Classical Elements of the Greek philosophers (1)
• Notion of elements first introduced in Antiquity by Greek philosophers
Chapter 1
Concept of Chemical Element
1 2
Classical Elements of the Greek philosophers (2)
• Empedocles of Akragas (v. 495-435 BC): all the structures in the world are
made of 4 “elements” or roots: fire, air, earth and water
(= the Classical Elements)
• Earth, water, air: three common states of matter (solid, liquid, gas)
Fire: energy, the agency through which matter changes from one form to
another
3 4
• Wanted to understand transformations they observed in nature: water freezes
and boils away, wood burns leaving behind ashes, metals melt
•
•
Search for unity: reduce complex world to a simpler scheme
Different opinions about prote hyle or “first matter”
– Thales of Miletus (c. 625-546 BC): water
– Anaximander of Miletus (c. 610-545 BC): apeiron, the ‘indefinite’ or
unknowable primary substance
– Anaximines of Miletus (c. 585-524 BC): air
– Heraclites of Ephesus (c. 544-484 BC): fire
Classical Elements of the Greek philosophers (3)
• Plato (427-347 BC): Greek philosopher and mathematician
• First used the term “element” (stoicheion)
stoicheion = letter, smallest unit from which a word is formed
• Associated four Classical Elements with regular platonic solids
• Conceived elements as consisting of atoms with regular geometric shapes
 Aristotle’s four element theory (1) Aristotle’s four element theory (2)

• Aristotle (384-322 BC): most influential Greek philosopher

• Discarded Plato’s mathematical approach, but kept Empedoclean theory of
four elements: Fire, Air, Earth, Water
• “Elements” are not fundamental matter
• Believed in the existence of a “primary material” which is a substrate for
“qualities” (hot, cold, dry and wet), but is inseparable from those qualities
• Simple perceptible bodies (“elements”) underlie perceptible bodies, but the
substrate and its qualities underlie the elements
• Provided each element with a pair of qualities

5 6

Aristotle’s four element theory (3) Aristotle’s four element theory (4)

• None of the elements was unchangeable: they could transform into one another • Modern understanding of protons and neutrons in β radioactive decay is
through the quality they had in common reminiscent of this kind of relationship:
Air could turn into Fire through the medium of heat – proton is not more or less fundamental than neutron
Water could become Earth through the medium of cold – neutron does not “contain” a proton
• According to Aristotle, all matter was composed of these four elements – In β- decay, a neutron is transformed into a proton, an electron and an antineutrino
• Unlike substances differed from each other only in the ratios in which the • Aristotle added the Aether as the 5th element: since no changes had been
elements are present observed in the heavenly regions, the stars cannot be made of the 4 elements,
• One substance could be transformed into another by changing the proportions but must be made of a different, unchangeable element
of the four elements
• Elements were converted into each other in an endless cycle, by interchanging
qualities (from dry to humid, from hot to cold, ..) giving rise to the objects of
the physical world
• Elements can be changed into one another, but not the qualities
• None of the elements is more fundamental than another; they can be
transformed one into another
• Elements have irreducible differences but enough similarity to make
transformation possible
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 Greek atomic theory (1)
• Concept of elements is closely connected to idea of atoms, but each does not
demand the other
• Leucippus of Miletus (5th century BC):
– Introduced the concept of atoms
– Atoms are tiny particles and are all made of the same primal substance
– They have different shapes in different materials
• Democritus of Abdera (c, 460-370 BC):
– Further elaborated concept of atoms
– Called particles “atomos” = “uncuttable”, “indivisible”
– Particles were so small that they could not be cut any further
– Atoms were thought to be solid and homogeneous
– Finite number of kinds
– In constant motion
– Move around in a void: “There is only matter and void”
– Their interactions as they moved through the void gave rise to the material world
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Greek concept of elements: summary
• Term “element” comprised 2 different notions in Antiquity:
– From Thales to Empedocles: concept of an abstract conserved entity
– Aristotle: direct carrier of properties (e.g. water as the carrier of the cold and the
wet)
• Aristotle placed more importance on the qualities than on their substance
11
Greek atomic theory (2)
• Other philosophers did not concept of void, empty space
• Elements must fill all the space
• Aristotle states that air would fill any void between the atoms
• Aristotle attacked atomic theory fiercely
• Because of Aristotle’s authority until the 17th century, atomism received little
further attention for about 2000 years, despite its logic
Alchemical principles (1)
• Alchemical idea of transmuting base metals (e.g. lead) into gold originated in
Aristotle’s idea that an element might be transformed into another element by
change of its qualities
• Alchemists deduced their own postulates about the unity of matter
• Transmuting agent: Philosopher’s Stone
– Could turn base metals into gold
– Man’s perfect medicine, elixir of life
• Alchemists applied Aristotle’s theory mainly to metals
• Alchemists used the term “principle” rather than “element”
• Arabic alchemist Jabir ibn Hayyan, also called "Geber" (c. 721-815)
– Metals have “fundamental qualities” (hot, cold, dry and wet)
– Metals have also “immediate qualities”: two principles (Sulfur and Mercury)
– All metals are mixtures of Sulfur and Mercury
– In base metals, Sulfur and Mercury are impure, but in gold and silver they attain
higher degree of purity
– Purest mixtures of Sulfur and Mercury yielded not gold, but the Philosopher’s
Stone, the smallest quantity of which can transform base metals into gold
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 Alchemical principles (2)
• Two principles Sulfur and Mercury are not synonymous with simple
substances metallic mercury and non-metallic yellow sulfur
• Two principles were rather like the four Classical Elements
– Sulfur represented fire, or the quality of combustibility
– Mercury represented water, or the quality of fusibility or liquidity
• Later, a 3rd principle was added: Salt
– Salt corresponded to quality of fixity (solidity, non-volatility
• When a chunk of wood was burnt, for example, the reaction products reflected
its constitution. Thus smoke referred to the presence of Mercury, flames
reflected the presence of Sulfur, while the remaining ashes referred to the
presence of Salt.
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15
Three-Principle Theory (Paracelsus)
• Three-Principles Theory is attributed to Swiss physician and alchemist
Theophrastus Philippus Aureolus Bombastus von Hohenheim, better known as
Paracelsus (1493-1541)
• By adding the 3rd principle, alchemical theory became more than a theory of
metallurgy, and embraced all the material world.
• Matter was constituted by a combination in varying proportions of the three
principles or `tria prima' (three primes): Sulfur, Mercury and Salt.
14
Boyle: The Sceptical Chymist
• Robert Boyle (1627-1691) published in 1661 his famous book The Sceptical
Chymist in which he provided some doubts with regard to the validity and
universality of the 4 elements of the ancient Greek philosophers, as well as the
3 principles of Paracelsus and his followers.
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 Boyle’s new definition of element Lavoisier and the chemical revolution

• Boyle noted that it was impossible to combine the 4 Greek elements to form
any substance and it was equally impossible to extract these elements from a
substance.
• Boyle proposed a new definition of an element that became the basis for the
modern definition of this concept:
• Antoine Lavoisier (1743-1794) published in 1789 his famous book Traité
Elementaire de Chimie (Elementary Treatise on Chemistry) which initiated a
revolution in chemistry.

An element is any substance that cannot be decomposed into a simpler

substance.

• Chemists should regard as elementary all those substances that they have not
yet been able to split up into two or more constituents, and should not limit
themselves by any preconceived notions of the number of these elements.
• If a substance is undecomposable, it is to be considered an element, and it will
retain that status for just so long as it withstands the efforts of chemists to
decompose it.
• For Boyle, experimental analysis is the arbiter of the elemental status of a
substance.
17 18

Lavoisier’s definition of element Boyle versus Lavoisier

• Lavoisier tried to get rid of the philosophical conception of elements as
abstract entities or principles
• Elements are simple substances that can be isolated and cannot be further
decomposed.
• Lavoisier identified the elements on an experimental basis:
An element is the endpoint of chemical analysis
• Operational definition: as the techniques of chemical analysis improved, then
substances scientists had any right to regard as elements could change.
• Elements are no longer abstract causes of the behavior of bodies, but they are
rather tangible bodies, characterized by real and well-defined properties.
• For Lavoisier, simple substance and element were synonyms.
• Lavoisier no longer considered water to be an element, but thought of it as a
compound substance (the components of which were the newly discovered
elements hydrogen and oxygen).
• Definitions of element by Boyle and Lavoisier look very similar
• Boyle: body which is not subject to analysis
– Is theorizing about microstructure of matter
– Did not dare to name any substances as elements
– Did not see any satisfactory method to determine which substances are true
elements
• Lavoisier: body which has not been analyzed by chemical methods
– Purely empirical approach
– Used state of the art analytical methods to decompose compound substances into
simple substances
– Did compose a list of simple substances or elements

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 Lavoisier’s list of elements (1) Lavoisier’s list of elements (2)

• List of 33 elements
• 23 of these substances turned out to be genuine elements
• Other were later proven to be compound substances (magnesia, barite,
alumina, silica)
• Some elements were fictitious: light and matter of heat

• Importance of Lavoisier's list is that it clearly showed that the material world
is not made of just a small number of chemical elements. On the contrary,
there are lots of different elements, and it was up to chemists to find them.

21 22

Laws of conservation of elements Dalton’s atomic theory

• (Restricted) law of conservation of elements: elements that enter into a
compound can recovered from it, both qualitatively and quantitatively
Hydrogen an oxygen gas combine to form water, but water can be split to form again
hydrogen and oxygen gas
• John Dalton (1766-1844) published in 1808 his famous book New System of
Chemical Philosophy, with the postulates that are the foundations of modern
atomic theory.

• Extended law of conservation of elements: law of conservation of elements

did not only imply that the elements that enter into the compound may come
out of it undiminished, but they are also actually present in the compound.

from the empirical fact that water could be both synthesized from hydrogen gas and
oxygen gas (2H2 + O2 → 2H2O), as well as being decomposed into
hydrogen and oxygen gas (2H2O → 2H2 + O2), Lavoisier concluded that both
gases were actually present in the water, i.e. 2H2O = 2H2 + O2.

• Lavoisier held rather naive opinion that all the properties characterizing a
certain element X were permanent and that they remained intact in all
compound substances containing this element X.
• Idea of permanent elementary properties was erroneous. 23 24
 Dalton’s list of elements Postulates of Dalton’s atomic theory

1. Elements are made of tiny particles called atoms.

2. The atoms of a given element are different from those of any other element,
and the atoms of different elements can be distinguished from one another by
their respective relative atomic mass.
3. All atoms of a given element are identical.
4. Atoms of one element can combine with atoms of other elements to form
chemical compounds, and a given compound always has the same relative
numbers of types of atoms.
5. Atoms cannot be created, divided into smaller particles, nor destroyed in the
chemical process, and a chemical reaction simply changes the way atoms are
grouped together.

