Comparative Inorganic Chemistry

571 Pages·1991·13.591 MB·English

by  Bernard Moody (Auth.)

Comparative
Inorganic
Chemistry
Third Edition
Bernard Moody, MA, CChem, FRSC
Edward Arnold
A division of Hodder & Stoughton
LONDON NEW YORK MELBOURNE AUCKLAND
The preparation of this 3rd edition led me to recall my many former students, however distinguished or
otherwise they have become as chemists or biochemists (or other forms of life), in candid and grateful
recognition of what they did for me by their efforts, albeit sometimes reluctantly, and their enterprising
laboratory work which has made the study of chemistry such a stimulating discipline (yet an art in some
of its preparatory aspects) and let me say, great fun.
© 1991 Bernard Moody
First published in Great Britain 1965
First edition 1965
Second edition 1969
Third edition 1991
Distributed in the USA by Routledge, Chapman and Hall, Inc.
29 West 35th Street, New York, NY 10001
British Library Cataloguing in Publication Data
Moody, Bernard
Comparative inorganic chemistry. - 3rd. ed.
1. Inorganic high pressure chemistry
I. Title
546
ISBN 0-7131-3679-0
All rights reserved. No part of this publication may be reproduced or
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Typeset in 10/llpt Times by Blackpool Typesetting Services Ltd.
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Preface to first edition
This book is an attempt to present in a systematic followed by an electronic treatment of certain
way the principles and facts needed to give a sound, aspects of oxidation and reduction to provide
coherent foundation to the study of Inorganic another unifying thread to the book, making the
Chemistry. It has been written with the needs of deduction of many equations possible.
students preparing for the Advanced Level Principles governing the extraction of elements
Examinations of the General Certificate of Educa- and some details of the processes, to show the essen-
tion in mind, and also for candidates attempting tial chemistry and give some idea of the magnitude
examinations for university and college Open and type of operation used, are grouped together.
Awards, and examinations for University Metals of growing importance, such as beryllium,
Entrance. The treatment is comparative and titanium and zirconium, are included. The general
reflects the shift in emphasis which has appeared in treatment followed removes a formidable quantity
Inorganic Chemistry in recent years. The principal of detail out of chapters on families of elements, a
aim is to teach the generalizations, many of them barrier which reduces the stamina of so many
subtle, which lie at the heart of Inorganic readers of conventional books. Likewise, the usual
Chemistry. To do this properly and with intellec- odd collections of data about alloys have been
tual honesty, factual detail must also be included. grouped in one chapter and treated generally. In-
The amount of Physical Chemistry included has dustrial processes linked with air, coal, water, salt
been cut to a minimum. It is hoped that the book and sulphuric acid have also been grouped together.
will complement an experimental approach to the
The study of each periodic group commences
subject, both in the laboratory and lecture room.
with an overall survey of the gradation of proper-
Answers to the fundamental questions of
ties and of the bonding encountered. While the
classical chemistry—why we accept the existence of
emphasis lies on the more important elements,
atoms and molecules—appear in the introductory
other elements of the family and their compounds
chapter. Classification of the elements has been
are introduced where a generalization is well
related to atomic structure. Evidence for the
illustrated. Compounds are given in the periodic
concept of energy levels has been included, a fun-
order of the other principal element combining,
damental notion taken on trust without thought by
and a cross-reference system avoids repetition.
so many of our pupils. Questions raised by the syn-
Each chapter includes qualitative tests, including
thesis of the transuranic elements have been
those for elements showing anomalous behaviour.
included to illustrate the way in which Seaborg and
Enough detail is included to support generaliza-
his co-workers have predicted the properties of
tions made and to link the book with laboratory
elements in the best traditions of Mendeléeff.
work, essential to the stimulating teaching of
Valency has been developed in detail to show the
Inorganic Chemistry.
evolution from its conception in the last century to
The treatment of transition elements is designed
the electronic theory, with a mention of the spin
to bring out their similar, yet graded, properties.
