Angelo Albini

Photochemistry
Past, Present and Future
Photochemistry
ThiS is a FM Blank Page
Angelo Albini

Photochemistry
Past, Present and Future
Angelo Albini
Organic Chemistry
University of Pavia
Pavia, Italy

ISBN 978-3-662-47976-6 ISBN 978-3-662-47977-3 (eBook)

DOI 10.1007/978-3-662-47977-3

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Preface

The chemical changes induced by light on substances have been long known. The
advancement of this discipline has been somewhat irregular, however, with an
outburst at the beginning of the twentieth century corresponding to the first
in-depth preparative studies on one hand and to the development of quantum
physics on the other hand, and a much more consistent development after 1950
when the general framework of this science was recognized.
As we now understand this phenomenon, absorption of a photon leads to an
electronically excited state, characterized by high energy and a strongly perturbed
electronic structure. The result often is an in-depth—but selective—chemical
transformation. As everyone can easily appreciate, photochemistry has a key role
in nature (e.g., chlorophyll photosynthesis, vision) and in a variety of applications.
Photography and other methods of reproducing an image, the fast hardening of
varnishes and of dental cement, and many other applications are based on photo-
chemical reactions.
Furthermore, photochemistry has a particular role in learning and teaching
chemistry, as was recognized already in 1926 (see Sect. 2.5), in that it concerns
all of the electronic states of a given species, in particular the lowest singlet excited
and triplet states, not only the lowest-lying (ground) one as does normal (thermal)
chemistry. Thus, not only one but at least two new dimensions are added to
chemistry by light absorption, and learning how to exploit and direct the system
toward a specific goal is one of the main issues of future time’s chemistry.
Retracing the path that has led to the present state of photochemistry may give
some hints of those that still lay open to exploration.
What has been attempted here is to understand the actual experiments and the
intellectual effort that have led to the development of this wonderful discipline, and
perhaps to extend the enthusiasm of scientists already engaged in the field toward
new facets of it.

v
vi Preface

I would have not expected writing this book to be such a hard task. I am grateful
to the many scientists from whom I had the opportunity to learn over the years and
I hope that the many inefficiencies of the manuscript will be indicated to me. The
colleagues who helped me in this adventure are thanked for their enthusiasm and
competence (prof. Maurizio Fagnoni, drs Stefano Protti, Davide Ravelli, Stefano
Crespi, and prof Elisa Fasani). My sons and my friends, in particular Mr Nicola
Scuro, are likewise thanked for their help.

Pavia, Italy Angelo Albini

Contents

1 Early Times of Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Light and Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Historic Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 The Framework of Photochemistry: The Laws . . . . . . . . . . . . . . . . 9
2.1 The Relation with Light Wavelength . . . . . . . . . . . . . . . . . . . . 10
2.2 Relation with Light Intensity . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.3 Early Attempts to Rationalize Photochemical Reactions . . . . . . 18
2.4 Relation with Light Quanta . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.5 Measured Quantum Yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.6 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.7 Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.8 The “Laws” of Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3 The Framework of Photochemistry: State Diagram . . . . . . . . . . . . 41
3.1 Absorption/Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2 The Triplet State: Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3 The Triplet State: Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.4 Paradigms of Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.5 Generalized Use of the State Diagram . . . . . . . . . . . . . . . . . . . 57
3.6 Moving Along the States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4 Some Paradigmatic Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.1 Photochemistry for Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.1.1 Some Exemplary Cases of Early Reported
Photoreactions: Santonin, Anthracene, 2+2
Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1.2 The Synthetic Potential of Photochemistry . . . . . . . . . 74
vii
viii Contents

4.1.3 A “Green” Synthetic Method . . . . . . . . . . . . . . . . . . . 78

4.2 Born to Measure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.2.1 o-Nitrobenzaldehyde and the Equivalence Law . . . . . . 79
4.2.2 Mechanism: Early Studies . . . . . . . . . . . . . . . . . . . . . 81
4.2.3 Mechanism: Modern Studies . . . . . . . . . . . . . . . . . . . . 83
4.2.4 o-Nitrobenzaldehyde as an Actinometer . . . . . . . . . . . 85
4.3 Oxygenation Reactions and Singlet Oxygen . . . . . . . . . . . . . . . 87
4.3.1 Photosensitized Oxygenations in Biologic Systems . . . 87
4.3.2 Oxygenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . 88
4.3.3 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.4 Inorganic Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4.1 Early Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4.2 Photochemistry and Photophysics of Transition Metal
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.4.3 Transition Metal Complexes as Sensitizers . . . . . . . . . 99
4.5 Energy from the Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.5.1 Ciamician in 1912 . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.5.2 Bodenstein in 1915 . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.5.3 The Beginning of Photocatalysis . . . . . . . . . . . . . . . . . 105
4.6 Cursory Elements of Photobiology . . . . . . . . . . . . . . . . . . . . . . 106
4.6.1 Photosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.6.2 Vision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.6.3 Vitamin D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.6.4 Medicinal Applications of Photochemistry . . . . . . . . . 117
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5 The Role of Photochemistry in Chemistry . . . . . . . . . . . . . . . . . . . 131
5.1 Photochemistry in Chemistry Meetings . . . . . . . . . . . . . . . . . . 131
5.2 The Role of Photochemistry, 1912–2013 . . . . . . . . . . . . . . . . . 133
5.3 Publications in Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . 134
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
6 Photochemistry, a Powerful Science . . . . . . . . . . . . . . . . . . . . . . . . 139
6.1 Harry Potter Meets Photochemistry . . . . . . . . . . . . . . . . . . . . . 139
6.2 This Is How It Happens: Time-Resolved Spectroscopy in
Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
6.2.1 Flash Photolysis with Lamps . . . . . . . . . . . . . . . . . . . 143
6.2.2 Laser Flash Photolysis and Pump-Probe
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
6.2.3 Two-Color Flash Photolysis . . . . . . . . . . . . . . . . . . . . 153
6.2.4 Local Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.2.5 Flash Photolysis with Different Detection . . . . . . . . . . 157
6.3 This Is How It Happens: Blocking the Intermediates . . . . . . . . . 158
6.4 Anything You Can Do, Photochemistry Can Do Better:
Generating Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.4.1 Carbocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
6.4.2 Carbenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Contents ix