25 26

Dalton’s atomic theory Contradiction in Dalton’s atomic model

• Dalton conceived atoms as both indestructible and unchangeable (not
transmutable)
• Each element was build up of one unique type of atom with a characteristic
atomic mass
• Elements that enter into a compound may not only recovered from it, but are
also in it.
• Dalton defined chemical atom as the smallest quantity of a substance, still
showing the properties of the whole
• For instance, a sulfur atom was to Dalton a small piece of sulfur stone and an
iron atom a small piece of iron metal.
• If an iron sulfide molecule consisted of a minute piece of sulfur joined to a
minute piece of iron, how then is it possible that the elements iron and sulfur
are deprived of almost all their characteristic properties, in spite of their being
present in the compound?
• Why is iron sulfide, though containing so much sulfur, inot dissolved by
carbon disulfide (a good solvent for sulfur)
• Why is iron sulfide not strongly ferromagnetic, though it contains so much
iron?

• The great success of atomic theory in the quantitative field (it explained laws
of conservation of mass, definite composition and multiple proportions) made
scientists overlook its apparent weakness in the qualitative field.

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 Mendeleev’s definition of element (1) Mendeleev’s definition of element (2)

• For Lavoisier, simple substance and element were synonyms
• Dmitrii Ivanovich Mendeleev (1834-1907) made clear
distinction between these 2 terms.
• Simple substance
– Somewhat material, endowed with physical properties and
capable of chemical reactions
– Able to display itself in the form of allotropic modifications and is distinguished
from a compound substance only by the homogeneity of its material parts
• Element
– Those material particles of simple and compound substances which determine their
behavior from a chemical and physical point of view
– Abstract, but strictly associated with the empirical experience: a material, although
invisible, part of a compound
– Corresponds to the idea of atom
• According to Mendeleev, carbon is an element, but coal, graphite and diamond
are simple substances
• In his book Principles of Chemistry (Osnovy khimii), Mendeleev wrote:
“Mercury oxide does not contain two simple bodies, a gas and a metal, but two
elements, mercury and oxygen, which, when free, are a gas and a metal.
Neither mercury as a metal nor oxygen as a gas is contained in mercury oxide;
it only contains the substance of the elements.“
• Almost all properties belonging to simple substances are lost during chemical
reactions; therefore simple substances are not suitable for classification of the
elements.
• One property could survive chemical reaction and belonged not to simple
substance, but to the abstract element: atomic weight of the elements
• For Mendeleev, periodic table is classification of elements, not of simple
substances

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Basic substance versus simple substance (1) Basic substance versus simple substance (2)

• Radiochemist Friedrich Paneth (1887-1958) • Examples of simple substances

expresses double meaning of concept element by terms
simple substance and basic substance – The element sodium, a highly reactive
• Basic substance silvery-colored metal
– Refers to what is indestructible in compounds
(survives in compounds)
– Completely unobservable to our senses
– Just bearer of properties, while at the same time devoid
of any property
– Identified by the atomic number Z
• Simple substance
– Refers to the form in which a basic substance, not combined with any other is – The highly reactive greenish colored gas
presented to our senses with a pungent odor commonly identified
– Realization of an uncombined basic substance as the element chlorine
– Allotropic forms of basic substance
– Does not survive in compounds
– Observable and isolable
– Persistent terminal product of process of chemical isolation
31 32
 Basic substance versus simple substance (3) Basic substance versus simple substance (4)

• Examples of basic substances • Basic substances do not possess properties, but simple substances do
– Sodium in sodium chloride • Statement “Carbon is black.” is wrong
– Chlorine in sodium chloride – Carbon, as a basic substance, is devoid of color
– The graphite realization of the basic substance carbon is black.
• It is wrong to claim that the density of carbon is 2.267 g cm-3
– Allotropic form exhibiting this density must be specified (graphite)
– Different allotropic forms of carbon have different densities

• Paneth: “A chemical element is the class of all atoms of equal nuclear charge.”
• Each position for element in periodic table represents a basic substance, which
• Sodium chloride formed by reaction of sodium and chlorine is not highly
is represented by a symbol.
reactive and not silvery, nor greenish or pungent.
• Element cannot be identified with a simple substance.
• Not properties of simple substances, but properties of compounds should be
• Simple substance can be retrieved from sodium chloride by various laboratory
compared when looking for trends and similarities in the periodic table.
procedures (e.g. molten salt electrolysis)

33 34

IUPAC definition of chemical element Term “element” with reference to nucleus

• Twofold definition:
Definition 1. A species of atoms; all atoms with the same number of protons in
the atomic nucleus.
Definition 2. A pure chemical substance composed of atoms with the same
number of protons in the atomic nucleus. Sometimes this concept is called the
elementary substance as distinct from the chemical element as defined under 1,
but mostly the term chemical element is used for both concepts.
• Confusion of dual meaning of element as simple substance or basic substance
can be avoided by using term “element” to refer to the nucleus, rather than to
the atom or to substance
• Element: A class of nuclei, all of which have the same atomic number
(W.B. Jensen, University of Cincinnati, USA)

• Advantages of this definition

Definition 1: refers to atoms – Simple
Definition 2 = definition of simple substance – Unambiguous
– Clearly highlights formal and systematic character of concept of element

• IUPAC definition is confusing

35 36
 Chapter 2
Periodic System

37 1

Periodic law Periodic system – periodic table

• Periodic law: after certain, but varying, intervals the chemical elements show • Terms “periodic system” and “periodic table” are often used as synonyms, but
an approximate repetition in their properties they are not.
• Periodic repetition of properties is the essential fact underlying the periodic • Periodic system (or periodic system of elements):
system. – More general term
• Periodicity is neither constant nor exact – The more abstract notion that fundamental relationships exist among elements
– Varying period length: 2-8-8-18-18-32-32 – Ordering of the elements by atomic number in such a way that they fall into natural
(unlike days of week, or notes in music scale) groups
– Repetition is approximate: gradual change in properties of elements in group – Different ways of displaying periodic system are possible
(compare different repeated notes in music scale that sound the same but are octave • Periodic table:
higher)
– More restricted term
• Some chemists do not like to use term “law” – 2D representation of periodic system
(not as law-like as laws in physics) – Attempt to represent periodic law graphically
• Periodicity is typical chemical law: approximate and complex, but still • More than 1000 versions of the periodic table have been published
fundamentally displaying law-like behaviour
• There is no ultimate of best periodic table; it depends on what one wants to
• It is regrettable that term “periodic law” is no longer fashionable highlight (chemical properties, electronic structure, spectroscopic properties)
• Dutch: “Tabel van Mendelejev”
In English term “Mendeleev’s Table” is not used
2 3
 Ordering the elements (1)
• Historically, the order of the elements was determined by equivalent weight,
then later by atomic weight, and finally by atomic number
• Equivalent weight: (1) Amount of metal that reacts with a fixed amount of
standard acid; (2) Amount of element that reacts with a fixed amount of
oxygen
– Empirical concept that does not rest on assumption that elements are composed of
atoms
• Atomic weight (atomic mass): equivalent weight multiplied by valence the
element assumes in compounds
– Assumes the existence of atoms and molecules
• Valence (or valency): (1) number of hydrogen atoms that unite with one atom
of the element; (2) number of homopolar covalent bonds an atom is capable of
forming
– Valence is a positive number
• Oxidation state: number of valence electrons an atom has gained or lost in in
a molecule
– Can be positive (loss of electrons by electropositive elements) or negative (gain of
electrons by electronegative elements
Prout’s hypothesis (1815-1816)
• English chemist William Prout (1785-1850)
– Observed that atomic weight of many elements were multiples of atomic weight of
hydrogen (with atomic weight hydrogen = 1)
– Hypothesis: hydrogen was primary matter (protyle)
– Experiments inspired by Prout’s hypothesis provided increasingly accurate set of
atomic weights
– Many elements have atomic weights differing less than 0.1 from whole number
– Mg (23.5), Cl (35.5), Cu (63.5), Zn (65.4) falsified Prout’s hypothesis and led to its
rejection
Ordering the elements (2)
• Atomic number (Z): number of protons, or units of positive charge, in the
nucleus of any of the atoms of element.
• Each element in the periodic table has one proton more than the element
preceding it.
• Element is defined by its atomic number
• All atoms of particular element always have the same number of protons,
although number of neutrons can be different (isotopes)
• As number of neutrons also tends to increase if one moves through the
periodic table, atomic number and atomic weight are approximately
proportional.
4 5
Döbereiner’s triads (1817 and 1829)
• In 1817, German chemist Johann Döbereiner (1780-1849) found that if
certain elements were combined with oxygen in binary compounds, equivalent
weights of compounds showed numerical relationship:
Equivalent weight SrO is arithmetic mean over those of CaO and BaO
SrO = (CaO +BaO)/2 = (59+155)/2 = 107
Current values: (56 + 153.5)/2 = 104.75
• Sr, Ca, Ba were said to form a triad
• In 1829, Döbereiner discovered 3 new triads
(based on atomic weights):
Br = (Cl + I)/2 = (35.470+126.470)/2 = 80.470
Na = (Li + K)/2 = (15.25+78.39)/2 = 46.82
Se = (S + Te)/2 = (39.239+129.243)/2 = 80.74144
6 7
 Newlands and the Law of Octaves (1864)
• English chemist John Newlands (1837-1898) suggested that when the
elements were arranged in order of atomic weights, any one of the elements
showed properties similar to those of the elements 8 places ahead and 8 places
behind in the list.
• Newlands called this “Law of Octaves”
• First clear announcement of law about repetition of properties of elements
after certain intervals
• Anticipated modern arrangement based on atomic number.
8 9
Julius Lothar Meyer (2)
• Published a diagram showing the periodicity among atomic volumes of
elements
• Graph contributed to general acceptance of periodic system
10
Julius Lothar Meyer
• German chemist Julius Lothar Meyer (1830-1895) discovered the periodic
system independently from Mendeleev, but gets less recognition.
• 1864: first table showing a regular variation of valency
Dmitri Ivanovich Mendeleev (1)
• Russian chemist Dmitri Ivanovich Mendeleev (1834-1907) is considered as the
leading discoverer of the periodic system
• Not the first to develop a periodic system, but his version(s) created the
biggest impact on the scientific community
• Mendeleev’s name is connected to periodic system like Darwin’s name is
connected to evolution theory and Einstein’s name to relativity theory
• Mendeleev felt urge to classify chemical elements while writing his textbook
The Principles of Chemistry (Osnovy khimii)
11
 Dmitri Ivanovich Mendeleev (2) Mendeleev’s Attempted System (1869) (Russian)

• Mendeleev struggled with question: “What is ultimate property on which

classification of elements should be based?”
• Almost all properties belonging to simple substances were lost during
chemical reactions, so that simple substances and their properties cannot be
used for classification.
• One property survived during chemical reactions, and this property did not
belong to simple substance, but to abstract basic substance: the atomic weight
(atomic mass)
• Basic substances possess one single, measurable, basic property which
remained unaffected during chemical reactions: atomic weight
• Belief that basic substances were “material” ingredients of simple substances
and compounds, convince Mendeleev to use atomic weight for classification of
the chemical elements.

