The Fontana History of Chemistry

FONTANA HISTORY OF CHEMISTRY

(Editor: Roy Porter)

THE FONTANA HISTORY OF

CHEMISTRY

William H. Brock

CONTENTS

COVER

TITLE PAGE

PREFACE TO THE FONTANA HISTORY OF SCIENCE

BIBLIOGRAPHICAL NOTE

INTRODUCTION

1 On the Nature of the Universe and the Hermetic Museum

Chinese Alchemy

Greek Alchemy

Arabic and Medieval Alchemy

Newton’s Alchemy

The Demise of Alchemy and its Literary Tradition

2 The Sceptical Chymist

Paracelsianism

Helmontianism

The Acid-Alkali Theory

A Sceptical Chemist

Boyle’s Physical Theory of Matter

The Vacuum Boylianum and its Aftermath

Newton’s Chemistry

The Phlogistonists

Conclusion

3 Elements of Chemistry

A Scientific Civil Servant

The Chemistry of Air

The Chemical Revolution

The Aftermath

Conclusion

4 A New System of Chemical Philosophy

Dalton’s ‘New System’

Dalton’s Life

The Atomic Theory

The Origins of Dalton’s Theory

Electrifying Dalton’s Theory

Chemical Reactivity

Prout’s Hypothesis

Volumetric Relations

Scepticism Towards Atomism

Conclusion

5 Instructions for the Analysis of Organic Bodies

Purity

The Basis of Chemistry

The Supply of Apparatus and Chemicals

Liebig, Organic Analysis and the Research School

Conclusion

6 Chemical Method

Classifying by Radicals

Classification by Types

7 On the Constitution and Metamorphoses of Chemical Compounds

The Establishment of Quantivalence

Kekulé and the Theory of Chemical Structure

The Triumph of Structural Theory

8 Chemistry Applied to Arts and Manufactures

The Alkali Industry

Dyestuffs and Colouring

9 Principles of Chemistry

Sorting the Elements

The Rare Earths

The Inert Gases

Manufacturing Elements

Mendeleev’s Principles

Conclusion

10 On the Dissociation of Substances Dissolved in Water

Proto-Physical Chemistry

Raoult and van’t Hoff

Electrochemistry from Faraday to Arrhenius

The Ionic Theory

The Reception of the Ionic Theory

11 How to Teach Chemistry

Frankland’s State-sponsored Chemistry

Armstrong’s Heuristic Method

Twentieth-century Developments in Teaching

The Laboratory

12 The Chemical News

Forming Chemical Societies

The Chemical Periodical

William Crookes, Chemical Editor

13 The Nature of the Chemical Bond

The Lewis Atom

Spreading the Electronic Theory

The Pauling Bond

14 Structure and Mechanism in Organic Chemistry

The Lapworth-Thiele-Robinson Tradition

The Michael-Flürscheim- Vorlãnder Tradition

The Electronic Theory of Organic Reactions

Organizing the Structure of Organic Chemistry

The Kinetics of Mechanisms

The Spread of Physical Organic Chemistry

Aromaticity

The Non-classical Ion Debate

Conclusion

15 The Renaissance of Inorganic Chemistry

Werner’s New Ideas

Sidgwick’s Electronic Interpretation of Co-ordination Chemistry

Australian Chemistry

Australian and Japanese Chemistry

Co-ordination Chemistry in Australia

Nyholm’s Renaissance

Conclusion

16 At the Sign of the Hexagon

Synthesis

Industrial Chemistry

Chemistry and the Environment

EPILOGUE

APPENDIX: HISTORY OF CHEMISTRY MUSEUMS AND COLLECTIONS

NOTES

BIBLIOGRAPHICAL ESSAY

INDEX

ACKNOWLEDGEMENTS

ABOUT THE AUTHOR

OTHER BOOKS BY

COPYRIGHT

ABOUT THE PUBLISHER

‘Chemical Industry, Upheld by Pure Science Sustains the Production of Man’s Necessities’, frontispiece to A. Cressy Morrison, Man in A Chemical World: the service of chemical industry (London & New York: Scribner’s, 1937) Reproduced courtesy of Scribner’s, Collier Macmillan, New York

PREFACE TO THE FONTANA HISTORY OF SCIENCE

Academic study of the history of science has advanced dramatically, in depth and sophistication, during the last generation. More people than ever are taking courses in the history of science at all levels, from the specialized degree to the introductory survey; and, with science playing an ever more crucial part in our lives, its history commands an influential place in the media and in the public eye.

