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ACCOUNTING Christopher Nobes

ADVERTISING Winston Fletcher
AFRICAN AMERICAN RELIGION Eddie S. Glaude Jr.
AFRICAN HISTORY John Parker and Richard Rathbone
AFRICAN RELIGIONS Jacob K. Olupona
AGNOSTICISM Robin Le Poidevin
ALEXANDER THE GREAT Hugh Bowden
ALGEBRA Peter M. Higgins
AMERICAN HISTORY Paul S. Boyer
AMERICAN IMMIGRATION David A. Gerber
AMERICAN LEGAL HISTORY G. Edward White
AMERICAN POLITICAL HISTORY Donald Critchlow
AMERICAN POLITICAL PARTIES AND ELECTIONS L. Sandy Maisel
AMERICAN POLITICS Richard M. Valelly
THE AMERICAN PRESIDENCY Charles O. Jones
THE AMERICAN REVOLUTION Robert J. Allison
AMERICAN SLAVERY Heather Andrea Williams
THE AMERICAN WEST Stephen Aron
AMERICAN WOMEN’S HISTORY Susan Ware
ANAESTHESIA Aidan O’Donnell
ANARCHISM Colin Ward
ANCIENT ASSYRIA Karen Radner
ANCIENT EGYPT Ian Shaw
ANCIENT EGYPTIAN ART AND ARCHITECTURE Christina Riggs
ANCIENT GREECE Paul Cartledge
THE ANCIENT NEAR EAST Amanda H. Podany
ANCIENT PHILOSOPHY Julia Annas
ANCIENT WARFARE Harry Sidebottom
ANGELS David Albert Jones
ANGLICANISM Mark Chapman
THE ANGLO‑SAXON AGE John Blair
THE ANIMAL KINGDOM Peter Holland
ANIMAL RIGHTS David DeGrazia
THE ANTARCTIC Klaus Dodds
ANTISEMITISM Steven Beller
ANXIETY Daniel Freeman and Jason Freeman
THE APOCRYPHAL GOSPELS Paul Foster
ARCHAEOLOGY Paul Bahn
ARCHITECTURE Andrew Ballantyne
ARISTOCRACY William Doyle
ARISTOTLE Jonathan Barnes
ART HISTORY Dana Arnold
ART THEORY Cynthia Freeland
ASTROBIOLOGY David C. Catling
ATHEISM Julian Baggini
AUGUSTINE Henry Chadwick
AUSTRALIA Kenneth Morgan
AUTISM Uta Frith
THE AVANT GARDE David Cottington
THE AZTECS Davíd Carrasco
BACTERIA Sebastian G. B. Amyes
BARTHES Jonathan Culler
THE BEATS David Sterritt
BEAUTY Roger Scruton
BESTSELLERS John Sutherland
THE BIBLE John Riches
BIBLICAL ARCHAEOLOGY Eric H. Cline
BIOGRAPHY Hermione Lee
BLACK HOLES Katherine Blundell
THE BLUES Elijah Wald
THE BODY Chris Shilling
THE BOOK OF MORMON Terryl Givens
BORDERS Alexander C. Diener and Joshua Hagen
THE BRAIN Michael O’Shea
THE BRITISH CONSTITUTION Martin Loughlin
THE BRITISH EMPIRE Ashley Jackson
BRITISH POLITICS Anthony Wright
BUDDHA Michael Carrithers
BUDDHISM Damien Keown
BUDDHIST ETHICS Damien Keown
BYZANTIUM Peter Sarris
CANCER Nicholas James
CAPITALISM James Fulcher
CATHOLICISM Gerald O’Collins
CAUSATION Stephen Mumford and Rani Lill Anjum
THE CELL Terence Allen and Graham Cowling
THE CELTS Barry Cunliffe
CHAOS Leonard Smith
CHEMISTRY Peter Atkins
CHILD PSYCHOLOGY Usha Goswami
CHILDREN’S LITERATURE Kimberley Reynolds
CHINESE LITERATURE Sabina Knight
CHOICE THEORY Michael Allingham
CHRISTIAN ART Beth Williamson
CHRISTIAN ETHICS D. Stephen Long
CHRISTIANITY Linda Woodhead
CITIZENSHIP Richard Bellamy
CIVIL ENGINEERING David Muir Wood
CLASSICAL LITERATURE William Allan
CLASSICAL MYTHOLOGY Helen Morales
CLASSICS Mary Beard and John Henderson
CLAUSEWITZ Michael Howard
CLIMATE Mark Maslin
THE COLD WAR Robert McMahon
COLONIAL AMERICA Alan Taylor
COLONIAL LATIN AMERICAN LITERATURE Rolena Adorno
COMEDY Matthew Bevis
COMMUNISM Leslie Holmes
COMPLEXITY John H. Holland
THE COMPUTER Darrel Ince
CONFUCIANISM Daniel K. Gardner
THE CONQUISTADORS Matthew Restall and Felipe Fernández-Armesto
CONSCIENCE Paul Strohm
CONSCIOUSNESS Susan Blackmore
CONTEMPORARY ART Julian Stallabrass
CONTEMPORARY FICTION Robert Eaglestone
CONTINENTAL PHILOSOPHY Simon Critchley
CORAL REEFS Charles Sheppard
CORPORATE SOCIAL RESPONSIBILITY Jeremy Moon
CORRUPTION Leslie Holmes
COSMOLOGY Peter Coles
CRIME FICTION Richard Bradford
CRIMINAL JUSTICE Julian V. Roberts
CRITICAL THEORY Stephen Eric Bronner
THE CRUSADES Christopher Tyerman
CRYPTOGRAPHY Fred Piper and Sean Murphy
THE CULTURAL REVOLUTION Richard Curt Kraus
DADA AND SURREALISM David Hopkins
DANTE Peter Hainsworth and David Robey
DARWIN Jonathan Howard
THE DEAD SEA SCROLLS Timothy Lim
DEMOCRACY Bernard Crick
DERRIDA Simon Glendinning
DESCARTES Tom Sorell
DESERTS Nick Middleton
DESIGN John Heskett
DEVELOPMENTAL BIOLOGY Lewis Wolpert
THE DEVIL Darren Oldridge
DIASPORA Kevin Kenny
DICTIONARIES Lynda Mugglestone
DINOSAURS David Norman
DIPLOMACY Joseph M. Siracusa
DOCUMENTARY FILM Patricia Aufderheide
DREAMING J. Allan Hobson
DRUGS Leslie Iversen
DRUIDS Barry Cunliffe
EARLY MUSIC Thomas Forrest Kelly
THE EARTH Martin Redfern
ECONOMICS Partha Dasgupta
EDUCATION Gary Thomas
EGYPTIAN MYTH Geraldine Pinch
EIGHTEENTH‑CENTURY BRITAIN Paul Langford
THE ELEMENTS Philip Ball
EMOTION Dylan Evans
EMPIRE Stephen Howe
ENGELS Terrell Carver
ENGINEERING David Blockley
ENGLISH LITERATURE Jonathan Bate
THE ENLIGHTENMENT John Robertson
ENTREPRENEURSHIP Paul Westhead and Mike Wright
ENVIRONMENTAL ECONOMICS Stephen Smith
EPICUREANISM Catherine Wilson
EPIDEMIOLOGY Rodolfo Saracci
ETHICS Simon Blackburn
ETHNOMUSICOLOGY Timothy Rice
THE ETRUSCANS Christopher Smith
THE EUROPEAN UNION John Pinder and Simon Usherwood
EVOLUTION Brian and Deborah Charlesworth
EXISTENTIALISM Thomas Flynn
EXPLORATION Stewart A. Weaver
THE EYE Michael Land
FAMILY LAW Jonathan Herring
FASCISM Kevin Passmore
FASHION Rebecca Arnold
FEMINISM Margaret Walters
FILM Michael Wood
FILM MUSIC Kathryn Kalinak
THE FIRST WORLD WAR Michael Howard
FOLK MUSIC Mark Slobin
FOOD John Krebs
FORENSIC PSYCHOLOGY David Canter
FORENSIC SCIENCE Jim Fraser
FORESTS Jaboury Ghazoul
FOSSILS Keith Thomson
FOUCAULT Gary Gutting
FRACTALS Kenneth Falconer
FREE SPEECH Nigel Warburton
FREE WILL Thomas Pink
FRENCH LITERATURE John D. Lyons
THE FRENCH REVOLUTION William Doyle
FREUD Anthony Storr
FUNDAMENTALISM Malise Ruthven
FUNGI Nicholas P. Money
GALAXIES John Gribbin
GALILEO Stillman Drake
GAME THEORY Ken Binmore
GANDHI Bhikhu Parekh
GENES Jonathan Slack
GENIUS Andrew Robinson
GEOGRAPHY John Matthews and David Herbert
GEOPOLITICS Klaus Dodds
GERMAN LITERATURE Nicholas Boyle
GERMAN PHILOSOPHY Andrew Bowie
GLOBAL CATASTROPHES Bill McGuire
GLOBAL ECONOMIC HISTORY Robert C. Allen
GLOBALIZATION Manfred Steger
GOD John Bowker
THE GOTHIC Nick Groom
GOVERNANCE Mark Bevir
THE GREAT DEPRESSION AND THE NEW DEAL Eric Rauchway
HABERMAS James Gordon Finlayson
HAPPINESS Daniel M. Haybron
HEGEL Peter Singer
HEIDEGGER Michael Inwood
HERMENEUTICS Jens Zimmermann
HERODOTUS Jennifer T. Roberts
HIEROGLYPHS Penelope Wilson
HINDUISM Kim Knott
HISTORY John H. Arnold
THE HISTORY OF ASTRONOMY Michael Hoskin
THE HISTORY OF CHEMISTRY William H. Brock
THE HISTORY OF LIFE Michael Benton
THE HISTORY OF MATHEMATICS Jacqueline Stedall
THE HISTORY OF MEDICINE William Bynum
THE HISTORY OF TIME Leofranc Holford‑Strevens
HIV/AIDS Alan Whiteside
HOBBES Richard Tuck
HORMONES Martin Luck
HUMAN ANATOMY Leslie Klenerman
HUMAN EVOLUTION Bernard Wood
HUMAN RIGHTS Andrew Clapham
HUMANISM Stephen Law
HUME A. J. Ayer
HUMOUR Noël Carroll
THE ICE AGE Jamie Woodward
IDEOLOGY Michael Freeden
INDIAN PHILOSOPHY Sue Hamilton
INFECTIOUS DISEASE Marta L. Wayne and Benjamin M. Bolker
INFORMATION Luciano Floridi
INNOVATION Mark Dodgson and David Gann
INTELLIGENCE Ian J. Deary
INTERNATIONAL LAW Vaughan Lowe
INTERNATIONAL MIGRATION Khalid Koser
INTERNATIONAL RELATIONS Paul Wilkinson
INTERNATIONAL SECURITY Christopher S. Browning
IRAN Ali M. Ansari
ISLAM Malise Ruthven
ISLAMIC HISTORY Adam Silverstein
ITALIAN LITERATURE Peter Hainsworth and David Robey
JESUS Richard Bauckham
JOURNALISM Ian Hargreaves
JUDAISM Norman Solomon
JUNG Anthony Stevens
KABBALAH Joseph Dan
KAFKA Ritchie Robertson
KANT Roger Scruton
KEYNES Robert Skidelsky
KIERKEGAARD Patrick Gardiner
KNOWLEDGE Jennifer Nagel
THE KORAN Michael Cook
LANDSCAPE ARCHITECTURE Ian H. Thompson
LANDSCAPES AND GEOMORPHOLOGY Andrew Goudie and Heather Viles
LANGUAGES Stephen R. Anderson
LATE ANTIQUITY Gillian Clark
LAW Raymond Wacks
THE LAWS OF THERMODYNAMICS Peter Atkins
LEADERSHIP Keith Grint
LIBERALISM Michael Freeden
LIGHT Ian Walmsley
LINCOLN Allen C. Guelzo
LINGUISTICS Peter Matthews
LITERARY THEORY Jonathan Culler
LOCKE John Dunn
LOGIC Graham Priest
LOVE Ronald de Sousa
MACHIAVELLI Quentin Skinner
MADNESS Andrew Scull
MAGIC Owen Davies
MAGNA CARTA Nicholas Vincent
MAGNETISM Stephen Blundell
MALTHUS Donald Winch
MANAGEMENT John Hendry
MAO Delia Davin
MARINE BIOLOGY Philip V. Mladenov
THE MARQUIS DE SADE John Phillips
MARTIN LUTHER Scott H. Hendrix
MARTYRDOM Jolyon Mitchell
MARX Peter Singer
MATERIALS Christopher Hall
MATHEMATICS Timothy Gowers
THE MEANING OF LIFE Terry Eagleton
MEDICAL ETHICS Tony Hope
MEDICAL LAW Charles Foster
MEDIEVAL BRITAIN John Gillingham and Ralph A. Griffiths
MEDIEVAL LITERATURE Elaine Treharne
MEMORY Jonathan K. Foster
METAPHYSICS Stephen Mumford
MICHAEL FARADAY Frank A. J. L. James
MICROBIOLOGY Nicholas P. Money
MICROECONOMICS Avinash Dixit
MICROSCOPY Terence Allen
THE MIDDLE AGES Miri Rubin
MINERALS David Vaughan
MODERN ART David Cottington
MODERN CHINA Rana Mitter
MODERN FRANCE Vanessa R. Schwartz
MODERN IRELAND Senia Pašeta
MODERN JAPAN Christopher Goto-Jones
MODERN LATIN AMERICAN LITERATURE Roberto González Echevarría
MODERN WAR Richard English
MODERNISM Christopher Butler
MOLECULES Philip Ball
THE MONGOLS Morris Rossabi
MOONS David A. Rothery
MORMONISM Richard Lyman Bushman
MOUNTAINS Martin F. Price
MUHAMMAD Jonathan A. C. Brown
MULTICULTURALISM Ali Rattansi
MUSIC Nicholas Cook
MYTH Robert A. Segal
THE NAPOLEONIC WARS Mike Rapport
NATIONALISM Steven Grosby
NELSON MANDELA Elleke Boehmer
NEOLIBERALISM Manfred Steger and Ravi Roy
NETWORKS Guido Caldarelli and Michele Catanzaro
THE NEW TESTAMENT Luke Timothy Johnson
THE NEW TESTAMENT AS LITERATURE Kyle Keefer
NEWTON Robert Iliffe
NIETZSCHE Michael Tanner
NINETEENTH‑CENTURY BRITAIN Christopher Harvie and H. C. G. Matthew
THE NORMAN CONQUEST George Garnett
NORTH AMERICAN INDIANS Theda Perdue and Michael D. Green
NORTHERN IRELAND Marc Mulholland
NOTHING Frank Close
NUCLEAR PHYSICS Frank Close
NUCLEAR POWER Maxwell Irvine
NUCLEAR WEAPONS Joseph M. Siracusa
NUMBERS Peter M. Higgins
NUTRITION David A. Bender
OBJECTIVITY Stephen Gaukroger
THE OLD TESTAMENT Michael D. Coogan
THE ORCHESTRA D. Kern Holoman
ORGANIZATIONS Mary Jo Hatch
PAGANISM Owen Davies
THE PALESTINIAN-ISRAELI CONFLICT Martin Bunton
PARTICLE PHYSICS Frank Close
PAUL E. P. Sanders
PEACE Oliver P. Richmond
PENTECOSTALISM William K. Kay
THE PERIODIC TABLE Eric R. Scerri
PHILOSOPHY Edward Craig
PHILOSOPHY IN THE ISLAMIC WORLD Peter Adamson
PHILOSOPHY OF LAW Raymond Wacks
PHILOSOPHY OF SCIENCE Samir Okasha
PHOTOGRAPHY Steve Edwards
PHYSICAL CHEMISTRY Peter Atkins
PILGRIMAGE Ian Reader
PLAGUE Paul Slack
PLANETS David A. Rothery
PLANTS Timothy Walker
PLATE TECTONICS Peter Molnar
PLATO Julia Annas
POLITICAL PHILOSOPHY David Miller
POLITICS Kenneth Minogue
POSTCOLONIALISM Robert Young
POSTMODERNISM Christopher Butler
POSTSTRUCTURALISM Catherine Belsey
PREHISTORY Chris Gosden
PRESOCRATIC PHILOSOPHY Catherine Osborne
PRIVACY Raymond Wacks
PROBABILITY John Haigh
PROGRESSIVISM Walter Nugent
PROTESTANTISM Mark A. Noll
PSYCHIATRY Tom Burns
PSYCHOANALYSIS Daniel Pick
PSYCHOLOGY Gillian Butler and Freda McManus
PSYCHOTHERAPY Tom Burns and Eva Burns-Lundgren
PURITANISM Francis J. Bremer
THE QUAKERS Pink Dandelion
QUANTUM THEORY John Polkinghorne
RACISM Ali Rattansi
RADIOACTIVITY Claudio Tuniz
RASTAFARI Ennis B. Edmonds
THE REAGAN REVOLUTION Gil Troy
REALITY Jan Westerhoff
THE REFORMATION Peter Marshall
RELATIVITY Russell Stannard
RELIGION IN AMERICA Timothy Beal
THE RENAISSANCE Jerry Brotton
RENAISSANCE ART Geraldine A. Johnson
REVOLUTIONS Jack A. Goldstone
RHETORIC Richard Toye
RISK Baruch Fischhoff and John Kadvany
RITUAL Barry Stephenson
RIVERS Nick Middleton
ROBOTICS Alan Winfield
ROMAN BRITAIN Peter Salway
THE ROMAN EMPIRE Christopher Kelly
THE ROMAN REPUBLIC David M. Gwynn
ROMANTICISM Michael Ferber
ROUSSEAU Robert Wokler
RUSSELL A. C. Grayling
RUSSIAN HISTORY Geoffrey Hosking
RUSSIAN LITERATURE Catriona Kelly
THE RUSSIAN REVOLUTION S. A. Smith
SCHIZOPHRENIA Chris Frith and Eve Johnstone
SCHOPENHAUER Christopher Janaway
SCIENCE AND RELIGION Thomas Dixon
SCIENCE FICTION David Seed
THE SCIENTIFIC REVOLUTION Lawrence M. Principe
SCOTLAND Rab Houston
SEXUALITY Véronique Mottier
SIKHISM Eleanor Nesbitt
THE SILK ROAD James A. Millward
SLEEP Steven W. Lockley and Russell G. Foster
SOCIAL AND CULTURAL ANTHROPOLOGY John Monaghan and Peter Just
SOCIAL PSYCHOLOGY Richard J. Crisp
SOCIAL WORK Sally Holland and Jonathan Scourfield
SOCIALISM Michael Newman
SOCIOLINGUISTICS John Edwards
SOCIOLOGY Steve Bruce
SOCRATES C. C. W. Taylor
SOUND Mike Goldsmith
THE SOVIET UNION Stephen Lovell
THE SPANISH CIVIL WAR Helen Graham
SPANISH LITERATURE Jo Labanyi
SPINOZA Roger Scruton
SPIRITUALITY Philip Sheldrake
SPORT Mike Cronin
STARS Andrew King
STATISTICS David J. Hand
STEM CELLS Jonathan Slack
STRUCTURAL ENGINEERING David Blockley
STUART BRITAIN John Morrill
SUPERCONDUCTIVITY Stephen Blundell
SYMMETRY Ian Stewart
TAXATION Stephen Smith
TEETH Peter S. Ungar
TERRORISM Charles Townshend
THEATRE Marvin Carlson
THEOLOGY David F. Ford
THOMAS AQUINAS Fergus Kerr
THOUGHT Tim Bayne
TIBETAN BUDDHISM Matthew T. Kapstein
TOCQUEVILLE Harvey C. Mansfield
TRAGEDY Adrian Poole
THE TROJAN WAR Eric H. Cline
TRUST Katherine Hawley
THE TUDORS John Guy
TWENTIETH‑CENTURY BRITAIN Kenneth O. Morgan
THE UNITED NATIONS Jussi M. Hanhimäki
THE U.S. CONGRESS Donald A. Ritchie
THE U.S. SUPREME COURT Linda Greenhouse
UTOPIANISM Lyman Tower Sargent
THE VIKINGS Julian Richards
VIRUSES Dorothy H. Crawford
WATER John Finney
WILLIAM SHAKESPEARE Stanley Wells
WITCHCRAFT Malcolm Gaskill
WITTGENSTEIN A. C. Grayling
WORK Stephen Fineman
WORLD MUSIC Philip Bohlman
THE WORLD TRADE ORGANIZATION Amrita Narlikar
WORLD WAR II Gerhard L. Weinberg
WRITING AND SCRIPT Andrew Robinson

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MODERN DRAMA Kirsten E. Shepherd-Barr
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MEDIEVAL PHILOSOPHY John Marenbon

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 William H. Brock
THE HISTORY OF CHEMISTRY
A Very Short Introduction
 Great Clarendon Street, Oxford, OX2 6DP, United Kingdom
Oxford University Press is a department of the University of Oxford. It furthers the University’s objective
of excellence in research, scholarship, and education by publishing worldwide. Oxford is a registered trade
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© William H. Brock 2016
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First edition published in 2016
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ISBN 978–0–19–871648–8
ebook ISBN 978–0–19–102585–3
Printed in Great Britain by Ashford Colour Press Ltd, Gosport, Hampshire
Contents

Acknowledgements

List of illustrations

Introduction

1 On the nature of stuff

2 The analysis of stuff
3 Gases and atoms
4 Types and hexagons
5 Reactivity
6 Synthesis

Epilogue
Sources of quotations
Further reading
Index
Acknowledgements

Most of my lengthy History of Chemistry, published over two decades ago, was
researched and written at the Chemical Heritage Foundation (CHF) in
Philadelphia where I spent 1999–2000 as an Edelstein International Fellow.
Considerable advances in the interpretation of the history of chemistry have
occurred since then, and the present book has provided me with an opportunity
to incorporate some of them.

In writing this very short introduction to the subject I am once again grateful to
CHF for awarding me a Doan Fellowship in September 2014 which allowed me
to use its excellent study facilities and to wallow among the books in its
wonderful Othmer Library. This American sojourn gave me time to contemplate
the problem Hugh Lofting’s Dr Dolittle faced when filling his children’s zoo:
‘What to leave out and what to put in?’ (Dr Dolittle’s Zoo, 1925). I acknowledge
the interest and help given me by the CHF library staff and fellow scholarship
holders, especially Stefano Gattei (Lucca). I am grateful to Professor Hasok
Chang (Cambridge) for suggesting that I should write this monograph. As
always, my wife Elvina has been a patient and interested support to me.
List of illustrations

1 The four elements and their qualities

2 Title page of Philosophi Ac Alchemistae (1529) attributed to Geber

Wellcome Library, London

3 Title page of Libavius’ Alchymia (1606)

Wellcome Library, London

4 Furnace with hooded distillation apparatus

Roy G. Neville Collection. Othmer Library of Chemical History, Chemical Heritage Foundation

5 Paracelsus
© Everett Historical/Shutterstock.com

6 The interior of a typical apothecary’s laboratory

Rijksmuseum, Amsterdam, gift of A. J. Rijk

7 Apparatus for washing and collecting air fixed inside solid bodies
Wellcome Library, London

8 Georg Ernst Stahl

Wellcome Library, London

9 Dalton’s atomic symbols

Roy G. Neville Collection. Othmer Library of Chemical History, Chemical Heritage Foundation

10 Water-cooled condenser usually attributed to Liebig

 Othmer Library of Chemical History, Chemical Heritage Foundation

11 Alexander Williamson
Edgar Fahs Smith Collection, Kislak Center for Special Collections, Rare Books and Manuscripts,
University of Pennsylvania

12 Kekulé’s sausage-shaped formulae

13 Kekulé’s oscillating benzene rings

14 Birkbeck Laboratory at University College London

Edgar Fahs Smith Collection, Kislak Center for Special Collections, Rare Books and Manuscripts,
University of Pennsylvania

15 Adolf Baeyer with his University of Munich students in 1877

Edgar Fahs Smith Collection, Kislak Center for Special Collections, Rare Books and Manuscripts,
University of Pennsylvania

16 Robert Burns Woodward (1917–79)

© Estate of Francis Bello/Science Photo Library

17 Beckman Model G pH meter (1934)

Beckman Coulter Heritage Council. Courtesy of the Chemical Heritage Foundation
Introduction

Wer sie nicht kennte

Die Elemente,
Ihre Kraft und Eigenschaft,
Wäre kein Meister
Über die Geister
[Anyone who does not know about the elements, their properties, their powers, will never be master
of the spirits.]
(Goethe, Faust, Part 1, Scene III)

Chemistry has always been the science of matter and a technology for creating
new things through metamorphosis and transmutation. According to recent
statistics there are now more than three million people in the world who call
themselves chemists and they publish over three quarters of a million research
papers annually. Most of these report the synthesis and properties of new
materials. In 1800 the elements and compounds known to chemistry numbered
only a few hundred; today, they number more than seventy-one million, or
roughly one substance for every one hundred of the seven billion people now on
earth.

Few of these substances, which include some hundred elements, actually exist in
nature; rather, they have been isolated, prepared, and studied by chemists in
particular times and places by an evolving repertoire of laboratory practices and
theoretical insights, and recorded in publications in various languages. Only
those chemicals that have been found useful have been given some kind of
permanent existence. The rest remain as historical virtual curiosities, though they
can be conjured into existence when required from the deep technical knowledge
chemists possess of the constitutions, structures, and interrelationships between
molecules.

Until William Whewell coined the word ‘scientist’ in 1834, those who devoted
all, or part, of their lives to the study of the natural world were referred to as
‘natural philosophers’. By the 17th century, however, specialization had begun
and natural philosophy tended to refer to the more mathematical and quantitative
interpretations of nature. Those involved in the study of plants and animals were
said to practice natural history, and those studying the properties and reactions of
different kinds of matter, and their exploitation to improve the human condition,
were referred to as chemists.

As bodies of knowledge and practice the individual sciences have always

enjoyed shifting boundaries. This is particularly true of chemistry which, until
the 1840s, included most of what was later known as experimental physics.
Although the scientific disciplines came to have fairly distinctive boundaries in
the 19th century, as university departments, academic journals, and professional
societies forged collective professional identities, chemistry never became an
isolated discipline. Indeed, we have now reached the stage in the 21st century
when cultural historians are asking whether it any longer makes sense to speak
of chemistry as a separate discipline, because the study of stuff has become so
interdisciplinary—with collaborative research and teaching involving
mathematicians, physicists, biologists, and engineers.

For the purposes of this short introduction to the history of chemistry, however,
we shall use the definition of chemistry proposed by the German organic chemist
Friedrich Kekulé in 1861: ‘Chemistry is the study of the material metamorphosis
of materials’. When Christian missionaries first began to translate western
textbooks into Chinese in the 1870s, they needed a term to stand for chemistry.
They coined the phrase hua-hsüeh, literally meaning ‘the study of change’. This
was an eminently sensible neologism, for chemistry is about change. As the
American historian of chemistry Robert Siegfried noted, there is a magic about
chemical change.

Bodies disappear and new bodies with different qualities appear in their stead. A piece of metal can
be added to a clear, colourless liquid, the metal disappears, and a blue colour appears. Based on
direct experience alone there is no explanation available.
This book describes how explanations were found and new transmutations were
discovered, studied, and exploited.
Chapter 1
On the nature of stuff

Early in our education we are introduced to the history of man in terms of stone,
bronze, and iron ages—terms first introduced by the Danish archaeologist
Christian Thomsen in 1836. However, the association of these terms with the
development of chemistry is hardly ever made explicit.

At first sight, the term ‘stone age’ does not seem to imply anything chemical; but
deeper reflection shows that it implies not merely the altering of stones to
fashion tools and buildings some two million years ago, but recognition of
different kinds of stuff (minerals) and their differing properties. Chemistry
helped to define culture. The Palaeolithic (Old Stone Age) paintings of Lascaux
and elsewhere show that stone-age peoples were able to prepare pigments to
colour their representations of animals (12,000–8,000 BCE); and it would have
been only a small step from this to the use of minerals and plants to extract
natural dyestuffs with which to colour cloth and clothing once society had
reached an agrarian stage of development.

By the time the bronze or copper age was reached, the working of minerals to
produce copper and zinc had been developed. The archaeological evidence for
mining and cupellation (the removal of lead in an ore by oxidation) is extensive,
while the analysis of food remnants at metallurgical sites implies that the early
metallurgists enjoyed a rich diet of meat and fish—suggesting that they were
admired and respected for their ability to transform useless hunks of rock into
valuable metal. These metallurgical practices continued with the discovery of
iron ore, which gave iron-age man the ability to produce weapons that made
animal hunting and butchering easier.

Archaeological chemistry combines analytical chemistry with the techniques of

industrial archaeology to investigate sites of metallurgical activity. Chemists in
the 18th century pioneered the investigation of ancient glassware and other
objects, but since large samples were required for analysis, archaeologists were
wary of deploying analysis on a large scale for fear of destroying evidence. This
reluctance to compromise specimens was dramatically altered from the 1960s
onwards, when new analytical instrumental techniques permitted the use of
exceedingly small samples of a material object.

Artisanal science
Excavations in Egypt and the former lands of Persia and Mesopotamia have
revealed the chemicals identified and exploited by these advanced civilizations
from the fifth millennium onwards. For example, natron, an impure form of
common salt extracted from dry lakes or from the evaporation of Nile water, was
used in embalming and food preservation. Perfume recipes have scarcely
changed for thousands of years. A basic ingredient has always been glycerol, a
viscous sugar alcohol. We know from Pliny’s Natural History (1st century CE)
that there was an extensive Roman technology that involved the exploitation of
the algae (Dunaliella salina) that is able to grow in the hostile environment of
salt evaporation pans. Pliny and others referred to it as flos salis or ‘flower of
salt’. The cells of this brick-red halophile contain glycerol and beta-carotene (the
precursor of vitamin A). Both these valuable commodities are still extracted
from the algae today as the basis of coloured perfumes just as they were in
Roman times.