Classification of the elements as basic substances

12 13

Main conclusions of Mendeleev’s first paper on

Mendeleev’s Attempted System (1869) (German)
periodic system
1. The elements, if arranged according to their atomic weights, exhibit an evident
periodicity of properties.
2. Elements which are similar as regards their chemical properties have atomic weights
which are either of nearly the same value (e.g., platinum, iridium, osmium), or which
increase regularly (e.g., potassium, rubidium, cesium).
3. The arrangement of the elements, or of groups of elements, in the order of their atomic
weights corresponds to their so-called valences as well as, to some extent, to their
distinctive chemical properties − as is apparent among other series − in that of lithium,
beryllium, barium, carbon, nitrogen, oxygen, and iron.
4. The elements which are most widely diffused have small atomic weights.
5. The magnitude of the atomic weight determines the character of the element, just as the
magnitude of the molecule determines the character of a compound body.
6. We must expect the discovery of many yet unknown elements, for example, elements
analogous to aluminum and silicon, whose atomic weight should be between 65 and 71.
7. The atomic weight of an element may sometimes be amended by a knowledge of those
of contiguous elements. Thus, the atomic weight of tellurium must lie between 123 and
126, and cannot be 128.
8. Certain characteristic properties of the elements can be foretold from their atomic
weights.
14 15
Mendeleev’s Natural System of the Elements (1870) Mendeleev’s predictions

• Classification of the elements as basic substances

• Elements are organized by increasing atomic weight (atomic mass) so that elements
with similar properties are in the same column
16 17

Problems with the periodic system Van den Broek (1913)

• Reversal of the pair tellurium-iodine (Te = 127.6; I = 126.9) • Atomic nucleus discovered in 1911 by Ernest Rutherford
– Problem solved by using atomic number to order elements • Dutch amateur physicist Antonius Van den Broek (1870-1926) was first to
– Reversal of pair cobalt-nickel (Co = 58.93; Ni = 58.69) was originally contributed propose that the atomic number (nuclear charge) determined placement of
to errors in atomic weight elements in the periodic table
• Questionable placement of transition metals in 8th group (violating concept of • Correctly determined atomic number of all elements up to Z = 50 (tin)
single occupancy) • Could not verify atomic numbers experimentally; just hypothesis
– Transition metals were integrated in long form of periodic table
• Position of hydrogen
– Still a matter of discussion (see further)
• Position and number of rare-earth elements
– Solved by work of Moseley
• Discovery of the noble gases
– Group 0 added to periodic table
• Existence of isotopes
– Problem solved by using atomic number to order elements
• Radioactivity
– Radioactive decay products are isotopes of known elements
18 19
 Moseley (1914)
Moseley (1914)

• English physicist Henry Moseley (1887-1915) found a relationship between

wavelengths of characteristic X-rays of an element and the value of its nuclear
charge.
• Wanted to test Van den Broek’s hypothesis
• Showed that Mendeleev’s ordering places elements in sequential order of
nuclear charge.
• Nuclear charge is identical to proton count and determines value of atomic
number Z of each element
• Atomic number defines a chemical element and gives integer-based sequence
for ordering of elements in periodic table
• Moseley determined absolute sequence of the elements and predicted which
elements were still missing at that time (Z = 43, 61, 72, 75)
• Correct placement of cobalt (Z = 27) before nickel (Z = 28), tellurium (Z = 52)
before iodine (Z = 53) in line with periodic trends.
• Total number and order of rare earths could be determined

20 21

Moseley (1914)
Niels Bohr (1921)

• Danish physicist Niels Bohr (1885-1962) offered explanation of periodic

system in terms of electron configuration (see Chapter 3).
• Each row in periodic table corresponds to filling of quantum shell of electrons
• Larger atoms have more electron sub-shells, so periods are becoming
progressively longer.

22 23
Pre-1949 placement of thorium, protactinium Pre-1949 placement of thorium, protactinium
and uranium (1) and uranium (2)
• Analogies have been noted between :
– Th and the members of Group 4 headed by Ti
– Pa and members of Group 5 headed by V
– U and the members of Group 6 headed by Cr
• [U2O7]2- and [Cr2O7]2-
UO2Cl2 and CrO2Cl2, MoO2Cl2
UCl6 and WCl6
• Th, Pa, U considered as transition metals
• Np and Pu do not show similarities with Re and Os, or with Tc and Ru
• Th, U, Np, Pu show +IV oxidation state
• ThO2, UO2, NpO2 and PuO2 are isomorphous (same crystal structure)
• Steady decrease in ionic radius from Th4+ to Pu4+
• Other evidence of similarities between Th, Pa, U, Np, Pu based on magnetic
susceptibility data, absorption spectra of ions in aqueous solutions and
crystals, spectra of gaseous atoms, crystallographic and chemical data
• 1949 (Glen T. Seaborg): actinide hypothesis
24 Existence of a second rare-earth series that begins with actinium (actinide series) 25

Post-1949 placement of thorium, protactinium

Different representations of the periodic system (1)
and uranium (3)

26 27
Different representations of the periodic system (2) 3D periodic tables

• Better name: 3D periodic models

• Claimed advantages:
– Illustrate continuity better than 2D or planar tables
– Capable of make explicitly a larger range of analogies because of greater flexibility
of inherent to 3D geometries
• Disadvantages
– In general expensive to construct
– Impossible to reproduce in books
– Not suitable as wall charts
– Impossible to get a simultaneous overview of entire table

https://www.meta-synthesis.com/webbook/35_pt/pt_database.php?PT_id=625

28 29

de Chancourtois’ telluric screw (1862) Crookes' vis generatrix (1898)

30 31
Alexander Arrangement of Elements (1965) Chemical tables (1)

• Based primarily on chemical and physical properties of elements

• Emphasis on values of highest oxidation state of elements
– Reflected in old numbering of groups: e.g. group VII reflects +VII oxidation state
of Cl in ClO4- rather than more common –I oxidation state in Cl-
– Labels A and B used to link groups with common maximum oxidation state, but
otherwise distinct chemical and physical poperties: e.g, Ca(II) and Zn(II)
• Criticism:
– Many exceptions to maximum oxidation state labels
• Group VII element F fails to attain +VII oxidation state
• All members of group IB have maximum oxidation states greater than +I
Cu(IV), Ag(III), Au(V)
• Only Ru and Os attain +VIII oxidation state in Group VIII
• Short periodic tables are typically chemical periodic tables

32 33

Chemical tables (2) Electronic configuration tables (1)

• Rely on periodic repetition in both nature (s, p, d, and f) and number of outer
electrons for isolated gas phase atoms.
• Based on quantum chemistry
• Electronic periodic tables are typically medium-long and long tables
• Presently preferred over chemical tables
• Criticism:
– Many (20%) violations from idealized filling rules
– Chemical similarities less evident (e.g. Mg and Zn)

34 35
 Electronic configuration tables (2) Short periodic table (1)

• 8 columns
• Based on Mendeleev’s 1870 periodic tables (Natural System of Elements)
• Standard periodic table for almost 100 years
• Original form had 8 column, labeled I to VIII, reflecting maximum valency of
elements in group
• Valencies are clearly seen in fluorine and oxygen compounds:

• This grouping brings together elements which are quite dissimilar, such as
metals and non-metals (e.g. vanadium and phosphorus in group V)
• Mendeleev split columns in two subgroups A and B
vanadium: VA phosphorus: VB
• Group VIII was not split: contains elements with properties that are very
similar and occurred in groups of 3: Fe-Co-Ni, Ru-Rh-Pd, Os-Ir-Pt
36 37

Short periodic table (2) Short periodic table (1870)

• For some elements (e.g. Cu, Ag, Au) not the maximum, but minimum valency
used for classification
• Noble gases have been added later as Group 0
– Reflects that Mendeleev had not foreseen room for these elements
– Reflects that their valency is 0 (little or no tendency to form compounds)
• Advantages:
– Simple and concise (8 columns)
– Reflect periodicity of chemical and physical properties
– Group together large range of elements that share same highest valence (e.g. Be,
Mg, Ca, Zn, Cd in Group II)
• Disadvantages
– Difficult to see trends in filling of atomic orbitals with electrons
– Does not show well that not all periods have the same length
– Transition metals do not fit well in table

38 39
 Short periodic table (1951) Short periodic table (modern)

40 41

Medium-long form periodic table (1) Medium-long form periodic table (2)

• 18 columns
• By far most common and most popular form of periodic table
• Advantages
– Clearly displaying groups of elements that have similar properties in columns
– Shown that not all periods have same length 2-8-8-18-18-32-32
– Gradual filling of electronic shells is clearly shown
– s, p, d, f blocks are clearly shown
– Transition elements are no longer excluded from other elements
– Fits better on an A4 page than long form periodic table
• Disadvantages
– Not very symmetrical (gaps and interrumptions)
– Lanthanides and actinides are footnotes to periodic table
• Complicated and controversial numbering
– Roman numbers, American and European A-B convention
– IUPAC numbering (group labels 1 to 18)
• Tells nothing about chemistry or logic
• Relationship with highest oxidation state is lost
• No numbering for actinides and lanthanides 42 43
 Medium-long form periodic table (3) Long-form periodic table

• 32 columns
• Advantages
– Every element can be incorporated in main body of table
(lanthanides and actinides are no longer footnotes)
– Shows every single elements in correct sequence of increasing atomic number
• Disadvantage
– Difficult to print on A4 page in book
• Preferred form for display in large lecture halls

44 45

Left-step periodic table (LSPT) (1) Left-step periodic table (LSPT) (2)

• Introduced by French engineer and amateur scientist Charles Janet in 1928
• 32-column table
• Advantages
– Aesthetically appealing
– More symmetrical and more regular than medium-long and long periodic tables
– Lanthanides and actinides become fully incorporated
– Ordering of blocks (f-d-p-s) is more natural than in conventional long form table
(s-f-d-p)
– Strongly emphasizes electronic structure of isolated atoms in the gas phase
– All period lengths are repeated: 2-2-8-8-18-18-32-32
(versus 2-8-8-18-18-32-32 in conventional long form table)
– Follows Madelung rule without any exception (see Chapter 3)
• Disadvantages
– Odd position of noble gas He above alkaline earth metal Be
– Non-metals are positioned between two blocks of metals

46 47
Janet's Left Step Periodic Table (1928) Step-pyramid periodic table (1)

• 32 column table
• Combines advantages and information content of the chemical table and the
electronic configuration table
• Bayley−Thomson−Bohr table
• Modified and promoted by William B Jensen (University of Cincinnati, USA)
in 1980s
• Unfortunately never enjoyed great popularity

48 49

Bayley’s periodic table (1882) Thomsen’s periodic table (1895)

50 51
 Bohr’s periodic table (1922)

52 53

Step-pyramid periodic table (5) Extended periodic table

• Advantages • 50 colums
– Aesthetic appeal due to its symmetric shape • For elements beyond Z = 118
– Easy to extraction electronic configuration for isolated gas atoms • Extends periodic table to Z = 168
– Different blocks (s, p, d, f) are easily recognized
• Element 121 will only mark formal beginning of g-block since theoretical
– Lanthanides and actinides (f-block elements) have been fully inserted in table calculations predict that first element with true g-orbital electron will occur at
– Uses both maximum oxidation state group numbers and A-B group modifiers Z ≈125
– Extension of A-B group modifiers to f-block (C series)
• No consensus on electron configurations of elements with Z > 120 and their
• Disadvantages placement in periodic table.
– Less familiar shape, and therefore not popular

• A: elements deriving their valence electrons solely from outermost n shell

B: elements capable of (but not necessarily) also employing electrons from the
n-1 shell
C: elements capable of (but not necessarily) also employing electrons from the
n-2 shell

54 55
 Number of possible elements? Island of stability

• Number of possible elements is unknown

• Predictions that periodic table ends soon after island of stability
(110 < Z < 126)
• Elements become very unstable (α decay and spontaneous fission)
• Other theories predict elements to Z ≈ 164 due to other islands of stability with
unknown stabilizing effects nuclear shell.

