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Textbook Ebook Mendeleev To Oganesson A Multidisciplinary Perspective On The Periodic Table Eric Scerri All Chapter PDF
Textbook Ebook Mendeleev To Oganesson A Multidisciplinary Perspective On The Periodic Table Eric Scerri All Chapter PDF
Textbook Ebook Mendeleev To Oganesson A Multidisciplinary Perspective On The Periodic Table Eric Scerri All Chapter PDF
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Oxford University Press is a department of the University of Oxford.
It furthers the University’s objective of excellence in research, scholarship,
and education by publishing worldwide. Oxford is a registered trade mark of
Oxford University Press in the UK and certain other countries.
Published in the United States of America by Oxford University Press
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© Eric Scerri and Guillermo Restrepo 2018
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Rights Department, Oxford University Press, at the address above.
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Printed by Sheridan Books, Inc., United States of America
CONTENTS
Introduction 3
CHAPTER 1 Heavy, Superheavy . . . Quo Vadis? 8
Paul J. Karol
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 H2Si=SiH2 is shorter than in H3Si-SiH3, just as in the carbon analogues.
But . . . there are no bottles of Si2H4; it’s a fleeting molecule seen only in a matrix
of solid Ne. And—hold on to your pants—quite unlike the carbon case, the
enthalpy of the bond-breaking reaction of H2Si=SiH2 to two SiH2 is actually
less than that to H3Si-SiH3 to two SiH3. And in a wide group of compounds,
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.
viii | Foreword
Mendeleev to Oganesson
Introduction
4 J. Emsley, Nature’s Building Blocks: An A-Z Guide to the Elements; E. Scerri, The Periodic Table,
Its Story and Its Significance, OUP, 2007; A Very Short Introduction to the Periodic Table, OUP,
2011; A Tale of Seven Elements, 2013; M. Kaji, H. Kragh, G. Pallo, The Early Reception of the
Periodic Table, OUP, 2015. M.V. Orna, M. Fontani, G. Fontani, The Lost Elements, The Periodic
Table’s Shadow Side, OUP, 2014.
4 | Mendeleev to Oganesson
mathematical physics. This is a topic that is of some importance to chemical
education, which habitually attempts to indoctrinate students into being able
to write the correct electronic configuration for any particular atom.
Jan C. A. Boeyens, a mathematical chemist, combines information on
nucleons with number theory to devise sequences that are related to the
periodic system. The author claims that all chemical phenomena displaying peri-
odic trends should be amenable to mathematical analysis. Boeyens also con-
cludes that the results of number theory are completely general and applicable
to disciplines other than chemistry.
Eric Scerri and William Parsons are the authors of “What Elements Belong
in Group 3 of the Periodic Table?” They claim that group 3 of the periodic table
should include lutetium and lawrencium as opposed to lanthanum and actin-
ium. The authors review the many arguments that have been proposed on
both sides of the debate and conclude that although the evidence in favor of the
proposed change is quite impressive there has yet to be a conclusive argument
to satisfy all parties. They proceed to then provide what they consider such a
conclusive argument by turning to a long-form presentation of the periodic
table and the demand that the elements be strictly ordered according to increas-
ing atomic number.
Paul Geerlings, a theoretical chemist, considers the relationship between
density functional theory and chemical periodicity. Geerlings criticizes the
quantum chemical approach to the periodic system based on isolated atoms
and orbitals. Instead he presents an alternative approach based on electron
density and on the amount of information among atoms. He adopts what may
be termed a more “realistic” approach to the chemical elements by considering
perturbed atoms rather than those in isolation.
Yu Liu, a semiotician, makes a semantic argument for having several periodic
tables. With reference to two particular periodic tables published by John
Newlands, the author examines the shifts of interests and meanings that Newlands
wanted to address. Liu claims that different kinds of relations were depicted by
Newlands including that of mereology, which in turn was related to the concept of
a chemical period. Liu concludes that chemical periodicity is far from having a
resolved meaning; rather, its meaning is constantly being negotiated.
Inorganic chemist and chemical educator Geoff Rayner-Canham discusses
several classifications of transition metals and one that includes groups 4 to 11
of the periodic table. The author suggests a novel classification based on the
aqueous chemistry of the compounds of elements. Rayner-Canham claims
that the traditional approach through groups and periods is not appropriate to
the similarities among transition elements. The author suggests a mixture of
vertical and horizontal similarities and that one element may take part in more
than one similarity class.
Bruce Railsback is the author of “The Earth Scientist’s Periodic Table of the
Elements and Their Ions: A New Periodic Table Founded on Non-Traditional
Concepts,” where chemical elements do not occupy a single position but rather
several of them, depending on their oxidation states. The table especially
introduction | 5
includes information on chemical elements present in materials of geochemi-
cal interest. Railsback’s table is divided into four blocks or neighborhoods
according to the oxidized forms of the elements: hard, intermediate to soft
cations, anions, and noble gases, which in turn are further divided into finer
neighborhoods. Railsback suggests that the table can be used to highlight
interactions between chemistry and various other disciplines.
The chemical historian Masanori Kaji analyzes the scientific and social con-
ditions which gave rise to Mendeleev’s system. He examines how Mendeleev’s
interests in analytical chemistry, isomorphism, specific volumes, indefinite
compounds, and the classification of organic substances led him to develop his
ideas of chemical element and to devise his periodic system. Kaji also shows
how the creation of the Russian Chemical Society motivated Mendeleev to
write his famous chemistry textbook, which in turn led him to discover the
periodic system. This chapter also includes a complete English translation of
Mendeleev’s letter replying to accusations that he was not doing “real work.”