Over the past two decades particularly, scholars have developed major new interpretations of science’s history. The great bulk of such work, however, has been published in detailed research monographs and learned periodicals, and has remained hard of access, hard to interpret. Pressures of specialization have meant that few survey works have been written that have synthesized detailed research and brought out wider significance.

It is to rectify this situation that the Fontana History of Science has been set up. Each of these wide-ranging volumes examines the history, from its roots to the present, of a particular field of science. Targeted at students and the general educated reader, their aim is to communicate, in simple and direct language intelligible to non-specialists, well-digested and vivid accounts of scientific theory and practice as viewed by the best modern scholarship. The most eminent scholars in the discipline, academics well-known for their skills as communicators, have been commissioned.

The volumes in this series survey the field and offer powerful overviews. They are intended to be interpretative, though not primarily polemical. They do not pretend to a timeless, definitive quality or suppress differences of viewpoint, but are meant to be books of and for their time; their authors offer their own interpretations of contested issues as part of a wider, unified story and a coherent outlook.

Carefully avoiding a dreary recitation of facts, each volume develops a sufficient framework of basic information to ensure that the beginner finds his or her feet and to enable student readers to use such books as their prime course-book. They rely upon chronology as an organizing framework, while stressing the importance of themes, and avoiding the narrowness of anachronistic ‘tunnel history’. They incorporate the best up-to-the-minute research, but within a larger framework of analysis and without the need for a clutter of footnotes – though an attractive feature of the volumes is their substantial bibliographical essays. Authors have been given space to amplify their arguments and to make the personalities and problems come alive. Each volume is self-contained, though authors have collaborated with each other and a certain degree of cross-referencing is indicated. Each volume covers the whole chronological span of the science in question. The prime focus is upon Western science, but other scientific traditions are discussed where relevant.

This series, it is hoped, will become the key synthesis of the history of science for the next generation, interpreting the history of science for scientists, historians and the general public living in a uniquely science-oriented epoch.

ROY PORTER

Series Editor

BIBLIOGRAPHICAL NOTE

So as not to encumber the book with footnotes, I have employed the simple device of indicating the source of a quotation by a superscript number. These sources will be found in the relevant notes section (often briefly) and more details are given in the bibliographical essay, which not only provides an up-to-date guide to the published literature, but is also my acknowledgement to the hundreds of historians whose work has guided me in writing this book. For historical convenience, trivial rather than systematic (IUPAC) names are used for inorganic compounds, viz. ‘alum’ rather than ‘aluminium potassium sulphate-12-water’. In the case of organic compounds, systematic names are used only for more complex compounds.

INTRODUCTION

That all plants immediately and substantially stem from the element water alone I have learnt from the following experiment. I took an earthern vessel in which I placed two hundred pounds of earth dried in an oven, and watered with rain water. I planted in it the stem of a willow tree weighing five pounds. Five years later it had developed a tree weighing one hundred and sixty-nine pounds and about three ounces. Nothing but rain (or distilled water) had been added. The large vessel was placed in earth and covered by an iron lid with a tin-surface that was pierced with many holes. I have not weighed the leaves that came off in the four autumn seasons. Finally I dried the earth in the vessel again and found the same two hundred pounds of it diminished by about two ounces. Hence one hundred and sixty-four pounds of wood, bark and roots had come up from water alone.

(JOAN-BAPTISTA VAN HELMONT, 1648)

Helmont’s arresting experiment and conclusion capture the essence of the problem of chemical change. How and why do water and air ‘become’ the material of a tree – or, if that sounds too biochemical, how and why do hydrogen and oxygen become water? How does brute matter assume an ordered and often symmetrical solid form in the non-living world? Helmont’s experiment also raises the issue of the balance between qualitative and quantitative reasoning in the history of chemistry. Helmont’s observations are impeccably quantitative and yet, because he ignored the possible role of air in the reaction he was studying, and since he knew nothing of the hidden variables of nutrients dissolved in the water or of the role of the sun in providing the energy of photosynthesis, his reasoning was to prove qualitatively fallacious.