6.4.3 Nitrenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

6.4.4 Aromatic Biradicals: Didehydrobenzenes and
Didehydrotoluenes . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.5 Anything You Can Do Photochemistry Can Do Better: Making
(Strained) Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7 Of Excited States Again . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
7.1 Expanding the State Diagram . . . . . . . . . . . . . . . . . . . . . . . . . 183
7.2 Upconversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
7.3 Multiphotonic Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
7.4 Quantum Yield of Excited States Larger than One . . . . . . . . . . 191
7.5 Ultrafast Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
7.6 Reactions via Upper States . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
7.7 The Future of Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . 199
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
8 Photochemical and Photocatalyzed Synthesis . . . . . . . . . . . . . . . . . 205
8.1 Application in Synthesis: Synthetic Sequences . . . . . . . . . . . . . 205
8.1.1 Photochemical Steps in Synthetic Planning . . . . . . . . . 206
8.1.2 Old and New Strategies in Synthesis . . . . . . . . . . . . . . 209
8.1.3 Synthesis via Chiral Auxiliary . . . . . . . . . . . . . . . . . . 211
8.2 Asymmetric (Photochemical) Synthesis . . . . . . . . . . . . . . . . . . 212
8.2.1 Absolute Asymmetric Synthesis . . . . . . . . . . . . . . . . . 212
8.2.2 Chirality Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
8.3 Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
8.3.1 Organocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
8.3.2 Catalysis: Only the Complexed Reagent Is Activated . . . 215
8.3.3 Catalysis: Atropisomerism . . . . . . . . . . . . . . . . . . . . . 216
8.3.4 Catalysis: Only the Complexed Form Is Reactive . . . . . 217
8.3.5 By Using a Strong Chiral Complex in a Way to Limit
Reversibility, Even When Hindered . . . . . . . . . . . . . . 218
8.3.6 Polyfunctional Catalysis . . . . . . . . . . . . . . . . . . . . . . . 219
8.3.7 By Resorting to an Intrinsically Fast Reaction, Such as
Proton Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
8.3.8 Catalysis: Chiral Memory . . . . . . . . . . . . . . . . . . . . . . 221
8.3.9 One-Pot Catalytic Procedure . . . . . . . . . . . . . . . . . . . . 222
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
9 Medicinal and Diagnostic Applications . . . . . . . . . . . . . . . . . . . . . . 227
9.1 Where and When . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
9.1.1 Photochemical Drug Release . . . . . . . . . . . . . . . . . . . 227
9.1.2 Applications with UV Light . . . . . . . . . . . . . . . . . . . . 228
9.1.3 Application with Near IR . . . . . . . . . . . . . . . . . . . . . . 229
9.1.4 Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
9.1.5 Transition Metal Complexes . . . . . . . . . . . . . . . . . . . . 232
x Contents

9.2 Photochemical Internalization . . . . . . . . . . . . . . . . . . . . . . . . . 233

9.3 Upconversion for the Photoactivation of Drugs . . . . . . . . . . . . . 233
9.4 Diagnostic Applications: Two-Photon Fluorescence . . . . . . . . . 235
9.5 Diagnostic Applications. Aggregation-Enhanced
Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
9.6 Antimicrobics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
10 Solar Energy Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
10.1 Non-photosynthetic Strategies . . . . . . . . . . . . . . . . . . . . . . . . . 246
10.2 Artificial Photosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
10.3 Dye-Sensitized Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
10.4 Comparing Different Approaches . . . . . . . . . . . . . . . . . . . . . . 254
10.5 Singlet Fission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
10.6 Hydrogen as an Energy Carrier . . . . . . . . . . . . . . . . . . . . . . . . 257
10.7 Socioeconomic Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
11 Actuators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
11.1 Photochromism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
11.1.1 Fluorescent Switches . . . . . . . . . . . . . . . . . . . . . . . . . 263
11.1.2 Electrical Functions of Photochromic Molecules . . . . . 268
11.2 Two Color/One Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
11.3 Photomechanical Actuators . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
11.3.1 Molecular Motors from Molecular Movements . . . . . . 272
11.3.2 Macroscopic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . 273
11.3.3 Mechanical Work from Crystal Deformations Caused
by Molecular Transformations . . . . . . . . . . . . . . . . . . 277
11.4 Self-Assembling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
12 Photochemistry and Green Synthesis . . . . . . . . . . . . . . . . . . . . . . . 285
12.1 Photochemistry for Bioresources . . . . . . . . . . . . . . . . . . . . . . . 285
12.2 Preparative Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
12.2.1 Assessing the Green Potential . . . . . . . . . . . . . . . . . . . 286
12.3 What to Be Afraid of and What Not to Be Afraid of in
Photochemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
12.4 Method of Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
12.5 Scaling Up a Photochemical Reaction . . . . . . . . . . . . . . . . . . . 292
12.6 Destructive Green Photochemistry . . . . . . . . . . . . . . . . . . . . . . 295
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
Chapter 1
Early Times of Photochemistry

1.1 Introduction

The perception of light is one of the fundamental experiences of living beings and
its power to reveal the world has always been recognized. In Genesis, creation of
matter is immediately followed by creation of light that allows to detect the created
world through its forms and colors:
And God said:
Let there be Light,
and there was Light.
And God saw the Light, that it was good;
and God divided the Light from the darkness.
(Genesis I: 1–4)
Similar tales are present in the oldest texts of other cultures. The deepest
impressions are expressed as an overwhelming flood of light, as Dante mentions
for the vision of Paradise:
I think the keenness of the living ray
Which I endured would have bewildered me,
If but mine eyes had been averted from it
(Paradise XXXIII: 76–78)
Light reveals matter through what is the most powerful sense for humans, sight,
and indeed the more so in contemporary society where the other senses have in part
lost their role. Not only that, light is also able to modify living beings, and this in a
way that is vital for them. Thus, mankind always perceived the relation between the
long days of solar irradiation in summer and the abundance of the fruits Earth
produced in that time and has attempted to exploit in the best way such an
inexhaustible source of energy and of materials. This has been achieved through

