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Author: qdsa

Conventionalities in formula writing

Introduction

Chemical formulas, those small icons which chemists are wont to scribble in their notebooks and in odd places, such as the back of an envelope, and which to the general public have become emblems of their profession, are an excellent topic for history. These artefacts remain today tools for communication within the community of chemists. They continue serving as didactic instruments in teaching. The establishment of an individual formula for a chemical compound or a substance chronicles the laboratory methods, both routine and specific, which came into play in order for it to be written down and to assume the status of the analog of a word, to be stored within the growing lexicon of chemistry.

When addressing this topic, the historical narrative, besides its usual needs for accuracy and for an unerring sense of the strange and original taste of the bygone, demands the twin crutches of philosophical and linguistic inquiries. I wish to provide these complements if not in full, at least in a manner suggestive of some of the main issues.

I shall concern myself with the period of consolidation, when formulas entered the language of organic chemistry and started becoming sterotyped, the approximate period 1865-1905. 1 Why choose such a periodization? Because it brackets, approximately, the birth of the modern chemistry journal, JACS was started in 1879, and that of the modern comprehensive repertory of new chemical compounds, Chemical Abstracts were launched in 1907. Kekulé announced in 1865 his cyclic structure of benzene. The Chemical Society published in London, in 1882, Nomenclature and Notation, the first guidelines for establishing systematic and uniform practice. And the American Chemical Society followed suit in 1884 by establishing its Committee on Nomenclature and Notation. The international conference convened in Geneva in 1892 established norms for chemical nomenclature. 2 And Alfred Werner, in 1895, gave a systematic nomenclature for coordination complexes. Key milestones in the history of molecular formulas – so-called “structural formulas”; I favor the adjective “molecular” since the meaning of “structural” has changed considerably over the twentieth century – include the serendipitous synthesis of mauveine (1857), the first synthesis of alizarin (1868) and the identification of ibogaine (1905); Gomberg first free radical appeared in print in 1900. The forty years 1865-1905 were thus for molecular formulas of organic compounds those of the rise in their practical use, of their standardization and also of the first challenges to the rules governing them.

As always in history of science, the risk of Whig history lurks at every corner of the retrodictive narrative. The danger is to read into the structural formulas, as they were used at the end of the nineteenth-beginning of the twentieth century, meanings which they had yet to acquire in the post-Gilbert N. Lewis and post-Linus C. Pauling eras. Examples of such potential anachronisms are: (i.) viewing benzene rings as ipso facto synonyms of “aromaticity;” (ii.) reading double bonds as implying shorter and stronger interatomic linkages; (iii.) interpreting loss of a water molecule in a dehydration process as a thermodynamic driving force for the observed conversion. The eerie superficial similarity of these late nineteenth formulas to our early twenty-first century formulas can easily become misleading.

Ferrocene

FERROCENE: IRONCLAD HISTORY OR RASHOMON* TALE?

Pierre Laszlo and Roald Hoffmann

A critical stance is essential to science. Proving other people wrong is a favorite private and public satisfaction — there is nothing some people like better. But, excess zeal discounted, doubt serves as a powerful impulse to the advancement of knowledge. We document it here with the discovery of the structure of ferrocene, a story which also plays up the virtue of the spoken word. [1] We base it on various published (and most fragmentary) accounts, supplemented with some very helpful correspondence from colleagues.

Diborane story

Just as with ferrocene, 1 the formula first written for diborane B2H6 was orthodox, in conformity with the usual paradigmatic rules regarding molecular structure. And it was wrong. Correcting the mistake showed an extremely unusual bonding picture for the molecule. Just as in the ferrocene case, it opened up a whole new chapter of chemistry, later recognized with the award of a Nobel prize to William N. Lipscomb in 1976 for “his studies on the structure of boranes illuminating problems of chemical bonding.”

I shall highlight here only a few episodes from the diborane story. In 1937, a former student of Linus Pauling, Simon H. Bauer – incidentally he is still active in research at Cornell, at the age of 88 – applied the technique of electron diffraction, a tool which he had learned to use at Caltech with Pauling, to diborane. He found and he reported a structure analogous to that of ethane, which therefore he wrote as H3B-BH3. 2 In 1942, Bauer reiterated his contention of the ethane-like structure for diborane. 3 At the same time of the early 1940s, H.I. Schlesinger, a chemistry professor at the University of Chicago, was also working on boron compounds. One of the reasons was his involvement in the Manhattan Project: it was thought that an isotope separation could be devised for uranium using such derivatives. In any case, Schlesinger was very much interested in the structure of diborane.

Protean

Science often advances upon willful transgression of a seeming interdiction. Examples which leap to a chemist’s mind are noble gas compounds, strained hydrocarbons such as tetrahedrane, activation (by organometallics) of even methane, and, to mention just one brilliant, more recent achievement, inclusion of an allene within the confines of a six-membered ring while preventing its conversion into a benzenoid. Such feats put all the cunning of a scientist into coaxing and, yes, coercing the system at hand to obey instructions from one’s daring imagination. As always, it is hard. Not for nothing is our playroom called a laboratory. And when the task is done and the time arrives to convey to others (who might not be privy to the anguish of the work) all that struggle and the majesty of the achievement, the scientist quite naturally lapses into metaphor. One such, founded in male 19th century language as much as in history, is some more or less prurient variant of “Unveiling the Secrets of Nature.” Another, evoking the thorny, twisted path to understanding and the long hours of toil in the laboratory, is “Wrestling with Nature.”

Circulation of concepts

Abstract

A major obstacle to chemistry being a deductive science is that its core concepts very often are defined in circular manner: it is impossible to explain what an acid is without reference to the complementary concept of a base. There are many such dual pairs among the core concepts of chemistry. Such circulation of concepts, rather than an infirmity chemistry is beset with, is seen as a source of vitality and dynamism.

Playing with molecular models

Abstract

Any serious study of molecular models has to mention play as a component essential to their use. A research chemist will use them not unlike a young child playing with a toy: exploring their features, trying out their resilience, probing their innards, tinkering, day-dreaming, and finding out in those ways new avenues for adventures of the mind and in the laboratory. Reasons for such assimilation of a molecular model to a toy are given and assessed critically.