• IUPAC defines an element to exist if its lifetime is > 10-14 s (> 10 fs)
= time for nucleus to form electron cloud
• Some chemists question whether atoms that don’t have time to interact can be
considered as elements, because no chemical properties can be assigned to
these atoms

56 57

Non-table shaped 2D periodic systems Philip Stewart's Chemical Galaxy (2003)

• Circular and elliptical periodic systems

– Highlight continuity of elements better than rectangular forms
• Spiral periodic systems
– Stress continuity rather than breaks at noble gases
– Existence of noble gases could have been predicted by using a spiral display

58 59
 Transitional elements and transition elements (1)
• Originally terms ‘transitional elements’, ‘Übergangsmetalle’ and ‘transition
elements’ used for group VIII triads:
Fe−Co −Ni Ru −Rh −Pd Os − Ir − Pt
60
Transitional elements and transition elements (3)
• Charles R. Bury (1921): first use of term ‘transition’ in terms of electronic
structure
– “8 −18 transition series”: change of occupancy of electronic shell from 8 to 18 e-
– “18 −32 transition series”: change of occupancy of electronic shell from 18 to 32 e-
• Term ‘transition metal’ is no longer connected to Group VIII but to d-block
elements
• d-block elements: ‘transition elements’
f-block elements: ‘inner transition elements’ (valence shell is not outer shell)
s- an p-block elements: ‘representative elements’
• Most chemists use terms ‘transition element’ and ‘d-block element’ as
synonyms
• d-block element = any element that uses either (n-1)d electrons or empty
(n-1)d orbitals in its bonding
• When (n-1)d electrons have ceased to function as valence electrons and have
become part of atomic core, element can strictly not be considered as d-block
element (cfr. Zn group)
62
Transitional elements and transition elements (2)
• Name suggested that triads represented gradual transition between one cycle of
increasing maximum oxidation state (e.g. K(I) to Mn(VII) on MnO4-) and
beginning of another cycle (e.g. Cu(I) to Br(VII) in BrO4-)
• Transitional elements
– ‘Bridging’ elements (between 2 periods)
– Similar in atomic weight and chemical properties
– Variable oxidation states (reflecting their transitional nature)
– Frequently resistant to attack by common reagents (hence name ‘noble metal’ for
heavier members)
– Later considered as imperfect ‘noble gases’
• Noble gases
– Were considered as more perfect transitional species than group VIII triads
– Much sharper contrast between element at end of period and beginning of next
period (e.g. Cl(VII) to K(I) compared with Mn(VII) to Cu(I)
– Transition occurs in 1 step instead of 3 steps
– Noble gases are chemically much less reactive than noble metals
61
Primary versus secondary classification
• Not all periodic tables adhere to same classification of elements
• Chemical elements are not always placed in exactly the same groups
• No agreement about accommodation of several elements: H, He,
f-block elements
• Construction methodology of periodic table: 2-step process
1. Primary classification:
• Elements are ordered according to increasing atomic number Z
• Long horizontal sequence of elements (= Mendeleev line)
• Ordering according to Z is unique and unambiguous; no discussion possible
2. Secondary classification:
• Cutting Mendeleev line at well-chosen positions and placing the different
sections (the periods) underneath each other so that elements with similar
chemical properties fall into same vertical column
• Natural are formed and they represent the periodic law graphically
• Different criteria possible for partitioning the Mendeleev line (valency,
electronic configuration, chemical and physical properties…). Causes a lot of
discussion
63
 Position of hydrogen in periodic table (2)
Position of hydrogen in periodic table (1)

• First element in periodic table (Z = 1)

• Different from all other elements
• No electronic core, only naked nucleus
• Valence shell consists of a single nodeless orbital only (1s)
• 1 valence electron, not loosely bound as in alkali metals
• 1 hole in its valence shell, not strongly electron-attracting as in the halogens
• Little chemical sense in advocating for a place of H in any specific column
• Five different positions have been proposed for H in periodic table:
1. in Group 1 (alkali metals), above Li
2. in Group 17 (halogens), above F
3. in Group 14 (carbon group), above C
4. above both Li and F
5. H should be treated as a stand-alone element, in center of periodic table

64 65

Position of hydrogen in periodic table (3) Position of hydrogen in periodic table (4)

66 67
 Position of hydrogen in periodic table (5)
Position of hydrogen in periodic table (6)

• Group 1 (above Li) is most popular position for H

Pro
– H is monovalent (as alkali metals) and forms compounds with same general
formula (e.g. HCl and LiCl)
– Same atomic ground term of H and alkali metals (2S1/2)
– At very high pressures (≈ 500 GPa) metallic hydrogen is formed
Con
– No alkali metals forms M- anions (unlike the hydride anion H-)
– MX salts ( M = alkali, X = halogen) are ionic solids, HX compounds are covalent
and gaseous
– Considering the ionization energy, H is incompatible with Group 1

68 69

Position of hydrogen in periodic table (7) Position of hydrogen in periodic table (8)

• Group 17 (above F) • Group 4 (above C)

Pro
– H forms covalent compounds with nonmetals, but ionic compounds with alkali
metals and most alkaline earths. Halogens do the same.
– H form negatively charged hydride anion (H-), just like the halogens form
negatively charged halide anions (e.g. F-)
– H, as a simple substance, exists in the form of diatomic molecules (H2), just like the
halogens
Con
– Atomic ground term of all halogens is 2P3/2, while that of H is 2S1/2
– Trend in electronegativities in series H, F, Cl, Br. I is counter-intuitive (one would
expect that first member of series has highest value, which is not the case for H)
– Alkali metals M react with H2O forming MOH and H2; M react with X2O (X = F.
Cl) to form MX and H2O
– Alkali hydrides MH react with H2O forming MOH and H2; no reaction occurs
between MH and X2O or (X = F, Cl).
– Considering the ionization energy, H is incompatible with Group 17
70
Pro
– Valence shell of H (1s1) is half-filled, just as that of C ([He]2s22p2)
– Electronegativity of H is between that of C and Si
– Hydrogen compounds are closely related to compounds with CH3 group instead of
H
– H−H and C−C bonds are of comparable strengths
Con
– Highly unusual to place monovalent element above tetravalent one
– Atomic ground state terms of H (2S1/2) and C (3P1) are very different
• Above both Li and F
Pro
– Highlights resemblance of H with both Group 1 and Group 17 elements
Con
– Duplication of elements in periodic table is not recommended
(violates approach of primary and secondary classification)
71
 Position of hydrogen in periodic table (9) Position of helium in periodic table (1)

• Stand-alone position centered between alkali metals and halogens • He has stable, closed 1s2 shell, comparable to stable, closed shell n(sp)8 of
Pro other noble gases
– Position is consistent with the elements at top of each group being significantly • He behaves similar to other noble gases and forms end point of a period
different from their congeners; • In all most periodic tables, He is placed together with other noble gases in
– H lies at head of entire table and can be expected to be strikingly different from all Period 18.
the elements
• In the left-step periodic table (LSPT), He is placed above Be in Group 2.
– It stresses H’s unique character
• Placing He above Be has pros and cons
– Approach does not exclude H from periodic table; H is just not placed in any group
Con
– No real cons based on chemical arguments
– Not a popular approach

72 73

Position of helium in periodic table (2)

He above Be?

• Arguments pro:
– Placement reproduces consistently large gap between properties of Period 1 and 2
elements (H is as much an alkali metal as Be is an alkaline earth metal)
– Valence shell of He (1s2) is more similar to that of Be ([He]s2) than that of Ne
([He]2s22p6)
• Arguments con:
– He would be absent from the group of noble gases
– In the periodic table, elements with large ionization potentials are expected in upper
right corner, whereas element with largest value (He) would be absent
– Similarity in valence shells of He and Be is not relevant in chemistry
– Be and other Group 2 elements have accessible p orbitals and show nsp hybrization
upon reaction with adjacent elements, whereas He has no accessible p orbitals
– Only electron configuration and atomic spectra of He that match those of alkaline
earths, but both alkaline earths and noble gases have same ground state term (1S0)
– There is a lack of real chemistry of helium (Na2He is formed under extreme
conditions but is a sodium electride with He(0))
• Conclusion: position of He as the first noble gas (and least reactive in periodic
table) is fully justified
74 75
 Position of f-block elements

• Three different opinions about positions of f-block elements:

– 15LaAc (recommended by IUPAC)
– 14CeTh
– 14LaAc (preferred version)
• Which elements belong to Group 3 (IIIB)?

scandium − yttrium − lanthanum − actinium (Sc − Y − La − Ac)

or
scandium − yttrium − lutetium − lawrencium (Sc − Y − Lu − Lr)

• A lot of chemical and physical evidence supports Sc − Y − Lu − Lr

• Confusion caused by incorrect older electronic configurations
• Modern spectroscopic work indicates that La and Ac should be considered as the first
members of the f-block, while Yb and No are the last members. Lu and Lr are 1st
members of d-block for Periods 6 and 7.