We cannot be certain when mankind first tamed fire from lightning strikes and
learned to kindle wood to make its reproduction readily available for the
purposes of cooking and heating materials; but this was certainly a precondition
for the production of pottery and glass (used in jewellery), and the extraction of
metals. Trees and bushes burn to leave a charred mass (charcoal) which was
found to release molten metals from rocks, stones, and minerals when they were
burned together. Archaeologists have found hearths in sites dated at 230,000
years old. The findings imply that various hominid species had learned how to
create, control, and propagate fire. Its control provided humans with warmth,
expanded their daylight hours, made migration and a peripatetic lifestyle
possible, and improved mankind’s diet, health, and longevity through the
processing of meat and vegetables. There is abundant archaeological evidence
that by 8,000 BCE mankind was using biochemical processes (fermentation) to
exploit grains of various kinds to bake bread and to create beer and wine.

The ability to control fire and temperature led to the first chemical technologies
—the production of pottery from fired clays and tempers (such as sand and
limestone), metals, glass, and bitumen products. The existence of exposed
bitumen in Mesopotamia led to the creation of crude asphalt obtained by mixing
the naturally found tar with chalk, sand, and gravels. Asphalt proved an efficient
sealant and mortar for housing and boat building. Another early chemical
technology was the production of plaster from gypsum or limestone that was
then used to make large blocks for building purposes.

Glass and dyestuffs

Glass appears to have been developed from the initial glazing of stones of quartz
using soda water. Such glass stones (‘Egyptian faience’) are found in sites dating
from 4000 BCE. From these objects there developed a genuine glass made from
sands (which contained iron salts as impurities), lime, soda, and heat dating from
about 2500 BCE. By the 6th century BCE, antimony ores were being added to the
glass fluxes in order to remove the green tinge of glass caused by its iron
content. Clearly this represents a programme of empirical development of
technology by trial and error of the kind familiar to the school children—let’s
see what happens when we heat this stuff with that. Applied chemistry (today’s
chemical engineering) is as old as mankind and was a sophisticated art long
before a science of chemistry emerged.

Glass must have puzzled ancient technologists: was it a metal, since it was
malleable when heated? Herodotus calls it ‘molten stone’ or water solidified by
heat. Its astounding manufacture from such disparate stuffs as sand, alkali, and
various oxides, and its astonishing ability to take up colour, may well have first
suggested the concept of transmutation. If glass could metamorphose into
valuable stones, might not metals generally be transmuted?
Among the ancient Egyptians, glassmaking was under the direct control of the
Pharaohs and considered a holy profession. Indeed, glass, not gold, was revered
as the noblest material. However, although glass could be moulded and coloured
to make artificial jewellery, glass blowing, using hollow reeds tipped with a clay
mouthpiece, appears not to have been introduced until the 1st century BCE, and
only then was glass moulded into beakers and dishes. Glass working in the
various areas of what were later described as the Holy Land had a continuous
history that culminated with the emergence of Venetian glass workers in the 15th
century. Glazed pottery followed from the discovery of glass and the further
ability of glazes to take decorative pigments to enhance a pot’s charm and value.

Such pigments were not merely obtained from crushed coloured rocks but also
from heated mixtures that warrant the term ‘synthetic’ materials. For example, a
blue pigment used extensively in Egyptian tomb painting was a complex of
calcium, copper, and silicon oxides. Evidence collected from Persia and
Babylonia has revealed even more sophisticated dyes and pigments.

Because of its stability, as much as for its striking colour, the most valued dye in
antiquity was royal purple (dibromoindigotin) which was extracted from
molluscs by boiling them in tin vessels. This produced a ‘white’ version of the
dyestuff that was readily absorbed by cloth. On reoxidation in the air the full
blue colour emerged—a striking transmutation. A virtually identical process
seems to have been used by the woad dyers of ancient Britain. Woad leaves were
crushed and rolled into balls and left to ferment. The balls were traded in this
form. A second fermentation in warm water produced a soluble form of indigo.
A cloth immersed in this liquid oxidized in air to the insoluble form of indigo
which was fixed into the textile fibres. The technology of dyeing cloth was to
remain little changed until the 18th century.

Metallurgy
While such usages of ‘manufactured’ chemicals signalled the ability of natural
stuffs to change their identities, appearances, and properties, it was the extraction
of metals from rocks and quarries that advanced these early examples of
chemical technology the most—as the terms bronze and iron ages imply. In this
respect, it is significant that the ores from which the common metals copper,
iron, tin, silver, and lead were first obtained by oxidation and reduction in a
smelting process were all (with the exception of tin) used as pigments before
they became the subject of metallurgical exploration. The oxides and sulphides
of arsenic and antimony (realgar, orpiment and stibnite) were used as pigments,
though the metals themselves were not separated until the 13th and 16th
centuries BCE. The red oxide of iron was used in the decoration of walls, while
copper minerals were used as cosmetics long before iron and copper became
objects of chemical manipulation. Of course, many metals such as gold, electrum
(an alloy of silver and gold), and copper existed naturally, but scarcely in such
abundance as to account for their widespread use.

It would appear that the earliest mines and metallurgical operations in the West
took place in Mesopotamia, and that metals were traded for use in Egypt.
Archaeologists are not certain how the necessary conditions for efficient
smelting of the common metals was achieved, though it seems probable that it
was a result of techniques that had first been applied in pottery making—that is,
using a kiln. Indeed, the common feature of ancient technology is the kiln, which
could serve both as an oven for cooking meat and baking bread, but was also
adaptable to hardening clay that had been shaped into pottery, and further
adapted by controlling the flow of heat to make glass, or to extract metals from
their ores. By yet further modification the kiln was adapted into a subliming and
distillation vessel.

As we shall see, from time to time, apparatus, instruments, and experimental

techniques have played a crucial role in accelerating the progress of chemical
knowledge or in pushing it in new directions. The kiln can be regarded as the
oldest piece of chemical apparatus and instrumentation in that it (and its
adaptations) propelled the advancement of metallurgy and the discovery of
alcohol and mineral acids.

Recipe literature
In a sermon by one of the Early Church Fathers (Theodoret of Cyrus), chemistry
was invoked to justify belief that the Divine Word had become flesh: sand
became glass, grapes produced wine, and wine became vinegar. In each
transformation a new stuff appeared and received a different name, and in each
case something superior and useful was created.
Ancient civilizations had knowledge of seven metals (gold, silver, copper, lead,
tin, iron, and mercury) and a wide variety of ‘chemicals’ that they exploited in
their pottery, jewellery, cosmetics, cooking, and weaponry, and as drugs. Our
knowledge comes from literary evidence in the form of Babylonian cuneiform
tablets and Egyptian papyri, and the many thousands of pre-1500 CE manuscripts
that record recipes for making pigments, paints, and inks.

As the Smithsonian Institution museum curator Robert Multhauf concluded,

‘practical chemistry appears to have changed very little during the twelve
centuries between the papyrus Ebers (c.1550 BCE) and the oldest extant Greek
treatise’ on the subject. He noted, however, that this did not mean that
development was non-existent. Progress was simply difficult and made up by the
accruement of small steps. Using later chemical knowledge, it is clear that these
ancient chemists had to master a large number of practical steps, most notably
the thermal control of chemical processes, to produce metals and minerals in a
state of comparative purity, or at least of more or less constant composition and
hence reliability.

The recipes in the so-called Stockholm papyrus, which dates from around 300
CE, tend to be either concerned with debasing gold to increase its bulk by adding
copper, or colouring the surface of other metals to make them look like gold.
How did the ancients judge whether such gold was genuine or spurious, or
impure? At least three tests were known to the Egyptians and were employed
well into the later Middle Ages in the Latin West. In the simplest test, a
touchstone, a black abrasive stone, was scored against a sample. The ‘artificial’
gold streak obtained on the touchstone was then compared with the colour of a
score obtained from a pure sample. A more sophisticated and non-damaging test
was to take comparative specific gravities of the test and pure samples. This is
the test that supposedly led to Archimedes’ ‘eureka’ moment in the bathtub, but
literary and pictorial evidence shows that it was known long before the time of
Archimedes. A third, truly chemical, test was by the use of fire. If the gold
sample was impure, when heated sufficiently strongly any impurities were
oxidized and discoloured the crucible in which the test or assay was made. Clay
crucibles may have been the first pieces of chemical apparatus invented, and
date from the 6th millennium.

Egyptian and Greek dyers, glassmakers, metallurgists, jewellers, and

pharmacists are known to have engaged in tincturing and colouring metallic
surfaces from at least the 4th century BCE onwards. Such procedures, some of
whose recipes have come down to us, were not necessarily fraudulent in practice
or intent, but were probably equivalent to the modern production of cheaper
synthetic materials. Joseph Needham, the Cambridge biochemist and historian of
Chinese alchemy, described this technology as aurifiction. Fraud, fakery, and
deliberate deceit were only too possible, and much of the rich and entertaining
literature on alchemy, such as Ben Jonson’s play The Alchemist (1610), hinges
on such trickery, human frailty, and greed.

Why do stuffs change appearance?

The 19th-century physicist John Tyndall noted in his journal, with some degree
of puzzlement, that his laboratory assistant, while dextrous in designing and
handling equipment, had no interest in why experiments worked or what
explained physical phenomena. It appears that no fundamental science was
involved in the artisanal practices of the ancients; indeed, almost all ‘industrial’
or ‘applied’ chemistry right up until the 18th century was purely ‘trial and error’
and empirical in nature. Today we would call this an engineering approach—
seeing what an object does rather than explaining why it does it.

This apparent indifference to what we regard as necessary scientific explanation

does not mean that artisans had no cultural notions about what they were doing
and witnessing. An Assyrian cuneiform text dating from the 8th century BCE, for
example, implies that rituals accompanied metallurgy, and this is confirmed by
the long historical association between the common metals and the seven
heavenly bodies known to ancient astronomers (e.g. the Sun with gold, the Moon
with silver, Mars with iron). That in turn shows that early mankind associated
heavenly phenomena with earthly events. Such ‘astrological’ links, and more
generally beliefs in the correspondence between the macrocosm and microcosm,
remained a fundamental part of chemistry until the 17th century. However, by
the 3rd century BCE a few lone thinkers in the Mediterranean, made rich by their
trading in the region, had begun to proffer explanations for transmutations and
changes applicable to both the natural world of the microcosm and to those
conducted by artisans in their workshops.

Speculations about matter

No theory was required by artisans in the empirical skills of perfume making,
glassmaking, cosmetics making, pottery making, bronze making, or the creation
of gold or gold-like objects. But the Greeks demanded to know why and how
such transmutations of form (what we call chemical change) were possible. Why
did metals or glass change appearance when melted with coloured minerals?
Why did beads of silver appear when galena (impure lead oxide) was heated?

Faced by such apparently realistic and successful examples of metamorphosis by

artisans, Greek philosophers saw these as real transmutations similar to the
change of water into air by evaporation, or the growth of an acorn into an oak
tree: that is, changes of essence and not of mere appearances. The Greeks were
thinkers, and asked themselves what matter was. How and why does it change in
appearance and properties?

The earliest thinkers, known as the Presocratics, suggested that change was an
illusion and that matter was ultimately just one material. Thales (c.625–c.547
BCE) famously suggested that the Urstoff, or primary matter, was water; others
suggested air or fire. Empedocles (c.494 BCE) proposed that there were four basic
materials: earth, air, fire, and water. Other suggestions were that matter was
infinitely divisible; or that division was limited until one came eventually to
indivisible atoms that differed only in shape and size and their rapid movements
in a void.

Aristotle (384–322 BCE), the most creative of these early philosophers, laid stress
upon the sensual qualities of matter, its hotness or coldness, its wetness or
dryness, and attached these qualities to the four elements of Empedocles (see
Figure 1). None of the elements was unchangeable. The element water was
obviously cold and moist, but when heated it transformed into air whose
qualities were hot and dry. These elements and their qualities made up the
composition of the metals, minerals, and plants of the observable microcosm.
For centuries the four elements were believed to be the roots of all matter, and
even to the present day they remain embedded in chemical terms such as
alkaline earths, rare earths, fresh (pure) air, inflammable air, aqua fortis, and
aqua regis.
1. The four elements and their qualities.

Aristotelian chemistry
In the hands of Aristotelian philosophers, the possible transmutation of one
metal into another was theoretically justified as the transfer of forms and
qualities that differentiated an otherwise basic, formless, underlying matter.
Later philosophers called this hylomorphism.

Aristotle’s categories and matter theory more or less obliterated those of his
teacher Plato (427–348 BCE), whose Timaeus had postulated a structural and
mathematical model of matter based on triangular and polyhedral forms. This
theory, too, had sensual and possibly technological roots, based upon the shapes
and textures of observable materials. However, such structural, corpuscular, or
atomic speculations were overwhelmed by the more powerful Aristotelian model
and only reappeared in the Latin West in the late Middle Ages.
Equally influential was Aristotle’s analysis of causation: what is a particular
stuff’s purpose (a final cause)? What makes a stuff have its particular shape,
appearance, and properties (formal cause)? What is it made from (material
cause)? And what causes it to express the properties that it does (efficient
cause)? In the case of a metal, for example, its purpose can be for construction,
its form or properties are given by it being a metal derived from its particular
qualities, its material nature is given by its composition from earth and water,
and its efficient cause is to be found in its long growth inside the earth from a
trapped dry smoky exhalation that coupled with another moist vaporous
exhalation. Other non-metallic minerals were formed in the same way depending
on the relative amounts of the two exhalations. In the hands of later Arab
chemists this explanation was developed into the sulphur-mercury model of
composition.

Alchemy
The earliest surviving Greek text concerning alchemy is ‘Of natural and hidden
things’ (Physika kai Mystika). In it we find for the first time the division of the
great work of making gold (chrysopoeia) into the four experimental stages of
blackening (nigredo), whitening (albedo), yellowing (citrinatus), and reddening
(rubedo). The book is often attributed to Democritus, possibly the atomist.
Transmutations are mainly done the dry way, that is by fire.

The development of the water bath, or bain marie as it is still known in Europe,
is attributed by Zosimus of Panopolis (fl. 300 CE), the greatest authority among
Hellenistic alchemists, to a female alchemist named Mary the Jewess. We know
nothing about where she lived, or when she was active, though from her
references to God as having directly revealed the secrets of nature to her and that
they were not to be passed on to those who were not of ‘the race of Abraham’,
her Jewishness is confirmed.

Zosimus quoted extensively from one of her manuscripts entitled On Furnaces

and Apparatus, and it is from this that we know she constructed and used some
eighty devices made from glass, clay, and metals to sublimate and distil various
materials like mercury, which she described as a ‘deadly poison, since it
dissolves gold, and the most injurious of metals’. Among her appliances, no
doubt derived from cookery, was a double vessel, the outer one of which was
filled with water and heated while the inner vessel contained the materials to be
treated by the gentle warmth.

It seems quite probable that, like Liebig’s 19th-century condenser, the water bath
had been in use for centuries before and that it was the fame and prestige of
Mary’s writings that led to it being forever associated with her name. Whatever
the truth of the association, her book on apparatus, which also included accounts
of various forms of still, influenced later Arabic alchemists and through them,
practical alchemy in Europe.

Zosimus and other Greek alchemists collected many alchemical recipes from
Mary including ones for the preparation of the philosophers’ stone, a mysterious
seed that supposedly precipitated an instantaneous transmutation. These
instructions, while clearly based upon real chemical manipulations by heat or
distillation, were already written in a figurative language that relied upon the
appreciation of analogies between metals and man, and matter and spirit.

Chemical language
The ancient (al)chemists obviously derived much of their apparatus and
manipulative techniques from the equipment used and developed by artisans,
technologists, metallurgists, and pharmacists, whose heating, cooking,
subliming, and distillation techniques were grist to the mill of later chemists.

Alchemy also provided later chemistry with the idea of a symbolic language for
practitioners of the art. Here, however, the multiplicity of synonyms for the same
thing served not merely to obscure matters for the uninitiated but to increase
greatly the degree of symbolic allusion—to the utter mystification of later
readers and interpreters. For example, according to one Greek alchemical
lexicon, mercury was ‘the seed of the dragon’, or ‘dew’, or ‘milk of the black
cow’, or ‘Scythian water’, or ‘water of silver’, ‘water of the moon’, ‘river
water’, and ‘divine water’. A Persian source lists over fifty synonyms for the
philosophers’ stone.

Given that the same synonyms were also used for different substances, the
resulting poetical muddle must have been as confusing for alchemical
practitioners as it is for later historians. Isaac Newton (1642–1727), for example,
spent years compiling an index chemicus in an attempt to make sense of
alchemical language and allegory. Why the secrecy and obfuscation of language?
We have to recognize that chemistry as late as the 17th century was still not a
public science and that in the absence of a patent system, methods for producing
medicines, or carrying out chemical procedures that had potential cash value in a
world of saleable commodities, were best kept secret or only shared among
cognoscenti. Moreover, gold making, if ever perfected, threatened state
economies, or it might be used to usher in the millennium as some religious
fanatics believed.

Historians have become adept at understanding obscure alchemical texts with

their extraordinary illustrations and multiple hidden names (Decknamen, as
scholars call them) for common substances. It turns out that these can be read
like cryptic crosswords as accurate accounts of physical and chemical changes
by reproducing alchemical recipes in the modern laboratory. Chemistry was to
be a rich source of metaphors throughout its history, and it seems chemical
metaphors were first adopted by bards who knew their audiences were familiar
with the blacksmith’s workshop.

Arabic alchemy
The development of the monotheistic religion of Islam in the 7th to 10th
centuries led to a period of profound learning in the Muslim empire that
embraced all the great centres of former Greek and Roman culture. The word
‘alchemy’, meaning ‘the art of chemistry’, is a reminder of the important
contributions that the Arabs made to chemistry. Several other Arabic words such
as alkali, alembic, elixir, and alcohol remain part of our English vocabulary.

Chemical and pharmaceutical recipes and apparatus were inherited by the Arabs
and developed by, among others, Jābir ibn Hayyān (c.721–815). We know little
of his life, but it is certain that a Jābirian school of chemists emerged that knew
and taught how to prepare mineral acids and alcohol through intricate
distillations. The generation of metals in the ground was now attributed to
interaction between highly purified and ethereal versions of mercury and
sulphur. Even more significantly, Muslim alchemists developed the model that
different metals contained internal and external qualities. Thus, if gold was hot
and wet externally, it was cold and dry internally; whereas silver was the
opposite. Hence to transform silver into gold, a reversal of qualities was needed.

Arabic and Syriac theoretical and practical knowledge passed to the Latin West
via a variety of geographically different translation routes. By the 13th century
we find many of the data accumulated by Arabic chemists summarized in the
Summa Perfectionis by a Franciscan friar named Paul of Taranto, who used the
pseudonym of ‘Geber’ (see Figure 2).

The relationship between the writings of Jābir and Geber caused much
controversy between German and British scholars in the early 20th century. We
now believe that the writings attributed to Geber, while based on Arabic
originals, included many original additions. The most important of these,
according to the detective work of the American scholar William Newman, was
a form of corpuscularianism derived from Aristotle’s concession that (despite his
objections to atomism) there were minima naturalis, or ‘molecules’ as we would
say, which limited the analytical division of matter.

In Geber’s writings, Jābir’s internal and external qualities were interpreted in

corpuscular terms. This gave new power to the notion of transmutation whereby
one searched for a tool that would lead to a structural rearrangement. One tool
suggested was mercury. But the Geberian school of alchemy was also thoroughly
Christian, so transmutations were also seen as metaphors for spiritual
transformation, improvements, and rebirth.
2. The title page of Philosophi Ac Alchemistae (1529) attributed to Geber
showing two chymists hard at work behind a distillation vessel.
What’s in a name?
The presumption of early 20th-century historians was always that there have
been obvious demarcation lines between chemistry and alchemy, and that these
were clear even before the 16th century. Our use of two different words implies
historiographically that the two fields were distinguished in the past—that there
were two distinct disciplines. Chemistry was mechanistic, alchemy was vitalistic
and spiritualistic. This interpretation is not supported by recent studies, which
show that alchemists often thought in terms of minimal particles or corpuscles,
and that they were interested in the quantities and weights of the stuffs they
reacted together just like real chemists.

The American chemist historian Lawrence M. Principe, working with William

Newman, has emphasized that any attempt at differentiation involves using
contemporary distinctions backwards. In the 17th century the terms alchemy and
chemistry were used interchangeably. Alchemy restricted to gold making
(chrysopoeia) is a later distinction. For example, we find books entitled New
Light on Chymistry (1604) that consist entirely of transmutation recipes (i.e. it’s
alchemical), while an influential book by Andreus Libavius (1560–1616) is
entitled Alchemia (1597) although it is not about gold at all, but concerned with
the chemical operations of distillation and crystallization, and the preparation of
pharmaceuticals (see Figure 3).

To avoid confusion, Principe and Newman have suggested that historians should
use the archaism chymistry when referring to early-modern chemical and
alchemical practices before the end of the 17th century. The current consensus is
that chemistry grew directly from what was called alchemy or alchymia. If we
consistently apply the term chymistry to all chemical practice before the 18th
century we also underline the fact that although the pre-modern world view was
quite different from those held by 21st-century chemists, its practical activities
were those that are familiar today. But if so, how did the terms alchemy and
chemistry become differentiated?
3. Title page of Libavius’ Alchymia (1606). This folio volume contains about
200 illustrations of chemical glassware, apparatus, and furnaces, as well as
designs for an ideal chemical laboratory.
Chymistry becomes chemistry
In De la Pirotechnica (1540) the Italian technologist Vannoccio Biringuccio
summarized existing knowledge on mining, metal, and glass working—
knowledge that had long been protected by the secrecy of the artisans’ guilds,
though frequently ‘leaked’ by the many ‘books of secrets’ that had circulated
since the appearance of Secretum secretorum in the 12th century.

Biringuccio was one of a rising band of ‘artist engineers’ who began to publish
the knowledge they had gained from their practical artisan workmanship, and to
compare this knowledge with the Greek classical heritage and the theories of
matter of the chymists. The result was a critical appraisal of the theoretical with
the observational. In particular, Biringuccio wanted to free alchemy from its
overlay of Hermeticism and to develop its quantitative aspects in order to
improve metallurgical techniques, especially for the production of artillery.
Another important handbook of the same ilk was Geog Agricola’s De Re
Metallica, published a decade after De la Pirotechnia.

It was only in the 18th century that the term ‘alchemy’ became restricted to the
futile task of the transmutation of base metals and ‘chemistry’ to the analysis and
synthesis of materials. Even then we find that ‘chemistry’ was largely restricted
to a medical context inherited from chemiatria or iatrochemistry (Chapter 2). It
is in this century that we see alchemists dismissed as frauds and alchemy as a
hopeless cause. By the time we reach the great French Encylopaedia of 1753,
chemistry is defined as the science ‘which concerns separations and unifications
of the principles making up bodies’, and alchemy as ‘the art of transmuting
metals’. In other words, the synonyms alchemy and chemistry have become non-
synonymous.

The disappearance of alchemy

The fundamental reason for the disappearance of alchemy (in the sense of
chrysopoeia) was that it did not work; what did work, however, was that
chymists could earn real money by being useful in helping a nation’s economy
and by preparing for sale various chymical nostrums.

The German chymist Johann Glauber, for example, made his fortune not from
making gold but by preparing and selling ‘sal mirabelle’, a wonderful salt he had
accidentally prepared when forming hydrochloric acid by the action of sulphuric
acid on table salt. Glauber’s salt, as it became known, and we know as sodium
sulphate, proved a highly efficient laxative. Another interesting alchemical
figure, Leonhard Thurneysser, became a rich man when, under the patronage of
the Elector of Brandenberg, he established a factory employing some 300 people
for the production of saltpetre, acids, alums used as mordants, glass, and
pharmaceuticals.

In the last decade, historians have traced the downgrading of alchemy into a
pseudo-science. This boundary work was largely done by French chemists
working in the Académie des Sciences from the 1740s onwards. It was achieved
by delimiting alchemy to gold making (whereas, as we have seen, it was rather
more than that) and dismissing alchemists as greed-driven frauds.

Alchemical facts were also taken out of their alchemical contexts, reinterpreted,
and transformed into reproducible chemical facts. For example, consider this
impressive and wonderful alchemical experiment. If a mixture of nitric acid,
mercury, and silver are allowed to stand for a couple of months, the mix
‘vegetates’ into a tree-like form of silver called Diana’s Tree. But whereas
alchemists had seen this tree as evidence of a vital spirit and a key step en route
to the philosophers’ stone, French chemists discussed it under the properties of
silver and as an example of mechanical crystal formation. They reinforced this
interpretation by showing how similar trees could be grown using lead or iron
instead of mercury.

We should note an important historiographical point here. The alchemists had

not lied about such trees: although the transmutation of base metals into gold
was a chimera, alchemists’ accounts of the chemical changes they witnessed
were not imaginary.

French chemists still had to concede alchemy’s theoretical possibility because of

their own growing commitment to corpuscular models of chemical change, but
they diminished its significance by only mentioning it under the rubric of the
chemistry of gold and not as a subject in its own right. French academicians had
the power to enforce the separation and distinction because its members, under
Royal prerogative, acted as reviewers for publications. So any gold-making
claims could be traduced and explained away by ordinary acid-alkali chemistry.
Moreover, the academicians extended this critical reviewing and boundary work
by reinterpreting older reports of transmutations as chemical facts.

Alchemy’s heritage
Alchemy, and chymistry more generally, bequeathed to modern chemistry a rich
variety of chemical operations, manipulations, techniques, and apparatus, but not
the conceptual frame of modern chemistry. Historians can explain alchemy’s
demise by its flaws—mysticism, metaphoric language, and its failure to work.
What did work was its application to useful arts and, above all, its service to
pharmaceutical practice. In such areas commercial gains were to be found that
were noticeably absent in the attempt to transform base metals into gold. The
alchemists’ primitive ideas of corpuscular composition also proved a useful
theoretical thread that led towards modern chemistry.

From the 1960s onwards, historians have increasingly viewed alchemy in its
cultural and historical context, and it is here we find that its practitioners made
no distinction between gold making and practical chymistry. Rulers in the
European courts supported both practices while scientific icons like Boyle and
Newton practised both.
Chapter 2
The analysis of stuff

The fundamental problem in chemistry is transmutation. How can two

homogeneous stuffs with very different properties merge to form another
homogeneous material whose properties are different from the reactants? Since
the reaction can be reversed and the original reactants regenerated, it would
seem that they are in some weird way still present in the product. But if so, why
are the properties completely different and not merely an averaging of the
reactants’ properties?

Aristotle had met the issue of homogeneity by teaching that the reactants’ forms
were present in the product ‘potentially’. This was not just a chemical problem;
it was one that medieval theologians wrestled with because of the issue of the
Catholic teaching of transubstantiation of bread and water into the body of
Christ. Consequently, any rejection of Aristotelian philosophy could be regarded
as a rejection of a fundamental Christian doctrine.

The rediscovery and publication of Lucretius’ didactic poem, De rerum natura

(On the Nature of Things), in 1473 brought Greek atomism back into circulation.
In principle, atomism gave a more satisfactory explanation of the homogeneity
problem. Atoms came in various shapes and sizes and different substances arose
from the various structures the atoms assumed.

The theory’s fatal weakness (apart from its atheistic implications) was that there
were no rules that explained why atoms adhered to each other in particular ways
other than unsatisfactory appeals to attraction and repulsion. Even so, we find a
general revival of corpuscular explanations among chymists during the 16th and
17th centuries; but their corpuscles were not featureless atoms, but property-
bearing particles that showed a compromise between original Greek atomism
and Aristotelian forms. Even in the 21st century, the problem of homogeneity
has to be explained by additional concepts that go beyond bare atoms: ideas of
valence, bonding, electronic shells, and orbitals.

We have seen how the origins of chymistry lay in the metallurgical, distillation,
and glassmaking activities of Graeco-Egyptian artisans. Knowledge of these
practices was passed on to the Arabic conquerors of Europe from the 9th century
onwards, and Arab chymists were able to isolate mineral acids such as nitric and
hydrochloric acids, as well as alcohol. When knowledge of Greek and Arabic
chymistry passed to the Latin West through translation and trade, these new
distillates were gradually put to use in the preparation of medicinal materials by,
among others, the Franciscan John of Rupescissa (fl. 1340), whose preparation
of ‘quintessences’ proved useful to Paracelsus (1493–1541) and his followers
(see Figure 4).

Paracelsus not only expanded the Arabic doctrine that two principles, sulphur
and mercury, were the roots of all things by adding a third principle, salt, but he
taught that the universe itself functioned like a chemical laboratory. God the
Creator, he believed, was a divine alchemist whose macrocosmic drama was
mirrored in the microcosmic world of man and earthly creatures. It followed that
physiological and pathological processes were chemical in nature, and that
disease was best treated by chemical medicines rather than by the herbal ones of
the ancients.
4. Furnace with hooded distillation apparatus. Hieronymus Brunschwig,
Liber de arte distillandi de compositis (Strassburg, 1512). This was the first
printed book to describe the preparation of distilled medicines
(quintessences) from plants and other materials.
Paracelsus and iatrochemistry
One of the most curious personalities of the 16th century was Theophrastus von
Hohenheim who was born in Switzerland in about 1493, the son of the town
doctor of Einsiedeln in the German-speaking Swabian canton. His childhood
was disturbed by the Swabian war in which Swiss cantons struggled for
independence against the authority of the Holy Roman Empire, and the family
sought refuge in Austria in 1502. As a child he suffered from rickets, but his
father instructed him in medicine and as a young man he also learned a good
deal by talking to miners and metallurgists.