Chemistry is best defined as the science that deals with the properties and reactions of different kinds of matter. Historically, it arose from a constellation of interests: the empirically based technologies of early metallurgists, brewers, dyers, tanners, calciners and pharmacists; the speculative Greek philosophers’ concern whether brute matter was invariant or transformable; the alchemists’ real or symbolic attempts to achieve the transmutation of base metals into gold; and the iatrochemists’ interest in the chemistry and pathology of animal and human functions. Partly because of the sheer complexity of chemical phenomena, the absence of criteria and standards of purity, and uncertainty over the definition and identification of elements (the building blocks of the chemical tree), but above all because of the lack of a concept of the gaseous state of matter, chemistry remained a rambling, puzzling and chaotic area of natural philosophy until the middle of the eighteenth century. The development of gas chemistry after 1740 gave the subject fresh empirical and conceptual foundations, which permitted explanations of reactions in terms of atoms and elements to be given.

Using inorganic, or mineral, chemistry as its paradigm, nineteenth-century chemists created organic chemistry, from which emerged the fruitful ideas of valency and structure; while the advent of the periodic law in the 1870s finally provided chemists with a comprehensive classificatory system of elements and a logical, non-historically based method for teaching the subject. By the 1880s, physics and chemistry were drawing closer together in the sub-discipline of physical chemistry. Finally, the discovery of the electron in 1897 enabled twentieth-century chemists to solve the fundamental problems of chemical affinity and reactivity, and to address the issue of reaction mechanisms – to the profit of the better understanding of synthetic pathways and the expansion of the chemical and pharmaceutical industries.

Returning to Helmont’s tree, an arboreal image and metaphor can be usefully deployed. The historical roots of chemistry were many, but produced no sturdy growth until the eighteenth century. In this healthy state, branching into the sub-disciplines of inorganic, organic and physical chemistry occurred during the nineteenth century, with further, more complex branching in the twentieth century as instrumental techniques of analysis became ever more sophisticated and powerful. Growth was, however, dependent upon social and environmental conditions that either nurtured or withered particular theories and experimental techniques.

Although conceived as a work of synthesis for the 1990s (there has been no extensive one-volume history of chemistry published since that of Aaron Ihde in 1964), The Fontana History of Chemistry draws extensively upon some of the themes and personalities treated in my own research as well as upon the post-war work of other historians of chemistry. Gone are the days of Kopp and Partington, when a history of chemistry could be allowed to unfold slowly in four magisterial and detailed volumes. My volume is designed to be neither a complete nor a detailed narrative; nor is it a work of reference like James R. Partington’s History of Chemistry, to which I, like all historians of chemistry, remain profoundly indebted. I am particularly conscious, for example, of ignoring developments such as photography (that most chemical of nineteenth-century arts), spectroscopy, Russian chemistry, or the emergence of ideas concerning atomic structure. In some cases, as with the omission of any emphasis on the role of Avogadro’s hypothesis in the nineteenth-century determination of atomic and molecular weights, the lacuna is justified historiographically; in other cases, as with my muted references to the roles of rhetoric and language in chemistry, it was a decision not to introduce a contemporary historiographic fashion in a book largely dedicated to a readership of chemists and science students.

In yet other cases, choices of subject matter, and therefore of omission, have stemmed from the decision to structure chapters around seminal texts, their writers and the schools of chemists associated with them. This principle of organization has been freely borrowed from Derek Gjertsen’s The Classics of Science (New York: Lilian Barber, 1984) and a book edited by Jack Meadows, The History of Scientific Development (Oxford: Phaidon, 1987), with which I was associated. To use a metaphor from organic chemistry, the book is arranged around textual types, each title standing symbolically for a paradigm, a theoretical, instrumental or organizational change or development that seems significant to the historian of chemistry. I have tried to lay equal emphasis upon the practical (analytical) nature of past chemistry as much as on its theoretical content, and, although it would have taken a volume in itself to analyse the development of industrial chemistry, I have tried to provide the reader with an inkling of the application of chemistry. Wherever possible I have stressed the significance of chemistry for the development of other areas of science, and I have noted some of the false steps and blind alleys of past chemistry as much as the developments that still remain part of the scientific record. Echoing Ihde’s incisive treatment, The Fontana History of Chemistry also provides a generous treatment of twentieth-century chemistry – albeit within the constraints of my chosen themes and typologies. I have tried wherever possible to illustrate the international nature of the chemical enterprise since the seventeenth century.