© Springer-Verlag Berlin Heidelberg 2016 1

A. Albini, Photochemistry, DOI 10.1007/978-3-662-47977-3_1
2 1 Early Times of Photochemistry

agriculture, the science and technique that improves the harvest unperturbed nature
produces, arriving at much better results (from men point of view). The beginning
of modern human culture is generally taken as the moment when previously
nomadic populations permanently settled. A more abundant harvest has been
necessary for the increasing population and has always been sought by mankind,
whether through ceremonies and sacrifices to the god sun in ancient times or by
introducing innovative agrochemical techniques in the modern ones.
The advancement of society has seen a more and more pervasive role of light.
Indeed, light was often taken as the symbol itself of progress guided by science.
This was enlightenment, out of the darkness of earlier, less technologically
advanced times. A celebrated example is the ballet “Excelsior” that was staged at
La Scala theatre in Milan in 1881 (story by Manzotti, music by Marenco) that
culminated in the triumph of light. Or at least, this was the predominating view
(at least among the upper classes) in the rapidly growing western world, in
particular during the industrial development from the eighteenth century up to the
early years of the twentieth century. Although an optimistic overall attitude based
on the confidence in a continuous improvement of mankind conditions may be no
more predominating 100 years afterward, vision-based communication develops at
an increasing pace and is more and more at the basis of society, with such media as
the net and television pervading everyday life.
As mentioned above, light has a strict relation with the modification of matter
and thus with the science that studies it, that is chemistry, through a dedicated
discipline, photochemistry. This has extended to an unbelievable variety of
applications, certainly primarily concerned with the reproduction of images, but
involving many other cases where the characteristics of light, that is, the
high-energy of UV and visible quanta and the possibility to deliver them when,
where, and how desired offer a decisive advantage, from building and operating
“intelligent” materials or machines to carrying out complex manipulations (includ-
ing surgery) at the submicroscopic level and to innumerable further applications.1
As illustrated in Sect. 2.5, already in 1926 it was remarked [1] that photochem-
istry is concerned with all of the electronically states of chemical entities, and thus
in a sense it is photochemistry that includes chemistry and not vice versa, since
ground states are but a particular case of electronic states. Furthermore, comparing
the reactivity of excited states with that of the corresponding ground states makes
particularly apparent the direct relation between chemical properties and electronic
structure of each species and thus the role of the electronic structure in the reactions
of chemical species. In view of this situation, it may be thought that all chemistry,
through photochemistry, is included in atomic physics, the science that studies the
intimate structure of the matter and thus the electronic structure of atoms and
molecules. This peculiar relation endows photochemistry both with a particularly

1
Sensu stricto, if the prefix photo is taken etymologically, this science should be limited to the
effect of visible light, but of course the affinity of UV and visible-light photochemistry is too strict
for allowing a separate treatment.
1.2 Light and Chemistry 3

rich approach for understanding and teaching chemistry - and science in general - as
well as with a rich vision toward innovation.
As a matter of fact, the applications of photochemistry are so rich and diverse
that the relation with a common basic discipline tends to be lost. This is unfortunate,
because the abovementioned central role of photochemistry is a continuous source
of inspiration and there is much to gain from conserving a unified point of view. In
this sense, some historic knowledge is helpful, as always in science. The present
volume is not a proper history of photochemistry, but rather a discussion of some
turning points during the formation of the basic postulates of photochemistry and an
attempt to present some directions of future development.

1.2 Light and Chemistry

Of the two parts of the word photochemistry, the former one refers to the discipline
that arrived first at a fully scientific description. The advancement of the under-
standing of what is light advanced rapidly from the experiments on the dispersion of
(visible) light and the corpuscle theory of colors by Newton (1704) [2] and the
discovery of ultraviolet (Ritter, 1801) [3] and infrared (Herschel, 1800) [4]
components to the formulation by Maxwell of the equations for the electromagnetic
field (1862–1864) and then to the theoretical contributions by Planck that con-
cluded that a black body emits light only in discrete bundles (quanta, 1900) and by
Einstein that viewed all quanta of light as actual particles (1905). These were later
called photons (as proposed by G. N. Lewis, 1926) in analogy to other elementary
particles that had been discovered, such as electrons and protons (and then phonons,
plasmons). The study of light-related effects is the core of modern physics and set
the stage for a particular role of photochemistry in that it combines photons with
molecular structure and thus with the properties of electrons and protons. Lewis
conceived photons as actual particles, different from the light they transported.
“Whatever view is held regarding the nature of light, it must now be admitted
that the process whereby an atom loses radiant energy, and another near or distant
atom receives the same Energy, is characterized by a remarkable abruptness and
singleness. We are reminded of a process in which a molecule loses or gains a whole
atom or a whole electron but never a fraction of one or the other. . . Had there not
seemed to be insuperable objections, one might have been tempted to adopt the
hypothesis that we are dealing here with a new type of atom, an identifiable entity,
uncreatable and indestructible, which acts as the carrier of radiant energy and, after
absorption, persists as an essential constituent of the absorbing atom until it is later
sent out again bearing a new amount of energy. If I now advance this hypothesis of a
new kind of atom, I do not claim that it can yet be proved, but only that consider-
ation of the several objections that may be adduced shows that there is not one of
them that can not be overcome. It would seem inappropriate to speak of one of these
hypothetical entities as a particle of light, a corpuscle of light, a light quantum, or a
light quant, if we are to assume that it spends only a minute fraction of its existence
as a carrier of radiant energy, while the rest of the time it remains as an important
4 1 Early Times of Photochemistry

structural element within the atom. It would be also cause confusion to call it merely
a quantum, for later it will be necessary to distinguish between the number of these
entities present in an atom and the so called quantum number. I therefore take the
liberty of proposing for this hypothetical new atom, which is not light but plays an
essential part in every process of radiation the name photon.” Lewis postulates that
the total number of (intrinsically identical) photons was constant in an isolated
system. Serious objections against this idea of the conservation of photons could be
raised on the basis of the thermodynamics of radiation and of the laws of spectros-
copy. As mentioned, Lewis thought that they could be overcome, but this theory
was never accepted and seems unpalatable today, although this is the last manifes-
tation of the view of light as one of the “imponderables” that can be accumulated in
matter, a representation that has a long tradition (see Sect. 2.3). The name photon,
however, remained and became of general use [5, 6].

