The Chemistry of Relations The periodic table examined through the lens of C.S. Peirce’s philosophy Christopher John Campbell University College London Department of Science and Technology Studies Submitted for the degree of Doctor of Philosophy in History and Philosophy of Science September 2017 Declaration I, Christopher John Campbell, confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. 2 Abstract This thesis explores Charles Peirce’s reception of Dmitri Mendeleev’s periodic arrangement of the chemical elements, the further impact of chemistry on Peirce’s philosophy, such as his phenomenology and diagrammatic reasoning, and the relations between Peirce's theory of iconicity and Mendeleev's periodic table. It is prompted by the almost complete absence in the literature of any discussion of Peirce’s unpublished chemistry manuscripts and the lack of attention given to the connections between Peirce’s early study of chemistry and his later philosophy. This project seeks to make a contribution to this otherwise neglected area of Peirce scholarship. 3 Acknowledgements I should like to acknowledge and thank my primary supervisor, Dr Chiara Ambrosio, for the tremendous support and guidance she has offered throughout this project: her energy, enthusiasm and scholarship have been nothing short of inspirational. Furthermore Chiara has always given most generously of her time, particularly in using her own research periods at Harvard’s Houghton Library to collect images of Peirce’s ‘chemistry manuscripts’. These unpublished manuscripts proved to be a most valuable primary source for this project. I received valuable comments in the early stages of the project from Professor Jon Agar, Dr Mats Bergman and Dr Simon Werrett and would like to thank them for their time and guidance. Finally, I have benefitted greatly by belonging to such a vibrant PhD community and from the many discussions held both informally and at various seminars, discussion groups and conferences. 4 Table of Contents Introduction Chapter 1 The Chemistry of Relations: Peirce and experiments with diagrams 1.1 Introduction………………………………………………………………………………………….. 19 1.2 Josiah Cooke: the rejuvenation of the chemistry curriculum at Harvard.. 21 1.3 Josiah Cooke’s laboratory……………………………………………………................... 25 1.4 Josiah Cooke’s reforms to the mathematical demands of chemistry…….. 28 1.5 Josiah Cooke’s text books………………………………………................................. 31 1.6 Josiah Cooke’s treatment of relations………………………............................. 35 1.7 Charles Peirce – relations between the chemical elements and their atomic weights.......................................................................................... 39 1.8 Josiah Cooke’s treatment of crystallography – a case of diagrammatic reasoning……………………………………………………………………………………………….. 42 1.9 Chemistry, diagrams and logical relations………………………….................... 44 1.10 Conclusion………………………………………………………………………….………………… 48 Chapter 2 Charles Peirce – a nineteenth century chemist 2.1 Introduction…………………………………………………………………………………………… 50 2.2 Nineteenth century atomism……………………………………………………………… 52 2.3 Peirce’s ‘The Chemical Theory of Interpenetration’ (1863)…………………… 61 2.4 Peirce’s ‘The Pairing of the Elements’ (1869) – classifying the elements according to their atomic weights……………………………............................. 78 2.5 The relationship between Peirce’s chemistry and his philosophical writings of the same period……………………....................…………………………… 81 2.6 Conclusions……………………………………..…………………………………………………… 85 Chapter 3 Dmitri Mendeleev and Charles Peirce – the relations between chemists, chemistry and philosophy 3.1 Introduction……………………………………………………………………………………….... 86 3.2 Mendeleev and Peirce on relations…………………………………………………....... 90 3.3 Peirce’s Reception of Mendeleev’s Periodic Table………………………………… 95 3.4 Phaneroscopy and the Periodic Table……………………………………………………. 105 3.5 Nineteenth century chemical valency and graphical formulae………………. 107 3.6 Peirce’s use of valency as a means of explaining his phenomenology…… 117 5 3.7 Conclusions………………………………………………………………………..…………………. 123 Chapter 4 Dmitri Mendeleev’s inquiry into the chemical elements and Peirce’s theory of iconicity 4.1 Introduction………………………………………………………………………………………….. 125 4.2 Peirce’s three orders of signs………………………………………………………………… 126 4.3 Examples of iconicity in chemistry………………………………………………………… 127 4.4 Arguments against iconicity……………………………………………………………........ 132 4.5 Mauricio Suárez’s approach to representation……………………………………… 137 4.6 Iconicity and paper tools……………………………………………………………………….. 145 4.7 Three aspects of iconicity and the process of inquiry……………………………. 