76 77

78 79
80 81

82 83
 Zn group (2)
Zn group (1)

• Some chemists make objections against termination of d-block at

Zn − Cd − Hg (Zn group)
• From a spectroscopic point of view, Zn group members are analogous to
alkaline earth metals (Group 2)
• From a chemical point of view, Zn and Cd most resemble Be and Mg, not only
in terms of their atomic radii, ionic radii, and electronegativities, but also in
terms of structures of their binary com-pounds and in their ability to form
complex ions with a wide variety of oxygen and nitrogen donor ligands
(including complex hydrates and amines)
• Prior to WOII, similarities between Be, Mg, Zn and Cd was considered to be
greater than similarities between Be, Mg and the rest of the alkaline earth
metals (Ca − Ra)
• Older inorganic chemistry books discuss Be and Mg in chapter on Zn
subgroup, rather than Ca subgroup

84 85

Zn group (3) Zn group (4)

86 87

Zn group (5)
• d-block element is defined as element that uses (n-1)d electrons or empty
(n-1)d orbitals in bonding
• All elements from Sc to Cu group exhibit 1 or more oxidation states that meets
these conditions and can thus be qualified as d-block elements. Members of
the Zn group do not
• Members of Cu group show several oxidation states, members of Zn group
only +II oxidation state
• In Cu group, filled (n-1)d10 shell is involved in bonding, even in M(I)
oxidation state. In Zn group, filled (n-1)d10 shell is not involved in bonding
and is part of atomic core, just as in p-block elements that follow Zn group
• On basis of these arguments, d-block should finish at Cu − Ag − Au
• It is sometimes stated that for educational reasons the more symmetric and
more logic commonly used table with Zn − Cd − Hg in the d-block is
acceptable
88
Primary, secondary and tertiary analogies
between elements (2)
90
Primary, secondary and tertiary analogies
between elements (1)
• Primary analogy (= intra-group analogy)
– Same maximum number of outer valence electrons (defined as those lying outside
the first noble gas or pseudo-noble gas core)
– Same idealized arrangement or configuration for valence electrons
– closely related pattern of lower oxidation states
– Elements fall in same group, as distinguished by both group number and modifier
(e.g. IA and IIIB)
– Indicated on most periodic tables
• Secondary analogy (= inter-group analogy)
– Same maximum number of outer valence electrons
– Differing valence electron configurations
– Elements certain similarities and analogies when in their maximum oxidation
states, but not necessarily in lower oxidation states
– Belong to the same family (same group number), but with different group modifiers
(e.g. family II, with groups IIIA and IIIB)
– Explicitly indicated on step-pyramid periodic table by connecting elements in
question with dotted diagonal tie-line
89
Primary, secondary and tertiary analogies
between elements (3)
• Tertiary analogy
– Elements exhibit certain similarities when at least one of the elements is in a lower
oxidation state, but elements have neither same maximum number of valence
electrons nor same electronic configurations
– In general not indicated in periodic tables
– Examples:
• Fe(III) and Al(III)
• Comparison of Cu(I), Ag(I) and Au(I) with alkali metals
91
 Isodonor, isoacceptor and isovalent elements (1) Isodonor, isoacceptor and isovalent elements (2)

• Isodonor elements (e.g. S and Cr; Cl and Mn) • Isovalent elements (e.g. Li and Na; Cl and Br)
– Contain same number of valence electrons – Same number of valence electrons and same number of valence vacancies
– Can contribute or donate same number of valence electrons in bonding situation – Show strong primary analogies
– Show weaker secondary analogies to one another – Same progression of oxidation states
– Display similarities in their highest positive oxidation states, but not in their lower – Can substitute for one another in molecule or reaction without altering overall
or negative oxidation states stoichiometry
– Belong to the same family, but not to the same group – Belong to the same group
• Isoacceptor elements (e.g. H and F; He and Ne)
– Contain same number of valence vacancies
– Can accept same number of electrons in bonding situation
– Show very weak tertiary analogies
– Display analogies in their lowest negative oxidation state, but not for their positive
oxidation states
– Belong to the same family, but not to the same group

92 93

Schrödinger equation (1)

• de Broglie proposed that a moving particle has wavelength l proportional to

Planck's constant, h, and momentum p so that l = h/p, a property we now

Chapter 3 •
known as wave-particle duality.
Negatively charged electrons do not orbit around nucleus, but "associate" with
positively charged nucleus as 3D resonant standing waves
Quantum Mechanical Basis • Modes of resonance for single electron systems such as H atom are described
by time-independent Schrödinger wave equation:

of the Periodic Table

• Schrödinger equation is 2nd order differential equation for wave-like electron
resonating in 3 dimensions about point positive charge.
• Solutions to Schrödinger wave equation correspond to modes of electron
resonance and are formally called wavefunctions

1 2
 1D resonant standing waves: vibrating string
Schrödinger equation (2)

• Physically acceptable solutions exist only for certain values of E

• Quantization of energy: electron can possess only certain discrete energies in
atom
• Wavefunction contains all dynamical information possible about electron,
including where it is and what it is doing (taking into account Heisenberg's
uncertainty principle)
• Probability of finding electron at given location ∝ ψ2
• ψ2 : probability density of electron
• Atomic orbital: wavefunction of electron in atom
(orbital = 1-electron wavefunction)

Source: https://physics.stackexchange.com Source: http://www.meta-synthesis.com

3 4

2D resonant standing wave vibrating: drum skin

3D resonant standing waves

Source: http://www.meta-synthesis.com Source: http://www.meta-synthesis.com

5 6
 Atomic orbitals: quantum numbers Atomic orbitals: shells, subshells and orbitals

• n = principal quantum number • All orbitals with given value of n belong to same shell
1≤n n = 1, 2, 3, 4, … • All orbitals of given shell with same value of l belong to same subshell
determines energy of bound electron • Individual orbitals are distinguished by value of ml.
• l = azimuthal or angular momentum quantum number
0 ≤ l ≤ n −1 l = 0, 1, 2, 3 for n = 4 Value of l 0 1 2 3 4
specifies magnitude of orbital angular momentum
• ml = magnetic quantum number Subshell designation s p d f g
-l ≤ ml ≤ +l ml = -2, -1, 0, +1, +2 for l = 2
specifies orientation of orbital angular momentum
• s = spin quantum number
fixed at ½
defines intrinsic spin angular momentum • Write sign of ml, even when it is positive: ml = +2, not ml = 2
• ms = electron spin magnetic quantum number
ms = -½ or +½
defines spin orientation (spin up +, spin down -) • In hydrogenic atom, all orbitals with same value of n have same energy and
• 4 quantum numbers are needed to define state of electron in hydrogenic atom: are said to be degenerate.
n, l, ml, ms 7 8

Atomic orbitals: electron spin Atomic orbitals: nodes

• Spin = intrinsic angular momentum of e- • Orbitals are best expressed in polar coordinates.
• Name suggests that e- can be considered as having angular momentum arising • Hydrogen orbital can be rewritten as product of
from spinning motion, comparable with daily rotation of planet around its function R(r) of the radius and function Y(θ,φ) of the
polar axis angular coordinates:

• Regions where wavefunction passes through zero are called nodes.

• However, spin is purely quantum-mechanical properties and this analogy must • Radial nodes occur where radial component passes through zero,
be viewed with great caution. • Angular nodes occur where angular component passes through zero.
• Only 2 orientations are allowed for the spin, distinguished by quantum number • Numbers of both types of nodes increase with increasing energy and are
ms: related to quantum numbers n and l.
ms = +½ spin up ↑
ms = −½ spin down ↓
9 10
 Many-electron atoms Aufbau principle and Pauli exclusion principle

• Many-electron atom: atom with >1 e- • Aufbau principle (or building-up principle) is procedure for arriving at the
• Even He with 2 e- is many-electron atom lowest-energy electron configuration of many-electron atoms, a list of
• Schrödinger equation for atom with N e- is function of 3N coordinates of all e-, occupied orbitals in the ground state.
and cannot be solved exactly. • Ground state electron configuration = specification of orbital occupation of
• Approximations are required to perform calculations. an atom in its lowest energy state.
• Assumption: each electron moves independently of the others in the field of • Step 1: establish order of energies of atomic orbitals
nucleus that is modified by negative charge representing average effect of all • Step 2: electron needed to build the atom are entering the orbitals, starting at
other e- in atom. the one with the lowest energy.
• Orbital approximation: each e- occupies atomic orbital that resembles those
found in hydrogenic atoms • Number of e- that can occupy any orbital is limited by fundamental feature of
• True wavefunction can be approximated by product of N hydrogenic nature: Pauli exclusion principle:
wavefunctions:
No more than two electrons may occupy a single orbital, and if two do occupy
Ψ = ψ(r1) ψ(r2) …. ψ(rN) a single orbital, then their spins must be paired.

Electron 1 is described by wavefunction ψ(r1), electron 2 by • “paired”: 1 electron spin must be ↑ and the other ↓. Pair is denoted ↑↓
wavefunction ψ(r2) ,.. • No 2 electrons can have the same 4 quantum numbers (n, l, ml, ms)
11 12

Penetration and shielding (1) Penetration and shielding (2)

• Order of atomic orbitals in many-electron systems is approximately order of

hydrogenic orbitals, but with important modifications arising from electron-
electron repulsions.
• In orbital approximation, we treat repulsion between e- in an approximate
manner by supposing that electron in orbital experiences Coulombic attraction
to the nucleus and Coulombic repulsion from all the other e- in atom.
• Approximation: e- experiences single central field, being the sum of field of
nucleus and average field of all other e- treated as a point negative charge
centred on nucleus.
• Point negative charge reduces nuclear charge from true value Ze to effective
nuclear charge Zeffe for specific e- in atom.
• e- that are on average closer to nucleus experience higher values of Zeff than
those that on average are further away.
• Shielding = reduction of nuclear charge
• Shielding parameter σ = correction to true nuclear charge
Zeff = Z − σ

13 14
 Penetration and shielding (3) Penetration and shielding (4)

• Across a period, Zeff increases • ns lower than np is general feature for many-electron atoms
• Once we know effective nuclear charge, we can write approximate forms of • As a result of penetration and shielding, order of energies in many-electron
atomic orbitals. atoms is typically:
• ns e- in valence shell is less shielded than np e-
e.g. in F: Zeffe = 5.13e for 2s electrons, Zeffe = 5.10e for 2p electrons ns < np < nd < nf

• Penetration = presence of electron inside shells in a given shell, s orbitals are the most
of other electrons penetrating and f orbitals are the least
penetrating.
• Penetration of 2s e- through the inner core is
greater than that of 2p e- because the latter
vanishes at the nucleus. Therefore, 2s electrons
are less shielded than 2p electrons.
• 2s e- has lower energy (is bound more
tightly) than 2p e-;
• 2s orbital will be occupied before 2p orbitals
• Ground state configuration of Li is 1s22s1
or [He]2s1 15 16

Energies of orbitals of many-electron atoms (1) Energies of orbitals of many-electron atoms (2)

• Order of orbitals depends strongly on number of electrons present in atom and

may change on ionization.
• K and Ca: 4s penetrates deeper in core of atom than 3d
• After Ar ([Ne]3s23p6), not 3d but 4s is filled:
K: [Ar]4s1 Ca: [Ar]4s2
• From Sc onwards: 3d < 4s
• For neutral transition metal atom, 3d is slightly lower than 4s
• Delicate equilibrium between orbital energy and electron repulsion
neutral atoms: 4s23dn
cations: 4s03dn
• From Ga onwards: 3d << 4s
valence electrons are in 4s and 4p orbitals

17 18
 Energies of orbitals of many-electron atoms (3)
Rules for filling of orbitals

• Pauli’s exclusion principle:

Orbitals can contain a maximum of 2 electrons which must be of opposite
spin.