1.3 Historic Notes

As mentioned, the observation of chemical effects of light is as old as mankind

itself. Accounts of the earlier history of photochemistry have been presented by
several authors. Long erudite lists of reference are of little usefulness, however.
Here, it has been chosen to present a brief historic profile based on a document itself
of historic value, the introduction written by a great authority, professor Ivan
Plotnikov. This well-known Russian-born scientist published in 1910 a book on
photochemistry which was followed in 1936 by a second, much extended, edition of
over 900 pages. The view he had on this science, or at least on some aspects of it, in
particular the unconditioned refusal of the Stark–Einstein “equivalence law,”
appeared obsolete at the time of the second edition, as it is discussed in Sect. 2.3.
However, Plotnikov can certainly not be accused of insufficient knowledge of the
matter or of insufficient exploration of the literature and his book is a rich mine of
data and thoughts [7].
The chapter devoted to the historic aspects of photochemistry in Plotnikov’s
book may thus offer a convenient approach. The key early events are presented and
discussed with reference to three periods, by adopting a scheme that he thinks had
general validity. The first one, during which much experimental material was
collected and progressively acquired a scientific character, lasted, he thought,
until the first third of the nineteenth century. Apart the role sunlight had in
monotheistic religions and cultures, he lists a series of important events, of which
some are reported below, as characterizing this period:
• 50 BC—Vitruvius mentions the light-induced fading of paintings.
• 1342 AC—Petrus de Alexandria describes the camera obscura (in principle,
already known to Aristotle’s).
• 1575—Niccolò Monardes in Venice reports the fluorescence of lignum
nephriticum.
1.3 Historic Notes 5

• 1602—Casciarolo in Bologna reports the phosphorescence of feldspar.

• 1674—Brand in Homburg reports the chemical luminescence of phosphor.
• 1725–1757—Several reports on the light sensitivity of inorganic salts appear
(FeCl3, AgNO3, AgCl) and applications for sympathetic inks and for
reproducing images are published.
• 1782—After several partial reports (by Priestley, Bergmann, Scheele,
Ingenhousz), Senebier publishes a comprehensive and successful book on the
effect of solar light on plants, oils, dyes, wood, etc. This not only mentions that
silver chloride blackens at light but also that this darkening depends on the color
of the light.
• 1785—Berthollet reports the photocleavage of HCl.
• 1790—Saussure builds the first photochemical photometer, based on the
development of gas by irradiation of chlorine water.
• 1802—The first photographs on silver paper by Wedgwood and Davy.
• 1814—Nièpce and Daguerre begin their work on photography.
• 1817—Grotthuss formulates the law that only absorbed light has a chemical
effect while studying the photodecomposition of iron salt solutions.
After this period, the moment would have been mature for the full blowing of
photochemistry as a science, as it happened with most disciplines. Unfortunately, at
least in the opinion of Plotnikov, a major stumbling block intervened, viz., the
enormous success of photography that concentrated the effort on technical aspects
of the chemistry of the silver salt emulsion, the sensitization, the stability of images,
and so on. Therefore, this is named the “technical–photographic period” and the
purely scientific advancement had been less significant that it may have otherwise
be. Furthermore, when a scientific issue was confronted, then the topic was ill
chosen. Thus, the first photochemical kinetic study was devoted to the formation of
hydrogen chloride from the components by Bunsen and Roscoe in the1850s [8, 9].
These authors found in their initial study that the progress of the reaction was
proportional to light intensity and time of irradiation. Unfortunately, this held only
under the conditions they had chosen, that is, under removal of the product and by
maintaining constant the concentration of the reagents. Then, they found a more
complex course in the presence of moisture and air and furthermore observed an
induction period. The authority of Bunsen spurred a large number of scientists to
concentrate their efforts on the study of this really complex reaction, perhaps
retarding the development of photochemistry in general. Apart from these consid-
erations, Plotnikov lists several key events of this second period lasting until the last
years of the nineteenth century, some of which are indicated below:
• 1838—Preparation of the first daguerreotype.
• 1839—Ponton discovers the sensitivity to light of paper tramped with a potas-
sium bichromate solution.
• 1843—Draper rediscovers, independently from Grotthuss, that only absorbed
light is chemically active.
• 1850—Regnault discovers the development of images by pyrogallol.
• 1851—Archer discovers the properties of collodium.
6 1 Early Times of Photochemistry

• 1852—Beer formulates the light absorption law.

• 1869—Fritsche discovers the dimerization of anthracene and other substances.
• 1869—Timiriaseff and Engelmann study quantitatively the assimilation of
carbon dioxide by green plants.
• 1872—Baumann discovers the photopolymerization of vinyl chloride.
• 1875—Balmer discovers the line structure of the hydrogen spectrum.
• 1879—Eder describes a mercury-oxalate photometer and establishes that
photochemical reactions have no temperature coefficient.
• 1894—Joly reports the first trichromatic print.
In the third part of his historic introduction, Plotnikov notices that, as it is
generally the case for a mature science, the development of contemporary photo-
chemistry was characterized by the advancement in theory coupled with the
advancement in experimental methods and instruments. The possibility of
obtaining quantitative data about the amount of light and matter in photochemical
reactions and the availability of convenient mercury arcs in substitution of solar
light opened the way for new applications. The initial phase of the development of
every discipline, “in which an accumulation of experimental data takes place, and
confusion of opinion prevails,” had been overgrown and photochemistry had
arrived where fundamental laws are established. This phase “always represents a
turning-point in the history of a given branch of science. . . characterized by great
intellectual exertion on the part of the leading investigators, as well as by the sharp
clash of mutually opposing tendencies.” A number of books were printed [10–12],
besides Plotnikov’s own, that related on the whole of photochemistry, whereas in
previous periods these had been practically limited to photography [13]. Single
events that Plotnikov considered important included:
• 1897—Kinetic characterization of the HI photolysis by Bodenstein.
• 1900—Ciamician and Silber begin their work on organic photochemistry.
• 1905—Trautz formulates a theory of chemiluminescence.
• 1904–1907—van’t Hoff suggests and Lazareff demonstrates the proportionality
between absorbed light and reaction (quantitative application of the Grotthuss
law).
• 1907—Warburg publishes the first paper on energy measurements in a photo-
chemical reaction.
• 1908—Plotnikov builds his light thermostat.
• 1908—Stark suggests that a molecule requires a quantum for reacting.
• 1908—Stobbe discovers the photochromism in the case of fulgides.
• 1910—D. Berthelot begins his studies on the photochemistry of organic
compounds.
• 1912—Einstein gives a thermodynamic base to the Stark hypothesis on the light
quantum.
Although a lessening of the rate of the scientific advancement in photochemistry
after the war was noticeable, Plotnikov hoped that this would have not lasted long
and the discipline would early find a shared, comprehensive theory as well as new
applications (he thought particularly of biology and medicine).
References 7

