Pioneering Ideas for the Physical and Chemical Sciences Josef Loschmidt's Contributions and Modern Developments in Structural Organic Chemistry, Atomistics, and Statistical Mechanics Pioneering Ideas for the Physical and Chemical Sciences Josef Loschmidt's Contributions and Modern Developments in Structural Organic Chemistry, Atomistics, and Statistical Mechanics Proceedings of the Josef Loschmidt Symposium, held June 25 - 27, 1995, in Vienna, Austria Edited by W. Fleischhacker Institute for Pharmaceutical Chemistry University of Vienna Vienna, Austria and T. Schonfeld Institute for Inorganic Chemistry University of Vienna Vienna, Austria Springer Science+Business Media, LLC Library of Congress Catalogin g in Publication Data Pioneering ideas for the physical and chemical sciences: Josef Loschmidt's contributions and modern developments in structural organic chemistry, atomistics, and statistical mechanics / edited by W. Fleischhacker and T. Schonfeld. p. cm. "Proceedings of the Josef Loschmidt Symposium, held June 25-27, 1995, in Vienna, Aus tria"—T.p. verso. Includes bibliographical references and index. 1. Loschmidt, J.—Congresses. 2. Organic compounds—Structure—Congresses. 3. Statisti cal mechanics—Congresses. I. Fleischhacker, W. II. Schonfeld, Thomas, 1923- . III. Josef Loschmidt Symposium (1995: Vienna, Austria) QD22.L85P56 1997 547.122—dc21 97-28671 CIP Proceedings of the Josef Loschmidt Symposium, held June 25-27,1995, in Vienna, Austria ISBN 978-1-4899-0270-2 ISBN 978-1-4899-0268-9 (eBook) DOI 10.1007/978-1-4899-0268-9 © Springer Science+Business Media New York 1997 Originally published by Plenum Press, New York in 1997 Softcover reprint of the hardcover 1st edition 1997 http://www.plenum.com 1098765432 1 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This volume presents the contributions delivered at the "Josef-Loschmidt-Sympo sium," which took place in Vienna, June 25-27, 1995. The symposium was arranged to honor Josef Loschmidt one hundred years after his death (8 July 1895), to evaluate the sig nificance of his contributions to chemistry and physics from a modem point of view and to trace the development of scientific fields in which he had done pioneering work. Loschmidt is widely known for the first calculation of the size of molecules (1865/66), which also led to values for the number of molecules in unit gas volume and for the mass of molecules. With critical analyses of problems in statistical physics he made important contributions to the development of that field, "Loschmidt's paradoxon" continuing to be a point of departure for present day studies and discussions. For decades there was little awareness that Loschmidt was a pioneer in organic struc tural chemistry. Only in recent years has Loschmidt's first scientific publication "Chemis che Studien I", published in 1861, become more widely known and it is now recognized that with his ideas on the structure of organic molecules he was greatly ahead of the chemists of that time. The papers in these proceedings are arranged in three sections: l. Organic structural chemistry (Chapters 1-12). 2. Physics and physical chemistry (Chapters 13-26). 3. Loschmidt's biography, Loschmidt's world (Chapters 27-33). The plenary lectures, which were delivered by scientists of great international renown, mostly coming from abroad, are presented at the beginning of Sections 1 and 2. These contributions and those of other conference participants from abroad were a great and highly appreciated honor for the Austrian scientific community. The venue of the Symposium was the University of Vienna. where Loschmidt was pro fessor from 1868 up to his retirement in 1891. The lectures were held in the traditional main building of the University, opened in 1884, and in the newly erected Centre of Pharmacy. It is hoped that the Josef-Loschmidt-Symposium of 1995 and these proceedings will not conclude the efforts to evaluate the work and the personality of this great scientist but will give impetus for further studies along the lines indicated here. * * * Great assistance for the preparation of these proceedings has been rendered by Erich Hrnecek, Robert Rosner, and David Westacott. W. Fleischhacker T. SchOnfeld v CONTENTS Organic Structural Chemistry I. The Significance of the Hydrogen Bond for Physiology: Aromatic Rings as Hydrogen Bond Acceptors* ..................... . Max F. Perutz 2. Natural Product Structure Elucidation: 1950 ~ 2000* 15 Carl Djerassi 3. Conformational Analysis: The Elevation of Two-Dimensional Formulas into the Third Dimension* ...................................... 