The chemical historian and educator William B. Jensen discusses Abegg’s
rule of eight, which represented the first attempt to interpret the periodic system
in electronic terms. Jensen reformulates and extends the rule to the concept of a
valence manifold by using valence electrons and vacancies. Several controversial
questions regarding the placement of elements in the periodic table are
addressed. Jensen concludes hydrogen and helium should be separated from
each other, that lanthanum and actinium should be grouped with the inner-
transition, and that the zinc group elements are main-block elements.
The studies of the philosophical views of Mendeleev have been mainly
based on translations of his scientific publications. However, as Michael
Gordin states in his chapter, Mendeleev wrote two explicitly philosophical doc-
uments that Gordin translates for the first time into English. These documents
are thoughts that Mendeleev appears to have hesitated from sharing openly.
“The Unit,” written under a pseudonym, reveals Mendeleev’s views on spiritu-
alism while “Worldview,” a posthumously published document, contains his
political and economic views in the midst of the first Russian revolution.
The final contribution in this multidisciplinary compilation is perhaps the
most philosophical of all the studies presented. In it Mark Weinstein considers
the methodology, and in particular the role of counter-evidence, in evaluating
generalizations. He then examines how the table permits a reinterpretation of
foundational epistemological notions of truth, and finally asks how the peri-
odic table supports our commitment to the fundamental nature of reality.
We hope that these essays will further stimulate interdisciplinary as well as
multidisciplinary studies on the central icon of chemistry—whose status is
still widely debated. There is still widespread disagreement as to whether it
should be regarded as a representation, a model, a law, and so on. Perhaps one
should avoid even trying to categorize it according to the usual criteria that are
imposed by philosophers of science; perhaps one should embrace the unique-
ness of the periodic system or simply regard it as the paradigm or framework
of modern chemistry.
6 | Mendeleev to Oganesson
Figure 0.1 Left to right: Rolando Alfaro, Elisa Seidner-Scerri, Eric Scerri, Alberto Vela,
Pieter Thyssen, Alfio Zambon, Inelda Hefferlin, Ray Hefferlin, Ana María Gutierrez,
Guillermo Restrepo, Margarita Viniegra, Heidi Rubio, Adolfo Gutierrez, Julio Gutierrez.
We end on a sad note in reporting that while this book was in press two of
the authors, Masanori Kaji and Jan Boeyens passed away. They will be deeply
missed by their families, friends and colleagues, including the editors and
other authors represented in this volume. We also acknowledge the passing of
Ray Hefferlin who spoke at the Cuzco meeting on the periodic table and who
appears in the group photograph above.
introduction | 7
CHAPTER 1 Heavy, Superheavy . . . Quo Vadis?
Paul J. Karol
Department of Chemistry, Carnegie Mellon
University, USA
234U
230Th 238U
234Pa
214Pb
Figure 1.1 Uranium decay series commencing with 238U and terminating at 206
Pb.
Downward arrows are alpha decays and upward arrows represent beta decays.
Figure 1.2 Thorium decay series commencing with 232Th and terminating at Pb.
208
Downward arrows are alpha decays and upward arrows represent beta decays.
10 | Mendeleev to Oganesson
223Ra 231Pa 235U
Figure 1.3 Actinium decay series commencing with 235U and terminating at 207
Pb.
Downward arrows are alpha decays and upward arrows represent beta decays.
In 1929, a bit before the discovery of the neutron, the Russian physicist George
Gamow, working in Niels Bohr’s institute, published the first theory of nuclear
structure (1930). In it he referred to a liquid drop model based on the theory of
capillarity. The drop model plays an essential role in discussing the behavior,
observed and predicted, for heavy nuclei. Gamow developed an expression for
the energy of such a drop, consisting (for simplicity) of alpha particles in which
the necessary attractive forces were short-ranged (as with capillary action in
a macroscopic liquid) but of unknown strength. By matching predictions of
the nuclear drop model energies with Aston’s 1927 published mass measure-
ments, Gamow was able to demonstrate a primitive agreement. There was a
major problem with the prediction though: At nuclear masses of 120 or higher,
instability toward radioactive decay was predicted despite the perceived
absence of instability through masses of about twice that value. The fact that
nuclear masses were approximately twice the atomic numbers was accommo-
dated, as usual for these times, by assuming that many more protons and
alpha particles in the nucleus were accompanied by a sufficient number of
electrons within the nucleus itself to account for the eventual balance and mass
number, A (equaling N + Z, number of neutrons plus number of protons).
Only a few years after the discovery of the neutron by British physicist
James Chadwick in 1932, Gamow’s nuclear drop model was adapted by
German theoretician Carl von Weizsäcker into an extended form of the liquid
drop model leading to the semi-empirical mass formula (1935), a very success-
ful stratagem for understanding major bulk characteristics of atomic nuclei.
On July 5, 1934, Czechoslovak newspapers reported that an element with
atomic number 93 and atomic weight 240 had been discovered in Joachimsthal
pitchblende by Odelon Koblic, Director of the National Uranium and Radium
233U 237Np
221Fr 225Ra
209Pb 213Bi
209Tl
Figure 1.4 Neptunium decay series commencing with 237Np and terminating at 209Bi.
Downward arrows are alpha decays and upward arrows represent beta decays.
12 | Mendeleev to Oganesson
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