Plotnikov had been somewhat hasty in judging that photochemistry had become
a mature science in 1930. In fact, many seeds were close to germinate, the
paradigms of photochemistry had been not yet formulated, the number of known
photochemical reactions was too small for reaching generalizations, and apart from
the fact that in many cases it was difficult to recognize which chemical change
occurred upon irradiation, key instruments that were able to afford a more detailed
view of excited states had yet to be devised and assembled.
In the present case, further extending his list of key dates would lead to a treatise
of photochemistry that may be conveniently found elsewhere. This will not be
attempted, therefore, and only a few indications are given of the main instrumental
advancements that made possible to understand the complex mechanism of photo-
chemical reactions. A list of dates can at any rate be found in the Webster’s timeline
history [14]:
• 1933—Jabłonski proposes a metastable electronic state for the long-lived emis-
sion of some dyes.
• 1940–1946—Lewis and Kasha recognize the role of triplet state and introduce
the state diagram.
• 1950—The role of triplet states in photochemical reactions is recognized.
• 1950—Flash photolysis instrument.
• 1950—The availability of modern chromatographic and spectroscopic tech-
niques makes possible to discover (and sometime rediscover) many photochem-
ical reactions; quantum yields are routinely determined.
• 1955—Steady-state luminescence routinely investigated for the role of excited
states, excited complexes, electron/energy transfer, and intermediates; steady-
state luminescence in rigid media.
• 1965—Time-correlated single-photon counting techniques for determining the
lifetime of short-lived excited states.
• 1970—Laser flash photolysis.
• 1970—Photochemical reactions in rigid matrix (rigid solvent, codeposition with
inert gas) with spectroscopic detection.
• 1980—Laser flash photolysis with IR detection.

References

1. Luther R (1926) General discussion. Trans Faraday Soc 25:515–525

2. Westfall RS (1962) The development of Newton theory of light. Isis 53:339–358
3. Frercksa J, Weberb H, Wiesenfeldt G (2009) Reception and discovery: the nature of Johann
Wilhelm Ritter’s invisible rays. Stud Hist Philos Sci A 40:143–156
4. Herschel W (1801) Observations tending to investigate the nature of the Sun, in order to find
the causes or symptoms of its variable emission of light and heat; with remarks on the use that
may possibly be drawn from solar observations. Phil Trans R Soc Lond 91:265–318
5. Lewis GN (1926) The conservation of photons. Nature 118:874–875
6. Lewis GN (1930) Quantum kinetics and the Planck equation. Phys Rev 35:1533–1537
7. Plotnikov I (1936) Allgemeine Photochemie. 2nd Ed. Walter de Gruyter, Berlin
8 1 Early Times of Photochemistry

8. Bunsen R, Roscoe HE (1857) XVII Photochemical researches. Part I. Measurements of the

chemical action of light. Phil Trans R Soc Chem 147:355–380
9. Roscoe HE (1857) XVII Photochemical researches. Part II. Phenomena of photo-chemical
induction. Phil Trans R Soc Chem 137:381–402
10. Sheppard SE (1914) Photo-chemistry. Longmans, Green, London
11. Kistiakowsky GB (1928) Photochemical processes. Chemical Catalog, New York
12. Rollefson GK, Burton M (1939) Photochemistry and the mechanism of chemical reactions.
Prentice Hall, New York
13. Hunt R (1854) Relations of light in its chemical reactions, embracing a consideration of all the
photographic processes. Longman, Brown, Green and Longmans, London
14. Parker PM (2009) Photochemistry Webster’s timeline history 1817–2007. Icon, San Diego
Chapter 2
The Framework of Photochemistry:
The Laws

The conceptual framework of photochemistry is now firmly established. Excellent

introduction to this discipline can be found in several recent books and appropriate
definitions for vocabulary of photochemistry have been published [1, 2]. The key
point is that this discipline is better defined as the chemistry of electronically
excited states and actually treats the chemical reactions of such states. The absorp-
tion of a photon is simply the most convenient way for generating them
(Scheme 2.1), although there are also thermal entries to excited states.

Reagent* Product '

hn

Reagent Product

Scheme 2.1 Different courses of photochemical (from an electronically excited state) and
thermal (from the ground state) reactions

The chemical behavior of excited states is quite different from the corresponding
ground state species, because of the different electronic structures. This perfectly fits
in the frame of present-day chemistry, where it is customary to rationalize reactions
on the basis of the electronic structure. However, arriving at such a view involved a
long and difficult path, where early investigators had to combine chemical results
with the new vision of the intimate nature of the matter physicists were revealing at
the time. The difficult step was in fact recognizing the peculiar object of this
discipline, viz., electronically excited states, and overcoming the tendency to depict
the chemistry observed as some kind of catalysis operating on a “normal” (ground
state) chemical reaction. This is apparent already in the language, where often terms
such as “photocatalyzed,” “photoinduced,” and “photo-accelerated” reactions were
used, in preference to straightforward photochemical reactions, in an attempt to

© Springer-Verlag Berlin Heidelberg 2016 9

A. Albini, Photochemistry, DOI 10.1007/978-3-662-47977-3_2
10 2 The Framework of Photochemistry: The Laws

incorporate photochemical reaction into the large realm of catalytic chemistry. These
terms continued to be used much after that the role of excited states had been clarified
and are basically inappropriate because, unlike catalytic effects that open new paths
in the ground state surface, here one has reactions starting from a high-lying state
located on a different surface (see further below).
This approach was not accessible to early investigators that noticed the effect
light had upon matter. In which way light caused a chemical effect? The search for a
relation between light and reaction observed led to the formulation of what are now
known as the “laws” of photochemistry. More detailed questions had to be
answered then. Could the kinetic methods that had been found so useful for thermal
reactions be applied to light-induced reactions? Were light-induced reactions basi-
cally different from their thermal counterpart? Were different intermediates
involved? By answering to these questions, the framework of photochemistry was
gradually built, mainly in the period 1910–1960, and may be discussed under two
headings, the laws of photochemistry and the state diagram.

