The Chemical History of Color

163 Pages·2013·2.513 MB·English

by  Mary Virginia Orna (auth.)

SpringerBriefs in Molecular Science
History of Chemistry
Series Editor
Seth C. Rasmussen, Fargo, USA
For furthervolumes:
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Mary Virginia Orna
The Chemical History
of Color
123
MaryVirginia Orna
Department of Chemistry
The College ofNew Rochelle
New Rochelle NY
USA
ISSN 2212-991X
ISBN 978-3-642-32641-7 ISBN 978-3-642-32642-4 (eBook)
DOI 10.1007/978-3-642-32642-4
SpringerHeidelbergNewYorkDordrechtLondon
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This volume is dedicated, from A to Z, to:
Alice Alexander (1903–1992), one of the
most colorful persons who has graced my life
Mary Jane Robertshaw, who got the color
wheels turning in the first place, and
ZviC.Koren,whocontinuestocolormyworld
Preface
Color has been an exciting and enjoyable part of human life ever since the color-
sensitive eye evolved over a million years ago. However, the junction between
color and chemistry, and color and history, is of more recent origin. The first
recorded use of chemistry to manufacture a color is the stunning set of cave
paintings found in the Grotte Chauvet in Southern France. Executed over 32,000
years ago (20,000 years earlier than Lascaux!), they are a testimony to early
humans’ ability to create beauty and to engage in abstract thinking. This volume
tracesthehistoryofcolorusageasachemicalendeavorfromtheearliestrecordsto
thepresentday.Itisatrajectorythatismoreorlessdirectsincethethreerequisites
of history, chemistry, and color function somewhat like a triple point in a phase
diagram:they keep us ontarget!Nonetheless,the historyofcolorchemistry finds
stopovers in color physics, atomic theory, ancient dye production, medieval
pigment synthesis, organic structural chemistry, and on up to the development of
the modern chemical and pharmaceutical industries.It is a journey pepperedwith
outstanding and fascinating personalities, and the difficulties they experienced in
delving intothe mysteries ofcolor.Color,asweshall see,is notonlyadelightto
the eye, but often a manifestation of the ultimate nature of the colored substance
itself.Colorpervadeseveryaspectofourlives,ourconsciousness,ourperceptions,
our language, our useful appliances and tools, our playthings, our entertainment,
our health, our diagnostic apparatus—all based in no small part on chemistry. As
such,colorisauniversalexperienceandphenomenon.Itschemicalhistory,asyou
shall see, is no less so.
vii
Acknowledgments
I am indebted to so many persons who have been helpful in the development of
thisvolume.Inparticular,IwouldliketothankAshleyAugustyniak,Alfred,Linda
and Daniel Bader, Christina Blay, Antonia Clark, Robin J. H. Clark, Carmen
Giunta, Jack Harrowfield, Ernst Hempelmann, Richard Hermens, Donna Jenkins,
Frederick H. Kasten, Jan Kochansky, Zvi C. Koren, Kathleen Mannino, Harold
T. McKone, Daniel Rabinovich, Roger Rea, Carolyn Reid, Silvia Rozenberg,
Adrian-Mihail Stadler, and Anthony S. Travis. I would also like to thank the
Chemical Heritage Foundation for the use of many images from its picture
collection.Iamverygratefulforthecommentsandsuggestionsofmyeditor,Seth
Rasmussen. Special thanks are due to Marco Fontani for his invaluable help in
obtaining hard-to-get references, and finally, I would like to acknowledge with
greatthanksPhilipOgataforhismeticulousreadingofthemanuscriptdraft,forhis
many helpful suggestions, and for his encouragement all along the way.
IwouldalsoliketoacknowledgetheinvaluablereferencehelpIreceivedatthe
Library of the College of New Rochelle, at the Donald F. and Mildred Topp
Othmer Library, Chemical Heritage Foundation, and at the Library of the
Academy of Natural Sciences, Philadelphia, Pennsylvania.
ix
Contents
1 Introduction: Colors, Natural and Synthetic,
in the Ancient World. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Working Definition and Nature of Color . . . . . . . . . . . . . . . . . 2
1.3 Natural and Synthetic Colors in the Ancient World. . . . . . . . . . 2
1.3.1 Blue Coloring Materials. . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.2 Red Coloring Materials . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.3 Yellow Coloring Materials. . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 Discovery of the Physics of Color. . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Theories on the Nature of Light . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Newton’s Famous Prismatic Dispersion Experiments. . . . . . . . . 12
2.3 Consequences of Newton’s Experiment . . . . . . . . . . . . . . . . . . 14
2.4 The Visible Spectrum Examined. . . . . . . . . . . . . . . . . . . . . . . 15
2.5 The Electromagnetic Spectrum . . . . . . . . . . . . . . . . . . . . . . . . 16
2.6 How We See Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.6.1 The Light Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.6.2 Interaction of Light with Matter . . . . . . . . . . . . . . . . . . 20
2.6.3 The Object Observed. . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.6.4 The Eye–Brain Detector-Interpreter. . . . . . . . . . . . . . . . 23
2.6.5 Primary Colors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3 The Chemical Causes of Color. . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1 Development of Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . 29
3.2 The Chemical Bond. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3 Electronic Transitions: The Hydrogen Spectrum . . . . . . . . . . . . 33
3.4 Color in Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.4.1 The MO Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
