear coloured?

wavelength λ of absorbed light

380 – 435 purple yellow green

435 – 480 blue yellow

480 – 490 greenish blue orange

490 – 500 bluish green red

500 – 560 green purple

560 – 580 yellow green violet

580 – 595 yellow blue

595 – 650 orange greenish blue

650 - 780 red bluish green

Wavelength of absorbed light λ in nm

2 225 420 (violet)

3 257 519 (green)

4 300 620 (red)

14 485 (blue green)

3.1.2 Azo dyes

colourless red violet

Figure 11 Synthesis of thymolphthalein

Figure 14 Schematic design of a photometer.

Figure 16: Absorption spectrum of a blue dye.

The experiment must be carried out under the

Wear protective gloves!

Preparation of the diazonium salt:

In a 100 mL round bottom flask add:

- 1.6 g sulphanilic acid

- 3 mL semi-concentrated sulfuric acid

Figure 17 Experimental setup for the synthesis of methyl

perature must not rise above 5 °C and must

After further cooling, 1.3 mL of N, N-dimethylaniline is added.

Disposal: The dye is needed for later experiments.

The experiment must be carried out under the

Wear protective gloves!

Preparation of the diazonium salt:

In a 100 mL round bottom flask, dissolve 1 g

Alkaline Orange / Acidic

Disposal: The dye is needed for later experiments.

The solutions must be strongly diluted!

Determine the maximum absorption of the dye.

methyl orange acidic: .......................... nm

wavelength λ extinction E of dye

Compare the two dyeing results:

The wool took darker shade of

than the cotton

Disposal: Disposal is via the sink.

The solution remained colorless

Disposal: Disposal is via the sink.

 1 small Erlenmeyer flask with thymolphthalein solution in acidic medium

 1 small Erlenmeyer flask with thymolphthalein solution in a basic medium.

The solutions must be strongly diluted!

Determine the maximum absorption of the dye.

Thymolphthalein acidic: .......................... nm

wavelength λ extinction E of dye

After 10 minutes, add a piece of cotton to