Paracelsus’ life was that of a wanderer. The only settled period in his life came
1527 when, as a result of impressing some influential humanists with his cures,
he was appointed municipal doctor in Basel. The job also included the inspection
of the apothecaries’ shops, and he was soon accusing apothecaries of cheating
their customers. He also offended local physicians by attacking what he saw as
outmoded and incorrect Galenic medicine, lecturing in German instead of Latin,
and dressing in workmen’s clothing rather than those of a gentleman physician.
A year after his appointment he was forced to leave Basel and resume his life as
a wanderer, preaching and practising medicine, and printing his tracts and
homilies as the opportunity arose. He died in Salzburg in 1541 and was buried in
an almshouse (see Figure 5).

For publication purposes, Theophrastus took the Latinized name of Paracelsus,

which has often been taken to mean ‘greater than Celsus’, the Roman medical
authority of the 1st century CE; but it was more likely simply an invented
Latinization of his family name, Hohenheim. His writings were filled with angry
diatribes against the Roman Catholic Church and at orthodox medicine. The
original heterodox ‘angry young man’, he welcomed confrontation and avoided
compromise. To come to terms with him in the 21st century is difficult, until one
realizes that in the 16th century religion and science were inseparably two sides
of the same coin. His medical and chemical work were but minor aspects of his
religious beliefs and goals for the complete reformation of society.
5. Paracelsus. From a woodcut frontispiece to an edition of his works
published in 1567. The crest is that of the Hohenheim family and the
pommel of his sword contains a universal medicine he named ‘azoth’.

In essence, Paracelsus was a ‘spiritualist’ who saw spirits from the stars and
heavens as the essences of chymical bodies. He saw his mission in life to reform
both natural philosophy and the theology of which it was part and parcel. Living
as he did in the turbulence of Protestant attacks on the Pope’s authority, and amid
the disturbances of the Peasants’ War against landlords and authority, and
everyone’s fears of a Moslem invasion of Europe from Turkey, Paracelsus
agitated for wholesale revolution in religious practice and natural philosophy,
believing that the millennium was at hand and that God had ordained him to be
an itinerant prophet to prepare for the second coming of Christ.

It was in this deeply religious context that Paracelsus made his medical and
chemical innovations. His reputation as a doctor probably lay in his
conservatism and non-interventionalism on the grounds that nature can perform
its own cures; to this he added a repertoire of medications—small doses of
chemical remedies. He saw alchemy not as gold making, but as a way of
separating useful objects from the useless through the extraction of their
essences. He derided his contemporaries’ adherence to Galen’s humoral theory
that assumed that disease was due to the upset of the normal balance of the four
humours—blood, phlegm, and yellow and black bile—that made up a patient’s
normal constitution, and he argued instead that diseases were specific and had
specific locations. He sought the causes of disease in inappropriate diet and from
‘poisons’ that were ultimately drawn from the stars.

Remedies could be identified from their ‘signatures’, using signs drawn from
shape and colour in plants that resembled or suggested analogies with specific
anatomical organs. For example, a yellow flower might indicate that it was
suited to the treatment of a diseased liver. Existing herbal medicine often used
similar arguments, but Paracelsus differed from herbal practitioners in not using
the flower or herb itself as a medication, but in using an extract produced from
the flower by chemical means such as distillation in alcohol. In addition, using
his chemical and metallurgical knowledge, he prepared and used small quantities
of metallic salts and distillates.

He thereby set in motion what became known as iatrochemistry or medical

chemistry. This was to have a revolutionary effect in that once chemical
therapies were accepted, chemistry had to become part of a physician’s training
at university. Alchemy or, more generally, chymistry, had never been accepted as
part of the university curriculum; academic chemistry was now to develop in a
medical context for the next two centuries.

Paracelsus’ own religious framework was a form of devout Trinitarianism, and

this evidently implied to him that matter and disease had a tripartite form and
occurrence. Consequently, he held that three principles constituted the stuffs of
the microcosm. Drawing on the Arabic and medieval material theory that metals
were made from two principles, sulphur and mercury, he added a third material
body, salt. He cited the way metallic lead took on very different tripartite
physical and chemical forms according to whether it was minium (red lead
oxide), ceruse (white lead carbonate), or a lead glass.

These transmutations could not be explained by a four-element theory, he

claimed, but were easily explained in terms of matter’s trinity of sulphur,
mercury, and salt. The burning of a stick illustrated this model. The combustion
was due to sulphur, the smoke was caused by mercury, and the remaining ash
was salt. In general, salt conferred solidity and taste; sulphur gave colour, smell,
and flammability; and mercury conferred volatility and metallicity. This was the
doctrine of the tria prima, the three principles.

It may well be asked why such an extraordinary man always figures in the
history of chemistry? The answer, besides the fact that his life vividly illustrates
the intimate connection between science and religion in the early-modern period,
is that his many followers promulgated a medical chemistry. Although there
were bitter disputes between physicians who stuck to the administration of
Galenic plant products as medicaments, and the Paracelsians who recommended
the use of chemically prepared medicines and (bio)chemical interpretations of
physiology, the Paracelsians won the war.

The ramifications of this iatrochemical movement were far-reaching. For the

Paracelsians, chymistry was to be the handmaiden of medicine. Most notably, it
meant that chemistry, or at least pharmaceutical chemistry, became part of the
European medical curriculum and established in universities. This was
something that alchemy (a technology) had never achieved in the Middle Ages.
This was to prove of mutual benefit both for the advancement of medicine and
for the emergence of academic chemistry.

The first professor of medical chemistry was appointed at the University of

Marburg in 1609, and by the end of the 17th century chemistry was firmly
established in medical faculties throughout Europe. To aid the instruction of
medical students, more and more chemical textbooks were published, the most
significant being by the Dutch polymath, Herman Boerhaave (1668–1738) at the
University of Leiden. Paracelsus also influenced a range of significant figures in
chemistry such as Helmont and Boyle, who used his doctrines as a foil in
demonstrating their own beliefs; and, finally, the doctrine of the tria prima had a
definite role to play in the development of ideas about composition and
combustion. Paracelsus was the trigger for the start of the chemical revolution.

Van Helmont’s water

Chymistry remained in a deeply religious context for the Flemish follower of
Paracelsus named Joan Baptista van Helmont (1579–1644) who lived and
worked in Brussels all of his life apart from travels in Europe as a young man.
As a Flemish nationalist he had a deep resentment towards the Jesuits and other
Schoolmen who occupied positions of educational and church authority in the
Spanish-occupied Lowlands. Like Paracelsus he wanted to reform medicine, but
abandoned practising it in 1609 to devote himself to empirical chymical
research. His writings led to his investigation by the Spanish Inquisition and, like
Galileo, he was forced to acknowledge his errors in 1630. He was condemned
again three years later and spent some years under house arrest for promulgating
‘the monstrous superstitions’ of Paracelsus.

His major work, Ortus Medicinae (Origins of Medicine, but anglicized in the
English translation of 1662 as Physick Refined or Reformed) was published
posthumously by his son in 1648 and influenced the work of Robert Boyle in
England and Boerhaave in the Netherlands. Helmont’s cosmology was as
grotesque as Paracelsus’ and we are always in danger of picking and choosing
the seemingly ‘correct’ bits.

For example, despite his having the idea of a primary matter that generates the
tria prima, and although he sometimes wrote in terms of atoms and the void, all
this was contextualized within an essentially Aristotelian framework that
replaced forms with ferments, seeds, spirits, and strange emanations like Gas,
Blas (a principle governing stellar movements and causing the tides on earth),
and Magnall (a principle of light), which functioned essentially to convey or
explain properties and qualities to individual substances and diseases. Such
‘seeds’ or ‘ferments’ were the necessary agents of transmutation of reactants into
products.

Helmont was much more empirical and experimental in his investigations of

nature than Paracelsus. He made extensive use of the balance, and careful
observations during his experiments that were clearly based on a belief that
matter was conserved during chemical changes. For example, he carefully
analysed the different exhalations or smokes that evolved when different
substances were burned (attributed to the element air by Aristotelians, and to the
mercury principle by Paracelsians). He termed these smokes ‘gas’ because of
their chaotic character in frequently exploding when collected in a closed vessel.
He was even able to differentiate many of them.

But what was the significance of gas for Helmont? Because it was an exhalation
he believed it was the pure essence of a substance, its spirit in fact, or what he
termed its archaeus, the material manifestation of the substance. Matter and
spirit were, for Helmont, two aspects of the same thing—unlike the dualistic
philosophy of matter and spirit that was being popularized by René Descartes, a
younger contemporary in the Netherlands about the time of Helmont’s death.
The term ‘gas’ soon disappeared since it was not taken up by other writers who
preferred to use the terminology of ‘airs’. We owe its revival to a French
dictionary compiler in 1766.

Helmont denied that chemical reactions were real transmutations. When metals
were dissolved in acids and apparently formed a watery solution, the metal could
be recovered weight for weight. The original quantity of a metal could also be
recovered when one metal precipitated another from a solution, as when iron
precipitated copper from a vitriol solution of copper. His most famous
quantitative experiment concerned the growth of a willow tree, from which he
deduced that that all matter was ultimately water. He began with a sapling
weighing 5 lbs which he planted in 200 lbs of soil. He watered the tree regularly
for five years, following which the tree had increased in size and weight to 169
lbs, while the soil had neither lost nor gained any weight.

A modern chemist sees this as an undetermined experiment because Helmont

had neglected the possibility that the tree absorbs nutrients from outside the soil
in which it was embedded, namely from the atmosphere; otherwise his
conclusion that the tree had grown solely from water seems impeccable. He was
critical of both the four-element and three-principle theories, and argued instead
for there being only one primeval element, water, though in practice he often
combined this with air as if that too were elementary.

Daniel Sennert’s corpuscles

The defenders of Paracelsian and Helmontian chymistry and medicine included
many physicians who found patronage in the courts of central Europe, and who
thereby acquired authority over and protection from the rival, critical Galenists
outside such aristocratic protection. Others found jobs in the medical faculties of
European universities.

An important iatrochemist was Daniel Sennert (1572–1637), a professor of

medicine at the University of Wittenberg. He found a median way that
reconciled the cosmologies of Aristotle, Galen, and Paracelsus with a
corpuscular tradition that had long lain underground in the writings of various
medieval chymists and which can ultimately be traced back to a theory of
minima naturalis. Sennert taught that the different properties of substances were
not due to the elements or principles of Aristotle or Paracelsus, but to a set of
particulate seminal (formative) principles that produced new and different
properties after the comingling and separation of reactants and combinations.

He backed up this primitive corpuscular theory with experimental observations.

For example, since the vapour derived from distilling spirit of wine penetrated a
wodge of writing paper, the vapour’s particles must be very small; the
phenomenon of sublimation could also be simply explained as due to the motion
of particles. When gold and silver were mixed to form an alloy, the gold and
silver had not disappeared but remained; the proof lay in the fact that they could
be regenerated by adding aqua fortis (nitric acid) to the alloy. Such commingling
and separability suggested particulate compositions.

We find the same arguments used by Boyle later, often copied word for word
without acknowledgement to Sennert. Substances were composed from ‘that into
which they are decomposed’ and vice versa. In such processes, matter was
resolved into the minima (the smallest particles of the substance), which were
then rearranged to form a new body whose properties resulted from a seminal
principle (or form) particular to the new substance. Sennert called such reactions
of separation and assembly diacrisis and syncrisis, and we can see in this the
fundamental notion of analysis and synthesis. The minima were not necessarily
indivisible atoms (a doctrine that could lead to accusations of atheism), but the
smallest identifiable parts of a substance that resisted any further decomposition
by any known chymical operations.

Sennert’s corpuscularianism was inherited from an alchemical tradition that can

be traced back to the 13th century in the work of Geber in the Summa
Perfectionibus, a work that drew upon Arabic and Aristotelian sources. A
striking feature was the idea that the two principles (sulphur and mercury) that
made up metals were themselves composed from very small particles of
elementary minima that in their turn were composed from the Aristotelian
elements earth, air, fire, and water.

Geber, and likewise Sennert, pictured a hierarchical model of composition which

Sennert was prepared to defend experimentally by appealing to the phenomenon
of sublimation of the real substances sulphur and mercury. When heated in a
still, these materials sublimed as sulphurous powder and discrete mercury
droplets, so revealing their particulate nature. This clear resistance to further
decomposition was evidence of their ‘strong composition’ which rendered them
homogeneous. Fire (heat) allowed the lighter and more subtle particles to
separate and ascend, leaving heavier, grosser particles behind. This implied that
homogeneity depended upon size and weight.

Geber had also appealed to the calcination of metals as another form of

sublimation. The experimenter detected a sulphurous smell as calcination
proceeded, leaving a powdered and frequently coloured mass behind (the oxide),
the different colours being explained as due to the different sizes and packing of
the non-volatile sulphur left behind. The fact that metals could be regenerated
unchanged after their solution in acids was additional clear evidence that they
persisted through an alchymical experimental procedure.

Robert Boyle and the reform of chymistry

Our view of Boyle as ‘the father of chemistry’, and the most famous British
natural philosopher before being eclipsed by Isaac Newton, has been completely
transformed during the past thirty years. Michael Hunter and his acolytes have
trawled through the huge archive of Boyle papers held at the Royal Society in
London to produce a new edition of his published and unpublished works,
correspondence, and laboratory notebooks. It turns out that Boyle was a great but
complicated man who devoted most of his scientific life to drawing the attention
of mathematically inclined natural philosophers to the merits of the chymists’
activities for demonstrating a corpuscular theory of matter.
Boyle (1627–91), a man of insatiable curiosity, and a rather chaotic, literary
output, was a Christian virtuoso who saw experimental philosophy as a way of
understanding and justifying God’s purpose and design. Besides being
potentially useful, Boyle seriously believed that mechanical philosophy
underwrote religion.

A rich and privileged Anglo-Irish aristocrat, he only began to be interested in

science when he was in his early twenties. Before then he was a religious ascetic
and cerebral moralist. His devoutness remained when he became an ingenious
experimentalist devoted to the demonstration that an atomic or corpuscular
philosophy was a better way of understanding God’s creation than the pagan
Aristotelianism and Paracelsianism of his day which, he believed, was propelling
scholars towards atheism and infidelity.

Recent research has also thrown light on Boyle’s education and the reasons he
deliberately obscured his sources of information, so that he re-emerges as a less-
original and even less-honest figure than he has been portrayed in traditional
historiography. By portraying his views as novel (and, to be frank, less clearly
and more verbosely than his sources), Boyle succeeded in beginning to build a
wall between past and contemporary chymical practice and future chemistry.

Boyle’s training as a chemist came from an American immigrant to England

named George Starkey (1628–65), who wrote under the alchemical nom de
plume of Eirenaeus Philalethes (‘peaceful lover of truth’). It’s a delicious irony
that although Starkey taught Boyle chemistry, Boyle never knew that Eirenaeus
was Starkey himself! Neither did Newton, whose chemistry, it turns out, was
strongly influenced by Eirenaeus.

Much of the skill of chymists such as Starkey lay in their scholarly interpretation
of other chymists’ texts and the testing and modification of their procedures, as
his surviving laboratory notebooks show. Understanding Decknamen was a hard
job; hence Starkey’s comment: ‘God sells secrets for sweat’. The tragedy of
Starkey’s career was that in choosing to publish under a pseudonym he wrote
himself out of history for over 300 years.

The very practical, lab-based nature of 16th-century alchemy and the

reasonableness of attempts at gold making are now clear. (Compare the no-more
fanciful hopes and aspirations of Victorian chemists that atmospheric nitrogen
would one day be fixable for the manufacture of fertilizers.) Alchemists like
Starkey and Helmont used the assayer’s balance as an essential tool in mass
balance reasoning concerning the relationship between reactants and products
whatever transformations occurred in between to the human senses. That is, they
were aware of a principle of conservation of mass. Alchemy, like the metallurgy
that it drew upon, was quantitative; its practitioners tested their conjectures, and
their theory-guided practice was founded on reproducible experiments.

For example, Helmont’s obscure recipe for the preparation of the so-called
‘alkahest’ (matter degraded to its ultimate simplest form), which Starkey
deciphered and revealed to Boyle, involved the preparation of an antimony–
iron–mercury amalgam. Such an amalgam, following Starkey’s recipe, when
added to silver or gold does, indeed, lead to an apparent multiplication of these
precious metals. But what Starkey and Boyle interpreted as chryopoeia (or metal
making more generally) by the internal rearrangement of particles of the
alkahest, we interpret as an efficient metallurgical process for the removal of
silver and gold impurities from impure antimony ores.

Boyle’s familiar demonstration that the volume of air trapped above a column of
mercury was inversely proportional to the weight (pressure) of the mercury was
also a good argument for the particulate nature of air—for how else could the air
be compressed unless the particles of air were separated and not continuous?
Similarly, his design of tests for acidity and basicity using coloured vegetable
materials like litmus as indicators was to play an important role in the future
analysis of materials.

Boyle used codes and ciphers to hide his alchemical interests and so bound
himself to both a modern and ancient tradition. Although Boyle’s rambling
dialogue, Sceptical Chymist (1661), brilliantly criticized both the Aristotelian
four-element theory and the Paracelsian system of three principles, he was
clearly struck by Helmont’s evidence that water might be the fundamental
principle of matter, but he preferred to see this as evidence that there was a
universal substratum of matter divided into corpuscles of different sizes and
shapes. Analysis by fire (heating) did not produce elements or principles, but
rearrangements of corpuscles making up matter.

Natural philosophers like Boyle, Descartes, and Newton were happy to think in
terms of an imaginary world of atoms and corpuscles; but the practical chemists
of the day, and particularly the iatrochemists and apothecaries, either had doubts
or were indifferent to such speculations. Their sole aim was to produce useful
and profitable medicines. It was the French pharmacists who drove the subject
forwards at the beginning of the 18th century with their work at the Académie
royale des science (founded in 1666) on the analysis of mineral waters and
plants. Despite Boyle’s scepticism, property-bearing principles continued to be
useful to experimental chemists; but they were no longer ‘simples’ but categories
or groups of stuffs. Salt, for example, embraced sea salt, saltpetre, vegetable and
animal salts, and various alkalis.

In France in particular, chemistry came to acquire a public following that was

reflected in the publication of large numbers of textbooks, many of which
appeared in multiple editions. Chemistry there became important because its
practitioners thought chemistry was worth teaching in order to encourage a
greater public interest and to demonstrate its increasing economic importance.
Chemistry had become an indispensable part of a Frenchman’s liberal education.

The early laboratory

Despite the grand vision of Andreas Libavius in the 16th century, of a building
with specialized room-laboratories, kitchen laboratory-workshops had remained
standard for centuries and did not alter substantially until the 1840s. After all,
cooking is a chemical process, and the problems of laboratory and kitchen
maintenance are not dissimilar: drains, ventilation, furnaces for heating, raw
materials, implements, and utensils. Not until the expansion of teaching (18th-
and early 19th-century chemists like Berzelius commonly only took one pupil or
apprentice at a time), and above all the introduction of organic chemistry, did
laboratories need to be very large.

A small room with windows and/or a chimney for ventilation was quite adequate
when apparatus was simple, consisting of flasks and alembics (distillation
devices), and when chemical, pharmaceutical, and metallurgical operations were
confined to heating, dissolving, and distillation. Not for nothing were chemists
known as ‘spagyrists’ or workers by fire, or placed in the same category as
smiths and farriers. Indeed, if we want to picture these early laboratories, we can
do no better than to examine the interiors of the workshops of apothecaries and
pharmacists, and not be misled by the often reproduced romanticized genre
paintings of alchemists painted by Flemish artists like Daniel Teniers (1610–90).

Surviving prints of the Utrecht laboratory of Boerhaave’s contemporary, Johann

Barchusen (1610–1723), in 1698, or of the dispensing laboratory of the
Amsterdam apothecary, Anthony d’Ailly, in the 1810s, both draw the eye’s
attention to the significance of furnaces and the ventilation of smoke and
obnoxious fumes through large ventilation hoods (see Figure 6). The parallels
with contemporary kitchens in the large houses of the period (e.g. that of the
Prince Regent at the Royal Pavilion in Brighton) are striking. The French chef
Marie-Antoine Carême (1784–1833) saw cooks as martyrs: ‘It is the burning
charcoal that kills us’. Indeed, the presence of deadly carbon monoxide in
laboratories and kitchens from the use of charcoal as a heating agent made
ventilation a priority.
6. The interior of a typical apothecary’s laboratory and workshop which
evolved into the modern chemical laboratory. The image is that of the
Amsterdam apothecary Anthony d’Ailly in 1812. The workshop gave access
his shop through the door on the left.

Physics versus chemistry

Although Boyle had rejected the mathematical way as being too obscure for the
general public, whereas the experimental was assimilable, many of his
contemporaries found Boyle’s work too hypothetical, and his rejection of
analysis by fire and of the familiar elements and principles impracticable. If
Boyle’s support for a mechanical philosophy that resolved matter and its sensory
qualities into shaped particles in motion seems like later physical chemistry that
was not the way other practising chemists saw it. To them Boyle had thrown out
the baby with the bath water.

The historian Victor Boantza has drawn attention in particular to the criticisms of
an early member of the Académie de sciences in Paris, Samuel Du Clos (1598–
1685). He was not at all impressed by Boyle’s work and ideas, and refused to use
any kind of mechanical philosophy in interpreting the programme of plant
analyses he and others conducted in the Académie’s laboratory. Du Clos
preferred to interpret his analyses in terms of the Paracelsian tria prima that
Boyle had so heavily criticized in his Skeptical Chemist (1661).

To Du Clos’ way of thinking, Boyle’s work showed ignorance of chymical

literature and a lack of personal empirical practice. (This was perhaps a dig at
Boyle’s use of paid assistants to perform experiments under his direction.)
Whereas his own work was empirical and demonstrable, Boyle’s was abstract
and ultimately merely descriptive.

As Boantza emphasized, both Boyle and Du Clos were in the business of

reforming and modernizing chymistry: Boyle’s strategy was to reduce chymistry
to ‘physico-chymical’ discourse; Duclos’ more practical aim was redefine
traditional chymical philosophy, paying particular attention to elemental theories
and modes of analysis. Both men agreed that neither the Aristotelian four
elements nor the Paracelsian three principles were the ultimate constituents of
compounds. But whereas Boyle rejected both theories completely, arguing that
analysis by fire did not reduce bodies to their principles but more likely reduced
them to their particles which then rearranged themselves, Duclos was prepared
to use principles heuristically—like scaffolding—to help explain the results of
analysis by fire (the dry way) or by distillation (the wet way). This operative
view of principles was to lead to Lavoisier’s pragmatic definition of elements in
1789.

French iatrochemists found the Paracelsian’s solid salts of the greatest interest,
and their composition of great significance. Pharmaceutical chemists at the
Académie de sciences like Wilhelm Homberg (1653–1715) paid rigorous
experimental attention to the identification, purification, and classification of
salts and how they were derived from the neutralization between chemically
active acids and bases, much of which was to provide the material for
Lavoisier’s Traité élementaire de chimie in 1789, where a salt was defined as a
duality of acidic and basic oxides.

In view of Lavoisier’s demand for precision in language it is interesting to note

that the research that French pharmacists conducted in searching for drugs in
plant extracts was logically self-contained and independent of any theory. The
unsystematic nature of the terms used by these pharmaceutical chemists
evidently did not prevent them from thinking consistently about the reciprocal
reactions and compositions of the substances their terms designated.

Newton’s chemistry and affinity

The reason why matter cohered and aggregated had always been rather a
mystery to chymists. Aristotle’s solution was simply that it was part and parcel
of being ‘earth’ or ‘water’, and later Aristotelians appealed to water as a binding
principle in mixed (compounded) bodies. However, cohesion was usually left as
an occult power (in the sense that it was an unknown cause) and variously
referred to as ‘love/hate’, or ‘similitude/dissimilitude’. Following his successful
mathematical analysis of planetary orbits in terms of a universal attractive
gravitational force, Newton suggested that something similar existed between
the particles of ordinary matter. In this case, however, the attractive forces
extended only a short distance from the particles and varied in strength from one
chemical species to another.
The investigation of chemical affinities became one of the absorbing problems of
18th-century chemistry. It seemed to French iatrochemists working with salts to
be the basis for the relationships they uncovered. Étienne Geoffroy (1672–1731),
who wrote of the rapports between chemical substances, produced the first table
of affinities in 1718, and increasingly elaborate ones were produced from the
1750s onwards. Like the much later periodic tables, affinity tables effectively
summarized the whole of chemists’ knowledge concerning displacement
reactions. The tables demonstrated the power of chemists to analyse the natural
world into its components and how this information could be put to practical use
—whether in preparing drugs or in explaining and improving chemical
manufactures. On the other hand, the tables offered no theoretical insight
concerning the causes of reactivity or comparative inertness.

Attempts by Newtonian chemists such as John Freind (1675–1728) and John

Keill (1671–1721) to quantify chemical attraction soon proved hopeless. The
Newtonian dream of a mathematical chemistry still lay two centuries away. On
the other hand, the rich information gathered in affinity tables by such expert
practical chemists as the Swede Torbern Bergman (1735–84) could also be
recodified as instruction books on how to determine the composition of an
unknown mineral or salt. One of the earliest and influential of these Handbooks
of qualitative analysis (as they became entitled) was published in German by
Heinrich Rose in 1829. As a result, the stinking poisonous gas, hydrogen
sulphide, became the most familiar reagent used in chemical laboratories—
especially after the Dutch pharmacist, P. J. Kipps (1808–64), developed an
apparatus for its continuous production.

The appearance of systematic analytical tables that, like cookery books, enabled
anyone to determine the composition of minerals, completed the emergence of a
coherent chemistry of the mineral kingdom (eventually to be labelled inorganic
chemistry). Principles of composition such as mercury, sulphur, and salt (or at
least as rarefied or idealized versions of these real substances) expanded into a
larger group of tangible homogeneous materials that were perceived
corpuscularly and as the chymists’ elements in explaining composition and the
affinities of substances.
Chapter 3
Gases and atoms

Historians have often referred to a ‘postponed revolution’ in chemistry compared

to the intellectual transformation of natural philosophy in the 17th century
associated with Copernicus, Kepler, Galileo, Descartes, and Newton. The delay
has been attributed to the fact that chemists had no understanding of the role of
air in chemical changes until the mid-18th century.

While the centrality of the role of gases in promoting Lavoisier’s new chemistry
cannot be denied, historians have more recently also associated the late 18th-
century transformation of chemistry with professional separations between
medically oriented pharmaceutical chemists and more academic philosophical
chemists. The latter ignored pharmacy and relegated it to an inferior intellectual
position, while instead promoting the application of chemistry to the
understanding and improvement of agriculture, mining, and technology
generally.

The pneumatic revolution

Helmont had referred to the aerial products of reactions between acids and
metals as gas because the products were chaotic and uncontrollable. They were
first ‘reigned in’ and controlled by the Oxford-trained physician John Mayow
(1641–79) in the 1660s.
Experiments with the new air pump devised by Robert Hooke and Robert Boyle
in the early 1660s using birds, mice, and candles had led Boyle to conclude that
atmospheric air acted as a transporting agent to remove impurities from the lungs
to the external air. In his remarkable Micrographia (1665), Hooke outlined a
theory of combustion that owed much to a contemporary meteorological theory
that was based upon a gunpowder analogy. According to this ‘nitro-aerial’
theory, thunder and lightning were analogous to the explosions and flashing of
gunpowder whose ingredients were sulphur and nitre. Since it was known that
nitre lowered the temperature of water and fertilized crops, Hooke suggested that
the nitrous particles trapped in the atmosphere were responsible for snow and
hail and the vitality of crops. Such notions can be traced back to the Polish
chymist Michael Sendovogius who, in 1604, had identified a sal nitrum (nitre) as
a universal salt and component of the atmosphere.

It was Mayow who developed the nitro-aerial theory to its fullest extent in 1674,
when he extended it to an even wider range of phenomena including respiration,
the heat and flames of combustion, calcinations, deliquescence, the maintenance
of body heat, the red colour of arterial blood, plant growth, and, once more,
weather conditions. He recognized saltpetre as containing a base and an acid
formed from one of air’s constituents, the air itself being a medium formed from
nitrous particles and materials that remained behind after respiration and
combustion.

Mayow showed that when a candle burned in an inverted round-bottomed flask

submerged in water, it consumed the nitrous portion of the air, causing the water
level to rise. Combustion, he thought, involved the mechanical addition of the
nitro-aerial particles to a metal which he knew from some of Boyle’s
experiments brought about an increase in weight. This explanation seemed to be
confirmed by the fact that an identical substance (the calx) was produced when a
metal was heated in air as when it was dissolved in nitric acid and then heated.

There is a superficial resemblance between Mayow’s nitro-aerial theory and the

century-later oxygen theory of combustion and respiration, but it is really only
the transference properties that are similar. In any case, Mayow’s model was
mechanical rather than chemical. Nevertheless, Mayow was undoubtedly an
ingenious experimentalist. Although he had not quite invented the pneumatic
trough for collecting gases, his method of transferring an air (gas) from one glass
vessel to another over water was original and influential. In particular, it
stimulated the clergyman Stephen Hales (1677–1761) to devise a system of
apparatus in which the aerial products of combustion could be ‘washed’ and so
purified through water and collected in vessels for quantitative estimation (see
Figure 6).

Inspired by Newton’s mathematization of nature in the Principia Mathematica

(1687), Hales was primarily interested in demonstrating that huge volumes of air
were contained within otherwise solid minerals and plants—hence the title of his
book on the subject, Vegetable Staticks (1727). Although he remained tied to the
belief that the gaseous products he generated were pure air (that is, he failed to
recognize that he had produced different gases), his ‘pneumatic trough’ proved to
be the point of entry into distinguishing a range of gaseous products in the
second half of the 18th century. For a time, too, his work seemed to reinvigorate
the idea of the four Aristotelian elements. Like Helmont’s willow tree
experiment, Hales’s work was based on underdetermined experiments (see
Figure 7).