theory. Many bond diagrams are given and the
Short accounts of the chemistry of titanium,
transition from ionic to covalent bond type is
vanadium and cobalt and certain principal valency
emphasized and related both to physical properties
states are included not only for the benefit of the
and to the position of elements in the Period Table,
scholarship candidate but also to justify the general
the long form of which is preferred. This is
trends mentioned.
viii Preface to first edition
Many industrial organizations were most Laporte Industries Ltd
helpful. Their generous help is most gratefully Magnesium Elektron Ltd
acknowledged and if any are omitted from the Marchon Products Ltd
following list, the author offers his sincere The Mond Nickel Company Ltd
apologies: Monsanto Chemicals Ltd
N. V. Norit-Vereeniging Verkoop Centrale
Albright and Wilson Ltd
Northern Aluminium Company Ltd
The Aluminium Development Association
North Thames Gas Board
The Associated Ethyl Company Ltd
Streetley Magnesite Company Ltd
The Association of British Chemical
The Tin Research Institute
Manufacturers
Union Oxide and Chemical Company Ltd
Borax Consolidated Ltd
The Zinc Development Association
BDH Chemicals Ltd
The British Iron and Steel Federation Care has been taken to include a wide range of
The British Metal Corporation Ltd questions from the various examination boards
The British Oxygen Company Ltd and scholarship groups. A full acknowledgement is
The Chilean Iodine Educational Bureau given with the questions.
The Copper Development Association I offer my sincere thanks to Mr. F. P. Dunn who
The Dead Sea Works Ltd read the entire book and suggested numerous
The Dow Chemical Company (UK) Ltd improvements in content and style and to Mrs.
Hoechst Chemicals Ltd Pauline Woodhouse who most competently
The Gas Council deciphered and typed a difficult manuscript.
Henry Wiggin and Company Ltd Finally, I wish to record my appreciation of the
Imperial Chemical Industries Ltd generous and patient help given to me by my
Imperial Smelting Corporation Ltd Publishers.
Johnson, Matthey and Company Ltd
The Lead Development Association 1964 B.J.M.
Preface to second edition
This book was written to project a personal view of University of Edinburgh, in keeping me abreast of
what Inorganic Chemistry should be like at about certain recent developments.
Vlth form level. The motivation came, I like to The Stock Notation for nomenclature was a
think, from a genuine dissatisfaction with the feature of the first edition and the underlying plan
books then available and not from a desire to of the book was organized on it. In this edition the
burden the market. The contents are based on the nomenclature has been completely revised to
chemistry which had been taught under the direc- comply with the IUPAC recommendations (The
tion of the author at Latymer Upper School and Nomenclature of Inorganic Chemistry (1957),
later, at Bristol Grammar School. That the first IUPAC, London: Butterworth Scientific Publica-
printing sold out within 3-4 months was all the tions, 1959) and with the suggestions put forward
more gratifying because a conscious attempt had by the Nuf field Foundation. A rationalized system
been made to present an individual approach, in of metric units, the Système International
the early infancy of the Nuffield developments. I d'Unités (SI) is coming into international use and
would like to express my warmest thanks to the the units in this book are based on that system.
many chemists who have either written to me or But for both nomenclature and units the estab-
sought me out to discuss what merit the book has, lished, or trivial, names and units are also given
to offer criticisms and constructive advice, and if where it seemed realistic and helpful to do so.
