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The Physico-Chemical Nature of the Chemical Bond: Valence Bonding and the Path of Physico-Chemical Emergence

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The Physico-Chemical Nature of the Chemical Bond: Valence Bonding and the Path of Physico-Chemical Emergence The physico-chemical nature of the chemical bond: valence bonding and the path of physico-chemical emergence by Martha Lynn Harris A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Graduate Department of the Institute for History and Philosophy of Science and Technology University of Toronto © Martha Lynn Harris 2008 Library and Archives Bibliothèque et Canada Archives Canada Published Heritage Direction du Branch Patrimoine de l’édition 395 Wellington Street 395, rue Wellington Ottawa ON K1A 0N4 Ottawa ON K1A 0N4 Canada Canada Your file Votre référence ISBN: 978-0-494-57876-6 Our file Notre référence ISBN: 978-0-494-57876-6 NOTICE: AVIS: The author has granted a non- L’auteur a accordé une licence non exclusive exclusive license allowing Library and permettant à la Bibliothèque et Archives Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par télécommunication ou par l’Internet, prêter, telecommunication or on the Internet, distribuer et vendre des thèses partout dans le loan, distribute and sell theses monde, à des fins commerciales ou autres, sur worldwide, for commercial or non- support microforme, papier, électronique et/ou commercial purposes, in microform, autres formats. paper, electronic and/or any other formats. The author retains copyright L’auteur conserve la propriété du droit d’auteur ownership and moral rights in this et des droits moraux qui protège cette thèse. Ni thesis. Neither the thesis nor la thèse ni des extraits substantiels de celle-ci substantial extracts from it may be ne doivent être imprimés ou autrement printed or otherwise reproduced reproduits sans son autorisation. without the author’s permission. In compliance with the Canadian Conformément à la loi canadienne sur la Privacy Act some supporting forms protection de la vie privée, quelques may have been removed from this formulaires secondaires ont été enlevés de thesis. cette thèse. While these forms may be included Bien que ces formulaires aient inclus dans in the document page count, their la pagination, il n’y aura aucun contenu removal does not represent any loss manquant. of content from the thesis. The physico-chemical nature of the chemical bond: valence bonding and the path of physico-chemical emergence Martha Lynn Harris Doctor of Philosophy, 2008 Institute for History and Philosophy of Science and Technology University of Toronto Abstract Through the development of physical chemistry and chemical physics over the late-nineteenth and early-twentieth centuries, the relationship between physics and chemistry changed to create a broad interdisciplinary framework in which chemists and physicists could make contributions to problems of common value. It is here argued that evolving disciplinary factors such as physical and chemical responses to the atomic hypothesis, the nature of disciplinary formation in Germany and the United States, the reception of quantum mechanics within physics and chemistry, and the application of quantum mechanics to the problem of chemical bonding by physicists and chemists, formed the chemical bond into a physico-chemical theory. In the late nineteenth-century context of early physical chemistry, the chemical bond was known as a physical link between atoms, which could not be studied by chemical means because of the lack of an adequate atomistic framework. Both chemists and physicists broadly accepted the atomistic hypothesis following the discovery of the electron at the turn of the twentieth century, which afforded theoretical study of chemical bonding. Between 1916 and 1919, Gilbert N. Lewis and Irving Langmuir proposed the valence bond to be a pair of electrons shared between two atoms, within the context of a ii cubic model of the atom. However, the lack of a physical mechanism for the shared electron pair prevented the formation of a fully physico-chemical view of bonding. In 1927, physicists Walter Heitler and Fritz London showed the stability of the valence bond was caused by the wave mechanical phenomenon of resonance. Chemist Linus Pauling extended their treatment of the valence bond to a theory of structural chemistry in The Nature of the Chemical Bond. His synthesis of the physical and chemical views, his value as a physico-chemical researcher during the 1930s, and the research of his contemporaries John Slater and Robert Mulliken show that a true physico-chemical blend was only realized within the amorphous discipline of chemical physics. Finally, it is seen that this interdisciplinarity of chemical bonding and its supporting framework force a re- evaluation of the reductionist criteria, and a re-definition of the chemical bond as a physico-chemical work. iii Acknowledgements I thank my parents, Dr. William Edgar Harris and Dr. Gretchen Luft Hagen Harris, for the many ways they have supported me during my undergraduate and graduate education. This thesis would not have been possible without their support and guidance. I thank my sister, Glenna Catherine Harris, for her support as a roommate, friend, and fellow doctoral candidate during the writing process. Thank you to my grandfather, Dr. Walter Edgar Harris, for sharing conversations about his experiences as a chemist, graduate student, and teacher as I wrote this thesis. Thank you to my aunt, Margaret Harris, for sharing her interest in the history and philosophy of science and tales of her graduate studies at the University of Toronto, and for always asking me for the latest in pop culture. I thank my committee members Dr. Margaret Morrison and Dr. Craig Fraser for their support during meetings, for their reading of earlier drafts of this thesis, and for their instrumental guidance during preparation for my doctoral specialist exam that formed the basis of this project. Thank you to Dr. Mary Jo Nye, Dr. Anjan Chakravartty and Dr. Donald Cotter, for their advice and comments on an earlier paper on reductionism and the chemical bond, which has been incorporated into this thesis. Thank you to friends and fellow students, Charissa Varma, Victor Boantza, Shana Worthen, Marionne Cronin, Jenny Crnac, Trevor Buttrum, Gill Gass, Isaac Record, Brigit Ramsingh, and the students of the IHPST common room for providing many welcome conversations, distractions and moral support during my time in Toronto. And finally, I thank my supervisor, Dr. Trevor Levere, for his unfailing support and guidance during my M.A. and Ph.D. studies, and for teaching me about many things. iv Table of Contents List of Figures................................................................................................................... vi Introduction....................................................................................................................... 1 Chapter 1: Physical chemistry and the origins of valency.......................................... 12 1. Physical chemistry and the Ionists. ................................................................................... 12 2. Nineteenth-century debates and the problem of the atom .............................................. 24 3. Growth of a new discipline: the institutional framework................................................ 37 Chapter 2: Atomism, chemical autonomy and the valence bond:.................................. Lewis, Langmuir and the cubic atom............................................................................ 48 1. Introduction......................................................................................................................... 48 2. The cubic atom and early valence bond theory................................................................ 51 2.1 Lewis’ academic influences .......................................................................................................... 51 2.2 Lewis, the atom, and the molecule................................................................................................ 57 3. Acceptance of the cubic atom............................................................................................. 68 3.1 Langmuir and the octet theory of valence..................................................................................... 68 3.2 Priority dispute: Lewis and the reception of the octet theory........................................................ 76 4. Emergence of chemical autonomy..................................................................................... 79 Chapter 3: Seeds of emergence: wave mechanics meets the valence bond................ 88 1. Introduction......................................................................................................................... 88 2. Wave mechanics meets the chemical bond ....................................................................... 89 2.1 Wave mechanics and the Heitler-London treatment ..................................................................... 89 2.2 The physico-chemical community responds................................................................................. 97 3. Pauling’s early career ....................................................................................................... 104 3.1 The ‘boy professor’ meets physical chemistry............................................................................ 104 3.2 Atoms in the grasp: physical chemistry meets the new physics.................................................. 109 3.3
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