151 4.8 Iconicity and the early periodic table…………………………………………………… 154 4.9 The first published form of Mendeleev’s system of elements (1869)……. 159 4.10 Conclusion……………………………………………………………………………………………. 162 Chapter 5 The Periodic Table and Iconic Robustness - novel questions and new predictions in the light of nature’s resistance 5.1 Introduction……………………………………………………………………..…………………… 163 5.2 The periodic table – nature strikes back……………………………………………..... 163 5.3 An epistemic approach to facing nature’s resistance…………………………….. 166 5.4 The rare earth elements……………………………………………………………............. 169 5.5 The noble gases……………………………………………………………………………..……… 179 5.6 Conclusion…………………………………………………………………………………………….. 195 Chapter 6 The Periodic Table: iconicity as an alternative view from practice to the debate around accommodation and prediction 6.1 Introduction………………………………………………………………………………………….. 197 6.2 Prediction and accommodation…………………………………………………………….. 199 6.3 The accommodation-prediction debate and the periodic table……………. 203 6.4 Accommodation and prediction: re-characterizing the arguments in terms of practice……………………………………………………………………………………. 213 6.5 Bringing together aspects of ‘accommodation’ and ‘prediction’ from the view point of Mendeleev’s representational practice………………............... 221 6.6 Conclusion…………………………………………………………………………………………….. 224 Conclusions....................................................................................................... 226 Bibliography…………………………………………………………………………………………………. 231 6 Table of Figures Figure 1: Preparation of nitric acid, from Stöckhardt’s Principles of 32 Chemistry Figure 2: Calculating the yield of nitric acid from the reaction between 32 potash nitre (potassium nitrate) sulphuric acid, from Cooke’s Chemical Problems and Reactions to Accompany Stöckhardt’s Elements[Principles] of Chemistry Figure 3: Diagram of the tetrakis-hexahedron crystalline form, from 46 Cooke’s Chemical Physics Figure 4: Diagrams of crystal systems, from Cooke’s Chemical Physics 47 Figure 5: Plate IV, from Dalton’s A New System of Chemical Philosophy 54 Figure 6: Testing Prout’s Law as modified by Dumas, from Peirce’s The 75 Chemical Theory of Figure 7: Differences between atomic weights determined 76 experimentally and values in accord with Prout’s hypothesis Figure 8: Peirce’s arrangement of the chemical elements, from ‘The 79 Pairing of the Elements’ Figure 9: Peirce’s attempt to find a mathematical relation between the 97 atomic weight and the succession of chemical elements according to Mendeleev’s system Figure 10: Peirce’s investigation into the atomic weights of the chemical 99 elements when arranged by periods Figure 11: Peirce’s atomic weight calculations 101 Figure 12: The rare earth elements 102 Figure 13: The graphical formula for alcohol (ethanol) 108 Figure 14: The graphical formula for succinic acid 109 Figure 15: Kekulé’s representations of the benzene molecules 110 Figure 16: Frankland’s graphical representations of atoms 111 Figure 17: Frankland’s graphic formula for succinic acid. 111 Figure 18: Cooke’s graphical formulae for water, alcohol and acetic acid 112 Figure 19: Cooke’s graphical formulae for the hydrocarbons propane, 112 propene and propine Figure 20: Peirce’s sketches showing iron as being both trivalent and 114 octavalent 7 Figure 21: Frankland’s graphical formulae showing the course of reaction 115 between marsh gas (methane) and chlorine Figure 22: Diagrams illustrating the valencies of hydrogen, oxygen, 117 nitrogen and carbon atoms Figure 23: A record of the claim Peirce made in 1896 for the design of a 118 generator to generate acetylene and other gases Figure 24: A schematic outline for the production of acetylene 119 Figure 25: Peirce’s explanation of distinctions of form within the 121 indecomposable elements of the phaneron Figure 26: Peirce’s explanation of distinctions founded upon form 123 compared to those founded on matter Figure 27: The chemical reduction of nitrobenzol to aniline 128 Figure 28: Graphical formulae of nitrobenzol and aniline 128 Figure 29: Isomeric forms of fumaric and maleic acids 130 Figure 30: ‘Lighthouse Hill’ by Edward Hopper 132 Figure 31: Isomorphic graphs 140 Figure 32: Heisenberg’s uncertainty relation 141 Figure 33: Diagrammatic representations of the benzene molecule 142 Figure 34: Diagrammatic representation of the cis-platin molecule 143 Figure 35: Berzelian formulae for alcohol, ether and ‘sweet wine oil’ 148 Figure 36: The first of Mendeleev’s two incomplete tables of February 156 17th, 1869 Figure 37: The first of Mendeleev’s two incomplete tables of February 157 17th, 1869 Figure 38: Mendeleev’s first table as a single sheet handout, 17th 159 February 1869 Figure 39: Mendeleev’s first table as a single