I have fallen short of their standards in this edition, Attention is drawn to the Royal Institute of
the fault is entirely mine. Chemistry Monograph no. 15: M L. McGlashan,
The 1960s have seen a rapid re-organization of Physico-chemical Quantities and Units (1968). In
some parts of the chemical and metallurgical indus- the first edition, values for ionic radii were based
tries, which in turn has required some reshaping of on those of V. M. Goldschmidt (1926). In the
certain chapters in this book. Although the pro- current edition the values adopted are those in the
duction of town gas from coal has almost com- Nuffield Book of Data, and recommended by
pletely disappeared in this country, the outline of Ahrens and Yatsimirskii, to avoid confusion to
the coal gas industry has been retained in this those pursuing Nuffield courses, but it must be
edition. The production of ammonia is now based emphasized that while internuclear distances are
on the steam re-forming of naphtha and will in the often known precisely, how far each ion extends is
not too distant future, if the price is right, be based arguable.
on North Sea gas. It is a pleasure to record the help In addition to minor corrections and improve-
given by the Agricultural Division of ICI Ltd at ments, sections have been added on the shape of
Billingham in supplying information and in co valent molecules, based on simple theory of
answering my questions prior to the rewriting of electrical repulsion, on the concept of lattice
this section. To Dr. M. J. Rhydderch for giving me energy and its relation to the transition from ionic
permission to draw on his account of Spray to covalent bonding and to the solubility of ionic
Steelmaking in the July 1968 edition of Science compounds, and on the importance of co-
Journal, and to the Editor of that journal, I extend ordination number. The terms ionic and co-ionic
my warmest thanks. I am also pleased to are still preferred to their alternatives (although
acknowledge the help given to me by my youngest these are given) largely for the reasons put
brother, Stuart Moody, BSc, PhD, of the forward by W. G. Palmer, my former Director of
x Preface to second edition
Studies at Cambridge, in his book on Valency Finally, I record my continued appreciation of
(Cambridge University Press) and used also in his the friendly and intelligent help given to me by my
university text, Experimental Inorganic Chemistry Publishers.
(Cambridge University Press).
1969 B.J.M.
Preface to third edition
The experienced reader will see numerous altera- theory is the springboard to what follows, the spin
tions in this edition including the rearrangement of theory and the idea of electron-pairs is developed,
some of the early chapters. Units have been and where it is helpful, molecular orbitals are not
brought in line with current internationally overlooked in the main text. In this edition there is
accepted recommendations, some features of the greater emphasis on the quantitative aspects of
text have been expanded and others modified. The ionization energies, electron affinity and exchange
alterations reflect changes in emphasis of the energy. As before, however, the criterion for inclu-
author's thinking and teaching, based on many sion of theory is strictly its relevance to the com-
years experience as a Chief Examiner at Advanced parative theme of the book. Bonding and structure
level in chemistry to two Examination Boards and merits a separate chapter after the electronic theory
are in turn a reflection of evolutionary change, or of valency. Bonding found in complex ions
perhaps tidal change would be a more apposite involves hybridization, inner and outer orbital
metaphor, in the subject. In particular it is hoped complexes, and a later discussion of the associated
that while the prime purpose of the book will be characteristic colours. Atomic, ionic, metallic and
enhanced by the changes, the book will also fulfil van der Waals' radii are dealt with in some detail
another function: it will continue to act as a foun- and the significance of lattice energies, the theory,
dation for early college and university courses, the relationship to oxidation states, solubility,
being a reliable infill for those aspects of chemistry interionic distance and physical properties,
which have been glossed over fleetingly in some extended. Much of the foregoing is developed
modern courses as the treasure-house of knowledge further in the introductory remarks at the
and achievement is plundered. beginning of each chapter on the respective
Periodic families of elements. The treatment is
The opening chapters are historical in a double
always comparative, concerned with finding rela-
sense: the route passes some of the important land-
tionships for use as a teaching aid as much as
marks of classical chemistry but more importantly,
anything else. Here, comparisons of ionization
the chapters trace the development of thinking in
energies, various radii, electronegativities and
the subject for they were written with many of the
standard electrode potentials are illustrated in
source papers to hand. Currently, and in the same
vein, such books as Francis Crick's What Mad simple graphical form. Crystallization and the
Pursuit (Basic Books, 1988), a personal view of crystalline state, formerly a middle order topic, has
been promoted to support the opening chapters
scientific discovery by the Nobel Prize winner (with
and now, in an expanded form to show the
James Watson and Maurice Wilkins) who dis-
theoretical building up of close-packed (and not so
covered the double helix structure of DNA, should
close-packed) metal structures, it follows the
be prescribed reading for all students. Therein lies
critical examination of bonding, at the simple level.
the cultural value of science.