Experimentalists of Hales’s era interpreted combustion in terms of a phlogiston

theory that had been introduced to French and British natural philosophers from
the work of a German chemist named Georg Stahl (1660–1734). Stahl’s
comprehensive theory was a development of a theory of composition that had
been proposed by a German chymist and entrepreneur in 1669 (see Figure 8).
Johann Becher (1635–82), contrary to Helmont, suggested that water was not the
sole element and that minerals were also generated from earth, of which there
were three kinds. One of these earths, which was fatty and sulphurous, he called
phlogiston. This earth was, he suggested, the cause of combustion and
combustibility.
7. Apparatus for washing and collecting air fixed inside solid bodies. From
Stephen Hales, Vegetable Staticks (London, 1727).
8. Georg Ernst Stahl, professor of medicine and chymistry at the University
of Halle. He developed the theory of combustion known as the phlogiston
theory in his edition of Johann Becher’s Physica Subterranea (Leipzig,
1703).

Stahl developed this view further, and supposed that the calcinations of metals
were caused by the release of phlogiston into the atmosphere from the heated
metals from where it was recycled into plants, animals, and minerals. The
process of calcination could be reversed by heating a calx (a simpler body than a
metal) with another substance rich in phlogiston, such as charcoal derived from
wood or bones. He listed many of the reversible transfers already familiar to
chymists, but also noted that such reversals were not apparent in the vegetable
and animal kingdoms where an organizing or vital principle was at work.

For Stahl, phlogiston explained not only combustion, but also metallicity,
acidity, and alkalinity, the colours and scents of flowers, and chemical reactivity
and composition. The theory was known to and adopted by French chemists in
the 1730s, and from thence absorbed by British and Scandinavian pharmacists
and chemists.

Combustion, composition, and language

The chemical revolution was not merely conceptual but also instrumental, in that
it involved the practical ability to manipulate, weigh, and measure gases using
accurate balances, glass apparatus, and eudiometers. The chemist who
transformed our views of elements and composition, and reorganized the way
that chemists communicated, was the French civil servant Antoine Lavoisier
(1743–94).

For Lavoisier, as for his British contemporaries Henry Cavendish and Joseph
Priestley, chemistry was purely a part-time avocation practised early in the
mornings of days occupied with committees and working for a tax company. He
owed much to a young wife who took notes, produced sketches of apparatus,
prepared his papers for the press, and translated foreign works for him to read. In
1772 Lavoisier had noted the implausibility of a theory which suggested that
something was lost (phlogiston) when a metal was burned in air when its weight
actually increased rather than decreased. This was not a new observation, but
this anomaly had been strikingly emphasized by the work of a Dijon lawyer.

In the spring of 1772, Lavoisier read an essay on phlogiston by Louis-Bernard

Guyton de Morveau (1737–1816). In a brilliantly designed experimental
investigation, Guyton showed that all his tested metals increased in weight when
they were roasted in air; and since he still believed their combustibility was
caused by the loss of phlogiston, he supposed that phlogiston was so light that it
‘buoyed up’ the bodies in which it was trapped.
Most members of the Académie des sciences, including Lavoisier, found
Guyton’s explanation absurd, and Lavoisier quickly deduced from his reading of
Hales that a more likely explanation was that, somehow, air was being ‘fixed’
during the process of combustion and that this occluded air caused the increase
in weight. It followed that ‘fixed air’ should be released when the calces of
metals were decomposed, just as had been suggested by Hales’s earlier
experiments.

Lavoisier verified this in October 1772 by using a large burning mirror

belonging to the Académie. When litharge (an oxide of lead) was roasted with
charcoal a considerable volume of ‘air’ was, indeed, liberated. Lavoisier was still
ignorant of the fact that his British contemporaries had shown that many
different kinds of air were produced in chemical reactions.

In Scotland, a decade earlier, Joseph Black (1728–99) had succeeded in

demonstrating that what we now call carbonates (e.g. magnesium carbonate)
contained a fixed air (carbon dioxide) which was fundamentally different in
physical and chemical properties from atmospheric air. Unlike the latter, it
turned lime water milky and would not support combustion. A few years later,
Henry Cavendish (1731–1810) studied the properties of a light inflammable air
(hydrogen) which he prepared by adding dilute sulphuric acid to iron. These
experiments were to stimulate the astonishing industry of the Unitarian
clergyman, Joseph Priestley (1733–1804), who, between 1770 and 1800,
prepared and differentiated some twenty new airs. These included (in our
terminology) the oxides of sulphur and nitrogen, carbon monoxide, hydrogen
chloride, and oxygen.

Hence, although largely unknown to Lavoisier in 1772, there was already

considerable evidence that atmospheric air was a complex mixture, and that it
would be by no means sufficient to claim that air alone was responsible for
combustion. Lavoisier was soon made aware of his chemical ignorance, and with
the firm intention of bringing about, in his own words, ‘a revolution in physics
and chemistry’, he spent a year studying the history of chemistry—reading
everything that chemists had ever said about airs since the mid-17th century and,
significantly, repeating their experiments. Ironically, far from clarifying his
ideas, his new familiarity with pneumatic chemistry led him to suppose that it
was Black’s fixed air (carbon dioxide) in the atmosphere that was responsible for
the combustibility of metals and their increase in weight.
Two things forced Lavoisier to change his mind. First, he became aware that
when heated the calx of mercury decomposed directly to the metal mercury
without the use of the charcoal necessary with other metals. No fixed air was
evolved. So how could the phlogiston theory be right? Here was a calx
regenerating the metal without the aid of the phlogiston supposedly incorporated
in charcoal.

The same phenomenon had come to the attention of Priestley. In August 1774 he
heated the mercury calx in a closed vessel and collected a new air which he soon
found supported combustion far better that ordinary air—hence he called it
‘dephlogisticated air’. Priestley reported this observation directly to Lavoisier
when he was on a visit to Paris in the autumn of 1774. Lavoisier’s repetition of
Priestley’s experiment changed his mind.

In March 1775 Lavoisier announced to the Académie des sciences that ‘the
principle which combined with metals during calcinations and increased their
weight’ was ‘pure air’ and not any particular constituent of air. Clearly, Lavoisier
was still confused and had to be corrected by Priestley later the same year, and
with this stimulus Lavoisier was able to produce a new theory. He wrote in 1778:

The principle which unites with metals during calcinations, which increases their weight and which
is a constituent of the calx is: nothing else than the healthiest and purest part of the air, which after
entering into combination with a metal, can be set free again; and emerge in an eminently respirable
condition, more suited than atmospheric air to support ignition and combustion.

Because this ‘eminently respirable air’ burned carbon to form the weak acid,
carbon dioxide, Lavoisier called the new gas ‘oxygen’, meaning ‘acid former’.
Thus by the late 1770s half of Lavoisier’s chemical revolution was over. Oxygen
gas was an element containing heat (or caloric, as Lavoisier called it) which kept
it in a gaseous state. In other words Lavoisier redefined heat (or caloric) as
something that altered the physical state of a substance without altering its
chemical species, and not as something removed from bodies during
combustion.

On reacting with metals and non-metals the heat was released and the oxygen
element joined to the substance, causing it to increase in weight. In respiration,
oxygen burned the carbon in foodstuffs to form carbon dioxide exhaled in
breath, while the heat released was the source of animal warmth. Lavoisier and
his fellow countryman, the mathematical physicist, Simon Laplace,
demonstrated this quantitatively with a guinea pig in 1783 by measuring the
amount of oxygen inspired by the pig and the amount of water its body heat
produced when it was packed in ice—the origin of the term ‘guinea pig’.
Respiration, he concluded, was just a slow form of combustion. The non-
respirable part of air (later called nitrogen, or azote in French) was exhaled
unaltered.

On the face of it Lavoisier might seem to have only transferred the properties of
phlogiston to oxygen gas, but there were major differences. Heat was absorbed
or emitted during most chemical reactions and was present in all substances,
whereas phlogiston was supposedly absent from non-combustible bodies. When
added to a substance, heat caused expansion or a change of state, something not
claimed by phlogistonists; above all, heat could be measured with a thermometer
and oxygen with a eudiometer, whereas phlogiston could not.

The water problem

Lavoisier remained cautious and did not immediately suggest the abandonment
of phlogiston. The main reason for this caution was that the phlogistonists could
explain why an inflammable air (hydrogen) was evolved if a metal was dissolved
in an acid whereas no air was produced when the calx (metal oxide) was treated
with the same acid.

The problem, of course, was that moisture (a compound of hydrogen and

oxygen) was so ubiquitous in chemical reactions that it was easy to overlook its
production. It was Priestley who first noticed the presence of water when an
electric spark was passed through a mixture of air and ‘inflammable air’
(hydrogen). In 1781 he mentioned this to Cavendish who repeated the
experiment and reported in 1784: ‘It appeared that when inflammable air and
common air are exploded in a proper proportion, almost all the inflammable air,
and near one fifth of the common air, lose their elasticity and are condensed into
dew. It appears that this dew is plain water.’ We are so used to knowing that
water is composed from hydrogen and oxygen that it is hard to realize what an
astounding discovery this was. How could two gases be transmuted into a
liquid?
It was this same experiment which led the precise Cavendish to record that a
bubble of uncondensed air remained, a fact reported later by Cavendish’s
biographer. The Scots chemist William Ramsay (1852–1916) was to recall
reading this observation in 1894 when he showed that the bubble contained an
unknown family of inert gases. For Lavoisier, Cavendish’s work was evidence
that water was not elementary. Assisted once again by Laplace, he showed that
water could be synthesized by burning inflammable air and oxygen together in a
closed vessel. For this reason, he renamed inflammable air, hydrogen, meaning
‘water-former’. He could now explain why metals dissolved in acids to produce
hydrogen whereas their calces did not. The hydrogen came not from the metal
(as the phlogistonists supposed) but from the water in which an acid oxide was
dissolved.

The new chemistry

Lavoisier was now in a position to bring about a transformation of chemistry by
eradicating phlogiston from its vocabulary. Since all chemical phenomena were
explicable without its assistance, it seemed highly improbable that the substance
existed. He concluded a paper published in 1785 with a fine piece of rhetoric:

Chemists have made phlogiston a vague principle which is not strictly defined and which
consequently fits all the explanations demanded of it. Sometimes it has weight, sometimes it has not;
sometimes it is free fire, sometimes it is fire combined with an earth; sometimes it passes through the
pores of vessels, sometimes they are impenetrable to it. It explains at once causticity and non-
causticity, transparency and opacity, colour and the absence of colours. It is a veritable Proteus that
changes its form every instance.

By collaborating with a younger generation of assistants whom he gradually

converted to his way of interpreting combustion, acidity, respiration, and other
chemical phenomena, and by holding soirées where experiments and discussions
could be held, Lavoisier won over a devoted group opposed to the idea of
phlogiston. In 1788 Lavoisier and his companions founded a new quarterly
periodical, Annales de chimie, to promote the new chemistry. Within a decade its
contributors took the new chemistry for granted so that it became much more
than a French journal promoting Lavoisier’s views. Its successive editorial
boards saw it as a European journal of international significance.

Three important converts were Guyton, Claude-Louis Berthollet (1748–1822),

and Antoine Fourcroy (1755–1809). Guyton, in particular, was exercised by the
inconsistent use of terms by chemists and pharmacists. Hitherto a substance
might receive a different name according to the place where it was derived, or
names might be based upon properties of smell, taste, colour, and usage.
Following the inspiration of the Swedish naturalist Carl Linnaeus, who had
begun to systematize the names of plants in 1737, Guyton suggested in 1782 that
chemical language should be based upon three principles: substances should
have one fixed name, names should reflect composition when known (or non-
committal terms if unknown), and names should generally be chosen from Latin
and Greek roots. It was while the four men were collaborating on a new
language for chemistry that Guyton was converted to Lavoisier’s new chemistry.

For his part, Lavoisier believed that language should express clear and distinct
ideas. Together, in 1787, the four chemists published a 300-page manual of
nomenclature reforms, one third of which consisted of a dictionary of new terms
for old ones. For example, ‘oil of vitriol’ became sulphuric acid, and its salts
sulphates instead of vitriols; ‘flowers of zinc’ became zinc oxide. The entire
nomenclature was based upon the names of elements. Thus the elements oxygen
and sulphur could combine to form either sulphurous or sulphuric acids
depending upon the quantities of oxygen combined. These acids when combined
with metallic oxides (the former calces) would form two groups of salts, the
sulphites and sulphates.

Because the new language was also a vehicle for the non-phlogiston chemistry, it
aroused much opposition. Nevertheless, through translation it rapidly became,
and still remains, the international language of chemistry. Lavoisier’s final piece
of propaganda for the new chemistry was a textbook published in 1789 called (in
English) An Elementary Treatise of Chemistry. Together with a much larger, less
elementary text published by Fourcroy in 1801, this became a model for
chemical instruction for several decades. In it Lavoisier defined the chemical
element as any substance which could not be analysed further by chemical
means. Such a definition enabled him to identify some thirty-three basic
substances, including some which later proved to be compound bodies.

By the mid-1790s the opposition to phlogiston had triumphed, and only a few
prominent chemists, such as Priestley (who emigrated to the United States in
1794) continued to believe in it. By then the French Revolution had put paid to
the possibility that Lavoisier would apply his insights to fresh fields of
chemistry. He was guillotined in 8 May 1794 for being a member of a firm of tax
inspectors.

The atomic theory

John Dalton (1766–1844), the son of a Cumbrian Quaker handloom weaver,
moved to Kendal in the heart of the English Lake District in 1781. There he
became interested in meteorology, a subject that was to influence his thoughts on
atomic theory. The records Dalton kept over a five-year period were published in
Meteorological Essays in 1793. In the same year Dalton moved to Manchester as
tutor in mathematics and natural philosophy at New College, where Joseph
Priestley had taught in the 1760s. Dalton found Manchester so congenial that he
decided to spend the rest of his life there. Not only was there an abundance of
paid work in Manchester for private tutors because of the rise of an industrial
middle class, but the presence of the Manchester Literary and Philosophical
Society, whose secretary Dalton became in 1800 and president from 1817 until
his death, proved a convenient venue for publicizing his scientific work.

Like Priestley, Dalton is best described as a natural philosopher rather than as a

chemist. Honed in the mechanistic tradition of Boyle and Newton, he believed
that matter was particulate and endowed with powers of attraction and repulsion.
However, Dalton moved away from the tradition of 18th-century matter theory
which had emphasized the homogeneity of matter. Instead, he identified material
particles with Lavoisier’s elements, i.e. with substances that could not be
chemically analysed. Thus, although Dalton spoke and thought of physical
atoms, his chemical particles were much more akin to the minima or molecules
of Aristotelian philosophers. Moreover, the identification of atoms and elements
meant that Dalton, unlike some chemists such as William Prout (1785–1850),
who speculated that Lavoisier’s elements were polymers of hydrogen, accepted
as many different kinds of atoms as there were chemical elements.

Dalton’s theory probably originated from his meteorological study of air in the
1790s. Dalton wondered whether, if air consists of a number of gases as well as
the water vapour precipitated as rain and dew, were these chemically combined
or merely mixed together statically? If the latter, how is it that air is apparently
homogeneous and does not consist of weighted layers of vapour, carbon dioxide,
oxygen, nitrogen, and hydrogen?
Dalton’s ingenious answer was to appeal to a model of self-repulsive air particles
that had allowed Newton to deduce Boyle’s law that pressure was inversely
proportional to volume. In Dalton’s revised model, however, the particles of each
gas in the atmosphere were self-repulsive, though completely unaffected by each
other. This produced mixing and atmospheric homogeneity. Although the model
was later modified by ideas of diffusion and the kinetic theory of gases, chemists
have always referred to the model as Dalton’s law of partial pressures.

Since Lavoisier had explained the gaseous state of matter by the combination of
heat (caloric) with elements or compounds—and heat particles were believed to
be self-repulsive—Dalton’s atmospheric model showed consistency. But in order
to explain why self-repulsive forces differed from element to element and why,
as his Mancunian friend William Henry pointed out, gases had different
solubilities in water, Dalton was forced to conclude that the sizes of atoms of
different elements varied. In order to calculate atomic sizes (volumes), densities
and weights were required. Gas densities could be crudely determined by
weighing equal volumes of gases on a sensitive balance, while atomic weights
would be calculated from existing analyses if simple assumptions were made
about atomic combination.

In about 1804 Dalton, having been through a long exercise to determine atomic
sizes, realized that in calculating relative atomic weights he had produced a new
quantitative basis for chemistry. With Dalton’s permission, this was first
publicized by Thomas Thomson in his System of Chemistry in 1807. Dalton
explored the theory’s implications in his own textbook in 1808 (see Figure 9).

Despite being plagued by methodological problems that were only resolved by

the Italian chemist Stanislao Cannizzaro (1826–1910) in the 1850s, and by
theoretical issues that were not resolved until the work of Rutherford and Soddy
in the 20th century, Dalton’s theory offered chemists a new, and enormously
fruitful, model.

Dalton’s originality lay in solving the problem of what philosophers have

labelled ‘transduction’, i.e. deducing the existence of the unseen from
macroscopic phenomena. The German chemist Benjamin Richter (1762–1807)
had already demonstrated in 1792 that when acids neutralized bases to form
salts, different quantities of acid were needed to neutralize a fixed amount of
each base. The amounts were not arbitrary: a fixed (or equivalent) weight of acid
reacted with a fixed weight of base.
9. Dalton’s atomic symbols and caption from New System of Chemical
Philosophy, vol. 1 (London, 1808).

This became known as a law of fixed proportions, and although Berthollet

argued that the concentrations of the reactants ought to lead to variable
proportions, the Spaniard Joseph Proust (1754–1826) provided sufficiently
convincing evidence for fixed proportions as to convince the small chemical
community of the time. (Berthollet’s argument was nevertheless important, but it
was another fifty years before it was developed into a law of mass action.)

Fixed proportions and equivalent weights implied, as Dalton saw, that matter
was not continuous and that the ultimate particles of matter combined according
to fixed rules. Knowing this, Dalton developed a way of calculating the relative
weights of the ultimate chemical particles of matter from observations and
measurements that were made in the laboratory.

To provide this calculus of chemical measurement Dalton had to make a number

of simple assumptions about how atoms probably combined to form compound
atoms, a process he labelled ‘chemical synthesis’. In the simplest case, when
only one combination of two elements could be obtained, he assumed it had to
be a binary combination, unless there was reason to suppose otherwise. In other
words, although two substances A and B might combine to form A2B2, it is
simpler to assume that they will usually form AB.

In the case of water, for example, and bearing in mind that hydrogen peroxide
was unrecognized before 1815, Lavoisier’s analysis had shown that 87.4 parts by
weight of oxygen combined with 12.6 parts of hydrogen. On the binary
compound assumption, therefore, this ratio, H:Ō::12.6:87.4, must also be the
ratio of the individual weights of the hydrogen and oxygen atoms that make up
the water molecule. Since hydrogen was the lightest known substance, Dalton
suggested that it should be taken as a standard of atom weights. Accordingly, if
the atomic weight of hydrogen is taken as one unit, the relative atomic weight of
oxygen is roughly seven. Improvements in analyses of water soon raised this to
eight.

By drawing on the already extensive corpus of published analyses, Dalton was

able to establish a lengthy list of relative atomic weights, which he first exhibited
in Manchester between 1803 and 1804. Ironically, as a result of the emergence of
electrolysis in the early 1800s, two British workers, Nicholson and Carlisle, had
already demonstrated that two volumes of hydrogen and only one of oxygen
were released when an electric current was passed through acidulated water. This
might have suggested to Dalton, as it did to his Swedish contemporary,
Berzelius, that water would be better expressed as H2O. Dalton stuck to his
simplest guns.

The French nomenclaturists of 1787 had noted various ways in which chemicals
could be symbolized by geometrical patterns. However, although this
represented an attempt to produce a simpler and more systematic notation than
the alchemists, such symbols were inconvenient to reproduce in print and so
never became firmly established. Typographical difficulties were also a factor in
preventing Dalton’s representation of elementary bodies by circles distinguished
only by horizontal and vertical diameter lines, shading, or by placing an
alphabetical letter within the circle. Although easy to draw and providing a
concrete two-dimensional portrait of round atoms, they proved cumbersome to
print (especially for multi-atom molecules) and never came into general use.

In 1813 Jöns Berzelius (1779–1848) introduced the modern notation whereby an

element is symbolized by the initial letter of its Latin name, using two letters
where elements might otherwise be confused: H, hydrogen; K, potassium
(kalium); C, carbon; but Cu, copper (from cuprum). Berzelius’ symbols, which
could easily be arranged algebraically to represent compounds, became generally
adopted from the mid-1830s onwards, when chemists also began to represent
reactions by means of equations.

Are atoms split?

Dalton was well aware of the arbitrary nature of his rules of simplicity. In the
second part of the New System of Chemical Philosophy published in 1810 he
stated that water might be a ternary compound, in which case oxygen would
have been sixteen times heavier than hydrogen: or, if two atoms of oxygen were
combined with one of hydrogen, oxygen’s atomic weight would be four. This
uncertainty was to plague chemists for another fifty years.
Why, though, did Dalton not exploit Gay-Lussac’s law of combining volumes,
formulated in 1808? Dalton rejected the Frenchman’s law on the grounds that if
equal volumes of gases at the same temperature and pressure contain the same
number of particles, n, then some of them would have to ‘split’, something that
by definition no atom could do:

Thus the oxygen atom would have to divide in order to produce two water
particles, occupying two volumes. Such division was made even more
prohibitive by the fact that Dalton conceived atoms to be surrounded by
atmospheres of heat which rendered them self-repulsive. Since there was no
conceivable way two self-repulsive particles could he combined, the kind of
atomic division apparently demanded by Gay-Lussac’s law seemed impossible.

Dalton’s views were reinforced by the electrochemical theory of combination

introduced by Berzelius in 1813 (Chapter 4). Because like electrical charges
were repulsive, atomic division was rendered implausible. Not until the time of
Cannizzaro in 1858, was a way round this conundrum found in terms of
molecular species. The trick was not to ask what held molecules together, but
simply to accept, on chemical and physical evidence (kinetic theory), that most
of the common elementary gases were diatomic.

Berzelius also introduced the notion of volume atoms. Assuming that the volume
occupied by the atoms of different gases were all the same, because water
consisted of two volumes of hydrogen and one of oxygen he arrived at H2O as
the formula of water; similarly he gave ammonia the formula NH3 in
contradiction to Dalton’s formulae HO and NH. For this reason his atomic
weights were radically different from those of Dalton’s, even more so since he
used an oxygen standard of sixteen (or sometimes one hundred) for relative
weights rather than Dalton’s hydrogen standard of one.

Berzelius devoted most of his life to determining accurate atomic weights,

arguing that it was the most important object of chemical investigation and one
worthy of ‘unresting labour’. Despite his great accuracy, many of his atomic
weights turned out to be incorrect. This was usually because he had to work
from oxides. In the case of the two iron oxides, for example, he found that the
quantity of oxygen (sixteen) that united with the same amount of iron were in the
ratio of 2:3. From this he assumed the formulae were FeO2 and FeO3, rather than
the FeO and Fe2O3 recognized later. Consequently Berzelius’ atomic weight for
iron was double the one agreed in later decades.

What was the chemical revolution?

Revolutions are exciting to write about, especially ones that are also set amid
political upheaval; but in the case of the chemical revolution historians may have
overlooked long-term trends and the fact that practical chemists had shunned the
mathematical physicists’ approach to material change.

They had seen Boyle’s and Newton’s approach as over-reductive in that it

ignored the richly mysterious nature of chemical change. For them, in the words
of French historian Sacha Tomic, chemistry was a practice involving ‘operations,
separations and combinations of substances that depended upon their properties
and technical uses’ rather than on the nature of matter itself. The American
historian Victor Boantza sees what he calls ‘the long chemical revolution’
extending from Boyle to Lavoisier as a clash between physical and chemical
perceptions. In that light, the phlogistonists’ resistance to the Lavoisian approach
can be seen as an attempt to hold a chemical as opposed to a physical method of
investigation.

Despite the fact that the anti-phlogistonists won the debate, chemists’ opposition
to physicists’ meddling with their science continued during the 19th and 20th
centuries, and even continues today with chemists’ refusal to allow the claim that
chemistry can be reduced to physics. The chemical revolution can also be
interpreted in terms of professionalization and the creation of new teaching
institutions, career pathways, and journals. Nor can the role of the state be
ignored, as governments (especially that of France) began to plan secondary and
higher education and qualifying systems.

It is perfectly legitimate to argue therefore that Lavoisier’s new chemistry was

the apogee of an evolutionary, rather than revolutionary, process. The
historiographical issue is best resolved by adopting the sophisticated approach of
John G. McEvoy who has argued for a multivalent approach which gives equal
weight, and interconnection, between theoretical, social, and institutional factors
in the construction of modern chemistry.

Had he lived, the signs are that Lavoisier would have applied his new approach
to vegetable and zoological chemistry. This was certainly the direction which
many of his disciples followed and to which we can now turn.
Chapter 4
Types and hexagons

In recent years historians of chemistry have emphasized the changing roles

between chemists and pharmacists during the chemical revolution, and the
connection with the emergence of organic chemistry as a discipline in the 1830s.

It was Lavoisier’s pharmacy-trained disciple Antoine Fourcroy who, as director-

general of public instruction, did much to bring French science under state
control. Fourcroy was the first chemist to establish that the bewildering variety
of compounds that could be extracted from plants and animals generally
contained just a few elements, namely carbon, hydrogen, oxygen, and nitrogen,
and just occasionally sulphur and phosphorus.

Rather than talking of vegetable chemistry and zoological chemistry, Fourcroy

divided chemistry into the two grand divisions of inorganic and organic. The
latter term continued to refer to substances extracted from living entities until the
1830s. By then, however, chemists had prepared so many derivatives of
extractable materials—that is, of substances that did not exist in the living world
—that the term organic chemistry came to have a wider meaning. It was not,
however, until 1858 that the German chemist Friedrich Kekulé (1829–96)
defined organic chemistry as the chemistry of carbon compounds.

Chemists in the 19th-century pictured atoms, and used atomic and molecular
models to create an academically and industrially significant discipline. ‘Paper
chemistry’ and chemists’ imagined worlds of molecules were to aid their studies
and progress.

Liebig’s achievement
The career of the Paris-trained German chemist Justus von Liebig (1803–73)
encompassed innovation in teaching, important contributions to organic
chemistry, and, above all, the application of chemistry to agriculture, physiology,
medicine, nutrition, and industry, as well as to the popularization of chemistry.

Liebig’s fame was not so much that he made any startling new chemical
discoveries (see Figure 10). It was largely due to his demonstration with his
Göttingen friend Friedrich Wöhler (1800–82) that it was possible to use the
paper tools of Berzelian chemical symbols to make sense of analytical results by
inspecting and juggling with the compositions of reactants and products.
10. Water-cooled condenser usually attributed to Liebig because he used it
extensively at Giessen.

Manipulating chemical symbols on paper was as significant as the introduction

of written, as opposed to oral, examinations in universities during the same
decades. As the German historian Ursula Klein has shown, the 1830s produced
novel ways of individuating, identifying, and classifying organic compounds,
chief of which was the exploitation of Berzelius’ chemical formulae and their
manipulation on paper in an attempt to understand the composition of the
dazzling parade of new derivatives that were totally unknown in nature.

Liebig, Wöhler, and their French contemporary Jean-Baptiste Dumas (1800–84)

excelled at this practice, and were considerably helped by the sophisticated
method of organic analysis with the so-called Kaliapparat (potash bulb
apparatus) that Liebig developed in 1830 when attempting to understand the
composition of plant alkaloids. The replication of these gravimetric experiments
in the 21st century has shown historians how accurate Liebig’s results were for
carbon, hydrogen, and oxygen content (though nitrogen content remained an
acute problem).

Liebig and Wöhler first met in 1826, when they ironed out their difference of
opinion over the apparently identical composition of Wöhler’s silver cyanate and
Liebig’s preparation of silver fulminate. They agreed that the two silver salts
were remarkable examples of different modes of combination among their
elements carbon, hydrogen, oxygen, and nitrogen.

In 1830, Berzelius coined the word isomerism to describe the remarkable

phenomenon whereby organic compounds with very different chemical and
physical properties were composed from the same elements in identical
proportions but in some unknown different physical arrangement. Wöhler
produced another striking example in 1828 when he showed that the product of
reacting silver cyanate with ammonium chloride was the ‘organic’ compound
urea (and not ammonium cyanate as he had expected).

Later generations of chemist-historians saw Wöhler’s ‘synthesis’ of an organic

compound as the destruction of vitalism in chemistry, but it is now interpreted as
a foundation myth invented by later chemists to provide an exciting take-off
point. In fact, Wöhler’s discovery of the isomerism between ammonium cyanate
and urea did nothing to abolish the view that organic compounds extracted from
vegetable and animals were under the control of something outside chemical
knowledge, a vital creativity.

Instead, vital force simply withered on the vine through the development of
synthetic organic chemistry. Isomerism was to be, and remains, a fundamental
concept in understanding (and simplifying) the bewildering variety of the now
millions of organic compounds that have been prepared by successive
generations of chemists. Without this clarifying concept and the idea of structure
that it eventually generated, organic chemistry would have long remained a ‘dark
forest’, as Liebig and Wöhler aptly described it in 1832.

The development of a rapid and accurate method of gravimetric organic analysis

using the Kaliapparat acted as a trigger for the explosion of organic (as opposed
to inorganic) chemistry. The two techniques of paper chemistry and accurate
compositional analysis forged the new discipline of carbon chemistry, as
opposed to the tradition of vegetable and animal chemistry, and enabled chemists
to classify and interpret analyses in terms of common groups or radicals and,
later, in terms of ‘chemical types’.