2.1 The Relation with Light Wavelength

The first topic concerns the two “laws of photochemistry” that correspond to the
following (or similar) statements:
1. Only light which is absorbed by a system can cause chemical change (first law,
Grotthuss or Grotthuss–Draper law).
2. For every quantum of light that is absorbed, one molecule of substrate reacts
(second law, Einstein or Stark–Einstein law).
These statements are not fully satisfactory in such a form and are usually reported
along with some specifications. On the other hand, they may sound as a mere
obviousness if, as everybody concurs at present, in every case it is one electronically
excited state, formed by absorption of one photon, that reacts in some way (see
Scheme 2.1). Actually, one may think that there is no need of laws of photochemistry,
and several textbooks dispense with this notion. At any rate, it seems wortwhile to
retrace the intellectual path underlying. Starting from the first law, that light needs to
be absorbed to have a chemical action seems obvious and, importantly, easy to check.
In the everyday practice, its application is taken for granted, and actually the first
move when planning a photochemical reaction is (or rather should be for the wise
experimentalist) measuring the absorption spectrum of the reagent and checking that
the emission spectrum of the lamp used does overlap at least to some degree with it;
otherwise, there is little hope to obtain any chemical effect. However, we are the great
grandchildren of the scientists that established this principle, and when this was done,
there was little experimental support. Thus, checking whether light was absorbed was
not an easy and precise operation as it is now.
Let us consider a photochemical experiment as it was carried out by the baron
Theodor Grotthuss, then living in his native Courland, a part of modern day Latvia
[3–5] (Fig. 2.1).
2.1 The Relation with Light Wavelength 11

Fig. 2.1 Title page of the

well-known paper by
Grotthuss on the chemical
action by light; see [6]

High-born Grotthuss carried out his experiments in the family palace, but
certainly was no simple-minded amateur, had an excellent background, and gave
important contributions to photochemistry and, even more extensively, to electro-
chemistry. He published his research in several European journals, but the photo-
chemical part is contained in a detailed paper presented at the Academy of
Courland. There he reported several experiments about the effect of light on salts
and the different results depending on whether air was present or not [6].
He remarked that no satisfactory general rationalization was available; in par-
ticular the proposal by Rumsford that light simply heated the sample was untenable.
He further explored the matter and in particular proposed to determine whether
light of different colors had a different chemical effect. From his observations he
concluded that “independently on its chemical nature, each body reacts more
strongly to the color that is complementary to that it shows in the normal state.
As an example, when a red light falls onto a red body, this either goes through
undisturbed, if such body is transparent, or is reflected with no loss if it is not
transparent. However, if a blue-green light ray (complementary to the red in the
Newton wheel [7]; see Fig. 2.2) hits the same body, then in both cases, much of the
ray is absorbed, that is, it penetrates with difficulty in the defects of the substance of
the body. This had to be, at least in many cases, the cause of a large chemical effect.
12 2 The Framework of Photochemistry: The Laws

Fig. 2.2 Newton wheel of

complementary colors; see
[7]

Should not the white silver chloride thus be transformed in the darkest colors of
the spectrum, since these colors are mainly complementary to its bright color and
therefore find the biggest resistance to the penetration in the substance and stay
there longer?. . .Should not the flea-colored lead oxide, to the color of which dark
violet is the least similar hue. . .be most extensively transformed (reduced) by the
less refracted rays (violet), if these were not the most contrasting ones to its own
color?” Several further examples follow in the list by Grotthuss, all of them
indicating that only colors absorbed are chemically active. In his pictorial view,
“light strives to pursue as easily as possible its path in the substance in which it
penetrates, and this tendency has to be the larger, the less similar is its color to the
natural color of the substance”. And the color of a substance had to do with its
structure. Already Newton had found that the ray of a color could go through
transparent bodies only when the appropriate oscillations or separation into
elementary parts was possible (“accessus facilioris transmissionis et reflexionis
luminis,” access of light more easily transmitted and reflected). At the places
where this did not happen, the colored light did not go through but was reflected
and/or absorbed (i.e., transformed into heat) in a way that “depended on the nature
of the substance hit by light.” Grotthuss thus suggested both optical properties and
photochemical reactions had a common origin in the structure of a substance.
After these initial observations, Grotthuss developed two chemical systems well
suited for finally answering the question of the dependence on the color, because
their high sensitivity allowed a fast comparison. These were the intensely red iron
rhodanide (or thiocyanate) and the blue iodine complex with starch, both of which
faded under irradiation. In the experiment, two thin tubes 18-cm long and 0.6-cm
diameter were filled with these solutions, a stopper was inserted, and the tubes were
2.1 The Relation with Light Wavelength 13

placed on the floor in front of a prism dispersing bright solar light over a spectrum
12-cm broad. In these thin tubes mixing of the aqueous solution was very slow,
actually occurring to a significant extent only when the tube was strongly shacken,
as Grotthuss tested. He took care to shift the tubes in such a way that the same color
fell always on the same spot, while the direction of solar rays changed during the
day. After 3 hours he lifted the tubes with care and observed the discoloration. The
rhodanide tube was fully discolored at the center of the spectrum (corresponding to
blue green) and more and more conserved as long as one proceeded toward either
extreme (orange, red on one hand; dark blue, violet, on the other one).
The iodine solution was markedly discolored where it had been hit by the yellow
ray and, when carefully replaced in front of the refracted light, fully bleached in that
part after a further hour exposure. Thus, the color complementary of that of the
solutions was both absorbed and chemically active, or as Grotthuss put it, light of a
color tended to destroy the body that has a color contrary to its own and to conserve
that that has the same or a similar one. This observation was occasionally verified
by other scientists [8].
Grotthuss further prepared an instrument for measuring light intensity, a
“chemical photometer,” built by connecting by short tubes a series of spherical flasks
of increasing volume. This was filled with the rhodanide solution and a stopper was
inserted in order to avoid contact with the atmosphere. When exposed to solar light,
the content of each flask bleached, starting from the smallest one and progressing to
the larger ones, each becoming colorless at regular time intervals, provided that solar
radiation remained constant (Fig. 2.3). This, he observed, would have been a conve-
nient instrument for measuring the intensity of solar light all over the world.
Further important points that he demonstrated, against the suggestion of previ-
ous scientists, are (1) that neither a specifically oxidizing nor a reducing effect
could be attributed to light, since under irradiation oxidations take always place
along with reductions; (2) that a specific color cannot be connected with a specific
chemical action, but only the fact that it is absorbed or not determines whether it has
some action; and (3) that photochemical reactions are not caused by heat originat-
ing from light absorption.
As a matter of fact, Grotthuss stated very clearly his findings but was not the first
to arrive at these conclusions [9]. Under the title “On the power light per se has of
changing not only colors, but sometimes also the surface of things, leaving the colors
unchanged,” a “commentary” from the Academy of Sciences and Arts in Bologna
reports a discussion of the theme that took place in 1757 and the contribution by
Beccari. This scientist is well known for his experiments on the phosphorescence of
minerals and on bioluminescence. In this case, it was question at the academy of how
to conserve the beauty of flowers, and one of the academician suggested protecting
them from the contact with air. “Why not from light?,” added Beccari. The proposal
was judged new, but many were not convinced that colors could be changed by light.
Beccari answered that not only the color but also the surface of materials could be
altered and then referred to his experimental work. He was interested by a previous
observation by Duhamelius, who had found that “the secretion of a shell when
exposed to sun light, became crimson, and the more so, the stronger was light. . . .
However, while a cloth bathed in that liquid became red when exposed to the sun,
14 2 The Framework of Photochemistry: The Laws