It remains the contention of the author that appar-
Two early chapters have been expanded and
ently quite simple concepts can be used to acquire
reorganized into four chapters. The properties of
a basic understanding and intuitive grasp of what
elements in relation to atomic structure has been
happens during chemical reactions, and an insight
separated from the matter of electronic configura-
into structural chemistry. The problem is age-old:
tion. Mass spectrometry has been promoted in this
to prepare the way for work at a higher level in such
edition from being a side issue. While simple octet
xii Preface to third edition
a way that the subject unfolds like a flower, with- There are a series of minor alterations to the
out implanting in the student the misunderstand- main text and for up-to-date interest, short topics
ings and old-fashioned prejudices of the teacher. touching on such matters as metal clusters (for
The problem is well known and has to be accepted organometallic catalysis) and so-called one
since it is inescapable. dimensional metals (replacing the silicon chip) are
While expanding the section on nuclear energy, added, to give, it must be admitted, a whiff of
the opportunity has been taken to discuss the current research. The text has been considerably
hazards associated with the generation of nuclear enhanced by many illustrations of molecular and
power and the chemical processing of the products ionic structures, with a continuing emphasis on
from nuclear reactors (and other sources). Current simple concepts like the electrical repulsion theory
medical disquiet about the effects of radiation is which accounts for (as an example) the octahedral
discussed along with other related issues including structure from which the square planar shape of the
politics and economics. nickel cyanide complex, Ni(CN)4~ may be derived.
Redox processes are again considered from first Certain aspects of pollution are also discussed in
principles but the use of equivalents has been this edition including the contamination of water
omitted, with calculations in titrimetry (volumetric supplies from the excessive use of chemical
analysis) indicated along molarity lines. The Stock fertilizers, the European concern over acid rain and
Notation, always a feature, has been extended as an the world problem of ozone depletion and the
alternative nomenclature for the oxoacids of the greenhouse effect.
halogens, to avoid stress for students following the Examination questions are included again but
Nuffield courses. Here, and later, the perceptive not for cramming! They have been vetted, pruned
reader will appreciate the experimental nature of and extended, not primarily for examination prep-
the underlying scheme upon which this chapter, aration but as a useful and surprisingly interesting
and later chapters is based. way of assessing how much of what has been read,
The discussion of Gibbs' Free Energy has been has penetrated and been retained.
taken further in looking at the principles governing I would like to acknowledge David Kitchen (ICI,
the extraction of metals. In the associated chapters Billingham) and Geoff Daniels (ICI, Runcorn) for
there are minor changes in emphasis and the their help with Chapters 12 and 14, respectively. In
Midrex process for iron is outlined. The retention addition to the organizations listed in the prefaces
of certain processes largely displaced in the United to the first and second editions, I would like to
Kingdom is explained by the wider readership of thank the following:
the book.
The section on acids and bases, which already The Fertiliser Manufacturers Association
ranged from the initial concept right through to The National Sulphuric Acid Association
non-protonic systems has been enhanced by inclu- The Royal Mint
sion of the Lewis theory, with its link to electron- The Royal Society of Chemistry
pairs and bonding. Perhaps it is appropriate here The Science and Engineering Research Council
to mention that while extra headings have been
introduced to facilitate reference, the temptation to Finally I would like to acknowledge the help of
subdivide various discourses has been resisted on my Publishers.
the assumption that the student is quite capable of
absorbing the study of (say) carbon dioxide,
carbonic acid and its salts in one digestible whole. 1991 B.J.M.
xiii Prefix for SI Units
A Note of Prefixes for SI Units
The following are the approved decimal fractions or multiples of the basic SI Units or of the SI specially
named derived units.