The ‘Giessen model’

Liebig’s contribution to the perfection of inorganic analysis and its dissemination
must not be underestimated. At the University of Giessen, and building upon the
long historical tradition of tests for mineralogical composition, he taught
systematic methods of inorganic analysis, though he left it to pupils and
assistants such as Carl Fresenius (1818–97) and Heinrich Will (1812–90) to
publish these methods. (Fresenius went on to create a famous school of
analytical chemistry in Wiesbaden that continues to this day.)

These systematic group separation methods (wet qualitative and quantitative

analysis) were to be taught to every student of practical chemistry into the 1950s.
The fame and celebrity status that Liebig sought as a young man came about
through teaching these systematic methods of inorganic and organic analysis.
Beginning with a majority of pharmacy students, he successfully attracted an
international body of chemistry students to the University of Giessen, where he
was appointed professor in 1824. From 1835 until he left for Munich in 1852, he
engaged in line-production research investigating the chemistry of living
systems of plants and animals. Whether Giessen was the model for future
research schools has been the subject of great historical interest, since the
‘Giessen model’ rapidly spread far and wide.

Two French brigands

Charles Gerhardt (1816–56) had been trained and educated by his father to run a
family white lead factory in Strasbourg, but Gerhardt fell so deeply in love with
chemistry that he rebelled and took advanced studies with Liebig in Giessen and
with Dumas in Paris. This led to a job in Montpellier, but disgusted with the poor
facilities in such a provincial city he resigned in 1851, returned to Paris, and
earned his living by private teaching in his own chemistry school. It was not
until two years before his tragically early death that he was appointed a professor
in his home town.

From 1844 onwards Gerhardt became a close friend of another rebellious

chemist, Auguste Laurent (1808–53), who had trained with Dumas in Paris and
worked in ceramic factories before teaching in Bordeaux. In 1846, appalled by
the poor facilities at the University of Bordeaux, he joined Gerhardt in his school
enterprise in Paris where they shared ideas about the reform of organic
chemistry. Neither man respected Dumas, their former teacher, because he
represented conservative chemical ideas and the establishment; both men were
tactless and quarrelsome, but between them they transformed the way organic
chemists viewed their chaotic subject.

By the 1850s, organic chemists were confident about the constitution and
quantitative ratios of the elements composing an organic compound (though, in
practice, their formulae might look different because there was no consistent
system of atomic weights). By then chemists were also aware that elements
‘clumped’ together in regular patterns, and that there was an internal ‘order’ of
elements within a compound, as indicated by the fact that the same empirical
formulae had to be given to isomers that had distinctly different properties.

Berzelius had been a pioneer in differentiating the clumps within molecules by

virtue of the dualistic system that, following Lavoisier’s inorganic system, he
promulgated from 1818 onwards. According to this electrochemical system of
classification, organic compounds consisted of a positive hydrocarbon radical
electrically linked to a negatively charged molecule that might contain more
carbon and hydrogen together with oxygen, nitrogen, and other elements. This
classificatory model was known as the radical theory; organic chemistry, in the
words of Liebig, differed from inorganic chemistry because it involved
compound, rather than simple, radicals. The radical model has persisted into the
21st century in the idea of ‘groups’, though these are no longer laboriously
identified by 19th-century methods of analysis, but by their optical signatures
that can be read spectroscopically or magnetically.

An alternative way of viewing the constitution of organic molecules had also

matured from the 1830s. This had been generated from a discovery by Dumas in
1834 that electronegative elements or radicals such as chlorine, bromine, and
cyanogens could be exchanged or substituted for hydrogen, in what Berzelius
interpreted as the electropositive hydrocarbon portion of a molecule.

For Dumas, substances of the same chemical type clearly contained the same
number of equivalents united in the same manner because they underwent the
same fundamental reactions. For example, acetic acid, CH3COOH could easily
be transformed into CCl3COOH, and both acids had very similar properties
when reacting with other reagents. (Dumas actually wrote the two acids
dualistically as C4O4,C4H2H6 and C4O4,C4H4Cl6, where C = 6.) Berzelius was
initially not at all happy with Dumas’ findings, but forced by the evidence, he
began to elongate his formulae by allowing substitution in only the
electropositive carbon grouping of an organic compound.

Meanwhile, Gerhardt, inspired by the ancient biological idea of a great chain of

being, or ladder of nature, explored the idea of classifying compounds by a
ladder of combination. Given the dazzlingly large numbers of organic
compounds that chemists had already differentiated by the 1840s, Gerhardt
supposed that a principle of plenitude operated, and that where two organic
compounds differed by two units of carbon and hydrogen, another compound
that differed by only one carbon and hydrogen unit must also exist. He soon
called this the principle of homology.

Paraffins formed a series of compounds that differed by CH2, and this applied
equally to the organic acids formed from them. It was a simple idea, but one that
had far-reaching implications for the learning and understanding of organic
chemistry. It was the equivalent of the epiphany of the language student on
learning that French verbs are only three in kind and that each conjugates in a
regular way; or that there are only strong and weak verbs in German.

Substitution had already occurred to Dumas’ pupil, Laurent. The latter opposed
the dualistic views of Berzelius and, influenced by his studies of crystallography,
where the principle of isomorphism revealed families of crystals with identical
shapes despite their being different salts, Laurent chose to view organic
molecules as unified or as ‘single edifice’ compounds, and not binary in
composition.
He called these crystal-like edifices ‘fundamental radicals’. Through substitution
of elements within such unitary compounds, new compounds could be produced
that he labelled ‘derived radicals’. These derivatives, in their turn, played the
same role as fundamental radicals, and in this way Laurent formed a natural
classification of organic compounds. This system formed the substance of his
posthumous treatise, Chemical Method (1854). When Laurent reviewed the
warfare between the Berzelian dualists and his own advocacy of a unitary model
he observed:

Experiments went for nothing: dualism had sworn to uphold its position … . I was an imposter, the
worthy associate of a brigand [Gerhardt], and all this for an atom of chlorine gas put in the place of
an atom of hydrogen, for the simple correction of a chemical formula!

The collaborators Gerhardt and Laurent realized their ideas of unitary

compounds and homologous series were complementary, and that this offered a
new way of classifying organic compounds.

Gerhardt first publicized the concept of homologous series in his widely read
Precis de chimie organique in 1844, and he stressed its usefulness with respect
to classifying and differentiating organic compounds of the form [(CH2) + H2O],
[(CH2)2 + H2O] and, more generally, [(CH2)n + H2O]. When such compounds
were oxidized, sulphonated, or halogenated, their empirical formulae retained
the same form. This enabled Gerhardt to declare that if the composition,
properties, and method of formation of a single substance obtained from one of
the series of acids were known, it would be possible to predict the composition,
properties, and mode of formation of all substances in a derived series.

Inevitably, Gerhardt’s critics (and there were many) accused him of practising
numerology rather than chemistry, but he was vindicated by his successful
prediction of many compounds seemingly missing from the series of alcohols
[(CH)2 + H2O], or the prediction of the boiling points of compounds hitherto
missing in a sequence. It should be emphasized that all this was empirical sorting
and classifying, and the true significance of the repeating units of CH2 only
became apparent when Kekulé introduced the idea of carbon chains in 1858.

One of the reasons why the formulae of organic compounds printed in chemists’
books and papers in the 1840s look so strange to us today is because chemists
were obsessed with a formal analogy between inorganic and organic compounds
while neglecting the assumption that equal volumes of matter in a gaseous or
vaporous state contained the same number of molecules. Amadeo Avogadro’s
hypothesis which had been proposed in 1811 seemed physically impossible to
Dalton and Berzelius, since it demanded that simple molecules like hydrogen
and oxygen were binary, H2 and O2. However, if the atoms were positively or
negatively charged, self-repulsion would drive them apart. When Berzelius and
others calculated the molecular moieties of organic acids and their derivatives
they chose to double the empirical formulae in order to ensure the presence of
H2O within the molecule.

Consequently, organic molecules were based upon a four-volume standard as

opposed to the two-volume scale in which water was H2O. Thus, sulphuric acid
was (SO3 + H2O), whereas acetic acid’s empirical formula was double that of
today’s, i.e. (C4H6O2 + H2O) rather than (C2H2O + H2O). It was Gerhardt who
drew attention to the anomaly that when four-volume formulae were used in
organic chemistry, in reactions that involved the elimination of water (the moiety
H2O), it appeared as H4O2 (or 2H2O), and not as the H2O it did in inorganic
eliminations. A similar discrepancy appeared in organic reactions that involved
the elimination of CO2.

Gerhardt argued that consistency could only be achieved if one standard was
used throughout chemistry, and that great simplification would be achieved by
using two-volume formulae. Nevertheless, it took another twenty years before
international agreement on a two-volume standard was reached. Ironically,
Gerhardt himself never contemplated using Avogadro’s hypothesis as a standard
for determining molecular formulae.

One apparent difficulty with two-volume formulae was that organic monobasic
acids (ones containing only one replaceable hydrogen atom) could not be written
as if they were hydrated anhydrides. This was somewhat ironic, given that
Humphry Davy (1778–1829)—the English discoverer of several post-Lavoisian
elements like sodium, potassium, and iodine—had shown, despite Lavoisier, that
the halogen acids (HCl, HI, etc.) did not contain oxygen. The difficulty was
eventually resolved through the work of Thomas Graham and Liebig on bibasic
and tribasic acids, which led to the notion that acids were better defined by their
replaceable hydrogens. This reconceptualization, once again, undermined the
simple dualistic electrochemical model of Berzelius and made the unitary model
of Laurent much more acceptable.

Nevertheless, throughout the 1840s chemists such as the Lancastrian, Edward

Frankland (1825–99), and the German, Hermann Kolbe (1818–84), continued to
find the radical model useful. Both men thought they were able to prepare and
isolate individual radicals of ‘methyl’, ‘ethyl’, and so on, just as if they were
new simple elements. Kolbe did this by the electrolysis of organic acids;
Frankland by reacting the iodide salts of organic acids with metals such as zinc
in sealed tubes under pressure:

It soon transpired that the boiling points of these hypothetical radicals did not fit
in with the notion of homologous series, and that what Frankland and Kolbe had
really prepared were the stable dimers of the supposed methyl and ethyl radicals:
i.e. not C2H3 and C4H5, but C2H6 and C4H10, ethane and butane. An unintended
consequence of this attempt to isolate radicals was Frankland’s discovery of a
range of organometallic compounds (his term) that were to prove of great
interest in the 20th century.

Chemical types
By the 1850s, Gerhardt had begun to suggest a new, far-reaching way of
classifying organic compounds that he named the type theory. Influenced greatly
by Laurent’s unitary idea of molecules, in which multiple substitutions of
different elements and radicals were possible, and by the previous work of
Dumas, he suggested that all organic molecules could be modelled on relatively
few inorganic prototypes; organic molecules were simply substitution derivatives
of the inorganic molecules hydrogen (H2), hydrogen chloride (HCl), water
(H2O), and, later, ammonia (NH3).
11. Alexander Williamson (1824–1904), professor of chemistry at University
College London.

Why four types when two might have done? The answer lies in the fact that
although Gerhardt and Laurent had undermined the simple form of Berzelius’
electrochemical theory, they realized that molecules did display polarity. Thus
H2 was the type that displayed the least polarity, and that when the hydrogens
were replaced by hydrocarbon radicals the relatively inert paraffin and olefin
homologous series were produced. Substitutions in HCl produced the more
active and polar organic salts such as ethyl iodide, C2H5I; and H2O, as
Gerhardt’s British disciple Alexander Williamson (1824–1904) demonstrated in
1850, provided an extremely elegant way of explaining the makeup of the
organic alcohols and ethers (see Figure 11). Types literally obliged inventiveness
among the typographers in the printing works, as elaborate brackets began to
pepper chemists’ printed papers:

Williamson stated proudly:

The method here employed of stating the rational constitution of bodies by comparison with water,
seems to me to be susceptible of great extension; and I have no hesitation in saying that its
introduction will be of service in simplifying our ideas, by establishing a uniform standard of
comparison by which bodies may be judged of.

If acetic acid is written as

there should be an anhydrous form (acetic anhydride)

It was Williamson’s particular triumph to predict this anhydride’s existence in

1851, and it was duly prepared by Gerhardt in the following year. Williamson’s
work on ethers was soon followed by Hofmann’s work at the Royal College of
Chemistry in London on the nitrogen-containing amines. Here ammonia, NH3,
became the model type (where R, R’, R’’ stand for various radicals):
Gerhardt lived just long enough to learn that Williamson’s colleague, William
Odling (1829–1921), proposed adding a marsh gas (methane) type, but not long
enough to witness how Kekulé used this to deduce the idea of carbon chains in
1858. The latter signalled a further triumph for Gerhardt’s reforms.

By hypothetically substituting radicals such as ethyl into water, he achieved a

rapprochement between the hitherto opposed radical and type classifications.
Moreover, by subsuming organic compounds under four inorganic types Kekulé
effectively brought about a unification of chemists and of chemistry. Organic
chemistry, in Kekulé’s hands, was to be the chemistry of carbon compounds—as
he subtitled his textbook, Lehrbuch der Organischen Chemie in 1861.

Frankland’s introduction of valency

Type theory (which soon embraced so-called ‘mixed types’ in which, for
example, the water and ammonia types were bolted together) implicitly
contained within it the important concept of valence, or the combining power of
individual atoms.

Frankland, whose fame derived from his exploration of organometallic

compounds like tin diethyl and stanethylium, had been the first to address this in
1852. He pointed out that the elements within an inorganic or organic compound
appeared to have a definite or fixed affinity for other atoms, or ‘only room, so to
speak, for the attachment of a fixed and definite number of the atoms of other
elements’. Thus hydrogen seemed to fix only one other attachment, oxygen two,
and nitrogen as many as five.

Frankland called this regularity ‘atomicity’, but it was soon being called
‘valence’ or ‘valency’, from the fact that the attachments could be regarded as
one, two, or more units that were ‘equivalences’ of hydrogen. Kekulé, following
Odling, took this further by suggesting that carbon had the ability to unite with
four equivalents of hydrogen and combine with itself to form chains such that
two joined carbons still had a combining capacity or valence of six, and a chain
of three carbons, eight, and generally nC = 2n + 2. Where this did not work,
namely with the olefins, C2H4, and acetylenes, C2H2, Kekulé boldly introduced
the idea that in such compounds two carbons could also mutually satisfy two or
three valences and so form double or triple bonds. (The term ‘bond’ had been
introduced by Frankland in 1866.)

Although the development of valence as an architectural concept for linking

atoms together within a molecule owed more to Kekulé than to Frankland, it was
the teaching and examining position of the latter as Hofmann’s successor at the
Royal College of Chemistry that enabled him to spread the concept of valency
through textbooks and government examinations.

Kekulé’s news from Ghent

Friedrich Kekulé had intended initially to train as an architect, but studied
chemistry with Liebig at Giessen instead. Liebig sent him to London for further
experience, and there he came under the influence of Odling and Williamson and
their enthusiastic support for the unitary and type theories of Laurent and
Gerhardt. After further private studies in Heidelberg, he was appointed professor
of chemistry at the University of Ghent in French-speaking Belgium in 1858. He
finally returned to Germany as a professor in Bonn in 1867.

Kekulé’s theoretical insights into the classification of organic compounds,

valence, and structural chemistry, and his suggestion of the hexagonal formula
for benzene, transformed organic chemistry. In his great paper of 1858, ‘On the
constitution and metamorphoses of carbon compounds and the chemical nature
of carbon’, in which he extended the quadrivalence of carbon in methane to all
of its compounds, Kekulé stressed how indebted he was to the English and
French schools of chemistry for his interpretation. With hindsight it can be seen
that at one stroke organic chemistry had been unified: chemists no longer needed
to separate ‘types’ for paraffins, ethers, amines, etc.—all organic compounds
were now embraced within the idea of carbon chains (catenation) and the notion
of carbon’s tetravalence.
In an after-dinner speech in 1890, Kekulé’s recalled daydreaming on an omnibus
while he was a postdoctoral student in London in 1855. In his imagination he
had visualized carbon atoms linking together to form long chains. Structural
organic chemistry demands imagination and the ability to think architecturally,
but Kekulé’s ideas did not involve connecting carbon atoms by lines in the
1850s. Instead, he imagined segmented wormlike entities made up from sub-
atoms. The sausage-shaped graphic formulae (Figure 12) that he first used in
lectures in Heidelberg in 1857 followed from this model, and seem confirmed by
Kekulé’s statement in 1867 that ‘polyvalent atoms, with respect to their chemical
value [valence], can be viewed in a sense as a conglomeration of several mono
valent atoms’. The graphic formulae that Kekulé used in his Lehrbuch der
Organischen Chemie were printed visualizations of this model, and he continued
to use type formulae as a means of classification.

Explicit line-connected chains were the independent idea of a Scots chemist

named Archibald Scott Couper (1831–92) who was working in Adolphe Wurtz’s
laboratory in Paris between 1856 and 1858. Couper’s paper, boldly titled ‘On a
new chemical theory’, had its publication unfortunately deferred until after
Kekulé’s own paper had been published. Mental illness then blighted Couper’s
blossoming career, and his significant contributions to paper chemistry remained
virtually unknown until the 20th century. Nevertheless, his graphic notation was
noted by the professor of chemistry at Edinburgh, Alexander Crum Brown
(1838–1922), who enthusiastically deployed such formulae in his thesis in 1861.
These line-drawn graphic formulae were then adopted by Frankland in his
lectures at the Royal College of Chemistry in London, as well as in his research
papers. Frankland was also an influential examiner for state tests, and in this way
he ensured the rapid adoption of such graphic formulae in the 1860s.
12. Kekulé’s sausage-shaped formulae. Univalent atoms like hydrogen were
represented by single circles, and multivalent atoms like carbon by
overlapping circles.

The benzene ring and ‘Kekulé’s dreams’

Historians of chemistry have tended to stress the slow evolutionary continuity of
Kekulé’s work in organic chemistry rather than the sudden emergence of
particular insights. We cannot be certain exactly when Kekulé hit upon the
structure of benzene as a closed chain of six carbon atoms, though it probably
occurred to him around the time of his first marriage in 1862.

Towards the end of his life, in typical self-deprecatory fashion, he said that,
while dozing, he had imagined a chain of dancing carbon atoms forming a closed
circle, like a snake eating its own tail. Historians have long debated the validity
and nature of Kekulé’s two ‘dreams’ on historical and chemical grounds. It must
also be recognized that the ‘Benzolfest’ of 1890 at which Kekulé recounted his
daydreams was designed less to honour Kekulé than to impress participants and
newspaper readers of the central economic significance of chemistry for the
Reich. Consequently, accounts of the speeches have to be used with caution as
historical texts.

Despite his declining powers, lethargy, and fixation with family history and
ennoblement—which his radical theorist rival Kolbe exploited in inexorable
criticism of Kekulé’s structure theory—Kekulé did have some significant
achievements after he moved to Bonn in 1867. In 1872, he proposed a daring
dynamic oscillation formulation for the structure of benzene that explained the
embarrassing lack of isomeric disubstituted derivatives in benzene that seemed
otherwise possible.

In the early 1880s, when several alternative possibilities had been touted for
benzene’s structure, including a prism formula proposed by Ladenburg, Kekulé
demonstrated a return of his old powers when he showed that a series of
experimental transformations of pyrocatechol and quinine were best and most
simply explained if benzene was a hexagonal closed carbon chain (Figure 13).

While it is convenient to suppose that it was Kekulé’s architectural training that

helped him conceive molecular structure and to play with molecular models,
what is more striking is the view he acquired from Williamson of the dynamic
nature of molecules. Architecture is essentially static, whereas Kekulé’s
conception of structure was much more fluid and imprecise. To that end, the
visionary giddy molecular dances cited in his speech at the Benzolfest in 1890
ring true.

13. Kekulé’s oscillating benzene rings. Collisions between the carbon and
hydrogen atoms in the hexagonal ring were supposed to lead to fluctuating
positions of the double bonds. This ‘resonance’ accounted for the absence of
isomeric disubstituted benzene compounds in the first and second positions
of the apex.

The triumph of structural theory

One of the strongest supporters of a structural view of organic chemistry was the
German-trained Russian chemist, Alexander Butlerov (1828–86). It was he who
pointed out how the theory would explain the existence of isomers. Two
substances with an identical empirical formula like ethyl alcohol and dimethyl
ether, C2H6O, had two different structures, CH3CH2–OH and CH3–O–CH3, and
it was the different positions of the atoms within the molecules that gave rise to
their different properties.

Further confirmation of structuralism came with the elucidation of

stereoisomerism, the phenomenon whereby two isomers differed only in one
physical property, namely the way their crystals rotated the plane of polarization
to the left or right, as Louis Pasteur (1822–95) first elucidated in 1848. In 1874,
the Dutch organic and physical chemist Jacobus van ’t Hoff (1852–1911)
explained Pasteur’s observations by suggesting that the four valence bonds of
carbon were directed towards the apices of a tetrahedron. This would allow the
possibility of asymmetry and the existence of two configurations of a molecule
that were the mirror images of each other. Soon chemists were applying these
geometrical ideas to other atoms like nitrogen and sulphur, and stereochemical
research became extremely fashionable until it culminated in the coordination
theory of molecular structure developed by the Swiss chemist Alfred Werner
(1866–1919) from 1891 onwards.

In Werner’s theory, which applied particularly to the kinds of organo-metal

compounds investigated by Frankland, molecular groups (later termed ligands)
could be distributed around a central metal in various geometrical forms.
Geometry among chemists became quite fashionable. The Germans Viktor
Meyer (1848–97) and Adolf von Baeyer (1835–1917), for example, introduced
the idea of steric hindrance to explain how ringed structures might set
themselves in one particular rigid form because a large molecular group
prevented the rotation of the two parts of the molecule into a different (isomeric)
structure; or at other times be quite unstable because the bonds between the
atoms were under strain.

Probably the greatest triumph of structuralism was to be seen in the work on

sugars of Emil Fischer (1852–1919) in the 1880s. Fischer found that there were
sixteen isomers of the sugars that shared the empirical formula C6H12O6; the
only difference between them was the extent of their optical activity produced by
the fact that each sugar had four asymmetric carbon atoms.
Bringing chemistry to order
In a short account of the development of chemistry it is impossible to do justice
to the hundreds of minor chemists without whose contributions the edifice would
never have been completed. To take but one example: Leopold Gmelin (1788–
1853) was a member of an important dynasty of physicians and apothecaries
going back to the 16th century and Wöhler’s teacher at the University of
Heidelberg. He was described by a contemporary as ‘one of chemistry’s
athletes’. He was certainly an important teacher: his pupils included Wöhler,
Will, Bunsen, and Williamson, as well as several generations of influential
pharmacists. As Berzelius famously remarked: ‘anyone who has studied
chemistry with Gmelin will have little to learn from me’.

Today, Gmelin is chiefly remembered by historians of chemistry for three

reasons: his skilled analytical work on the chemistry of digestion which he
undertook with his physiological colleague Friedrich Tiedemann in the 1820s;
his remarkable ordering of the elements into chemical triads that foreshadowed
the later periodic system of classification; and for his monumental Handbuch der
Chemie which went through four editions during the author’s lifetime and
continues to be produced by the Gmelin Institute in Berlin to this day.

Gmelin’s original idea was to summarize all known chemical knowledge, but he
soon found it was impossible for one man, however athletic, to keep up with the
phenomenal progress of organic chemistry in the 1830s. The last edition of the
Handbook, which was translated into English by Henry Watts (librarian of the
London Chemical Society) between 1848 and 1872, was largely restricted to
inorganic chemistry. Gmelin’s decision gave the Russian-German organic
chemist Friedrich Beilstein (1838–1906) the opportunity to devise a similar
encyclopaedic survey of organic chemistry from 1881 onwards. Beilstein’s plan
was to provide an account of the physical and chemical properties of every
organic compound described in chemical literature and identified by its
molecular formula. Before his death Beilstein handed the enormous task of
compilation over to the German Chemical Society that Hofmann had founded in
1867. ‘Beilstein’, as it is called by chemists, continues to this day in online
searchable form.

An acute problem faced by compilers of such handbooks, let alone laboratory

workers, was agreement on the naming of compounds for indexing purposes. In
1892 an international group of organic chemists and editors of chemical journals
met in Geneva to forge agreement on nomenclature. They agreed to use the
structural theory as the basis for giving systematic names to chemicals, the idea
being that the name itself would enable any chemist to deduce a compound’s
structural formula and to find it in Beilstein.

Common diethylether, for example, became ethoxyethane and common names

such as olefiant gas and acetylene became ethane and ethine respectively. The
citric acid of lemon juice, C6H8O7, became the more formidable 2-
hydroxypropane-1,2,3-tricarboxylic acid. The Geneva conference was necessary,
but chemists paid a heavy price for inventing systematic names for unambiguous
structures—namely the loss of public understanding. Doubtless this explains the
persistence of a common nomenclature. Water remains water and only rarely is it
necessary to write dihydrogen oxide to avoid ambiguity.

During a 19th century of chemical ‘giants’ it is worth emphasizing Williamson’s

pivotal role in the development of 19th-century chemistry. Not only did his
demonstration of the power of the water type help lead to the concepts of
valence and structure, but the elegant work on etherification also suggested how
chemists might in future investigate the mechanism of chemical changes as
individual atoms exchanged positions in stages through intermediate
compounds.

His visualization of atoms in motion, and reactants and products in dynamic

equilibrium, were to influence the development of physical chemistry
profoundly. As a firm believer in the existence of atoms, Williamson did much to
eradicate the predominant scepticism of his fellow chemists. These profound
academic contributions were accompanied by a remarkable personal generosity
of spirit. He personally educated successive groups of Japanese students at
University College London, many of whom kick-started the modernization of
hitherto isolated Japan on their return. Their descendants ensured Japan’s place
at the forefront of later chemistry.
Chapter 5
Reactivity

There has always been a close relationship between the teaching of chemistry
and physics. Indeed, since the 18th century what are now seen as separate
experimental disciplines were taught in a unified way. Robert Bunsen was
famous for saying that a chemist who professed not to know any physics could
not be a genuine chemist.

The rise of organic chemistry soon put a strain on the amount of information and
experimental demonstrations that a single professor could lecture on. It was this
fact, together with the limited opportunities for chemists trained in Germany to
find academic posts, that caused several chemists in the 1850s to transform
themselves into physicists.

In teaching the elements of light, heat, sound, electricity, and magnetism they
frequently became interested in the physical properties of matter and how these
affected chemical transformations. The result was the emergence of a third
specialized area of chemistry known as physical (or, sometimes theoretical or
general) chemistry. Physical chemistry, not inorganic or organic, was destined to
become the basis upon which chemistry was to be taught. These developments
necessarily led to changes in the design of chemists’ work spaces for teaching
and research.

Why do homogeneous substances interact? By the mid-19th century many

different kinds of chemical change had been recognized and systematized in
textbooks. Sometimes elements combined together directly; at other times one
element substituted for another. Compounds could dissociate and then
reassociate, or two compounds could undergo a double decomposition with an
exchange of partners. Elements and compounds could be oxidized or reduced by
the addition of oxygen or the removal of hydrogen; and sometimes a compound
could be induced to undergo isomeric change.

It became the task of physical chemists to explain these different transformations

in terms of exchanges between atoms and molecules powered by energy changes
and the shifts in equilibrium that underlay all reactivity. Physical chemists found
ways of expressing chemical change in mathematical terms, and so brought
generalization and systematization to chemical practice. They entered an ideal,
imagined world that provided a guide to the behaviour of real substances.

Berthollet’s investigations of reactions at the beginning of the 19th century had

led him to the idea that chemical transformation depended upon physical
conditions and that affinities could be satisfied in dozens of different ways,
leading to the claim that compounds were not formed in definite proportions.
Such a view seemed impossibly complicated and was quickly replaced by the
Daltonian view that chemical changes proceeded in definite quantities or
proportions.

Consequently, it was not until mid-century that a few chemists returned to the
question first raised by Berthollet: what were the conditions for chemical
equilibria, and what were the mechanisms involved in chemical reactions when
one homogeneous stuff interacted with another to produce other completely
different homogeneous substances?

Are physical properties regular?

One early physical research programme was established by Hermann Kopp
(1817–92), a colleague of Liebig’s at Giessen who subsequently joined Robert
Bunsen (1811–99) at Heidelberg. Kopp was interested in how physical
properties like melting and boiling points were affected by changing
composition. Could it be shown, he asked himself, that the physical constants
associated with substances, like melting and boiling points, were functions of the
chemical nature of molecules?

It seemed for example that in the homologous series identified by Gerhardt,

melting points (a useful way of establishing the purity and identity of an organic
compound) increased as one paraffin was transformed into another by the
addition of CH2. As Kopp demonstrated in the 1840s, a difference of nCH2
corresponded to about n19°C in boiling point for organic paraffins, acids, esters;
and that a difference of n carbon atoms produced boiling point differences of
n29°C; or that the additions of hydrogen atoms alone to a compound caused
compounds to boil at n5°C lower. Physical properties were clearly a function of
a compound’s stoichiometry.

Kopp spent nearly all his career when he was not investigating the history of
chemistry (in which he was also a pioneer) making meticulous experimental
determinations of physical properties with the aim of being able to offer
arithmetical or geometrical series formulae to calculate the physical properties of
newly discovered compounds. It is a curious fact that, at the same time as
Kopp’s programmes, other chemists, inspired by Prout’s hypothesis, were trying
to formulate arithmetical relationships between the atomic weights of elements.
A good deal of what was then referred to as ‘chemical physics’ involved
Pythagorean musings.

Kopp died in 1892 without having produced a satisfactory and exact way of
correlating physical properties with molecular composition; but he produced a
wealth of data that proved extremely useful for analytical and synthetic
chemistry. In the 20th century his work stimulated the production of
compilations of physical data such as Kaye and Laby’s Tables of Physical and
Chemical Constants in 1911; this has remained in print ever since, and expanded
from 150 pages to over 600 pages in successive editions.