Fig. 2.3 Chemical

photometer by Grotthuss.
Exposing to a constant light,
balls filled with the
actinometer bleach one after
the other; see [6]

even when covered by a rather thick glass, this did not happen when it was covered by
a brass foil, thin as it may be. Glass was able to transmit light, the metal foil not at
all.” This hypothesis was confirmed by Beccari (compare Sect. 4.4.1). He noticed that
a sample of “luna cornea” (silver chloride) was white when freshly prepared but after
some time tended to take a yellow hue and later turned almost to violet (the AgCl
2.1 The Relation with Light Wavelength 15

activation by invisible UV light was noticed by Ritter; see Sect. 1.2). He attributed
this change first to air and second to light. He checked this point experimentally in
this way. He placed a sample of luna cornea in a glass container and put this at 8 ft
from a window, so that solar light flooded it. After some time, he remarked that the
part of the sample that faced the window—and received more light—had become
violet, while the opposite face—that was not exposed to light—retained the original
color. It could be concluded that light exerted an impulse toward color change. For
confirming this, Beccari turned the container in such a way that the back face was
now turned toward the window. And to make the experiment still more convincing,
he covered half of the container by a dark screen, in order to see what would happen
in the covered part. Indeed, all of the samples became violet, except the part covered
by the screen, where the initial color was conserved, and this clearly supported the
role of light in changing colors, even if air had its own. Beccari then reported further
experiments carried out by the late G. Bonzius by exposing strips of paper dyed by
various substances to light in air. By comparison he also explored the effect upon
exposing some of these strips to light after having evacuated the containers and also
by keeping them in the dark at a temperature higher than that reached under solar
irradiation. He found that some of the dyes were bleached even in the absence of air
and concluded from these experiments that light had per se the power of affecting
colors. Thus, the notion that absorption was required for chemical action of light was
present in the scientific literature around the world, but apparently only locally, and
did not reach a large diffusion [10, 11].
Two decades after Grotthuss report and not being aware of it, William Draper1
proceeded after similar lines and investigated in which way light and light-sensitive
substances interacted. His purpose was highly practical, he aimed to enhance the
corrosion of exposed photographic plates, in order to produce engraved (and thus
stable) Daguerreotypes by deep etching, and he was actually successful in this
project. In this technique, the image was formed on a silvered metal plate that had
been activated by exposing it to iodine vapor. After exposing in the camera, the
image was revealed through the action of mercury fumes, but the stability of the
image remained moderate. Draper prepared a light-sensitive plate by iodization at
the appropriate level and exposed it “to the diffuse light of the day, setting it in such
a position that it behaved like a mirror and reflected the light falling upon it through
the window to the objective of a camera oscura, which formed an image of it upon a
second sensitive plate.”
As soon as the first plate had become brown, the scientist closed the opening of
the camera, “mercurialized” the plate, and found that the rays reflected by the first
plate “had lost the quality of changing silver iodide in silver.” Thus, the rays which
had impinged on the surface of yellow silver iodide “had lost the quality of causing
any further change on a second similar plate.” In other words, the active color had
been absorbed by the first plate and was no more present in the reflected ray.

1
Professor at the University of the City of New York and founding president of the American
Chemical Society.
16 2 The Framework of Photochemistry: The Laws

Furthermore, he illuminated an iodinated plate through a solar spectrum formed by

a prism and after 5 min “mercurialized” the plate. He found that the less refrangible
colors (blue violet) produced the strongest blackening, and the other end of the
spectrum also had some action, though a lower one. On the other hand, the center of
the spectrum corresponding to the yellow light had no effect at all.
Several further experiments were carried out, in every case supporting that the
silver iodide present on the plate reflected yellow light, which had no effect on it,
and absorbed the other rays that on the contrary caused a chemical effect. The ray
absorbed also caused heating of the sample [12].
Draper built a light concentrator based on a convex lens that had been prepared
in such a way that the focal point remained the same during all of the sun progress in
the sky. The sample was placed in that point and irradiated. Considerable heath was
evolved, as shown by the melting of various substances, including silver chloride.
In chlorine water, water was consumed much faster than it was by exposure to
non-concentrated light, and iron oxide oxalate evolved carbon dioxide and led to a
precipitate of the Fe(II) oxalate, likewise at a much enhanced rate.
However, a ray that had caused the reaction of a chlorine water solution caused
no more reaction when directed on a second tube containing the same solution. In a
particularly convincing experiment, when a tube containing a solution of iron(III)
oxalate was placed within a larger tube containing the same solution, reaction in the
internal tube began only after that the external part had been completely consumed.
Many other experiments were carried out with oxides and sulfides, and concen-
trated light had results not different from those obtained under non-concentrated
light; only the rate was increased. Draper arrived at the conclusion that the chemical
effect could not be separated from the absorption of light and was proportional to
it. In conclusion, the chemical action produced by the rays of light depended upon
the absorption of those rays by sensitive bodies, just as an increase of temperature is
produced by the absorption of heat (or at least this is the comparison that he drew).