xi
xii Contents
3.4.2 The VB Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.4.3 The Free Electron Model. . . . . . . . . . . . . . . . . . . . . . . 37
3.4.4 Modification of Witt’s Terms and Classification
of Colored Organic Compounds . . . . . . . . . . . . . . . . . . 37
3.5 Colored Inorganic Compounds . . . . . . . . . . . . . . . . . . . . . . . . 38
3.5.1 Electronic Transitions in Coordination Compounds. . . . . 38
3.5.2 Color in Chelate Complexes. . . . . . . . . . . . . . . . . . . . . 40
3.5.3 Charge Transfer Transitions. . . . . . . . . . . . . . . . . . . . . 41
3.5.4 Semiconducting Materials . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4 Colorant Usage from Antiquity to the Perkin Era. . . . . . . . . . . . . 47
4.1 Body Paint, Face Paint, Hair Coloring, Cosmetics. . . . . . . . . . . 47
4.2 Ceramics, Glasses, Glazes and Stained Glass . . . . . . . . . . . . . . 48
4.2.1 The Nature of Glasses. . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2.2 The Desired Properties ofGlazes: Colorants inGlazes. . . 49
4.2.3 Stained and Painted Glass . . . . . . . . . . . . . . . . . . . . . . 51
4.3 Artists’ Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.3.1 Literature Sources for Ancient, Medieval,
and Renaissance Technical Practice. . . . . . . . . . . . . . . . 54
4.3.2 Pigment Use in Manuscript Painting. . . . . . . . . . . . . . . 57
4.3.3 A Digression on Two Blue Pigments: Iron Blue
and Ultramarine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3.4 Pigment Use in Mosaic Painting. . . . . . . . . . . . . . . . . . 60
4.3.5 Pigment Use in Fresco Painting . . . . . . . . . . . . . . . . . . 61
4.3.6 Pigment Use in Oil Painting. . . . . . . . . . . . . . . . . . . . . 63
4.4 Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4.4.1 Tyrian Purple. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.4.2 Natural Colorants from Around the World. . . . . . . . . . . 67
4.4.3 Emergence of the Dye Industry . . . . . . . . . . . . . . . . . . 69
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5 Beyond Perkin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.1 Early Attempts at Dye Synthesis in the Years
Following Mauve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.2 Hofmann’s Early Theoretical Work. . . . . . . . . . . . . . . . . . . . . 80
5.3 Evolution: From Craft to Science . . . . . . . . . . . . . . . . . . . . . . 81
5.4 Structural Developments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.5 Adolf von Baeyer and the Synthesis of Indigo . . . . . . . . . . . . . 83
5.6 From Madder to Alizarin: A Convoluted Journey . . . . . . . . . . . 85
5.7 Synthesis of Alizarin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.8 Conclusion: Legacy of the Dye Industry. . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Contents xiii
6 Major Analytical Techniques Based on Color: Volumetric
Analysis; Chromatography; Spectroscopy; Color Measurement. . . 93
6.1 Volumetric Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6.2 Chlorophyll and Chromatography . . . . . . . . . . . . . . . . . . . . . . 95
6.3 Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.4 Color Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
7 Color on the Biological and Biochemical Front. . . . . . . . . . . . . . . 111
7.1 Reduction and Oxidation of the Vat Dyes . . . . . . . . . . . . . . . . 111
7.2 Research on the Color of Blood . . . . . . . . . . . . . . . . . . . . . . . 112
7.3 The Towering Figure of the Multifaceted Paul Ehrlich. . . . . . . . 113
7.3.1 Ehrlich’s Early Colorful Work with
Histological Staining. . . . . . . . . . . . . . . . . . . . . . . . . . 113
7.3.2 Ehrlich’s Major Ideas . . . . . . . . . . . . . . . . . . . . . . . . . 114
7.3.3 The Birth of Chemotherapy . . . . . . . . . . . . . . . . . . . . . 114
7.3.4 The Salvarsan Story . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7.3.5 A Summary of Paul Ehrlich’s Accomplishments
from the Standpoint of Dyes and Colors . . . . . . . . . . . . 117
7.3.6 Paul Ehrlich: The Person. . . . . . . . . . . . . . . . . . . . . . . 118
7.4 Some Other Biochemical Spin-Offs from the German
Dye Industry and Paul Ehrlich’s Legacy. . . . . . . . . . . . . . . . . . 119
7.4.1 Gerhard Johannes Domagk (1895–1964) . . . . . . . . . . . . 119
7.4.2 Paul Hermann Müller (1899–1965). . . . . . . . . . . . . . . . 120
7.4.3 Monoclonal Antibodies . . . . . . . . . . . . . . . . . . . . . . . . 120
7.5 More Colorful Natural Products Chemistry. . . . . . . . . . . . . . . . 121
7.5.1 Chlorophyll . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.5.2 The Carotenoids and Xanthophylls . . . . . . . . . . . . . . . . 123
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
8 Finale: Color in Foods, Photochemistry, Photoluminescence,
Pharmaceuticals, Fireworks, Fun, and the Future. . . . . . . . . . . . . 129
8.1 Color in Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.2 Photochemistry and Photoluminescence . . . . . . . . . . . . . . . . . . 131
8.2.1 Film and Photography. . . . . . . . . . . . . . . . . . . . . . . . . 132
8.2.2 Photoluminescence:Fluorescence
andPhosphorescence. . . . . . . . . . . . . . . . . . . . . . . . . . 134
8.2.3 Photoluminescence: Lasers. . . . . . . . . . . . . . . . . . . . . . 136
8.2.4 Color in Fireworks: Pyrotechnics . . . . . . . . . . . . . . . . . 137
8.3 Color in Pharmaceuticals: Pills and Tablets . . . . . . . . . . . . . . . 138
8.4 Color for Fun and Enjoyment. . . . . . . . . . . . . . . . . . . . . . . . . 138
8.5 Color in the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
xiv Contents
Author Biography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147