Helmont’s tree leads us both backwards and forwards in time – forwards to when evidence accrued that air (and gases) did participate in chemical change, and backwards to the ancient traditions of elements and of transmutation that Helmut had inherited. The book opens with the roots of chemistry and the social, economic and religious environments that promoted it before the time of Helmont. In particular, the opening chapter examines early chemical technologies and their rationalization by Greek philosophers in theories of elements or, more iconoclastically, in terms of corpuscules and atoms. The tree enters here again, for one of the perennial proofs for the existence of elements and for their number was the destructive distillation of wood by fire – an important phenomenon empirically (for it was the model for distillation techniques generally) and cognitively because it was the basis of the concepts of analysis and synthesis. Chemistry was, and is, concerned with the analysis of substances into their elements and the synthesis of substances from their elements or immediate principles.

The possibility of manipulating elementary matter into substances of commercial or – at the extreme – of spiritually uplifting value, such as silver and gold or an elixir of life, led to alchemy. The latter’s origin, as well as its formal connections with chemistry, are complex and even contentious. However, our contemporary demand for science to have empirical validation, as well as our respect for the technological manipulation of Nature’s resources for the benefit of humankind, can be traced back to the philosophical spirit of enquiry that underpinned alchemical investigations. And it goes without saying that alchemy provided early chemistry with much of its apparatus and manipulative techniques, as well as the idea of a formal symbolic language for practitioners of the art.

Each of the sciences, no doubt, has its own difficulties and peculiarities when it comes to presenting its historical development to a diverse audience of professional historians, scientists, students and laypersons; but chemistry, like mathematics, possesses a particularly intimidating obstacle in its language and symbolism, which potentially obscures what are usually quite simple theoretical ideas and experimental techniques. As William Crookes noted in 1865 when reviewing a book on stuttering that had been inappropriately sent to Chemical News for review:

Chemists do not usually stutter. It would be very awkward if they did, seeing that they have at times to get out such words as methylethylamylophenylium.

However, if (as Peter Morris has noted) the historian avoids chemical detail and language, the scientific story become exigious and almost trivial. For this reason, while the first twelve chapters should present little difficulty to a sophisticated general reader, I have not hesitated to use technical language in the five chapters that are devoted to twentieth-century chemistry. Because this is a history, and not a textbook, of chemistry, I have not defined and explained symbols, equations and technical vocabulary. These chapters will present little difficulty to readers who have a secondary or high-school foundation in chemistry (and will have the privilege of being critical of my treatment). At the same time, it is to be hoped that there is sufficient of a human interest story in the intellectual and experimental worlds of Pauling, Ingold, Nyholm, Woodward and the other giants of twentieth-century chemistry, to propel the non-chemical reader towards the final pages.

The history of chemistry has served and continues to serve many purposes: didactic and pedagogic, professional and defensive, patriotic and nationalistic, liberalizing and humanizing. As I write, especially in America, where words like ‘chemical’, ‘synthetic’ and ‘additive’ have unfortunately become associated with the pollution, poisoning and disasters caused by humans, the history of chemistry has come to be seen by leaders of chemical industry and educators as a possible way of revaluing chemical currency: that is, of demonstrating not only the ways in which chemistry plays a fundamental role in nature and our understanding of cosmic processes, but also how it is essential to the economy of twentieth-century societies. In other words, the history of chemistry not only informs us about our great chemical heritage, but justifies the future of chemistry itself. Such a justification echoes the liberal and moving words of the first major historian of chemistry, Hermann Kopp1:

The alchemists of past centuries tried hard to make the elixir of life … These efforts were in vain; it is not in our power to obtain the experiences and views of the future by prolonging our lives forward in this direction. However, it is possible and in a certain way to prolong our lives backwards, by acquiring the experiences of those who existed before us and by learning to know their views as if we were their contemporaries. The means for doing this is also an elixir of life.