The broad highway of thermodynamics

The most important area of chemistry to be influenced by physics was
thermodynamics, a science that arose when physicists and engineers began to
concern themselves with the efficiency of the steam engines and electric motors
that had come to dominate industrialized parts of the world.

Chemical thermodynamics had begun earlier with thermochemistry. This can be

traced back to the 18th-century studies of specific and latent heats made by
Joseph Black, who showed that different substances had different capacities for
absorbing heat. In addition, large amounts of heat that were not registered by a
thermometer were required to melt a solid or boil a liquid. Specific heats proved
useful when the École Polytechnique-educated Pierre Dulong (1785–1838) and
Alexis Petit (1791–1820) found a simple relationship between an element’s
specific heat and its atomic (or equivalent) weight. Their empirical relationship,
atomic weight multiplied by specific heat equals 6.4, proved useful in
determining atomic weights, as Berzelius showed.

As the word suggests, thermodynamics concerns the transformation of heat into

the useful work of a machine. By the 1840s, physicists like Rudolf Clausius
(1822–88) in Germany had established the first law of thermodynamics: that
energy (a measure of the ability of molecules in motion to generate heat and
power) was conserved. He meant by this that whenever work was done through
the agency of heat, a quantity of heat was consumed that was proportional to the
amount of work done; conversely, the expenditure of an equivalent quantity of
work produced an equal quantity of heat.

Clausius promoted a new, molecular way of understanding heat as the

mechanical motion of particles, as opposed to Lavoisier’s imponderable caloric.
Clausius knew sufficient chemistry to perceive chemical change as dissociation,
and was encouraged by Williamson’s work in England on the mechanism of
etherification. Heat drove molecules apart and overcame the intrinsic affinities or
attractions between coupled particles. There came a stage in a reaction, however,
when the forces of attraction and thermal dissipation entered equilibrium.

In 1873 another German chemist, August Horstmann (1842–1929), took this

much further by asking himself what the extent of dissociation was in any
particular reaction and equilibrium. Noting the work of Clausius, he posited that
the limit of any dissociation depended upon the entropy of the reaction reaching
a maximum.

Although Lavoisier’s purpose in using a guinea pig was to compare its body heat
with the heat evolved when carbon was burned to carbon dioxide (see Chapter
3), the experiment led many other chemists to investigate the heats of reactions.
Between 1838 and 1840, Berzelius’ Russian pupil, Germain Hess (1802–50),
showed that the heat evolved in a chemical reaction (later named enthalpy) is
always constant no matter whether the reaction takes place in one or several
steps. This soon became known as Hess’s law, one of the many eponymous rules
that are ubiquitous in chemistry. With the physicists’ enunciation of the first law
of thermodynamics it became clear that Hess’s law was simply a consequence of
the fact that energy could neither be created nor destroyed.

Chemists were far slower to adopt the second law of thermodynamics, mainly
because they could not understand the concept of entropy or see how it could be
useful to their laboratory practice. This was true even of those chemists who had
the necessary mathematical knowledge to follow thermodynamic notation and
equations. This was especially the case with the remarkable rigorous
mathematical treatment of chemical equilibria made by the American physicist J.
Willard Gibbs (1839–1903) in the mid-1870s. His three papers laden with 700
equations appeared baffling to ordinary chemists, and even Clerk Maxwell,
Britain’s greatest physicist since Newton, found them incomprehensible.
However, once the Austrian physicist Ludwig Boltzmann (1844–1906) had
described the motion of gas particles as statistical averages in the 1870s
(statistical mechanics), it became easier to interpret entropy in terms of disorder.
Thus, the higher the entropy, the higher the disorder within a molecular system:
entropy, then, was the driving power of chemical reactions. In the physical
changes from solid through liquid to gas, entropy increased as the molecules
became increasingly disordered.

Textbooks of thermodynamics suitable for chemists only began to appear in the

1900s as chemistry departments began to teach mathematics for chemists.
However, notations, symbols, and positive and negative signs were used
inconsistently, and it was not until the American chemists Gilbert N. Lewis
(1875–1946) and Merle Randall (1888–1950) published their text
Thermodynamics in 1923 that consistency was established.

One of their innovations that gave clarity to physical chemistry was to

emphasize the idea of the ‘free energy’ of chemical substances, that is, the
maximum of work that can be drawn from any chemical process. Free energy
was not a new idea, having been introduced by Gibbs and others in the 1870s,
but it was Lewis and Randall who demonstrated how it could be used to produce
a deeper understanding of chemical reactions and produce useful numerical data.

In 1909, following suggestions from German mechanical engineers, the Dutch

physicist Kamerlingh Onnes (1853–1926), who is best known for his
liquefaction of helium in 1908, suggested that the portion of free energy that
could be produced in actual chemical reactions, namely the total heat of a
substance available between agreed temperature points, should be named the
enthalpy (Greek, ‘heat inside’) of a substance. The term was not much used in
chemical literature before the 1950s, by which time the historical ideas of
chemical affinity had become obsolete and replaced by thermodynamics.

From the 1960s onwards, thermodynamics, and the calculations and data it
generates, have been presented in terms of ‘the three “e”s’: energy, entropy, and
enthalpy—universally symbolized by G (free energy, from Gibbs), S (entropy,
probably from Sadi Carnot, the French engineer who had first studied the
working of steam engines in abstract terms), and H (enthalpy, from Hess’s law).

Periodicity
The biochemist and science writer Isaac Asimov once pointed out a curious
parallel in the histories of 19th-century inorganic and organic chemistry. In both
cases chemists seemed to be overwhelmed by their materials. In inorganic
chemistry there seemed to be too many elements, to the evident concern of Prout
and others; in the case of organic chemistry there were too many compounds, as
Wöhler implied in his famous remark about the subject being a jungle.

Order and coherence was given to organic chemistry by the ideas of valence and
molecular structure in the decades between 1850 and 1880. In these same
decades order was given to inorganic chemistry by the Germany-trained Russian
chemist Dmitri Mendeleev (1834–1907). Both of these orderings hinged on the
recommendation of Cannizzaro at the first ever international congress of
chemists at Karlsruhe in 1860: that all chemists should accept Avogadro’s
hypothesis that equal volumes of gases at the same temperature and pressure
contained an equal number of molecules. Accepting such a rule provided an
agreed list of atomic weights that provided unique empirical formulae for
organic chemists, which could then be used in determining structural formulae,
and weights that were to produce Mendeleev’s periodic table.

Although many precursors had tried to find order among the sixty or so known
elements, it was while Mendeleev was casting around for a way of structuring a
chemistry textbook in 1869 that he hit upon the periodic law. According to this,
when elements are arranged according to the magnitude of their atomic weights,
they display a step-like alteration in their properties such that chemically
analogous elements like the alkali metals (lithium, sodium, potassium, etc.) and
the halogens (fluorine, chlorine, bromine, iodine) fall into natural groups.

Philosophers of chemistry have argued over whether the iconic periodic table
was accepted because it was predictive of unknown elements or simply because
it accommodated the known elements in an elegant and memorable way rather
like the 18th-century affinity tables. It was certainly the case that chemists paid
little attention to it until Mendeleev’s predictions of unknown elements such as
gallium and scandium were substantiated in 1875 and 1879 respectively.

Signature tunes
In 1666, Newton made the famous demonstration with a prism that white light
consisted of light of different colours. It had also been long known, chiefly by
makers of fireworks, that many salts burned with a coloured flame. However, it
was not until the 19th century that serious attempts were made to use flame
colours to identify the presence of particular metals or elements in a sample of
an unknown substance.

It was while exploring the use of coloured flames to identify the presence of
elements in springs around Heidelberg that Robert Bunsen designed the gas
burner that is named after him. It was designed to produce both a non-luminous
flame for flame analysis, as well as a normal flame for combustion. As a senior
professor at Heidelberg, Bunsen was successful in persuading the Baden
government to appoint Gustav Kirchhoff (1824–87) to a chair of physics. It was
Kirchhoff who suggested to Bunsen that he could refine flame analysis by
looking at the flames through a prism, which would break the light into a
characteristic spectrum.
The new instrument, which they named a spectroscope, proved to be a powerful
new analytical instrument—one that in various shapes and forms continues to be
probably the most important instrument in contemporary chemistry. When
Bunsen and Kirchhoff announced the perfection of the instrument in 1859, they
were able simultaneously to reveal that they had detected and isolated two new
elements with it: caesium and rubidium. Within five years two other elements,
thallium and indium, had been discovered through spectroscopy, and the
instrument also began to revolutionize astronomy and create a new subdiscipline
of cosmochemistry.

It was now possible to detect elements in the sun, the stars, and distant nebulae,
and even to detect the presence of an unknown element in the sun that the British
astronomer Norman Lockyer (1836–1920) named helium in 1868. This was first
example of analysis at a distance where the chemist no longer directly handled
the substance that was being identified.

The fact that individual elements had such distinctive and often complex spectra
—their signature tunes—also raised theoretical questions concerning their
meaning and cause. Once again, Prout’s hypothesis raised its head. Could one
detect patterns of elements of lower atomic weight in the spectra of heavier
elements, as Lockyer suggested in the 1870s after studying solar spectra? Were
heavier elements disintegrating or ‘dissociating’ into elements of lower atomic
weight in the hot atmospheres of the stars? Why, in the language of the time, did
some lines (the principals) stand out? Why were some lines sharper, or more
diffuse, than others? (This terminology was to continue into 20th-century
quantum chemistry in the notation of s, p, d, and f orbitals.) Were there
mathematical patterns to be found in the distribution of spectra among the
elements?

Many bizarre Pythagorean papers on such topics were published, though it was
not until a Swiss school teacher, Johann Balmer (1825–98), pointed out in 1885
that the first four lines of a hydrogen spectrum could be expressed in a simple
equation that linked wavelengths in centimetres with a constant and a simple
arithmetical series. This observation, which was clarified by the Swedish
physicist Johannes Rydberg (1854–1919) in 1890, remained a curiosity until
other spectroscopists, who were exploring the hydrogen spectrum in the infrared
and ultraviolet, discovered new patterns that corresponded to simple variations
of the Rydberg formula series.
None of this made much sense until the Dane, Niels Bohr (1885–1962), building
on the simple model of the planetary atom of electrons rotating around a nucleus,
showed that, when reckoned by the new quantum theory of Max Planck (1858–
1947), the energy lost when an electron transferred from one outer orbit to an
inner one would follow a Rydberg series.

In the hands of Bohr, spectra turned out to be expressions of the electronic

structures of atoms and molecules. By the mid-1920s, spectroscopy had
integrated a good deal of physical and inorganic chemistry. Using the periodic
table as his guide, and earlier speculative models of atomic structure, Bohr was
able to assign orbital structures to each of the known elements in such a way that
provided for the first time an explanation of their characteristic valences. Thus
the alkali metals in Group 1 of the periodic table all possessed a single electron
in their outermost orbits (e.g. lithium, 2,1; sodium (2,8,1, etc.), whereas the
halogens in Group 7 lacked a single electron that would complete an orbit (e.g.
F, 2,7; Cl, 2,8,7, etc.). The rare gases were inert because their outermost
electronic orbits were completely filled.

Ideal gases
Robert Boyle is still best remembered by the scientific community for his
demonstration that the volume of a sample of atmospheric air is inversely
proportion to the pressure exerted on it. In other words, the volume decreases as
the pressure is increased.

Boyle’s law, as it became known, was found to be true for the individual gases as
they were isolated during the 18th century. By the 19th century, following the
development of mathematical analysis, it was possible to state Boyle’s law in the
form of an equation, pv = k, where p and v are the respective pressures and
volumes, and k is a constant. Between 1780 and 1802 French experimentalists
also showed how the pressures and volumes of gases were dependent on
temperature (Charles and Gay-Lussac’s law)—indeed, it was intuitively obvious
that gases expanded on heating. In 1832, during his investigations of the physics
lying behind the behaviour of steam engines, the French engineer, Émile
Clapeyron (1799–1864), combined the two gas laws into what became known as
the ideal gas law, pv = kt, where t is the temperature.
Although Newton had provided a rational explanation of Boyle’s law in terms of
repulsion between the particles that made up a volume of air or a gas, it was not
until the 1850s that a sophisticated kinetic theory of gases emerged in the hands
of Clausius. By imagining the particles of gas to be in motion, he suggested that
temperature was purely a function of the kinetic energy of the collective
particles, and by using data published by the French experimental chemist Henri
Regnault (1810–78), he formulated what he described as the general equation for
an ideal gas, pv = Rt, where t is the temperature expressed in the absolute
temperature scale that had been suggested as a standard by the Glaswegian
physicist William Thomson (1824–1907) some years before. (He gave the
symbol R for the gas constant both in tribute to Regnault and to Clapeyron, who
had already used the symbol to stand for ratio.)

The gas analogy

The effects of passing an electric current through a solution (electrolysis) had
intrigued chemists ever since Alessandro Volta (1745–1827) described the
properties of his battery in 1800. Electrolysis had led to the development of
Berzelius’ overarching electrochemical theory that dominated inorganic and
organic chemistry until the 1850s.

What exactly happened during electrolysis was the subject of one of Michael
Faraday’s most important investigations during the 1830s. Faraday (1791–1867)
was the first chemist to subject electrolysis (a word coined on Faraday’s behalf
by the Cambridge polymath, William Whewell, in 1831) to quantitative
investigation by establishing that the amount of a chemical compound that was
decomposed in solution was directly proportional to the amount of electricity
that was consumed. Thus, when copper sulphate solution was subjected to a
current of electricity, the amount of copper deposited at the cathode (Faraday’s
term for the negative end of a circuit) depended on the amount of electricity
consumed.

By comparing the weights of electrochemical deposits produced from the same

amount of electricity, Faraday was also able to show that they were in the
proportion of their equivalent or atomic weights. This generalization not only
gave a new way of determining equivalent weights, but confirmed that the nature
of matter was intimately connected to electricity. Following Berzelius’ theory of
salts, Faraday also supposed that the current dissociated the molecules of copper
sulphate into positively charged copper and a negatively charged ‘sulphate’
group. Adopting Whewell’s suggestions, he named these charged molecules
ions, and anions and cations according to whether they were positively or
negatively charged. There was no assumption that these ions were already
present in the solution.

During the 1850s, Clausius, as a result of his development of a kinetic theory of

gases, suggested that in both the liquid and gaseous states, molecules continually
bombarded one another and exchanged positions. In asserting this he drew upon
Williamson’s work on etherification, in which radicals changed position in
double decompositions. Clausius was the first chemical physicist to suggest that
there was a partial dissociation and ionization of electrolytes.

Following his brilliant demonstration that stereoisomers in organic chemistry

depended upon the fact that organic groups were arranged around a tetrahedron,
van ’t Hoff turned his attention to physical chemistry and the age-old problem of
affinity. Was there some way to measure forces of affinity? Perhaps affinity was
related to osmotic pressure—the force that had to be applied to prevent a solvent
from diffusing through a membrane. Botanists, who were naturally interested in
osmosis as a phenomenon of plant life, had previously developed a convenient
apparatus for determining osmotic pressures, and van ’t Hoff set about using
membranes to measure the affinity that salts had for water—the water of
crystallization of solid salts.

It was while making his measurements that it suddenly struck the Dutch chemist
that there was an analogy between osmotic pressure and the pressure component
of the ideal gas equation. Whereas in the gaseous state pressure was inversely
proportional to the volume, in the case of solutions the osmotic pressure was
directly proportional to the concentration of solute (that is, inversely
proportional to the volume). It followed that osmotic pressure obeyed the gas
law pv = nRt (where n is a measure of the number of molecules present), and
that at equal osmotic pressure and temperature, equal volumes of solutions
contain an equal number of molecules—exactly the same number which, at the
same temperature and pressure, is contained in an equal volume of gas. If this
sounds suspiciously like Avogadro’s hypothesis, it is, and the analogy between
the behaviour of a perfect gas and the solute in a dilute solution was complete.
Further experimental results showed that there were considerable deviations
from the gas law unless the dilution was great enough for the volume occupied
by molecules to be ignored. Even then, inorganic salt solutions gave much
higher readings of osmotic pressure than the gas law predicted. A similar
disparity had been noticed in measurements of freezing point depressions when
identical amounts of different salts were added to water. Undismayed, van ’t
Hoff’s solution was to add an empirical correction factor, i, into the gas equation,
pv = iRt. Curiously, it seemed that the i factor always had to be greater than one;
for example, in hydrochloric acid it was 1.98, and for sodium sulphate 1.82.
These findings and suggestions were published in 1885 and noticed by a young
Swedish doctoral student.

Ionic theory
Svante Arrhenius (1859–1927) was the son of an estate manager, born at Wijk
near Uppsala, Sweden. He read chemistry and physics at the local university
before studying the properties of electrolytes at the University of Stockholm for
his doctorate in 1884. The thesis was not well received, making it difficult for
him to obtain an academic appointment for some years.

In 1887 he developed the dissociation theory. According to this, in a weak

electrolyte, molecules were already dissociated (ionized) before a potential
difference was applied to them. The theory, according to which dilute solutions
obey a general gas law, pv = iRt, where i is a measure of dissociation, tied in
beautifully with van ’t Hoff’s views on osmotic pressure. Together Arrhenius,
van ’t Hoff, and the German Wilhelm Ostwald (1853–1932) launched the
Zeitschrift für physikalische Chemie in 1887.

Despite difficulties with strong electrolytes (whose behaviour was not

satisfactorily explained until the 1930s), the ionic theory found rapid use among
chemists and biochemists. In 1889 Arrhenius applied van ’t Hoff’s equation for
the temperature dependence of chemical equilibria to the kinetics of chemical
reactions, showing that reactivity depended upon what he called ‘activation
energy’. The notion that molecules require a certain critical energy to react has
proved fundamental in understanding reaction mechanisms within living
systems.
Arrhenius was awarded the Nobel Prize in Chemistry in 1903 for his theory of
electrolytic dissociation, which also enabled biochemists to develop the pH scale
of hydrogen concentration and to understand how living tissues ‘buffered’
themselves against excessive acidity or alkalinity—the basis of homeostasis in
living systems. Arrhenius became an international figure in science. His
originality lay in an ability to move between fields on the boundaries of
established disciplines—something that many later chemists proved good at.

Kinetics
In his dispute with Proust at the end of the 18th century, Berthollet had argued
against compounds being formed in definite proportions on the grounds that if
one reactant was present in greater amounts it would inevitably combine with the
other reactant in variable amounts. What Berthollet was thinking was that the
respective masses of reactants were bound to affect the course of combination. In
the 1850s this law of mass action was taken up by Williamson, who suggested
reactions were frequently in dynamic equilibrium—in which case, if one reactant
was increased in concentration the overall reaction would shift in a particular
direction.

This concept was explored by a Norwegian chemist, Cato Guldberg (1836–

1902), and his mathematical colleague, Peter Waage (1833–1900), in 1863; they
expressed Williamson’s idea in terms of the concentrations of the reactants and
the speed of formation of products. If the forward reaction was twice as fast as
the reverse reaction, the equilibrium was far to the right; conversely, if the
reverse reaction was twice the rate of the forward reaction, the equilibrium
would shift to the left. In both cases the rates depend solely on the frequency of
collision between molecules. By making the concentration of the reactants
greater, the forward rate would increase.

Guldberg and Waage showed, using square brackets to represent concentrations,

that [C][D] divided by [A][B], which represent the concentrations of the reverse
and forward reactions respectively, will be a constant they named as the
equilibrium constant. This constant came to play a major role in understanding
chemical kinetics and the mechanisms of chemical reactions. However, because
they wrote in Norwegian it was not until the 1880s that their work became
noticed and utilized.
The changing laboratory
The principal problem presented by chemical work is fairly obvious. Chemists
produce obnoxious and sometimes dangerous fumes (British school children
have nicknamed it ‘stinks’ ever since the 1870s). Laboratory atmospheres need
ventilation beyond that supplied by open windows. The latter might suffice for
one experimenter, but not for a gathering of twenty to thirty students.

Prior to the 1860s, the usual way of dealing with these ventilation problems was
either (as Liebig did) to use window ventilation backed up by chimney hoods, or
to put a laboratory in the basement adjacent to the main drains and chimney (as
at the Royal Institution and, later, at the Pharmaceutical Society). The
Pharmaceutical Society’s laboratory (1842) was actually built in the back garden
of a house in Bloomsbury Square, with skylights and sliding vents leading to the
main chimney where evaporations could be conducted. Drains from the sinks led
directly into the town sewers. Hydrogen sulphide gas was also on tap and in its
own ventilation shaft.

The Society’s design worked well enough for the chemists in it, but drifting
smells made life uncomfortable for those in the rooms above. Consequently, in
the 1860s the laboratory was moved to the top storey of the building, and where
there were laboratories for several scientific disciplines this became the preferred
solution: put the chemists next to the sky! Even so, by the 1870s it was clear that
more powerful ventilation systems were necessary, and using electric fans on the
roof that sucked air through the ventilation shafts solved the problem. Ventilation
hoods, sand baths, drying ovens, and water supplies for filter pumps became
essential design specifications (see Figure 14).

The rise of physical chemistry at the end of the 19th century brought further
changes to laboratory design. Instruments and techniques such as ultraviolet and
infrared spectroscopy, spectrophotometers, X-ray cameras, mass spectrometers,
and chromatography began to offer new, simpler, and faster methods of
analysing materials and directly assigning a structure to them. Such physical
methods had completely replaced wet and dry methods of analysis by the 1960s,
so that today the traditional laboratory bench of Liebig’s and Kolbe’s time has
lost its scaffold of reagent shelves and returned to a table-like appearance.
14. Birkbeck Laboratory at University College London. The foreground
area was mainly used by University College School for demonstrations.
From a lithograph of 1875.

The inert gases

The unexpected discovery of the so-called rare or inert gases by the physicist
Lord Rayleigh (1842–1919) and the chemist William Ramsay (1852–1916) in
the 1890s, and Ramsay’s placement of them in the periodic table as a new group,
also did much to substantiate the usefulness of the periodic law. Serious puzzles
remained of course, notably where to place the large number of so-called rare
earth elements (lanthanides) which had virtually identical properties. A solution
had to await new insights into the structure of the atom that the discovery of X-
rays, radioactivity, and the electron produced from the 1890s onwards.

Despite attempts by Ramsay and many other chemists to form compounds with
the rare gases, they remained obstinately inert. Hitherto all elements and
compounds known to chemists displayed transformations and transmutations,
but these gases were totally unreactive. Chemists were, of course, familiar with
the relative inertness of nitrogen as a gas, or gold and platinum among metals, or
the paraffins among organic compounds. But given a hammer blow from heat,
electricity, or pressure, such substances were always transformable.

Argon refused to react no matter what physical conditions to which it was

subjected. To make matters worse, when its specific gravity was determined it
was clear that argon was monatomic, unlike any of the common elementary
gases. The explanation for the inertness of argon and its congeners was
forthcoming only when Bohr developed the model of electronic shells in which
the inert gases had full complements of electrons in their outer shells. As Linus
Pauling (1901–94) pointed out in 1932, this completeness need not necessarily
prevent compound production if an inert gas was reacted with a sufficiently
energetic reactant such as fluorine. Curiously, Pauling’s observation went
unheeded and the first of the inert gas compounds, xenon fluoride, was not
prepared until 1962 by Niels Bartlett (1932–2008).

Social chemists
Despite the lead shown by first France and then Germany in the development of
chemistry in the early 19th century, it was the British who first organized
chemists into a Chemical Society. The London Chemical Society (now the Royal
Society of Chemistry) was formed in 1841, largely in response to the
development of chemistry on the continent and the feeling that British chemists
were being left behind, particularly in organic chemistry. The French followed in
1857 with the Société chimique de France. On his appointment to a chair at the
University of Berlin in 1865 Hofmann, who had been the leading light of the
London Chemical Society, organized the Gesellschaft Deutscher Chemiker.
Other countries followed swiftly, the most important being the formation of the
American Chemical Society in 1876 as a result of an earlier commemoration of
Joseph Priestley at his former home in Pennsylvania.
Each of these organizations began to publish proceedings and transactions in
their own journals which, in turn, helped to forge national chemical
communities, so that by the 1880s there was a proliferation of literature for the
chemist to follow in a variety of languages and in a variety of specialisms.
Abstracts and translations became necessary, as well as guides and surveys to
what had been already published, such as the serialized handbooks of Gmelin
and Beilstein (see Chapter 4).

International meetings of chemists, made possible by the transformation of

transport that decreased the tyranny of distance, were initially held to decide
upon standards. These began in 1858 when Kekulé and others called chemists to
Karlsruhe to adjudicate on standards for atomic weights, and this was followed
by the meeting in Geneva in 1892 to formulate rules for organic nomenclature
(Chapter 4).

The relentless increase in specialization soon led to conferences arranged around

particular subjects within the categories of analytical, inorganic, organic, and
physical chemistry. For example, in 1923 the Faraday Society, a society
specializing in physical chemistry founded in London in 1903, held a meeting on
the electronic theory in chemistry. Overseas study, travel to conferences, and
socializing in different academic and industrial contexts, meant that 20th-century
and contemporary chemists form what the Swedish historian Staffan Bergwik
has called ‘capillary networks through which the physical sciences migrate
through laboratories, universities, academies and industries’.

In answering the questions ‘What changes in a reaction?’, ‘How fast do changes

take place?’, and ‘How complete are the changes?’, physical chemists made
chemistry much more mathematical. This was the first of many substantial
alterations that the discipline of chemistry underwent as the subject moved into
the 20th century.
Chapter 6
Synthesis

The shape and scale of chemistry was shaken by a series of transformations in

the 20th century: two world wars; a shift from coal to oil as the feedstock for
chemical industry; the introduction of physical instrumentation, quantum
mechanics, and electronic theories; and the organization of academia and
industry to create Big Science as opposed to the more individualized research of
previous centuries.

Underlying these important changes was the theme of synthesis of natural

chemicals and the creation of artificial materials. Accompanying the
transformations that the discipline of chemistry underwent, there was a shift
from European dominance of the subject to the US and, from the 1960s onwards,
the emergence of new centres of research in the Soviet Union, Japan, and China.
Closely connected with this globalization was the impact of two world wars and
the so-called ‘Cold War’, which effectively made research sponsored by
governments and the military the paymasters of most chemical work just as it
did in the world of physics.

Another dramatic change was that what had been a male-dominated profession
saw women engage with chemistry in ever increasing numbers. Within chemical
practice itself, there was an instrumental revolution after 1950 which saw the
virtual disappearance of dry and wet analyses and their replacement by
electronic machinery; by the same token, the way that chemistry was taught and
the way textbooks were written were necessarily transformed.
Finally, although historically chemistry had always had a close affiliation with
pharmacy and medicine, the subject made a decided shift towards the biological
sciences after World War II, as well as becoming what some commentators have
seen as a service science to other areas of the physical sciences as the
neologisms astrochemistry, geochemistry, and materials science may imply. To
others, however, this was seen as the infiltration of chemistry into the other
sciences and chemistry becoming the fundamental basis—the central science—
for the study of nature.

The beginnings of organic synthesis

Alchemists, chymists, and chemists have always been involved in imitating and
improving nature. According to the OED, the first recorded use of the term
synthesis occurred in the lectures of Peter Shaw, an English Newtonian lecturer
and disciple of Boerhaave. Lavoisier successfully analysed and synthesized both
‘air’ and water. He commented in his Elements of Chemistry (1790) that
chemists must never be satisfied that they know the composition of a substance
unless it has been both analysed and synthesized—something that was implicitly
built into the 18th-century tables of affinity.

By the beginning of the 19th century the classification of materials as animal,

vegetable, and mineral had become simplified into the duality of
mineral/inorganic and organic/organized. Wöhler’s artificial preparation of urea
(see Chapter 4) confirmed the phenomenon of isomerism and that organic
compounds obeyed the same Daltonian laws and that their construction was
possible.

But how could the chemist determine the ways in which atomic arrangements
differed in isomers and in organic compounds generally? The answer was
through metamorphosis, or the analysis of degradation of organic compounds
into simpler products whose compositions were known with some certainty. This
is why many early papers on organic compounds are entitled ‘on the
metamorphosis of x, y, z, etc.’ In effect, chemists used the term metamorphosis
instead of synthesis and hoped that the isolation and identification of common
(or very similar or related) degradation products would lead to an understanding
of parental composition.
Liebig and his school at Giessen became masters of this form of ‘analytical
synthesis’ or ‘synthetical experiments’ by exploiting the accurate quantitative
analyses made possible by the Kaliapparat, improved purification techniques,
and the Pythagorean possibilities of paper chemistry based on stoichiometric
deductions. The task facing chemists was challenging. The empirical formula of
quinine C20H24N2O2 tells one nothing about how the atoms are arranged; it is
like being told to find an intelligible word (quinine) made up of the letters
N2QEUI2.

By the 1830s, however, chemists had Berzelius’ electrochemical theory and Gay-
Lussac’s concept of radicals to guide them. By using empirical molecular
formulae, the analysis of decomposition products, and radical and
electrochemical theories, Liebig and his successors—notably Hofmann working
in London at the Royal College of Chemistry—began to deduce compositional
arrangements. For example, the metamorphoses of benzaldehyde and uric acid
suggested that the radicals benzoyle and uril provided a common constitutional
arrangement. Liebig and Wöhler’s one hundred-page, 1838 paper on uric acid
identified some sixteen new derivatives.

Such successes led Liebig and Wöhler to announce boldly in 1838 that:

The production of all organic substances no longer belongs just to organisms. It must be viewed as
not only probable, but as certain, that we shall produce them in our laboratories. Sugar, salicin, and
morphine will be artificially produced. Of course, we do not yet know how this goal can be achieved
because we do not yet know how the precursors out of which these compounds arise. But we shall
come to know them.