• Aufbau principle (building-up principle):

Electrons enter and fill lower energy orbitals before higher energy orbitals.

• Hund’s rule:
When there are degenerate (equal energy) orbitals available, electrons will
enter orbitals one-at-a-time to maximise degeneracy, and only when all
orbitals are half filled will pairing-up occur.

• Madelung’s rule:
(1) With increasing atomic number Z, orbitals are filled in order of increasing
N=n+l
(2) For fixed N, orbitals are filled in order of increasing n

19 20

Hund’s rule Hund’s rule

• When more than 1 orbital of the same energy is available for occupation, such
as when the 2p orbitals to be filled in B and C, Hund’s rule has to be adopted:

When more than one orbital has the same energy, electrons occupy separate
orbitals and do so with parallel spins.

Alternative formulation:

When there are degenerate (equal energy) orbitals available, electrons will enter
the orbitals one-at-a-time to maximise degeneracy, and only when all the orbitals
are half filled will pairing-up occur.

• This is rule of maximum multiplicity

21 22
 Madelung’s rule Orbital filling sequence

• Madelung’s rule: orbitals fill in order n + l (lowest n first).

• Sequence:
(n = 1) + (l = 0) = 1 1s
(n = 2) + (l = 0) = 2 2s
(n = 2) + (l = 1) = 3 2p
(n = 3) + (l = 0) = 3 3s
(n = 3) + (l = 1) = 4 3p
(n = 4) + (l = 0) = 4 4s
(n = 3) + (l = 2) = 5 3d
(n = 4) + (l = 1) = 5 4p
(n = 5) + (l = 0) = 5 5s
and so on...

• ‘Explains' why 4s orbital has lower energy than 3d orbital, and gives periodic
table its characteristic appearance.
23 24

Left-step Periodic Table (LSPT)

LSPT reflects Madelung’s rule

25 26
 Exchange energies (1) Exchange energies (2)

• Aufbau principle is based on premise that successive orbitals have quite large
energy separations and electron-electron repulsion effects are unimportant
• When these conditions are not met, electron congurations which diverge from
those predicted strictly according to the aufbau principle are observed
• Pair of e- with parallel spins experience less repulsion than pair in separate
orbitals with anti-parallel spins. Difference is described as the exchange
energy, K
• Difference results from spin correlation, i.e. quantum mechanical effect
which states that 2 e- in orbital do not move completely independently
• 2 e- with opposite spins occupy smaller volume than 2 e- with parallel spins
and therefore experience more repulsion
• Relative exchange energies for alternative electron configurations is estimated
3(3-1)/2 = 3
by calculating number of pairs of e- with parallel spins and multiplying it by K
2(2-1)/2 = 1
• n(n−1)/2 pairs of e- with parallel spins for n parallel spins

27 28

Exchange energies (3) Exchange energies (4)

Atoms listed in left column: attributed to exchange energy effects and associated
5(5-1)/2 + 2(2-1)/2 = 10 + 1 = 11 with either full or half-full d and f shells.
Other exceptions associated with similar energies 4d/5s, 5d/6s, 5d /4f, 6d/5f
Exchange energy d7 = 11K orbitals

29 30
 Exchange energies (5) Closed shells and half-filled shells (1)

• Repulsion between 2 e- in different orbitals is smaller than that between 2 e- in
the same orbital
• If energy difference between 2 orbitals is smaller than difference in electron
repulsion for the 2 electron configurations then there is energy stabilization by
the 2 e- occupying different orbitals.
Parallel spins are maintained parallel spins, in order not to lose the favourable
exchange energy contribution
• So occupation of orbitals of higher energy can result in reduction in repulsions
between 2 e- that would occur if the lower-energy orbitals were occupied.
• Quantum mechanical description of atom is based on spherical shell model and
this suggests that atoms with complete shells may have greater stabilities than
those with incomplete shells
• Complete shells have no inherent stability
• Atom with closed shell configuration is only more stable than adjacent atoms
if its electrons are less available for bonding
• Energy of electron in orbital may be associated with ionization energy
• Plot of ionization energy vs atomic number basis for defining applications and
limitations of the shell model

31 32

Closed shells and half-filled shells (2) Closed shells and half-filled shells (3)

• `Inert' or `noble' gases which have completed shells have significantly higher
ionization energies than those of adjacent atoms
• Orbital separations are sufficiently large to provide well-defined shell structure
corresponding to filling of rows in Periodic Table
• Filling of shell coincides with maximum in effective nuclear charge
⇒ orbitals are contracted and more energy is required to remove e- from
influence of nucleus
• Orbital energies become less well separated as Z increases
⇒ closed shell concept becomes less valid down a column of Periodic Table
(xenon is more reactive than lighter noble gases)
• Alkali metals: valence electron resides in orbital with new principal quantum
number, n, which has radial distribution function with maximum well
separated from core electrons ⇒ large average distance of e- from nucleus
makes it relatively easy to remove e- from atom

33 34
 Similar properties of elements with similar
electronic configurations (1)
• Quantum mechanical interpretation of Periodic Table has highlighted
important fact that adoption of common valencies and oxidation states by
elements is associated with elements having closely similar electronic
configurations
Group 1: ns1np0
Group 2: ns2p0
Groups 13−18: ns2npy (y = 1−6)
• Columns of elements show common oxidation states and valencies because
they share generic electronic configurations
• Less clear for transition elements, lanthanides, and actinides: energies of the
valence orbitals are sufficiently similar that elements within same column
exhibit different ground state electronic configurations
35
Similar properties of elements with similar
electronic configurations (3)
• Square planar complexes of Ni, Pd, and Pt are related because the metals are
capable of forming similar empty hybrid orbitals from valence orbitals with
common values of l quantum number and have common d8 electronic
configurations associated with M2+ ions
• [ML4]2+ complexes are each associated with total of 16 valence electrons, d8
from metal and 8 donated by the 4 ligands
37
Similar properties of elements with similar
electronic configurations (2)
• Ni, Pd, Pt compounds show many similarities because of same number of
valence electrons occupying valence orbitals with the same l quantum number
values
• Properties and structures of molecules are determined primarily by
combination of valence orbitals used to form the bonds and number of
electrons occupying the orbitals
• Ni, Pd, and Pt all form square planar complexes when metals are in their +2
oxidation states
• Bonding via dsp2 hybrid orbitals which point towards ligands which define
square plane (Ni: 3d4s4p2, Pd: 4d5s5p2, Pt: 5d6s6p2)
• n quantum number are different, but orbitals have same orientation
• Hybrids are empty and can accommodate lone pairs of ligands
• M2+ ions have common electronic configuration nd8(n+l)s0(n+l)p0
(n = 3, 4, or 5)
• When atoms are ionized, nd orbitals are stabilized more than (n + 1)s and
(n + 1)p orbitals ⇒ ground state is more stable with d orbitals occupied
36
Similar properties of elements with similar
electronic configurations (4)
• Chemical and structural properties of elements and their compounds are
determined mainly by the total number of valence electrons
• Precise electron occupations of (n+1)s, (n+1)p and nd orbitals for column of
elements is relatively unimportant
• Periodic relationships are not undermined by atoms in column which do not
have same number of electrons occupying orbitals with the same l quantum
number
• Remember: electronic configurations indicated in Periodic Table are those of
isolated neutral atoms in the gas phase!
38
 General observations

• Group trends = trends within 1 column of Periodic Table

• All members of certain group in s or p block have similar, with increasing
Chapter 4 atomic mass gradually changing, physical and chemical properties and form
compounds with similar stoichiometry:
– Same number of valence electrons
Vertical Trends in the Periodic – (Mean) distance of electrons from nucleus increases with increasing atomic number
– Increase of the tendency to donate electrons within group (ionisation energy
decreases)
Table (Group Trends)

1 2

Atomic sizes (1) Atomic sizes (2)

• Increment in principal quantum number (n) generally results in increase in

atomic size within a group
• Difficult to define radius of isolated atom
• Metallic radius: half of distance between nuclei of nearest neighbour atoms in
metal lattice of solid
• Covalent radius: contribution to covalent bond
length where bond order is 1
• Ionic radius: distance between centres of cation and
anion, assuming that radius of O2- ion is 140 pm

3 4
 Atomic sizes (3) Atomic sizes (4)

• Groups 1 and 2
– metallic radii increase with principal quantum number n
– effect is not linear, but approximately parabolic, with incremental increase
becoming smaller as n increases
• Group 13
– discontinuity is observed at Ga (transition metal contraction)
– radius expansion at Tl is smaller than predicted (lanthanide contraction)
• Zeff increases across series, because valence electrons are not effectively
screened from nucleus by electrons in same valence shell
• Zeff (Ga) experienced by valence electrons larger than extrapolated from Zeff
(B) and Zeff (Al)
• Prior to Ga, 3d shell has been filled for 1st time
• Zeff seen by 4s (Ga) >> Zeff seen by 4s (Al) due to 3d shell
⇒ valence electron shell Ga is contracted

• Zeff (Tl) experienced by valence electrons larger than extrapolated from Zeff
(Ga) due to inefficient screening by 4f shell ('lanthanide contraction‘)

5 6

Atomic sizes (5) Atomic sizes (6)

• For transition elements, change in radius in going from 3d to 4d metals is

much larger than that from 4d to 5d
• Results from filling of 4f shell prior to occupation of 5d orbitals, an inefficient
screening by 4f shell ('lanthanide contraction‘)

7 8
 Atomic sizes (7) Atomic sizes (8)

• Groups 14−17 • Relative sizes of atoms in group have important implications for structural and
– radii in general increase with the principal quantum number n chemical properties
– transition metal contraction is again evident for 3rd period elements • Down in group:
– transition metal contraction more pronounced for Group 14 and 15 than for – Coordination number increases (larger central metal ion)
Group 16 and 17 – Lattice energies of ionic compounds decrease
– Hydration enthalpy decreases

9 10

Ionization energies (1)

• Ionization energy I (or ionization potential) is the minimum energy needed to

remove an electron from a gas phase atom:

A(g) → A+(g) + e-(g) I = E(A+,g) − E(a,g)

• First ionization energy, I1, is the energy required to remove the least tightly
bound electron from the neutral atom
• Second ionization energy, I2, is the energy required to remove the least
tightly bound electron from the resulting cation, and so on.
• Ionization energies are expressed in eV or kJ/mol (1 eV = 96.49 kJ/mol)
• Successive ionizations of species require higher energies
• Ionization energies correlate strongly with atomic radii: elements that have
large atomic radii generally have low ionization energies (easy to remove
electron)
• Down a given column of elements 1st ionisation energies generally decrease
• As the principal quantum number n increases, maximum in radial distribution
function for valence orbital moves progressively farther from nucleus. 11 12
Ionization energies (3) Electronegativities (1)