2.2 Relation with Light Intensity

In order to support the hypothesis of the proportionality between chemical action

and intensity of the light ray, Draper set up to prepare a convenient instrument for
measuring light intensity (recall that the experiments were done with solar light or
by using flames as light sources). Those previously used were admittedly not
sufficiently sensitive and precise, and the result was subjective, e.g., it depended
on the observer’s opinion to establish whether a Daguerro-type plate was stained or
not. He chose as a reference the reaction between hydrogen and chlorine as a highly
sensitive system, “affected by rays of the feeblest intensity and of the briefest
duration.” He called the instrument “tithonometer” [13] because this was meant
to measure Tithonic light, a name he introduced in order to design specifically the
chemically active light. The name arose from that of Τιθωvoς, semi-god and lover
of Ηως, the sunrise, and thus was, he thought, a more precise alternative to actinic
light (from the Greek ακτις, ray). The instrument he built “consisted in a glass tube
2.2 Relation with Light Intensity 17

bent into the form of a siphon, in which chlorine and hydrogen could be evolved
from muriatic acid, containing chlorine in solution, by the agency of a voltaic
current” (Fig. 2.4). Passing the current through Pt electrodes in x, y develops
hydrogen and chlorine that fill the transparent tube a–c that is protected from
light by a cap. When the two gases have filled the tube and the system is in
equilibrium (with the components in exactly equal amounts), which requires a
few seconds (and presumably an admirable skill), the cap is taken away from the
“sentient” part, the tube a–d, and thus exposed to light. The gases begin to react and
the liquid in siphon c–f to descend (Fig. 2.4). Periodical reading gave a constant
result when a lamp of constant intensity was used and Draper concluded that the
effect caused by light was proportional to the intensity.

Fig. 2.4 The tithonometer

by Draper. A mixture of
hydrogen and chlorine is
prepared by electrolysis in
the tube a–d. When this is
exposed to light, the change
in volume of gases is
monitored in the tube c–f;
see [13]
18 2 The Framework of Photochemistry: The Laws

This result was challenged both qualitatively and quantitatively. Thus, Herschel
did think “that the rays effective in destroying a given tint, are in a great many
cases, those whose union produces a color complementary to the tint destroyed,
or at least one belonging to that class of colors to which such complementary tint
is to be referred,” but admitted that this rule was not general and that it “was to
be interpreted with considerable latitude” [14]. From the quantitative point of
view [15], the majority of researchers in photochemistry tended to assume
that the amount of chemical change in a given system effected by light of a
specified wavelength was proportional to the light absorbed and later studies
appeared to support the validity of the original experiment [16], though very
delicate.
The above statement was referred to as the Draper law or, when the Grotthuss
paper was rediscovered, the Grotthuss–Draper law, generally stated in a qualitative,
rather than quantitative, way. Notice that the quantitative aspect, indeed quite
important in both of the original proposals by the two scientists, was rather referred
to as the Bunsen–Roscoe law. This was stated as “in two photochemical reactions,
if the product of the intensity of illumination and the time of exposure are equal, the
quantities of chemical material undergoing change will be equal” [17].2
Plotnikov later took pain in demonstrating [19] that taking the Grotthuss–Draper
law in a quantitative sense, that is, that not only light has to be adsorbed, but that the
effect is proportional to the radiation absorbed, could replace the Stark–Einstein
law, but he obviously missed the point. The equivalence law states much more
precisely that absorption of one quantum of light causes one photochemical act.
Whether this applies in every single case or, more correctly, which is the mean
probability that this statement applies to one type of “acts” or to another one, and
under which conditions it can be affirmed that this applies to a chemical reaction, is
another question (see below). That the effect is proportional to the absorbed flux—
provided that the terms are properly defined—is obvious.

2.3 Early Attempts to Rationalize Photochemical Reactions

Both Draper and Grotthuss were concerned with the mechanism underlying the
effect of light unto matter. In order to appreciate their contribution, it must be
recalled that although the theory of light as oscillating electric and magnetic fields
had been formulated, the relation with chemical structure of the media it traversed
had not yet been established (see above). Along with “ponderable” elements (the
mass), the existence of “imponderable” entities, such as light, heat, and electricity,
was still postulated for rationalizing chemical reactions. The fact that the darkening

2
This is known as the “reciprocity law” in photomedicine but rarely named in this way in
photochemistry; see, e.g., [18].
2.3 Early Attempts to Rationalize Photochemical Reactions 19

of silver iodide was caused only by a part of the visible spectrum (blue-violet light)
as well as by ultraviolet light led Draper to admit that rays causing a chemical effect
were further “imponderables” different from those that were revealed in vision. He
thought that “it depends on the chemical nature of the ponderable material what
rays shall be absorbed . . . and . . . whilst the specific rays thus absorbed depend
upon the chemical nature of the body, the absolute amount is regulated by its optical
qualities.” In his late years, Draper accepted the unifying application of oscillatory
theory to both calorific and chemically active rays, since these obeyed to the same
laws as luminous rays [20] and thus there was no reason to maintain a categorical
separation.
The important point, however, was considering the photochemical effect an
intrinsic property of the chemical substance. Draper thought that the particles of
matter are in a continuous oscillation and that color and temperature of bodies and
finally their chemical constitution are in part depending on the strength and in part
on the frequency of the vibrations that propagated over the ether and transmitted to
the material. Draper explained the relation between absorption of light and chem-
ical activation as promoting vibrations, so that, when in a molecule not every atom
could follow a certain vibration, then light of a certain wavelength was only
partially transmitted and in part was absorbed and caused the cleavage of the
molecule. While in thermal activation, molecular vibrations could be transmitted
in any direction to other molecules, it was in the nature of the molecules that in this
particular case this did not happen. Whether a chemical activation occurred
depended on the wavelength and the frequency of the vibration, but the amount
of the activation depended on the intensity of the radiation absorbed [21]. As for
Grotthuss, when republishing his papers, Ostwald commented on the primogeniture
of the law preceding the (independent) Draper formulation by 24 years, as well as
the important characterization of photochemical reactions and the prophetically
perceived analogy between photochemical and electrochemical processes. In fact,
being electrochemistry his main topic of interest, Grotthuss was in the best position
to appreciate the relation with electrochemistry and indeed concluded that “gener-
ally and in best accord with the facts, the chemical effect of light can be compared
with that of polar electricity (Galvanism). Light separated the parts of many
ponderable compounds and forced them to give new compounds through its own
imponderable elements (+E,
E), exactly as the poles of the Volta battery, only to a
higher degree,” a formulation that conserves its appeal even today (apart the
“imponderable” issue; see above).
As mentioned above, the analogy between photochemistry and electrochemistry
was an important guide for understanding these phenomena. Ostwald thought that
light in some way accumulated energy in the substances until reaction occurred but
that science was very far from understanding how this happened [22], and Nernst,
while lamenting that photochemical reactions could not be described by leading to
equilibrium as thermal reactions, thought that “in the chemical action of light we
are dealing with phenomena analogous to the formation and decomposition of
chemical compounds under the influence of electric current” [23].