25 Ernest L. Eliel 4. Thoughts and Experiments on a Chemical Etiology of Nucleic Acid Structure* ........................................ 41 Albert Eschenmoser 5. Loschmidt's Graphic Formulae of 1861: Forerunners of Modern Structural Formulae* 65 Alfred Bader 6. Spheres from Dalton to Loschmidt: Insights into the Ways of Thinking ofa Geniust 81 Gunter P. Schiemenz 7. 10sefLoschmidt's Last Scientific Publication: "Stereochemische Studien r,t . . . 89 Christian R. Noe 8. Richard AnschUtz, Archibald Scott Couper, and 10sefLoschmidtt 101 Alfred Bader 9. Organic Chemistry in Austria and Loschmidt's "Chemische Studien" t 109 Robert Rosner 10. Loschmidt and Venn: Symbolic Logic in Chemistry and Mathematicst 119 Ian D. Rae vii viii Contents II. Loschmidt's Achievements and Shortcomings in Elucidating the Structure of Organic Molecules: .............................. 129 Raluca-Silvia Moraru and Edwin Scheiber 12. Configurational Stability and Reactions of Benzylic Carbanions with an Acyloxy or Dialkylphosphoryloxy Substituentt .••....•..•••.••..• 133 Friedrich Hammerschmidt and Achim Hanninger Physics and Physical Chemistry 13. The Precise Determination of Loschmidt's Number (Avogadro Constant) as a Step towards a Redefinition of the SI Unit of Mass'" .............. 139 Peter Becker 14. Loschmidt's Reversibility Argument and the H-Theorem* 153 Herbert Spohn 15. The Arrow of Time: Statistics and the Universe* . . . . . . . . . . . . . . . . . . . . . . . . . . 159 Hermann Bondi 16. Stability of Matter'" 163 Walter Thirring 17. Visualization and Nanomanipulation of Molecules in the Scanning Tunnelling Microscope'" ........................... 179 Wolfgang M. Heckl 18. Considerations about the "Constitution of the Ether"t 193 Viktor Gutmann 19. Four Papers by Loschmidt on the State of Thermal Equilibriumt ••.••..••••.. 199 Dieter Flamm 20. Loschmidt's Papers "Experimental-Untersuchungen fiber die Diffusion von Gasen ohne Porase Scheidewiinde" t . . . . . . . . . . . . . . . . 203 Othmar Preining 21. The Periodic System of the Elements and Prout's Hypothesis: Use and Interpretation by Josef Loschmidtt ............... . . . . . . . . .. 207 Michael Jenner 22. Josef Loschmidt and the Reality of Molec uie st ........................... 217 Henk Kubbinga 23. Loschmidt's Article "On the Size of Air Molecules" and Subsequent Work on Related Aspects of Atomistics t .. . . . . . . . . . . . . . . . . 223 Nikolaus Bachmayer and Thomas SchOnfeld 24. Microscopic Time-Reversibility and Macroscopic Irreversibility- Still a Paradox?t .............................................. 233 Harald A. Posch, Christoph Dellago, William G. Hoover, and Oyeon Kum Contents ix 25. Imaging of Atomic Structures of Metals and Alloys by High Resolution Transmission Electron Microscopy t . . . . . . . . . . . . . . . . . 249 H. Peter Karnthaler, Thomas Waitz, Bernhard MingIer, and Christian Rentenberger 26. Trace Gas Analysis with Integrating Spheres t . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257 Heinz Schimpl, Heinrich Hess, Anton Ziegler, and Stefan Brandes Loschmidt's Biography, Loschmidt's World 27. Josef Loschmidt - Some Biographical Remarks t 263 Hannelore Sexl 28. From Curiosity to Passion: Loschmidt's Route from Philosophy to Natural Sciencet 269 Peter M. Schuster 29. Scientific Discussion and Friendship between Loschmidt and Boltzmannt 277 Dieter Flamm 30. JosefLoschmidt's Economic Ideas: Protective Tariffs and National Welfaret 283 Fritz Weber 31. Chemical Education in the Habsburg Monarchy's Universities and Technical Colleges around 1861 t ......................................... 289 Alois Kembauer 32. The Development of Chemical Formulae and Equations: An Evaluation of School Textbooks of the Period 1830-1871 : 297 Kurt Kolli 33. The Leading Chemical Company in the Habsburg Empire: "Der Osterreichische Verein flir chemische und metallurgische Produktion zu Aussig a.d. Elbe" t .•.•......•.•....•...•.......•... 30 I Klaus Oberhurnmer Appendix A. The Scientific Publications of J. Loschmidt 307 Appendix B. The Josef-Loschmidt-Symposium 1995 .......................... 309 Contributors ........................................................... 311 Index. .. . .. . .. . .. . .. . .. . .. . . .. . . . .. .... .. .. .. .. . .. . .. . .. . .. . .. . .. . . ... 315 ·Plenary lecture t Sectional lecture : Poster presentation Pioneering Ideas for the Physical and Chemical Sciences Josef Loschmidt's Contributions and Modern Developments in Structural Organic Chemistry, Atomistics, and Statistical Mechanics