• Electronegativity of element is power of atom to attract electrons when it is

part of compound
• Measured by electronegativity coefficient χ
• Electronegativity is atomic property to describe electron distributions in
molecules
• If atom has strong tendency to acquire electrons, it is said to be highly
electronegative (e.g. elements close to F)
• element with low electronegativity de scribed as electropositive
• Periodic trends in electronegativity can be related to size of atoms and electron
configuration.
• If atom is small and has almost closed shell of electrons, it is more likely to
attract electron to itself than large atom with few valence electrons
• Different electronegativity scales in use: Pauling, Mulliken, Allred−Rochow
• Allred−Rochow scale related electronegativity to force exerted by nuclear
charge of atom in region where electron density of the bond is largest:

13 14

Electronegativities (2) Electronegativities (3)

15 16
 Electronegativities (4)

• Trends in electronegativities across Periodic Table:

– Electronegativities generally decrease down a column (Group)
– Ga, Ge, As, Se, and Br have higher electronegativities than expected
(transition metal contraction)
– Tl, Pb, and Bi have higher electronegativities than expected
(lanthanide contraction)
– Large decrease in electronegativity between 2nd and 3rd row elements (C to Si, N to
P, O to S, and F to Cl); less dramatically for subsequent rows
– Electronegativities increase across period because Zeff increases and r decreases
• Electronegativity differences between atoms influence polarities of bonds;
determine not only their ionic character, but also their chemical reactivities
• Change in bond character with increasing electronegativity differences:

covalent → polar covalent → polarized ionic → ionic

• No sharp border between different bond types

• CsF χA - χB = 3.24 100% ionic
17 18

Polarisabilities and polarising powers (1) Polarisabilities and polarising powers (2)

• Atoms and ions are not hard undeformable spheres

• Electron clouds which surround nucleus may be distorted by electrostatic
fields generated by electric charges on neighbouring atoms
• Ease of electron cloud deformation depends on:
– volume of atom or ion
– Number of electrons associated with atom
– Electron density probability function
• Large atoms or ions with low electronegativities: highly polarizable
• Small atoms with high electronegativities: weakly polarizable
• Polarizability (α): ability of atom or ion to be distorted by electric field
• Positively charged cation adjacent to negatively charged anion causes
distortion of the electron cloud anions ⇒ formation partial covalent bond
• Polarisability of anion Am-

19 20
 Polarisabilities and polarising powers (3)
• Polarising power of a cation Mn+
21
Polarisabilities and polarising powers (5)
• As size of cation decreases its polarising power increases and covalent
contribution becomes more significant: LiF > NaF > KF > RbF > CsF
• As the size of the anion becomes smaller its polarisability decreases and
bonding becomes more ionic, i.e. covalent contribution decreases: NaI > NaBr
> NaCl > NaF
• As charges on cation and anion are varied, following trend in covalent
character is observed: AlN > MgO > NaF
• High polarising powers of Li+ and Be2+ arising from their high charge/size
ratio make their compounds significantly more covalent than those of other
group members
23
Polarisabilities and polarising powers (4)
22
Relative orbital energies and overlaps (1)
• Increase in principal quantum number n down a column of Periodic Table
leads to increase in sizes of valence orbitals
• On descending the column, s orbital contracts relative to the p and participates
less in covalent bonding
• Strengths of covalent chemical bonds depend on extent of overlap between
orbitals on adjacent atoms in molecule; overlaps between atoms separated by
sum of their covalent radii decrease down column
• Relative energies of ns and np valence orbitals of p block elements vary across
periods and down groups of Periodic Table
• For p block element, ns orbital is significantly more stable than np because of
greater effective nuclear charges it experiences
24
 Relative orbital energies and overlaps (2)
25
Relative orbital energies and overlaps (4)
• Separation between s and p orbitals becomes larger across row of elements and
ionization energies of s orbitals are very high for Group 17 elements
• This trend make s orbital less available for bonding and chemical bonding
depends increasingly on overlapping abilities of p orbitals
• s orbitals are essentially core-like for Group 17 and 18 elements
• Transition metal contraction influences 4s orbital ionization energies for
Groups 13 and 14:
– Ga and Ge have higher ns orbital energies than simple extrapolation may have
suggested
– 4s orbitals of these elements are more core-like and less involved in bonding
27
Relative orbital energies and overlaps (3)
• Ionization energies of 2s and 2p orbitals of 2nd row elements are high due
contracted nature of orbitals
• Orbitals overlap very strongly with orbitals of other atoms at short internuclear
distances
• 2nd row p block elements form particularly strong multiple bonds.
• s (and p) orbital ionization energies are very similar for 3rd and 4th row
elements, but significantly smaller than those for 2nd row elements
• Relatively expanded valence orbitals of heavier elements lead to poorer
overlaps and generally weaker bonds
• Strength of bonding interactions deteriorate particularly rapidly down the
group
26
Melting points and enthalpies of atomization (1)
• When elements of particular column of Periodic Table have similar structures,
melting and boiling points reflect strength of interaction between atoms or
molecules (e.g. for S8 and I2)
• Standard enthalpy of atomisation of element : enthalpy change
associated with transfer of 1 mole of element from its standard state to that of
gaseous atoms at 298 K
• provides precise estimate of strength of interactions in solid state
28
 Melting points and enthalpies of atomization (2) Melting points and enthalpies of atomization (3)

• Group 1 elements all have body-centered cubic metallic structures
• Melting points suggest that the metal-metal bonding interactions become
progressively weaker down in Group
• Same trend observed for
• Strength of the metal-metal bonding depends primarily on ability of their s
valence orbitals to overlap with s orbitals of neighbouring atoms in the infinite
metallic lattice
• Same trend for Group 2 elements
• Metallic elements generally adopt close-packed structures (cubic or
hexagonal) with small energy differences
• Large variations in structure are observed for p-block elements as elements
become progressively more metallic downwards in Group
• Dramatic changes in structures in Group are reflected in melting points
• Many of p-block elements occur in several modifications (allotropes), which
have significantly different chemical and physical properties

29 30

Melting points and enthalpies of atomization (4) Melting points and enthalpies of atomization (5)

• Group 17 elements (halogens) show solid-state structures based on infinitely

packed diatomic molecules X2
• Regular increase in melting points
• intermolecular interactions (van der Waals) in solid state between X2
molecules depend upon polarizabilities of molecules
• F2: least polarizable molecule ⇒ lowest melting point
• I2: most polarizable molecule ⇒ highest melting point

31 32
 Densities (1) Densities (2)

• Relative increase in atomic masses down a column usually outweighs effect of

larger atomic volumes ⇒ densities generally get larger
• Steady increase in densities is observed for Groups 1 and 13 and for all other
groups in the Periodic Table, with the exception of Group 2

33 34

Densities (3) Group 1: Alkali metals

• In Group 2, effect of increasing relative atomic masses (RAM) outweighs

increasing atomic volumes

• When is plotted, observed trend in density is reproduced

35 36
 Group 1: Alkali metals Group 1: Alkali metals

Lithium

Rubidium crystals (silvery) compared to cesium crystals (golden)

Sodium Potassium
37 38

Group 1: Alkali metals Group 1: Alkali metals

39 40
 Group 1 trends (1) Group 1 trends (2)

1. All the metals are malleable and become softer down the column. 6. Reverse order of reactivity observed for reactions of alkali metals with N2 and
– Li has to be cut with a knife C (Li most reactive)
– Rb and Cs have consistency of a putty – Only Li reacts with N2, forming nitride Li3N
2. Reactivity of the metals towards H2O (and O2) increases down the column – Only Li and Na react with C to form the carbides M2C2 (M = Li or Na)
– Li reacts slowly with H2O 7. Li and Na form a number of hydrated solid salts, K forms a few and Rb and Cs
– Na reacts vigorously with H2O none (due to decreasing charge density down in group)
– K causes the evolved H2 to ignite 8. Solubilities of the hydroxides in water increase down the column:
– Rb and Cs react explosively with H2O LiOH < NaOH < KOH < RbOH < CsOH
– In reaction with O2, Li forms Li2O, Na forms peroxide Na2O2, while K, Rb, Cs 9. Alkali metals do not readily form complexes with ligands such as NH3 and
form superoxides MO2 CN- , but polydentate ligands such as crown ethers and cryptands with oxygen
3. Li does not replace H in Ph−C≡C−H, whereas other alkali metals do and nitrogen donor atoms do form stable complexes
4. All elements form salts with typical ionic properties – Bonding in complexes is primarily electrostatic
– Halides are ionic and not hydrolyzed – Relative sizes of cation and cavity are important
– Oxides and hydroxides are basic 10. Li alkyls are covalent and readily soluble in hydrocarbon solvents; while Na
– Hydrides are ionic and strongly reducing agents and K alkyls are ionic and not soluble in hydrocarbon solvents
5. Thermal stabilities of carbonates, nitrates, sulfates, peroxides, and superoxides
increase down the column
41 42

Crown ethers

43 44
 Anomalous properties associated with lithium Group 2: Alkaline earth metals

• High enthalpy of atomization of lithium metal, high hydration enthalpy of Li+

and its small size make it stand out from other members of alkali metal series
1. Li reacts very slowly with H2O, but it is only alkali metal to form nitride with
N2
2. Li salts are generally less soluble in H2O, but more soluble in organic solvents
3. Li salts are much less thermally stable because, lattice energy of Li2O is much
greater than those of original salts
– Li2CO3 decomposes at 700 °C; Na2CO3 and K2CO3 do not decompose below 800°C
– LiOH decomposes upon heating to Li2O and H2O, whereas NaOH and KOH do not
show this reaction
– Li does not form a stable hydrogencarbonate
4. Greater electronegativity of Li leads to the formation of less polar (more
covalent) organometallic compounds with oligomeric structures, rather than
3D infinite structures for the heavier elements of Group 1
5. Organometallic compounds of Li are more covalent and more soluble in
organic solvents and less reactive
6. High charge/size ratio of Li+ leads to more stable complexes with simple
ligands containing oxygen and nitrogen donor atoms 45 46

Group 2: Alkaline earth metals Group 2: Alkaline earth metals

Barium
Calcium
Beryllium

Magnesium Strontium Radium

47 48
 Group 2: Alkaline earth metals Group 2 trends (1)

1. Reactivity:
– Be least reactive; does not react with H2O even at red heat and does not react with
N2 .
– Mg only reacts at a reasonable rate with steam
– Ca and Sr readily tarnish in moist air
– Ba readily tarnishes even in dry air
2. Ionic character of compounds increases down the group
– Be forms highly covalent compounds generally with sp3 tetrahedral geometries, e.g.
[BeF4]2-
– Mg forms more polar compounds with 6-coordination
– Ca, Sr and Ba form increasingly ionic compounds with higher coordination
numbers (8 is particularly common)
3. Organometallic compounds
– Be: covalent and rather unreactive
– Mg: 2 classes of reactive organometallic compounds, RMgX and R2Mg. RMgX
(Grignard reagents) are often used in organic synthesis
– Ca, Sr, Ba: organometallic compounds are more and insoluble in organic solvents
(due to their ionic character)
49 50