In London, Hofmann laid down a vocabulary of reagents and reactions that

enabled chemists to be more confident about arrangements of atoms within
molecules. In a paper on toluidine, published in 1843, Hofmann declared that the
time was drawing near when the information gleaned from metamorphoses and
analytical experiments would be sufficient to enable chemists to construct
valuable commodities like quinine. Naphthalene (he pointed out in 1849) is
abundantly available from coal gas production and is easily transformed into an
alkaline base, naphthalidine, C20H9N [C=6, 0=8]. But if quinine was
C20H11NO2, the sole difference was two equivalents of water [HO]. Hofmann
was not so naive as to hope that adding water would achieve a synthesis; instead
he forecast that eventually an appropriate metamorphic reaction would be
discovered.

With aspirations such as these pervading the laboratory at the Royal College of
Chemistry, it is scarcely surprising that 18-year-old William Perkin (1838–1907)
should attempt to transform allyltoluidine into quinine in 1856 by removing
hydrogen and adding oxygen. When this experiment failed he tried aniline
instead, and serendipitously created the British dyestuffs industry with the
beautiful mauve dye that resulted. Hofmann was to follow suit on his return to
Germany in 1865 and create the complementary and eventually world-leading
German industry.

Frankland recognized that the organometallic compounds he had prepared would

be powerful aids to synthesis, by which he meant the chemist’s ability to build
up new compounds ‘stone by stone’ with a view to understanding their atomic
configurations. His German friend Kolbe had already shown in 1845 that there
really was no difference between inorganic and simple organic compounds, by
accidentally constructing acetic acid from its elements via carbon disulphide and
tetrachloroethylene intermediates. Between 1863 and 1870 Frankland exploited
zinc ethyl and other organic reagents, including ethyl acetate, in the construction
of ethers, and dicarboxylic and hydroxyl acids. This meticulous work revealed
clearly the structure and relationship of these compounds, while its methodology
had great bearing on the growth of the chemical industry.

In determining chemical structures, chemists soon became adept at manipulating

molecules by using reactions that followed regular patterns. For example, to
increase a carbon chain by two atoms of carbon, two different aldehydes (CHO
group) are heated together in the presence of a sodium salt of a fatty acid; the
two aldehydes join together with the elimination of water. This became known
as Perkin’s reaction or condensation, after it was devised by Perkin to make
cinnamic acid. Hofmann devised a reaction whereby a ring compound
containing nitrogen could be sprung apart to form an open chain, and this
became known as a Hofmann degradation. By the 20th century, organic chemists
were taught and memorized hundreds of these ‘named reactions’, all of which
could be exploited in planning syntheses.

By 1860, Marcellin Berthelot felt able to publish a book entitled Chimie

organique fondée sur la synthèse and to lay down rules for the progressive
synthesis of organic compounds from first principles by ‘the sole aid of chemical
means’ (i.e. no vital forces were invoked). However, his yields (like those of
Kolbe before him) were ridiculously low and it took another decade of structural
modelling, laboratory building, and the development of new glass apparatus and
experimental techniques before the hopes and dreams of Liebig, Hofmann, and
Berthelot concerning useful (and industrially exploitable) synthetic pathways
began to be fulfilled.

The first half of the 20th century was dominated by the determination of the
structures and synthesis of naturally occurring compounds for which the Nobel
Prizes instituted in 1901 were frequently the reward. Two important exemplars
were the German chemists Baeyer and Fischer. The son of a Prussian military
officer, Adolf von Baeyer (1835–1917) was born in Berlin and studied chemistry
with Bunsen and Kekulé at the University of Heidelberg. He taught organic
chemistry in Berlin and Strasbourg before succeeding Liebig at the University of
Munich in 1873, where he spent the rest of his career (see Figure 15).

In 1905 he was awarded the Nobel Prize in Chemistry for his 1880 synthesis of
the natural dyestuff, indigo. The synthesis, which was subsequently scaled up
commercially by the Badische Anilin- und Soda-Fabrik (BASF), destroyed the
economy of agriculturally produced indigo and confirmed the ability of organic
chemists to synthesize natural products.

Baeyer’s pupil, Emil Fischer (1852–1919), held chairs at the universities of

Erlangen and Würzburg, before spending the remainder of his life from 1892 at
the University of Berlin and the newly established government-funded Kaiser
Wilhelm Institute. Fischer extended the work of Baeyer by the synthesis of
complex organic compounds that enabled him to establish the exact constitutions
and structures of sugars, enzymes, purines, and proteins. He thereby laid the
chemical foundations for biochemistry and the study of macromolecules, and
established a methodology of degradation and synthesis in natural products
chemistry that remained in use until the 1950s, when physical and instrumental
methods of structure determination became firmly established.
15. Adolf Baeyer with his University of Munich students in 1877.

His ‘lock and key’ model of enzyme action was announced in 1894 and proved
extremely fruitful. In 1897 Fischer established that biologically important
molecules such as uric acid, xanthine, adenine, and guanine were related to a
heterocyclic nitrogenous base he named purine. Subsequently, he synthesized
many purines, including the barbiturate that was exploited commercially as
Veronal. From 1899 onwards Fischer turned to the structure of proteins, showing
them to be composed from amino acids grouped in polypeptide chains. By 1916
he had synthesized over a hundred polypeptides.

Fischer was the first German to be awarded the Nobel Prize in Chemistry in
1902—in recognition of his syntheses of sugars and purines. With his black
beard and pince-nez, Fischer was an awesome figure in the laboratory which he
ruled like an army general. His over 350 research students included the
chemistry Nobel Prize winners, Fritz Pregl (1923), Adolf Windaus (1928), Hans
Fischer (1930), and Otto Diels (1950); and for medicine, Karl Landsteiner
(1930) and Otto Warburg (1931). Despite ill health caused by the dangerous
chemicals he worked with, he was an active patriot during World War I,
organizing Germany’s chemical and food supplies. His disillusionment following
the death of two of his sons on the battlefront caused his suicide in 1919.

The American Robert Woodward (1917–79), working at Harvard, was the most
prominent synthesizer in the mid-20th century (see Figure 16). He triumphantly
synthesized quinine (1944), cholesterol and cortisone (both in 1951), chlorophyll
(1960), and vitamin B12 (1976). Ironically he was to receive the Nobel Prize in
1965 not for synthesis, but for his deduction of rules derived from quantum
mechanics concerning the conservation of orbital symmetry. This demonstrates
the way physical chemistry had transformed organic chemistry since the 1930s
and deeply affected the way viable synthetic pathways were sought by organic
chemists.

Woodward’s European rival was the Glaswegian, Alexander Todd (1907–97),

who was awarded the Nobel Prize in Chemistry in 1957 for his elucidation of the
structures and syntheses of nucleosides, nucleotides, and their co-enzymes, as
well as the related problems of their phosphorylation. This work was a necessary
preliminary to the elucidation of the structure of DNA by the non-chemists
James Watson (a zoologist) and Francis Crick (a physicist) in 1952. Todd also
worked extensively on adenosine triphosphate, vitamin B12, and other natural
products, including plant and insect pigments. A towering physical presence in
organic chemistry, he was nicknamed ‘Lord Todd Almighty’.

These triumphant structural determinations of natural products were surpassed

by the ability of 20th-century chemists to create new, unnatural substances,
beginning with plastics and resins, and polymers such as rayon and nylon. On
the other hand, the ability to synthesize a molecule was not necessarily useful.
For example, amid wartime pressure to treat dangerously infected wounds,
British chemists made great efforts to synthesize penicillin, the first of the
antibiotics, but it proved too difficult to scale up production; instead penicillin
was manufactured by culturing the mould directly, as were other antibiotics
whose structures were known such as streptomycin and tetracycline. This
refashioned brewery technology soon became known as biotechnology.

Chemistry, as the science of transmutations and substitutions, turned the natural

world upside down. The imitation of nature led to the possibility of breaking
with Nature and surpassing it to form an artificial world. However, none of this
would have been possible without the physicists’ analysis of the deep structure
of the atom that had begun at the end of the 19th century.

16. Robert Burns Woodward (1917–79), America’s most successful organic

chemist.

The electronic age

Research in the 19th-century on the conduction of electricity was marked by a
series of brilliant and intensely visual investigations by German and British
experimentalists. The two most outstanding investigators were Johann Hittorf
(1824–1914) and William Crookes (1832–1919), whose research was made
possible by the innovations and improvements in glass blowing and vacuum
pump technology instituted by the Bonn instrument-maker, Johann Geissler
(1815–79).

Hittorf, a physical chemist, investigated how gas spectra altered under changing
pressure. It was during his experiments to map gaseous discharge and to quantify
the variation of electric force and temperatures that he discovered shadows on
the phosphorescent patches glowing on the discharge tubes. From this he
inferred that ions were emitted from the cathode, though he left it to others to
develop the notion of cathode rays.

By then (1879) Hittorf’s work had been completely overtaken by Crookes, who
had approached gaseous discharges from a completely different direction,
namely the puzzle of what went on inside a discharge tube. Geissler’s technique
for evaluating the quality of a vacuum by residual glow during conductivity
encouraged Crookes to interpret his work as evidence for a fourth state of matter
he called ‘radiant matter’. The Crookes tube, as his form of discharge tube
became known, not only allowed Conrad Röntgen (1845–1923) to uncover X-
rays in 1895, but paved the way for J. J. Thomson’s postulation of the electron in
1897, thus opening the way for models of the atom in terms of a nucleus
surrounded by electrons.

Once Thomson had shown that the electron was a subatomic particle, he spent a
decade investigating heavier positive particles that were also produced during
the discharge of electricity through gases. Together with his assistant, Francis
Aston (1877–1945), in 1912 they constructed a mass spectrograph, using a
camera to record spectra. The positive ray spectra produced in this machine
proved to be a superb way of identifying and distinguishing ions and the
different isotopes of elements. With many improvements over the next fifty
years, the mass spectrometer (as it was renamed) became a major analytical tool
not only for chemists but in almost every area of scientific and industrial activity.

One of the anomalies Mendeleev had to deal with in the periodic table were ‘pair
reversals’, where a group of elements with similar properties contained an
element with an atomic weight that was higher than the element that followed in
the atomic weight sequence. For example, the atomic weights of tellurium and
iodine were 128 and 127, but if iodine was placed before tellurium in the
periodic table it would be displaced from the halogen Group 7 where it clearly
belonged. To Mendeleev this suggested that the atomic weight of tellurium was
probably incorrect.

The reason for pair reversal only became apparent when knowledge of isotopes
was suggested by Frederick Soddy (1877–1956) in 1912. Some elements such as
tellurium possessed up to half a dozen isotopes, including an abundant one of
mass 128. This mass had the effect of creating an average atomic weight greater
than that of iodine which has only one isotope of mass 127.

Around the same time the Oxford physicist Henry Moseley used the frequency
of the most intense line in an element’s X-ray spectrum to show that there was a
more fundamental way of ordering elements, namely their atomic number or the
size of the nuclear charge. Moseley’s work, coupled with that of Soddy and
Aston on isotopes, revealed the reason for reversal anomalies in Mendeleev’s
periodic table. Before his untimely death at Gallipoli in 1915, Moseley also
demonstrated the probable existence of a number of undiscovered elements,
which were gradually identified over the following decades.

With his first instrument Aston was able to announce that neon was a mixture of
two isotopes; and within a few months he had analysed a sufficient number of
other elements to be able to announce a ‘whole number rule’ according to which,
if atomic masses were calculated with respect to oxygen (mass 16) then they
were all integers, just as Prout had suggested. He concluded that atomic weights
determined by chemical methods were merely ‘fortuitous statistical effects’
caused by the relative quantities of the isotopic constituents. In the case of neon,
the relative abundances of Ne22 and Ne20 (a nomenclature introduced by Aston)
produced a non-integral atomic weight of 20.1. Was Prout’s hypothesis true after
all?

The problem here was that hydrogen was anomalous. With a mass number of
1.008 it did not obey the whole number rule. The solution was found in
Einstein’s special theory of relativity and the famous equation linking energy,
mass, and the velocity of light: e = mc2. The American maverick chemist,
William Harkins (1873–1951), suggested in 1915 that atoms might be
considered to be helium ions (nuclei) surrounded by electrons. The helium
‘atoms’ were so closely packed together in elementary atoms that they lost mass
in the form of energy.

Aston seized upon this packing concept in 1920 to explain the hydrogen
anomaly, but used Prout’s original idea of hydrogen atoms forming other
elements rather than helium. Suppose elements were constructed from hydrogen
atoms of individual mass 1.008. Mass was only additive, he argued, when
nuclear charges were relatively distant from one another. In the case of atoms
other than hydrogen, mass was lost within the atom in the form of a binding
energy as the individual atoms of hydrogen were squeezed or packed together.

As Aston slowly improved the accuracy and sensitivity of the mass spectrometer
through the 1920s, it became apparent that the whole number rule was not exact
and that there were many deviations. Aston codified these deviations by defining
a new function called the ‘packing fraction’, defined as the divergence of an
atomic mass from a whole number divided by its mass number. By plotting these
fractions against mass numbers Aston obtained a simple curve, which threw
important light on nuclear abundances and stabilities. The packing fraction,
along with atomic mass and atomic number, soon became the three defining
atomic constants for both chemists and physicists, and Aston was awarded a
Nobel Prize in 1922 for his work on isotopes and the whole number rule.

Making organic chemistry physical

Although 19th-century organic chemistry became a coherent subdiscipline based
upon knowledge of bonding and structure, and inorganic chemistry had come to
order through the periodic law, chemistry remained essentially an empirical
science of analysis and synthesis based upon centuries-old techniques of
extraction, distillation, etc. It was for this reason that Ernest Rutherford could
dismiss chemists as mere stamp collectors compared to physicists like himself,
who were ‘true’ scientists. Ironically, this was to change largely because of
Rutherford’s own work in revealing the structure of the atom. Atomic structure
explained why the periodic table worked, as well as introducing new ideas
concerning why organic reactions proceeded in the way they did.

Three important innovators in physical organic chemistry were the two English
chemists, Arthur Lapworth (1872–1941) and Christopher Ingold (1893–1970),
and the American Louis Hammett (1894–1987). Lapworth was the transitional
figure who linked 19th-century structural theory with models of electronic
valence. Interestingly, Lapworth married one of three musically gifted sisters
who each married a chemist—the other two married the organic chemist, W. H.
Perkin Jr (1860–1929), and the pioneer of silicon chemistry, Frederic Kipping
(1863–1941). The marriages are a reminder that chemists are often found to be
talented musically, the most famous example being the Russian organic chemist,
Aleksandr Borodin (1833–87).

The 19th-century assumption that there was one unique structure for each
compound was soon found wanting in the identification of tautomerism, in
which a compound flips from one structure to another. As chemists became more
familiar with the electron, notably after G. N. Lewis suggested that substances
coupled together by completing an octet of electrons in their outer electronic
shells, Lapworth developed ideas about electrons moving through double-
bonded organic compounds under the influence of other polarized elements or
compounds. In some ways this represented a return to Berzelius’ earlier
electrochemical theory.

Lapworth’s ideas were adopted and extended by the Oxford chemist Robert
Robinson in the 1920s, and it was he who introduced the ubiquitous and iconic
curved arrow symbolism for electron movement in 1922. However, Robinson
was not greatly interested in electronic theory except as an adjunct to
understanding the structures of natural products, and he left it to his London rival
Ingold to use the electronic theory to classify organic reaction mechanisms
generally using kinetics, spectroscopy, and other tools.

Ingold introduced a kinetic terminology of substitution and elimination reaction

mechanisms in a review paper in 1934, and in his subsequent magnum opus
Structure and Mechanism in Organic Chemistry (1953). His collaboration with a
Welsh colleague Edward Hughes (1906–63) became on a par with that of Liebig
and Wöhler a century before, though it should be noted that much of Ingold’s
early theoretical work had been done with his wife, Hilda, a pupil of Martha
Whiteley.

Meanwhile, at Columbia University in New York, Louis Hammett used his

knowledge of physical chemistry to develop equations for acidity and rate
constants that could be used in elucidating mechanistic pathways. His genius
was to develop a simple way of measuring the rate constants of reactions in
organic chemistry. This made it easier for chemists to determine particular
mechanisms of reactions. Hammett’s pioneering textbook, Physical Organic
Chemistry (1940), although little known in Europe until a decade later, not only
introduced the term, but ensured that American chemists would actually forge
ahead of their European competitors, as post-war Nobel Prizes clearly indicate.

In 1946 American chemists held the first of an annual series of reaction

mechanism conferences and began to take over leadership in the growing field of
physical organic chemistry. European wars had led British postgraduates to
abandon further studies in Germany; they now turned to America instead.

The chemists’ wars

The Great War of 1914–18 was the first conflict in which European chemists
were involved in both defensive and offensive research. In 1914 Germany was
still the world’s leader in chemical research and the supply of chemicals.
Consequently, Britain had much catching up to do. The Chemical Society played
its part through its library, which proved a valuable resource of information on
pure and applied chemistry.

The Society (like other learned societies) found itself mired in controversy as to
whether honorary German Fellows should be stripped of their membership. The
Council’s decision not to do so caused widespread criticism and controversy in
the press; in 1916 the Council capitulated and the names of Baeyer, Fischer,
Nernst, and Ostwald (to name the most distinguished German chemists) were
removed. It was not until 1929 that four of the surviving names were re-elected,
and that new Germans and Austrian chemists were admitted. Strangely, there
seems to have been no reciprocal action by the German Chemical Society.
Despite the government’s action in making qualified scientists reserved
occupations in 1915 (following the tragic death of the chemist Henry Moseley
that year), some eighty-three British chemists lost their lives on the battlefields
of Europe.

The war that erupted in 1914 is popularly known as ‘the chemists’ war’ because
of the use of poisonous gas warfare. In fact, less than 1 per cent of war casualties
were directly attributable to the use of chemical warfare, and the phrase was first
used in 1917 to describe the way chemistry had been marshalled to place Great
Britain on a war footing. By analogy the 1939–45 war has been called ‘the
physicists’ war’ because of the effort that was placed upon making an atomic
bomb. In fact, chemists were closely involved in the separation of uranium
isotopes and in the manufacture of heavy water. And without their skills there
would have been no bomb.

In both world wars the chemical industry was dominated by the drive to improve
and raise production levels of conventional high explosives and metal production
for cannon. The petroleum soap (napalm) devised by the Harvard chemist Louis
Fieser (1899–1977) killed more Japanese than the atomic weapons that
destroyed Hiroshima and Nagasaki combined. Its use during the Korean War
(1950–3) and the prolonged Vietnam war (1955–75) became a symbol of the
evils of warfare and was responsible for a chemophobic swing against chemistry
that has had a lasting effect on popular culture.

All 20th-century wars were chemists’ wars, because the blockading of shipping
and the cutting of land supply routes forced both the Allies and the Axis powers
to find new ways of preparing materials that were in short supply or in inventing
substitute materials. The best-known example is the scaling up of the Haber
process for fixing nitrogen that could be used both to prepare nitric acid for use
in explosive weapons and for the production of fertilizers to aid food production.
Its application to explosives was directly caused by the Royal Navy’s blockade
of German shipping carrying Chilean nitre that had hitherto been the source of
both fertilizer and explosives.

Although Germany was able to scale up the Haber process in time, British
chemists had been left in ignorance and instead industrialized an older German
process for ‘fixing’ nitrogen by making calcium cyanamide by passing nitrogen
over calcium carbide. Ammonia was then generated from the cyanamide by
exposing it to steam. Ammonia was also extracted from urban gas plants. In both
Germany and Britain ammonia was then converted to nitric acid by a method
that Wilhelm Ostwald had patented in 1902, whereby ammonia was oxidized in
the presence of a platinum catalyst. Platinum was far too expensive to use in this
process, and during the 1914–18 war German chemists found a cheaper catalyst
of iron and bismuth oxides, thus enabling Germany to continue the war after
1916.

On the ammunition front, chemists had to scale up production of various

aromatic organic compounds for the manufacture of TNT, amatol, and lyddite
for high-explosive shells as well as smokeless cordite as a propellant. In every
case chemists were met with bottlenecks as one problem produced another. For
example, cordite was made by nitrating cellulose to make guncotton. This was
then mixed with nitroglycerine and petroleum jelly. But to make the cordite
suitably potable the nitroglycerine jelly had to be dissolved in acetone before it
could be extruded into a tubular form.

However, acetone, normally prepared by the distillation of wood, was in short

supply. The problem of acetone production was solved by a chemist at the
University of Manchester, Chaim Weizmann (1874–1952). He developed an
acetone fermentation process based upon brewery methods. Subsequently, a
grateful British government signed the Balfour Agreement which gave Zionists
like Weizmann a homeland in Palestine. Weizmann was one of the few chemists
to have become president of a nation.

German chemists faced similar problems, as blockades that restricted cotton

supplies meant that guncotton had to be prepared by an alternative method using
rags and wood pulp, and glycerine prepared from sugar fermentation. Max
Delbrück (1850–1919), a German brewery chemist, devised fermentation
processes whereby yeast could be used to produce animal feed. These were early
signs of the application of chemistry to the biotechnology that gained industrial
significance after the 1960s.

Chemists also contributed to the improvement of glass manufacture, because

high-quality optical glass was needed for surveying instruments in warfare;
dyestuffs were another area where Britain, which had lost out to Germany (and
to France to a lesser extent) at the end of the 19th century, was forced to make its
own dye materials. Similar shortages of raw materials were experienced in
Germany and Turkey; without direct access to Far Eastern natural rubber,
German chemists explored synthetic alternatives which gave their chemists a
strong start in the new area of polymer research, which not only produced many
new synthetic fabrics, but also proved of long-term value in gaining an
understanding of biological chemical systems.
The momentum of war-driven chemical research did not cease in 1918, nor did it
in 1945. All these examples, including the use of chemical warfare, were
expressions of what John Agar has termed ‘organized science and managed
innovation’. It is doubly ironic that the German research on chemical warfare
agents was promoted in peacetime in the production of insecticides; one of these,
devised by Haber and named Zyklon B, was to be used to gas Jews in
concentration camps during the 1940s.

Women in chemistry
Probably the most important consequence of the 20th-century wars was that
strong links were established between government, the military, industry, and
academia. These continued through the short peace of the 1920s and 1930s,
before becoming even more firmly established during World War II and the
subsequent Cold War of the 1950s and 1960s.

Warfare in the 20th century brought new opportunities for women chemists,
most of whom were drafted into fundamental bench work needed in testing
reactions and synthesizing products of importance. Martha Whiteley (1866–
1956), who was to be among the first twenty-one woman elected to the Chemical
Society in 1920, headed a team of women at Imperial College in London that
manufactured the local anaesthetic beta-eucaine, a derivative of cocaine.

Many more ordinary women were drafted into the chemical industry to perform
heavy manual work in the manufacture of explosives. In the aftermath of war,
the huge chemical industries built up by America, Germany, and Britain were
not decommissioned and dismantled. Instead they were merged to form large and
powerful companies. In Germany in 1925, BASF, Bayer, Hoechst, and other
companies formed IG Farben with 100,000 male and female employees; in
America Du Pont expanded into new areas of manufacture; while in Britain,
Imperial Chemical Industries (ICI) was formed in 1926 from the merger of most
of the surviving alkali and dyestuffs manufacturing companies.

These industrial companies provided women chemistry graduates with new

opportunities for employment as they combined marriage and family with
scientific careers. Until then, as male chemists’ entries in biographical
dictionaries confirm, they had tended to abandon research careers after marriage
to male chemists they met during their training in postgraduate laboratories.

The instrumental revolution

The most ‘creative toolmaker’ of the 20th century was the American
blacksmith’s son, Arnold Beckman (1900–2004). As a teenager he became
interested in how microscopy and photography could be used to study the fine
structure of metals; while still in high school he founded a company to make
metallurgical instruments.

Following a conventional chemical training at California College of Technology,

he became struck by the fact that the productivity of the local orange-tree
industry was dependent on soil acidity. The logarithmic pH scale of acidity had
been introduced by the Danish biochemist Soren Sørensen (1868–1939) in 1909
(pH stood for potential hydrogen ions, with zero for extreme acidity and fourteen
for extreme basicity). Measurements of pH involved elaborate volumetric
analysis off site until Beckman packed everything into a simple portable meter
that calculated the pH electronically (see Figure 17). The device was patented in
1934 when he left academia and founded an instrument company that not only
manufactured Beckman pH meters but also absorption spectrophotometers that
found a use in the growing industrialized food industry.

Beckman was in a good position when chemical practice underwent an

instrumental revolution in the 1950s. Infrared spectroscopy had begun in the late
19th century when two former British army officers who were working for the
government’s educational department detected correlations between infrared
spectra and the functional groups of organic compounds. In the early 1900s the
American physicist William Coblentz published data on the spectra of over a
hundred organic molecules.

However, for various reasons these findings did not lead to this form of
spectroscopy being used in structural determinations. This occurred in the 1930s,
when petroleum chemists found the need for a rapid way to identify the different
fractions of distilled petroleum. Infrared spectroscopy then became an essential
tool as the world wars encouraged a switch from coal to oil as the principal
feedstock for the chemical industry. The adoption of ultraviolet and infrared
spectroscopy, nuclear magnetic resonance, and mass spectrometry transformed
compounds into an abstract artwork of spectral lines or curves by an electronic
machine.

17. Beckman Model G pH meter (1934). This cubic box (roughly a foot in
width, depth, and height) was a voltmeter that used an acid-base responsive
electrode to give a direct conversion of voltage differences to differences of
pH at the temperature of measurement. It was one of the first portable
laboratory instruments available. With its hidden mechanism, it was also
the first chemical ‘black box’.

There were many consequences in the 1960s and 1970s. The new instruments
were expensive to purchase and maintain, so academic research became even
more dependent on industrial and government financial support; interpretation of
the data depended upon quantum mechanical considerations and this, coupled
with the abandonment of traditional methods of wet and dry analyses, forced
changes in the way that chemistry was taught. In France, for example, theories of
atomic structure and the periodic table only made their appearance in secondary
schools in 1978.

Teaching laboratories in schools and universities were reshaped in these decades,

and syllabuses were reconstructed so that far greater emphasis was placed upon
physical chemistry, electronic structure, and quantum chemistry. Synthetic
chemistry was no longer a tedious process to confirm a possible structure, but
became a logical way of strategically determining the structures of ever more
complicated compounds, and even designing new materials from scratch. The
understanding of reaction mechanisms was also revolutionized by the revelation
of the roles played by ‘unstable’ intermediates during molecular transformations.

Finally, physical instruments opened up the possibility of better understanding of

biochemical pathways in living systems and of revealing the extent of pollution
in the environment. Regarding the latter, the delicacy of the chemists’
instruments has made it possible for governments to legislate and monitor the
dangerous products of our working worlds.

Chemistry’s millennium
The British historian John Agar has interpreted the history of 20th-century
science in terms of problems that arose in the everyday existence of human life
such as warfare and health. Since the 1950s universities have ceased to be purely
academic institutions (‘ivory towers’) devoted to the teaching and promotion of
individual disciplines. In our contemporary ‘post-academic’ world they have
become inter and transdisciplinary, as well as utilitarian, institutions. Like
industry and business generally, universities now have to make money and are
consequently directed by politics and economics.

This has been no bad thing for chemistry’s fortunes insofar as it has made its
central role in the circle of the sciences much more prominent; it has become an
essential science. The Japanese historian of polymer science Yasu Furakawa has
described molecular biology, for example, as a fusion of the methods,
techniques, and concepts of organic chemistry, polymer chemistry, biochemistry,
physical chemistry, X-ray crystallography, genetics, and bacteriology. Much the
same might be said of the synthetic materials and technology that now dominate
our computerized man-made world.
Epilogue

The introduction of electronic instruments into analytical and synthetic

chemistry in the 1960s is an appropriate point to conclude this short account of
the history of chemistry. Of course, the subject has not stood still during the past
sixty years.

On the negative side, the chemists’ wars of the 20th century had already
coloured public perception of chemistry as a destructive science; this perception
of chemistry’s ambivalence was further exacerbated by a more general
chemophobia produced by revelations of the pollution trails left by heavy
industry, the widespread use of pesticides in agriculture and veterinary medicine,
and the devastating explosion of a chemical plant in Bhopal in 1984.

While the historian can take a long-term view of this image problem, namely
that chemistry has always been associated with risk and that explosions and
pollution have been recurrent events, new analytical techniques and risk
assessment legislation are undoubtedly having a remedial effect. Instruments like
James Lovelock’s miniature electron-capture detector of the 1950s played a
major role in revealing the extent of man-made pollution and its alarming effects
on the protective atmospheric ozone layer, and the potential of carbon dioxide
emissions for disturbing climate.

More positively, computers replaced the laboratory notebook, and with their aid
chemists began to study perfect three-dimensional structural models and design
new molecules on the screen. This ability has led to new ways to craft drugs that
can inhibit undesirable metabolic processes. Combinatorial chemistry was
developed by pharmaceutical companies in the 1990s. By reacting together
multiple ingredients rather than single ones, huge numbers of compounds and
their derivatives were created in one reaction and the resultant ‘library’ of
compounds screened for possible use as drugs. Pharmaceutical companies have
spent millions of pounds on automating these syntheses and the preparation of
individual compounds are only scaled up when a promising molecule is detected.

The American chemist L. R. Corey also introduced what he called retrosynthesis

in the 1990s. In this technique, the substance whose structure is to be determined
and synthesized is broken down into simpler molecules whose structures are
known and whose individual synthesis has been already achieved. This
knowledge can then be used to plan a synthesis of the wanted molecule. While
mainly used in pharmaceutical research and drug design, these latest synthetic
techniques have also had aesthetic appeal with syntheses being attempted and
achieved purely for intellectual enjoyment.