Fraction Prefix Symbol Multiple Prefix Symbol
IO"1 deci d 10 deka da
io-2 centi c IO2 hecto h
lO"3 milli m 103 kilo k
IO"6 micro μ IO6 mega M
IO"9 nano n IO9 giga G
IO"12 pico P IO12 tera T
IO"15 femto f
IO"18 atto a
Example Mg km2 μ8 2
= (103kg)(103m)2(10-6s)-2
= 103kgx 106m2x 1012s"2
= 1021kgmV2
Note that the prefix must be written immediately adjacent to the unit, i.e. touching it in normal writing
and separated from the next unit by a small space.
e.g. kg mm, Mg, nm but kg m2s"2K"1mol"1 ( = J K^mol"1)
Further cm2 always means (0.01m)2 and never 0.01m2 which may trap the unwary when faced with,
say, km2 or μ8~2 as above.
1
The development of fundamental ideas
in 19th century chemistry
Science and chemistry individual profession but it is generally agreed that
any definition of science must indicate the methods
The Latin word scientia was Anglicized to 'science' by which scientific knowledge is obtained as well as
and applied to any formal branch of knowledge the knowledge itself. Sir Richard Gregory defined
until the beginning of the 17th century when its use science as organized and formulated knowledge of
became gradually restricted to the natural sciences. natural objects and phenomena derived from veri-
At the beginning of the last century the term philo- fiable observations and experiments.
sophy was usually applied to all branches of know- The concept of hypothesis and the crucial experi-
ledge, science having the same meaning. With the ment lie at the heart of any understanding of
rapid advances in science as we know it, came a science. Starting from the collection of verifiable
separation of the two terms. Philosophy was divided observations, classification may lead to general
at first into moral philosophy and natural philos- statements called laws for which explanations are
ophy and science into moral science and natural sought. To this end, hypotheses are formed. A
science. Moral refers to man and his ways: thus, hypothesis is the principal intellectual tool of the
moral law is concerned with the requirements to scientist. Hypotheses are intelligent guesses and
which right action must conform, and moral sense, require the possession of imaginative and intuitive
the power of distinguishing between right and powers. They enable the planning of observations
wrong. Natural in this context has a diffuse mean- and experiments so that predictions based on one or
ing: it concerns everything external to man and his more rival hypotheses may be tested. Experiments
conduct. Thus, natural philosophy and natural are designed to ask specific questions of nature. A
science were equivalent in meaning but the former crucial experiment enables a choice to be made
has declined in use and only survives in the 'Chairs between rival hypotheses. Science advances by the
of Natural Philosophy' at the older universities, formulation of hypotheses, with the prediction
philosophy being retained nowadays for the older from them of results which may be tested by experi-
branches of formal knowledge. The adjective, ment. Theories to account for observed phenomena
natural, is usually dropped from Natural Science are then propounded. Hypotheses which seem well
although its use is retained in the 'Schools of Natural established become theories. But these must be
Science' serving to distinguish them from the modified or discarded as fresh evidence is uncovered
'Schools of Moral Science' of the older universities. which proves at variance with them. Of course,
The divisions of Natural Science, or the Natural chance plays a role in scientific discovery and a clear
Sciences, are well known: fundamentally, Physics sequence of events is not always apparent. Most
is the general study of matter, heat, light, elec- hypotheses by their nature will prove wrong, but by
tricity, etc., Chemistry involves the separation and the critical examination of such concepts, science
detailed examination of selected kinds of matter, progresses. With hypotheses established, an
while Biology is the study of living organisms, organized structure based on reason is erected.
Geology, the study of the Earth, and Astronomy, In the study of Chemistry, the naturally oc-
the Universe. However, it is extremely difficult to curring mixtures of the Earth's crust must be
define science itself and the term is still sometimes separated and purified so that an examination of
used in its earlier sense, as in 'he is a scientific the characteristic properties of the components of
bowler', i.e. skilful. Scientists follow a highly the mixtures and their relationships with each other