Mendeleev To Oganesson A Multidisciplinary Perspective On The Periodic Table

2018·6 MB·English

by  Eric Scerri, Guillermo Restrepo

Mendeleev to Oganesson

Mendeleev to Oganesson
A Multidisciplinary Perspective on the
Periodic Table
Edited by eric scerri and
guillermo restrepo
1
1
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© Eric Scerri and Guillermo Restrepo 2018
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Library of Congress Cataloging-in-Publication Data
Title: Mendeleev to Oganesson : a multidisciplinary perspective on the
periodic table.
Description: New York, NY : Oxford University Press, [2018] | Includes index.
Identifiers: LCCN 2017034854 | ISBN 9780190668532
Subjects: LCSH: Periodic table of the elements. | Periodic law. |
Chemistry—History—19th century. | Chemical elements.
Classification: LCC QD467 .M4294 2018 | DDC 546/.8—dc23 LC record available at
https://lccn.loc.gov/2017034854
9 8 7 6 5 4 3 2 1
Printed by Sheridan Books, Inc., United States of America
CONTENTS
Foreword by Roald Hoffmann vii
Introduction 3
CHAPTER 1 Heavy, Superheavy . . . Quo Vadis? 8
Paul J. Karol
CHAPTER 2 Nuclear Lattice Model and the Electronic
Configuration of the Chemical Elements 43
Jozsef Garai
CHAPTER 3 Amateurs and Professionals in Chemistry: The Case
of the Periodic System 66
Philip J. Stewart
CHAPTER 4 The Periodic System: A Mathematical Approach 80
Guillermo Restrepo
CHAPTER 5 The “Chemical Mechanics” of the Periodic Table 104
Arnout Ceulemans and Pieter Thyssen
CHAPTER 6 The Grand Periodic Function 122
Jan C. A. Boeyens
CHAPTER 7 What Elements Belong in Group 3 of the Periodic
Table? 140
Eric R. Scerri and William Parsons
CHAPTER 8 The Periodic Table Retrieved from Density
Functional Theory Based Concepts: The Electron
Density, the Shape Function and the Linear Response
Function 152
Paul Geerlings
CHAPTER 9 Resemioticization of Periodicity: A Social Semiotic
Perspective 177
Yu Liu
CHAPTER 10 Organizing the Transition Metals 195
Geoff Rayner-Canham
CHAPTER 11 The Earth Scientist’s Periodic Table of the Elements
and Their Ions: A New Periodic Table Founded on
Non-Traditional Concepts 206
L. Bruce Railsback
CHAPTER 12 The Origin of Mendeleev’s Discovery of the Periodic
System 219
Masanori Kaji
CHAPTER 13 Richard Abegg and the Periodic Table 245
William B. Jensen
CHAPTER 14 The Chemist as Philosopher: D. I. Mendeleev’s
“The Unit” and “Worldview” 266
Michael D. Gordin
CHAPTER 15 The Philosophical Importance of the Periodic
Table 279
Mark Weinstein
Index 305
vi | Contents
FOREWORD
the icon of our profession has remained strong and deeply useful because
of its nonreducible chemical nature, because of its flexibility in both definition
and utilization. And it remains alive not only because of its essence, the way it
organizes our elements, but also because of the natural challenges it provokes.
Let me explain.
The periodic table has evolved as chemistry has evolved; its meanings are
now multiple. That is its strength, not a putative weakness. Useful chemical
concepts evolve by appropriation. So the line of Kekulé’s time, a symbol for a
then-unknown persistent connection between atoms, in time was assigned the
meaning of a shared Lewis pair. This was further coopted by Pauling to stand
for a covalent wavefunction. In a similar way, the periodic table of Mendeleev,
which began as a summary of valence regularities of the elements in combina-
tion, was reinterpreted in the new atomic theory of Bohr (and by the quantum
chemistry that followed) as the outcome of a sequential, quantum-mechani-
cally determined filling of atomic orbitals. The table is alive because it can
accommodate alternative interpretations that are of chemical utility, that sug-
gest similarities and fruitful substitutions—in chemical reactions to be tried,
in physical properties to be desired.
And what do I mean by the challenges it engenders? There were the initial
ones, of atomic weights to be believed or not. Quandaries to be added on to, by
asking why a table of chemical proclivities in compounds should have any-
thing to do with filling the orbitals of isolated atoms. Should we, for instance,
worry or not about the fact that the electronic configurations of the ground
states of isolated Ni, Pd, Pt atoms are all different? No, for there is no ambigu-
ity in the configuration taken on by the most common valence state, II, of
those atoms in their compounds. And yes, we should think (if not worry) about
what that ambiguity in Ni, Pd, Pt ground state atomic configurations tells us of
how close the nd, (n-1)s levels are in the three transition series,
I was asked once by Chemical & Engineering News to pick an element to write
about. I picked silicon. Not because I had done many calculations on silicon-
containing compounds, but because . . . it was to me the most obvious example
of that essential tension of identity, of similarity and difference, of being the
same and not the same. Of course, just as the periodic table implies, silicon
forms analogues of methane, ethane, and ethylene. And the Si-Si bond length
in H Si=SiH is shorter than in HSi-SiH, just as in the carbon analogues.
2 2 3 3
But . . . there are no bottles of Si H ; it’s a fleeting molecule seen only in a matrix
2 4
of solid Ne. And—hold on to your pants—quite unlike the carbon case, the
enthalpy of the bond-breaking reaction of H Si=SiH to two SiH is actually
2 2 2
less than that to HSi-SiH to two SiH. And in a wide group of compounds,
3 3 3
silicon goes five- and six-coordinate, whereas carbon resists that, with a
vengeance.
Should we abandon the periodic table, look for a resemblance between C
and Al or P? Nonsense. The periodic table gains in interest because (a) we see
its limitations, and (b) we try to understand them. Not to substitute another
numerology for that the table represents, but to reason out the “why?” that
makes compounds of Si different from those of C.
We now have prime evidence for a multitude of exoplanets with conditions
approaching those of Earth. Many low-probability accidents of evolution must
intervene before conscious, intelligent life develops on these. But the chances
of that happening have been much increased by our discovery of the exoplan-
ets. A survivor and an optimist, I have no special desire to see the future; we
will find a way, despite what we have done to the planet. Except for one thing—
how I would like to learn, in that encounter with extraterrestrial intelligence
that must come, how the ETs represent the periodic table! The regularities of
atoms, ions, and molecules will be there in their world; but given the vagaries
of evolution, the diverse ways we see things worked out in our world, our ET
friends will not look the way we do. And the accidents of that piece of cultural
evolution we call chemistry (that I am certain will transpire on their world) will
have been constructed by them with a different mindset, with different sym-
bols. I just long to see their “table.”
Roald Hoffmann
viii | Foreword
Mendeleev to Oganesson