Chemists have also continued to make extraordinary, surprising, and useful

discoveries. Carbon, for example, was shown in 1985 to have an allotropic form
different from its known varieties of graphite, diamond, and charcoal. This new
form, which contained sixty atoms of carbon formed in the shape of a football,
was cumbersomely named Buckminsterfullerene in honour of the American
architect who had devised the similarly shaped geodesic dome. Fullerene and its
derivatives (some in the shape of cylinders called nanotubes) quickly became the
subject of much synthetic research.

Even more sensationally, in 2003 a one-atom-thick two-dimensional form of

graphite was prepared consisting of flat sheets of hexagonally ringed carbon
with valuable electrical conduction properties. Named graphene, it has been
quickly put to work in the creation of new extremely light construction materials
and faster semiconductors. By analogy, chemists have found that graphene-type
allotropes can also be formed by phosphorus (phosphorene), silicon (silicone),
germanium (germanene), and arsenic (arsenene). Needless to say, like isotopes a
century ago, the existence, or creation, of such diverse allotropes raises the
philosophical question as to what chemists mean by an element.

A new technology has emerged, nanotechnology, which refers to the

manipulative transformation of matter at an atomic or molecular level. This was
something that chemists had always done before at a macroscopic scale through
analysis and synthesis; now this can be carried out at the nanoscopic scale, atom
for atom. Here quantum effects become important and confer extraordinarily
valuable properties on materials—optical, electrical, and structural. The resultant
‘materials science’ concentrates on the synthesis and construction of molecules
of commercial, industrial, and pharmaceutical significance.

The exploration of this atomic material world involves not just chemists, but
biochemists, physicists, and engineers. In an age of cross-disciplinary,
transdisciplinary science and technology, several historians, sociologists, and
philosophers of science have queried whether the concept of distinct scientific
disciplines like chemistry, physics, and biology serves a purpose any longer.
According to this view, chemistry has metamorphosed into biochemistry,
biotechnology, nanotechnology, and materials science. Driven by technology, it
has dissolved into a service science.

While there are sound arguments for this view, which has implications for the
way the sciences are presently taught in schools and universities, practising
chemists prefer to see chemistry as the central science that underpins the
physical and biological sciences. Far from dissolving, it has, in effect, taken over
these other disciplines. As Liebig said in his popular writings in the 1840s,
‘Alles ist Chemie’—everything is chemistry.
Sources of quotations

Introduction
Friedrich Kekulé, Lehrbuch der organischen Chemie (Erlangen: F. Enke, 1861), p. 1.
Robert Siegfried, From Elements to Atoms. A History of Chemical Composition (Philadelphia: American
Philosophical Society, 2001), pp. 1–2.
Chapter 1: On the nature of stuff
Robert P. Multhauf, The Origins of Chemistry (London: Oldbourne, 1966), p. 27.
The Journals of John Tyndall (typescript), Royal Institution of Great Britain, 6 February 1854.
Chapter 2: The analysis of stuff
William R. Newman and Lawrence M. Principe, Alchemy Tried in the Fire (Chicago: Chicago University
Press, 2002), p. 180.
Chapter 3: Gases and atoms
Antoine Lavoisier, Memorandum of 20 February 1773, quoted in Henry Guerlac, Lavoisier: The Crucial
Year (Ithaca, NY: Cornell University Press, 1961), p. 229.
Antoine Lavoisier, ‘Mémoire sur la nature du principe qui se combine avec les métaux pendant leur
calcinations’, Oeuvres de Lavoisier, 6 vols (Paris: Imprimerie Impériale, 1862–93), vol. 2, p. 123.
Henry Cavendish, ‘Experiments on air’, Philosophical Transactions of Royal Society, 74 (1784), 119–53, at
p. 129.
Sacha Tomic, Comment la chimie a transformé le monde (Paris, 2013), p. 64 (my translation).
Chapter 4: Types and hexagons
August Laurent, Chemical Method (London: Cavendish Society, 1855), p. 203.
Alexander Williamson, ‘Theory of etherification’, Quarterly Journal Chemical Society, 4 (1852), 229–39,
at p. 239.
Edward Frankland, Sketches from the Life of Edward Frankland (London, 1902), p. 187.
Friedrich Kekulé, ‘Ueber die Constitution des Mesitylens’, Zeitschrift für Chemie, 10 (1867), 214–18,
reprinted in Richard Anschütz, August Kekulé, 2 vols (Berlin, 1929), vol. 2, pp. 5–30.
Chapter 5: Reactivity
Staffan Bergwik, ‘An assemblage of science and home: the gendered lifestyle of Svante Arrhenius’, Isis,
105 (2014), 265–91, at p. 281.
Chapter 6: Synthesis
Justus Liebig and Friedrich Wöhler, ‘Untersuchungen über die Natur der Harnsäure’, Annalen der
Pharmacie, 26 (1838), 241–340, at pp. 314–15.
Further reading

The principal reference work in English is James R. Partington, A History of

Chemistry, 4 vols (Macmillan: London, 1965–70); but see also the more
digestible work of Aaron J. Ihde, The Development of Modern Chemistry (New
York: Harper & Row, 1964). More recent analytical accounts include William H.
Brock, The Fontana History of Chemistry (London: HarperCollins, 1992;
published in America as The Norton History of Chemistry (New York: Norton,
1993); and reissued as The Chemical Tree (New York: Norton, 2000); John
Hudson, The History of Chemistry (Basingstoke: Macmillan, 1992) is aimed at
practising chemists; David M. Knight, Ideas in Chemistry: A History of the
Science (London: Athlone Press, 1992); Bernadette Bensaude-Vincent and
Isabelle Stengers, A History of Chemistry (Cambridge, MA: Harvard University
Press, 1996) previously published in French (Paris, 1993); Trevor H. Levere,
Transforming Matter: A History of Chemistry from Alchemy to the Buckyball
(Baltimore, MD: Johns Hopkins University Press, 2001); and Peter J. T. Morris,
The Matter Factory: A History of the Chemistry Laboratory (London: Reaktion
Books, 2015). A valuable source on chemical technologies (a subject that I have
largely ignored) is Charles Singer, Eric J. Holmyard, and A. Rupert Hall, eds,
History of Technology, 8 vols (Oxford: Clarendon Press, 1954–84). There are
two international journals of the subject: Ambix: The Journal of the Society for
the History of Alchemy and Chemistry (1937 onwards) and The Bulletin of the
History of Chemistry published by the Division of the History of Chemistry of
the American Chemical Society (1988 onwards).
Chapter 1: On the nature of stuff

James R. Partington, Origins and Development of Applied Chemistry

(Longmans, 1935) is for reference only; more readable are Robert P. Multhauf,
The Origins of Chemistry (London: Oldbourne, 1966) and Ronald F. Tylecote,
History of Metallurgy, 2nd ed. (London: Institute of Materials, 1992); William
Eamon, Science and the Secrets of Nature: Books of Secrets in Medieval and
Early Modern Culture (Princeton, NJ: Princeton University Press, 1994); Philip
Ball, Bright Earth: Art and the Invention of Colour (Harmondsworth: Penguin
Books, 2001; Chicago: University of Chicago Press, 2003); William R.
Newman, Promethian Ambitions: Alchemy and the Quest to Perfect Nature
(Chicago: University of Chicago Press, 2004) and his Atoms and Alchemy
(Chicago: University of Chicago Press, 2006); Joseph B. Lambert, ‘The deep
history of chemistry’, Bulletin History of Chemistry, 30, no. 1 (2005), 1–9;
Marco Beretta, The Alchemy of Glass: Counterfeit, Imitation, and Transmutation
(Sagamore Beach, MA: Science History Publishing, 2009); and L. M. Principe,
The Secrets of Alchemy (Chicago: University of Chicago Press, 2013). For an
entertaining book that provides instructions and interpretations of alchemical
experiments, see Cathy Cobb, Monty L. Fetterolf, and Harold Goldwhite, The
Chemistry of Alchemy (Amherst, NY: Prometheus Books, 2014).
Chapter 2: The analysis of stuff

Allen G. Debus, The English Paracelsians (London: Oldbourne, 1965); Robert

P. Multhauf, The Origins of Chemistry (London: Oldbourne, 1966); Frederic L.
Holmes, Eighteenth-Century Chemistry as an Investigative Enterprise (Berkeley,
CA: University of California Press, 1989); Antonio Clericuzio, Elements,
Principles and Corpuscles: A Study of Atomism and Chemistry in the
Seventeenth Century (Dordrecht: Kluwer, 2000); Philip Ball, The Devil’s Doctor:
Paracelsus and the World of Renaissance Magic and Science (London:
Heinemann, 2006); William R. Newman, Atoms and Alchemy: Chymistry and
the Experimental Origins of the Scientific Revolution (Chicago: Chicago
University Press, 2006); Charles Webster, Paracelsus: Medicine, Magic and
Mission at the End of Time (New Haven, CT: Yale University Press, 2008);
Victor D. Boantza, Matter and Method in the Long Chemical Revolution
(Farnham: Ashgate, 2013).
Chapter 3: Gases and atoms

Archie and Nan Clow, The Chemical Revolution (1952); Frank Greenaway, John
Dalton and the Atom (London: Heinemann, 1966); Donald S. L. Cardwell (ed.),
John Dalton and the Progress of Science (Manchester: Manchester University
Press, 1968); Elisabeth Patterson, John Dalton and the Atomic Theory (New
York: Doubleday, 1970); Arnold Thackray, John Dalton: Critical Assessments of
his Life and Science (Cambridge, MA: Harvard University Press, 1972); William
H. Brock, Fontana History of Chemistry (1992), chapter 4; Arthur Donovan,
Antoine Lavoisier. Science, Administration and Revolution (Cambridge:
Cambridge University Press, 1993); Mario Beretta, The Enlightenment of Matter
(1993) for the development of chemical nomenclature; Maurice P. Crosland, In
the Shadow of Lavoisier: The Annales de Chimie and the Establishment of a
New Science (Faringdon: British Society for the History of Science, 1994);
Robert E. Schofield, The Enlightenment of Joseph Priestley (University Park,
PA: Pennsylvania State University Press, 1997) and its sequel The Enlightened
Joseph Priestley (University Park, PA: Pennsylvania State University Press,
2004); Robert Siegfried, From Elements to Atoms: A History of Chemical
Composition (Philadelphia, PA: American Philosophical Society, 2002);
Jonathan Simon, Chemistry, Pharmacy and Revolution in France, 1777–1809
(Aldershot: Ashgate, 2005); Victor D. Boantza, Matter and Method in the Long
Chemical Revolution (Farnham: Ashgate, 2013).
Chapter 4: Types and hexagons

O. Theodor Benfey, From Vital Force to Structural Formulas (Boston:

Houghton Mifflin, 1964); Colin A. Russell, The History of Valency (Leicester:
University of Leicester Press, 1971); Alan J. Rocke, The Quiet Revolution:
Hermann Kolbe and the Science of Organic Chemistry (Berkeley, CA:
University of California Press, 1993); Colin A. Russell, Edward Frankland:
Chemistry, Controversy and Conspiracy in Victorian England (Cambridge:
Cambridge University Press, 1996); William H. Brock, Justus von Liebig: The
Chemical Gatekeeper (Cambridge: Cambridge University Press, 1997); Alan J.
Rocke, Nationalizing Science: Adolphe Wurtz and the Battle for French
Chemistry (Cambridge, MA: MIT Press, 2001); and for those who read French,
Sacha Tomic, La pratique de l’analyse chimique et l’émergence de la chimie
organique: une enterprise pluridiscipline (1790–1835) (Rennes: Le Square,
2013).
Chapter 5: Reactivity

M. M. Patterson Muir, A History of Chemical Theories and Laws (New York: J.

Wiley, 1907; reprint New York: Arno Press, 1975); J. W. van Spronsen, The
Periodic System of Chemical Elements (Amsterdam: Elsevier, 1969); C. A.
Russell et al., Chemistry as a Profession (Milton Keynes: Open University,
1977); John Servos, Physical Chemistry from Ostwald to Pauling: The Making
of a Science in America (Princeton, NJ: Princeton University Press, 1990);
William H. Brock, The Fontana History of Chemistry (London: HarperCollins,
1992), chapter 10; Mary Jo Nye, From Chemical Philosophy to Theoretical
Chemistry (Berkeley, CA: University of California Press, 1993); Keith Laidler,
The World of Physical Chemistry (Oxford: Oxford University Press, 1995); Eric
Scerrie, The Periodic Table: Its Story and its Significance (Oxford: Oxford
University Press, 2007); Peter Atkins, Physical Chemistry: A Very Short
Introduction (Oxford: Oxford University Press, 2014).
Chapter 6: Synthesis

Lutz F. Haber, The Chemical Industry 1900–1930 (Oxford: Clarendon Press,

1971); Anthony S. Travis, The Rainbow Makers: The Origins of the Synthetic
Dyestuffs Industry in Western Europe (Bethlehem, PA: Lehigh University Press,
1993); Roy MacLeod, ‘Chemists go to war’, Annals of Science, 50 (1993), 455–
81; Roald Hoffmann, The Same and Not the Same (New York: Columbia
University Press, 1995); Yasu Furukawa, Inventing Polymer Science
(Philadelphia, PA: University of Pennsylvania Press, 1998); Peter Morris, ed.,
From Classical to Modern Chemistry: The Instrumental Revolution (Cambridge:
Royal Society of Chemistry, 2002); Marelene and Geoff Rayner-Canham,
Chemistry was their Life: Pioneer British Women Chemists 1880–1949 (London:
Imperial College Press, 2008); John Agar, Science in the Twentieth Century and
Beyond (Cambridge: Cambridge University Press, 2012); Michael Sutton,
‘Chemists at war’, Chemistry World, 11 (August 2014), 44–7; Mark Miodownik,
Stuff Matters: The Strange Stories of the Marvellous Materials that Shape our
Man-made World (London: Viking, 2014); Catherine Jackson, ‘Synthetical
experiments and alkaloid analogues: Liebig, Hofmann, and the origins of organic
synthesis’, Historical Studies in Natural Science, 44 (2014), 319–63. Although it
demands some technical knowledge, a readable history of quantum chemistry is
Kostas Gavroglu and Ana Simõs, Neither Physics nor Chemistry (Cambridge,
MA: MIT Press, 2012).
Index

A
Académie des sciences 23, 41, 43–4, 53–4
acetone 126
acids 18, 27, 35, 40, 44, 47–8, 56, 61, 77, 124, 129
formation by oxygen 55, 57
pH scale 129–30
affinity 45–6, 82, 91, 94, 96, 102
tables 45–6, 111
Agar, John 127, 131
Agricola, Georg 22
air 34, 40, 47, 49, 111
dephlogisticated (oxygen) 54
fixed (carbon dioxide) 53–5
inflammable (hydrogen) 53, 56
as mixed gases 60
air pump 48
alchemy 15–16, 22–5
Arabic 17–20
Greek 15–16
heritage of 24–5
separation of alchemy from chemistry 20, 22–4
alcohol 18, 27, 80
alkahest 39–40
ammonia 66
analysis 22, 36–7, 40, 44–5, 59, 71, 98, 111, 122, 133
dry (fire) 44, 110
 inorganic 72
organic 70
plant 43–4, 70
wet 46, 110
Annales de chimie 58
antibiotics 117
apothecaries 29, 40, 42, 87
apparatus 11, 15–17, 21, 24, 41, 46, 49, 52, 69, 70, 98, 106–7, 119, 129, 133
archaeology see chemistry
archaeus 35
Archimedes 10
argon 107
Aristotle 13, 18, 26, 36, 38
four causes of 14
four elements of 13, 35, 40, 44, 49
Arrhenius, Svante 103–4
Asimov, Isaac 96
Aston, Francis 120–2
astrology 12
atom bomb 125
atomic numbers 120
atomic weights 64, 66, 92–3, 97, 101, 120
atomicity see valence
atomism 13–14, 26–7, 34, 40, 59–61, 91, 113, 118, 122
aurifiction 11
Avogadro, Amadeus 76–7, 96–7, 102
azote (nitrogen) 55
azoth 30

B
Badische Anilin-und-Soda-Fabrik (BASF) 115, 128
Baeyer, Adolf von 87, 115–16, 124
balance, chemical 34, 39, 52, 61
Balmer, Johann 99
Barchusen, Johann 42
base 44, 48
Bartlett, Niels 108
Becher, Johann 49, 51
Beckman, Arnold 128–30
Beilstein, Friedrich 88, 109
benzene 81, 84–6
Bergman, Torbern 46
Bergwik, Staffan 109
Berthelot, Marcellin 114
Berthollet, Claude-Louis 58, 63, 91, 104
Berzelius, Jöns 41, 64, 66, 70–1, 73–4, 76–7, 93–4, 101, 123
Bhopal disaster 133
biochemistry 116, 131
biotechnology 117, 127
Biringuccio, Vannoccio 22
Black, Joseph 53–4, 93
blas 34
Boantza, Victor 43–4, 67
Boerhaave, Herman 33–4, 42, 111
Bohr, Niels 99, 108
boiling points 76, 78, 92
Boltzmann, Ludwig 95
Borodin, Aleksandr 123
Boyle, Robert 25, 33–4, 36, 38–41, 43, 48, 67
Boyle’s law 60, 100
bronze age 4–5, 8
Brown, Alexander Crum 84
Brunschweig, Hieronymus 28
Bunsen, Robert 87, 90, 92, 97–8, 115
Bunsen burner 98
Butlerov, Alexander 86

C
calcination 37, 48, 51–2
caloric (heat) 55, 61, 94
calx 52, 56
Cannizzaro, Stanislao 61, 66, 96
carbon and its allotropes 134–5
Carême, Marie-Antoine 43
Carlisle, Anthony 64
cathode rays 119
Cavendish, Henry 52–3, 56–7
Celsus, Aulus Cornelius 29
Charles’ law 100
chemiatria see iatrochemistry
chemical change 3, 12
chemical revolution 52, 66–7
Chemical Society of London 88, 108, 124
chemistry, its definition 2–3, 71, 81, 135–6
archaeological 5–6
French 41
industrial 131, 133–4
inorganic 46, 68, 96, 122
Japanese 89
mathematical 46, 95, 99, 109
medical 32
organic 41, 67, 68–90, 96, 108, 111, 122–4
organo-metallic 81, 87
paper 70–1, 112
physical 89–105, 107, 117, 123, 131
pneumatic 47–52, 54
20th-century 110–11, 133–6
chemophobia 125, 133
chrysopoeia (gold making) 15, 23, 39–40
chymistry, definition of 20
Clapeyron, Émile 100
classification 76, 78, 83, 97
Clausius, Rudolf 93–4, 100, 102
Coblentz, William 129
cohesion 45
combustion 33, 48–9, 52–5
oxygen theory of 49, 57
condenser 69
conferences, chemical 109
conservation of matter 34, 39
coordination theory 86
Corey, L. R. 134
corpuscularianism 18, 25, 27, 36–8, 40, 46 see also atomism
Couper, Archibald 83
Crick, Francis 117
Crookes, William 119
crucible 11
D
d’Ailly, Anthony 42
Dalton, John 59–64, 76, 91
law of partial pressures 61
Davy, Humphry 77
Decknamen 17, 39
Delbrück, Max 127
Democritus 15
Descartes, René 35, 40
Diana’s tree 23–4
Diels, Otto 116
diffusion 60
dissociation 94, 98, 103
distillation 9, 15, 20, 27–8, 31, 44
DNA 117
drugs 134
Du Clos, Samuel 43–4
Dulong, Pierre 93
Dumas, Jean-Baptiste 70, 72–4, 78
dyestuffs 6–8, 113, 127

E
Eirenaeus Philalethes 39
electrochemical theory 65, 73, 77, 79, 101, 112, 123
electrolysis 101
electronic theory 109, 123
elements, four Aristotelian 13
definition of 44, 58–60, 135
rare earths (lanthanides) 107
specific heats and 93
symbols 64, 70, 123
Empedocles 13
energy 91
of activation 104
free 95–6
enthalpy 94, 96
entropy 94–5
enzyme action 116
equations 65
equilibrium constant 105
equivalent weights 63
ethers (etherification) 81, 89, 102
eudiometer 52, 56
exhalations 14, 34
experiments, underdetermined 35, 49
explosives 126, 128

F
Faraday, Michael 101
fermentation 6, 126–7
Fieser, Louis 125
fire 6, 40
Fischer, Emil 87, 115–16, 124
Fischer, Hans 116
fixed proportions, law of 63
Fourcroy, Antoine 58–9, 68
Frankland, Edward 78, 81–2, 84, 87, 113–14
Freind, John 45
Fresenius, Carl 72
fullerenes 134
Furakawa, Yasu 132

G
Galen (Claudius Galenus) 31, 36
gas 34, 47, 49, 66
ideal 102–3
inert 56–7, 100, 107–8, 121
poisonous 125
Gay-Lussac, Joseph 65, 100, 112
Geber 18–19, 37
Geissler, Johann 119
Geoffroy, Étienne 45
Gerhardt, Charles 72–5, 79–81, 92
German Chemical Society 88
Gibbs, J. Willard 95
Glauber, Johann 23
glass 5–7, 9, 21–2, 27, 52, 114, 127
Gmelin, Leopold 87–8
Gmelin Institute 88, 109
Goethe, J. W. 1
gold 8, 10, 36, 39
Graham, Thomas 77
graphene 134–5
Greek science 12
groups see radicals
Guldberg, Cato 105
Guyton de Morveau, Louis-Bernard 53–4, 58

H
Haber, Fritz 125–7
Hales, Stephen 49–50, 53
Hammett, Louis 122–3
Harkins, William 121
helium, 98, 121
liquefaction of 96
Helmont, Joan Baptista 33–5, 47, 49
Henry, William 61
Heroditus 7
Hess, Germain 94
Hittorf, Johann 119
Hoff, J. H. van’t 86, 102–3
Hofmann, Wilhelm 88, 108, 112–14
Homberg, Wilhelm 44
homogeneity, problem of 26–7, 37, 46, 60, 91
homology 74–5, 92
Hooke, Robert 48
Horstmann, August 94
Hughes, Edward 123
humoral theory 31
Hunter, Michael 38
hydrogen 53, 56, 63
hydrogen sulphide 46, 106
hylomorphism 14
I
iatrochemistry 22, 31, 40, 44
indicators, chemical 40
indigo 8, 115
industry, chemical 125, 128
Ingold, Christopher 122–3
Hilda, wife of 123
instrumental revolution 110, 116, 128–31, 133
ions 102–4, 119–20
isomerism 70–1, 86, 91, 102, 111
isomorphism 75
isotopes 120–2, 125

J
Jābir ibn Hayyān 17–18
John of Rupescissa 27
Jonson, Ben 11

K
Kaliapparat (potash bulb apparatus) 70–1
Karlsruhe Congress (1860) 96
Kaye and Laby 93
Keill, John 45
Kekulé, Friedrich 2, 68, 81–6, 109, 115
dreams of 83, 85
kiln 9
kinetic theory of heat 60, 100
kinetics, chemical 104–5, 123
Kipping, Frederic 122
Kipps, P. J. 46
Kirchhoff, Gustav 98
Klein, Ursula 70
Kolbe, Hermann 78, 85, 107, 113–14
Kopp, Hermann 92

L
laboratories 41–3, 105–6, 114, 131, 134
Ladenburg, Albert 85
Landsteiner, Karl 116
language, chemical 16–17, 44, 58–9, 109
symbolic 16, 24, 62, 64
Laplace, Simon 55, 57
Lapworth, Arthur 122–3
Laurent, Auguste 73, 75, 79, 82
Lavoisier, Antoine 44, 47, 52–9, 61, 63, 67, 73, 94
Lewis, Gilbert N. 95, 123
Libavius, Andreus 20–1, 41
Liebig, Justus 15, 69–73, 77, 82, 105, 107, 112, 115, 123, 136
Linnaeus, Carl 58
Lockyer, Norman 98
Lovelock, James 133
Lucretius (Titus Lucretius Carus) 26

M
McEvoy, John G. 67
macrocosm and microcosm 12–13, 27, 31–2
magnall 34
Manchester Literary and Philosophical Society 59–60
Mary the Jewess 15–16
mass action, law of 63
mass spectrometer 120–1
materials science 111
Maxwell, J. C. 95
Mayow, John 47–9
mechanical philosophy 38, 43, 60
mechanism, reaction 89, 91, 105, 123–4, 131
medicines, chemical 27
Galenic 32, 44
Mendeleev, Dmitri 96, 120
mercury 18, 34, 37
metallurgy 4–5, 8–9, 11, 22, 27, 29, 31, 39, 42
metals 9, 14, 35
calcination of 37, 48
formation of 14, 18, 32
increase in weight 48, 52–4
metamorphosis see transmutation
metaphors, chemical 17, 20
meterorology 59–60
Meyer, Viktor 87
minima naturalis 18, 36, 60
models, atomic and molecular 69, 83, 85, 134
Moseley, Henry 120, 125
Multhauf, Robert 9

N
nanotechnology 135
napalm 125
natron 5
natural philosophy, 38, 47, 60
definition of 2
Needham, Joseph 11
Newman, William R. 18, 20
Newton, Isaac 17, 25, 38–40, 44–5, 49, 60, 67, 97
Nicholson, William 64
nitro-aerial theory 48
nitrogen, fixation of 124–5
Nobel Prize, chemistry 104, 115–17, 122–4
nomenclature reform 58, 64, 88–9, 109

O
Odling, William 81–2
Omnes, Kamerlingh 95–6
osmotic pressure 102–3
Ostwald, Wilhelm 104, 124, 126

P
packing fraction 122
Paracelsus (Theophrastus von Hohenheim) 27, 29–34, 36, 38
paraffins 75, 92
Pasteur, Louis 86
Paul of Taranto 18
Pauling, Linus 108
penicillin 117
periodic table 45, 96–7, 99, 107, 120, 122
periodicals, chemical 108–9
Perkin, William Sr 113–14
Perkin, William Jr 122
Petit, Alexis 93
pH scale 104
Pharmaceutical Society, London 105
pharmacy 24, 33, 42, 47, 68, 72, 111, 134–5
French 41, 44
philosophers’ stone 16, 24
phlogiston theory 49–54, 56–7, 59
physics 44–5, 67, 90
pigments 4–5, 7–8
Planck, Max 99
Plato 14
Pliny (Gaius Plinius Secundus) 5
pneumatic trough 49
polymers 117, 127, 132
pottery 6–7, 9
Pregl, Fritz 116
Priestley, Joseph 52–6, 59, 108
Principe, Lawrence M. 20
Proust, Joseph 63, 104
Prout, William 60
Prout’s hypothesis 92, 96, 98, 121

Q
quantum theory 99, 117, 131, 135
quinine 112–13, 117
quintessences 28

R
radicals, chemical (groups) 73–5, 78, 87, 112, 129
Ramsay, William 56, 107
Randall, Merle 95
Rayleigh, Lord (John W. Strutt) 107
reactions, named 114
Regnault, Henri 100
religion and science 30
remedies, chemical 31
respiration 49, 55, 57
Richter, Benjamin 61
Robinson, Robert 123
Röntgen, Conrad 119
Rose, Heinrich 46
Royal College of Chemistry 84, 112–13
Royal Institution of Great Britain 105
Royal Pavilion, Brighton 43
Royal Society of London 38
Rutherford, Ernest 61, 122
Rydberg, Johannes 99

S
sal mirabile (sodium sulphate) 23
sal nitrum (nitre) 48
salt
as a principle 27, 31, 41
as compounds 44, 58, 61, 101
Sendovogius 48
Sennert, Daniel 35–7
Shaw, Peter 111
Siegfried, Robert 3
signatures, doctrine of 31
societies, chemical 108–9, 124–5
Soddy, Frederick 61, 120
Sørensen, Soren 129
spagyrists 42
spectroscopy 97–9, 119, 123, 129
Stahl, Georg 49–50
standardization 77
Starkey, George 39–40
steric hindrance 87
Stockholm papyrus 10
stone age 4
structure, chemical 71, 83, 85–7, 89, 96, 114, 122, 134
sublimation 36–7
substitution 75
sulphur-mercury theory 14, 18, 27, 32, 37
symbols see elements
synthesis 1, 22, 36–7, 63, 71, 110–17, 122, 131–4
analytical synthetic experiments 112, 134

T
tautomerism 123
Teniers, Daniel 42
textbooks, chemical 95, 97, 111, 131
Thales 12
Theodoret of Cyrrhus 9
thermodynamics 91–6
1st law 93–4
2nd law 94–5
Tiedemann, Friedrich 88
Tomic, Sacha 67
Thomsen, Christian figure 1
Thomson, J. J. 119–20
Thomson, Thomas 61
Thomson, William 101
Thurneysser, Leonhard 23
Todd, Alexander 117
transduction 61
transformation see transmutation
transmutation 9, 12, 14, 16, 18, 20, 22, 26, 32, 34–5, 39, 91, 112–13, 118
transubstantiation 26
tria prima (three principles) 32–5, 40, 43–4
types, chemical 71, 74, 78–9, 81–3
Tyndall, John 11

U
University College, London 79, 89
University of Giessen 72
urea 71, 111
uric acid 112, 116
V
valence 81–2, 89, 96, 99, 122
ventilation 43, 105–6
vital principle 52, 71, 114
Volta, Alessandro 101

W
Waage, Peter 105
war
Korean 125
Vietnam 125
World War I 116, 124
World War II 125
Warburg, Otto 116
water 13, 35, 40, 45, 49, 56–7, 63, 65, 111
water bath (bain marie) 15
Watson, James 117
Watts, Henry 88
Weizmann, Chaim 126
Werner, Alfred 86
Whewell, William 2, 101
Whiteley, Martha 123, 128
whole number rule 121
Will, Heinrich 72, 87
Williamson, Alexander 79–81, 85, 87, 89, 94, 102, 104–5
willow tree experiment 35, 49
Windaus, Adolf 116
Wöhler, Friedrich 70–1, 87, 96, 111–12, 123
women in chemistry 110, 127–8
Woodward, Robert 117–18

X
xenon fluoride 108

Z
Zosimus of Panopolis 15–16
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