Group 2 trends (2) Group 2 trends (3)

1. Oxides become progressively more basic down the group 4. Complex formation
– BeO and Be(OH)2 are amphoteric and react with acids and strong bases such as – Mg2+ and Ca2+ show reatest tendency to form complexes (O-donor ligands)
NaOH – Stability with small charged anions: Mg2+ > Ca2+ > Sr2+ > Ba2+
– MgO is basic and Mg(OH)2 weakly basic and do not dissolve in NaOH solution – Stability with NO3-, SO42- and IO4-: Ba2+ > Sr2+ > Ca2+ > Mg2+
– Oxides of Ca, Sr and Ba are basic and their hydroxides are strongly basic – Stability with EDTA4-: Mg2+ < Ca2+ > Sr2+ > Ba2+
– Solubilities in water: Ba(OH)2 > Sr(OH)2 > Ca(OH)2 > > Mg(OH)2 – Crown ethers and cryptands form stable complexes with Ca2+ and Mg2+
2. Halides
– BeX2 (X = F, Cl, Br or I) are covalent polymers which are readily hydrolysed and
are Lewis acids forming adducts BeX2L2 (L = Lewis base)
– Halides of Ca, Mg, Sr, Ba are essentially ionic and are soluble in water
3. Hydrides
– BeH2: covalent polymer
– MgH2: partially ionic
– CaH2, SrH2, BaH2: very ionic and hydridic in their properties

H4EDTA Ca(EDTA)2-
51 52
 Group 2 trends (4) Anomalous nature of beryllium

5. Biological role 1. High enthalpy of atomization of Be causes it to be harder, higher melting,

– Mg: chlorophyll (tetrapyrrole molecule)
– Ca: important structural role in cross-linking polymer chains (e.g. in collagen)
6. Thermal stabilities of nitrates, carbonates, and peroxides increase down the
group
7. Solubilities of sulphates, nitrates, and chlorides decrease down the group
8. Solubilities of halides in alcohols increase down the group
53
more dense, and less reactive than the heavier members of the group
2. High size/charge ratio of Be2+ leads to more covalent compounds and more
stable complexes than those of other Group 2 cations.
– Compounds with anomalously low melting points and enthalpies of formation
– Compounds are more soluble in organic solvents
– Compounds are stronger Lewis acids
– Halides are hygroscopic and fume when exposed to moist air
3. BeO and Be(OH)2 are amphoteric, unlike oxides and hydroxides of other
Group 2 elements
4. BeCO3 and BeSO4 decompose more readily on heating than the heavier Group
2 salts, due to high lattice energy of BeO
5. Be does not form a peroxide or superoxide
6. Be only reacts with steam, not with liquid water
54

Group 13: Earth metals Group 13 trends (1)

1. Chemistry of B is different from that of Al (and heavier Group 13 elements)

– Its oxide and hydroxide are acidic whereas those of Al are amphoteric
– B is semi-conductor whereas Al is a metal
– B is very inert and only attacked by hot concentrated oxidising acids, whereas Al
dissolves in non-oxidizing acids
– No simple salts of B3+ are known, whereas those of Al3+ are numerous and well
documented
– B forms a wide range of hydrides which have cage structures. (AlH3)4 has a
polymeric structure
– Stereochemistries of many B compounds are based on trigonal sp2 and tetrahedral
sp3 geometries. Al forms many compounds with tetrahedral, trigonal bipyramidal,
and octahedral geometries
– Multiple pπ−pπ bonding in B−N, B−O, and B−F compounds is much more
significant than that for corresponding Al compounds
2. Al, Ga, In, Tl all form a range of compounds in +3 oxidation state and
compounds in +1 oxidation state become progressively more stable down
Group 13

55 56
 Group 13 trends (2) Group 14: Carbon group

3. Oxides of Al and Ga are amphoteric and In and Tl oxides are more basic
4. Octahedral aqua-ions [M(OH2)6]3+ are acidic and the pKa values for the
equilibria:

are Al ≈5; Ga ≈ 3; In ≈ 4; Tl ≈ 1; showing that Al ion is least acidic

and Tl ion the most acidic
5. MX3 compounds are Lewis acids
Lewis acid strengths: Al > Ga > In
6. Stability of hydrides decreases down the Group (no stable Tl−H compounds
exist)
7. Al is resistant to corrosion because of impermeable oxide layer, but is soluble
in non-oxidizing mineral acids.
Ga and In dissolve readily in acids
Tl dissolves only slowly in H2SO4 and HCl
8. AlN, GaN, and InN have wurtzite structures analogous to cubic BN, but show
no analogue of graphite-type structure of BN.
57 58

Group 14 trends (1) Group 14 trends (2)

1. Stabilization of (+2) oxidation state relative to (+4) of the elements down the 3. Catenation (i.e. ability of element to form compounds with element−element
group bonds)
– Halides, oxides, and sulfides of M2+ ions become more stable on descending the – Element − element mean bond enthalpies decrease in order: C−C > Si −Si > Ge −
group; SiCl4, SiBr4, and SiI4 are all stable. PbCl4 decomposes at 105 °C and PbI4 Ge > Sn − Sn > Pb − Pb
does not exist – Range of ring and polyhedral molecules diminishes down the group
– PbCl2 may only be converted to PbCl4 by heating in a stream of Cl2 4. Multiply bonded compounds
– Stabilities of MII and MIV organometallic derivatives behave differently: PbEt4 – Ability to form multiple bonds diminishes in series: C − C > Si − Si > Ge − Ge >
which can be readily stored is more stable than PbEt2, which is not isolable as a Sn − Sn, > Pb − Pb, because the pπ−pπ overlaps become less favourable
solid.
5. Elements become progressively more metallic down the column
– Compounds in lower oxidation state are more ionic, less likely to form molecular
structures, the halides are less readily hydrolysed and the oxides are less acidic. 6. Oxides become more basic down the column
2. Hydrides and alkyls become less stable down the column – CO2 and SiO2 are acidic oxides
– M−H and M−C mean bond enthalpies decrease down the column; hydrides and – SnO2 is amphoteric
alkyls become thermodynamically less stable and kinetically more reactive – GeO2 is mainly acidic with slight amphoteric character
– Organometallic derivatives of Si and Ge are more reactive than those of C, because – Si − O mean bond enthalpies are particularly large and this leads to wide range of
the M − C bonds are more polar and central atom can expand its coordination silicates
number more easily 7. Typical coordination numbers increase down the group
– C: tetrahedron
59 – Heavier elements: tetrahedron, octahedron 60
 Group 14 trends (3)
8. Heavier elements form wider range of complexes and more cationic
complexes. Si, Ge, Sn, and Pb all form oxalato-complexes [M(ox)3]2- and
cationic complexes [M(acac)3]+, where acac is acetylacetonate
9. Ease of reduction of halides
Although C−Cl and Ge−Cl bonds in tetravalent compounds are reduced to the
corresponding hydrides by Zn and HCl, Si − Cl and Sn − Cl bonds are not
10. SiH4 hydrolyses in presence of trace amounts of base more readily than CH4,
GeH4, and SnH4
61
Group 15 trends (1)
1. Hydrides become less thermally stable and more reactive down the group.
M−H and M−CH3 mean bond enthalpies decrease in strength down the group
and consequently hydrides and alkyls become less stable
2. Majority of nitrogen compounds are covalent.
Exception: nitride compounds (with N3- anion)
3. Multiple bond formation
– Nitrogen forms very strong multiple pπ−pπ bonds to itself and neighbouring
elements belonging to the same row, e.g. C≡N-, N≡N, N≡O+
– Compounds of P, As, and Bi with multiple bonds may be obtained if large groups
are introduced into themolecules, e.g. P2R2 and As2R2-
– Multiply bonded compounds of Sb are not known
4. Increased metallic character
– Elements become increasingly metallic down the group in their chemical and
physical properties
– Down the group oxo cations, e.g. SbO+ and BiO+ become more prevalent
5. Oxides become more basic down the group: P and As oxides are acidic, Sb2O3
oxide is amphoteric, and Bi2O3 is basic
63
Group 15: Pnictogens
62
Group 15 trends (2)
6. Halides become more ionic and increasingly adopt infinite structures in
preference to molecular ones down in the Group
7. Catenation occurs in the order: N < P > As > Sb > Bi. Phosphorus forms wide
range of ring and cage compounds because of high value of mean bond
dissociation enthalpy D(P−P)
8. Negative oxidation states
– For nitrogen, N3- ion is well established in ionic nitrides of electropositive elements.
– Anionic derivatives of heavier elements frequently retain element−element bonds,
e.g. Sb42-, As113-
9. Hydrolysis of halides
+5 oxidation state: PF5 is not readily hydrolysed, AsF5 is hydrolysed,
SbF5 vigorously reacts with water, BiF5 reacts explosively with water
+3 oxidation state: NF3 is unreactive, PF3 reacts only with OH- not H2O, AsF3,
SbF3 are soluble in water, BiF3 is insoluble in water, soluble in inorganic acids
64
 Group 15 trends (3) Group 16: Chalcogens

10. Stabilization of +3 oxidation state relative to +5:

– Trend less defined than in Group 14
– Alternation in stabilities is observed: +5 oxidation state halides are unknown for N,
well defined for P, only stable for As as the fluoride, well defined for the fluoride
and chloride of Sb, and only known for the fluoride of Bi
– Stability halides (+3 and +5 oxidation state): F > Cl > Br > I
– Bi(V) and N(V) oxides and oxoacids are strongly oxidising whereas P(V) is very
stable and As(V) and Sb(V) are mildly oxidising

65 66

Group 16 trends (1) Group 16 trends (2)

1. Elements become progressively more metallic down the column. 6. Formation of molecular compounds with strong multiple bonds is particularly
– Po has chemical and physical properties characteristic of a metal important for oxygen
– Te lies on the borderline (metalloid) – pπ−pπ bonds: CO
2. Chemically, metallic character of heavier elements reflected in : – pπ−dπ bonds: OsO4
– Increased tendency to form cationic species – pπ−fπ bonds: UO22+
– Ionic character and basicities of their oxides 7. Increasing size of the atoms leads to compounds with progressively larger
– Increased tendency to form complexes maximum coordination numbers:
3. Non-metal character of earlier members of Group reflected in: – O: CN = 2 and 3 (exceptionally 4)
– Molecular nature of stable elemental allotropes – S: CN = 6
– Ability to form anions, e.g. O2- and S2-, which result from completing the octet – Te: CN = 8
– Compounds resulting from anions, e.g. Na2E, CaE (E = O, S, Se...) become – Rate of hydrolysis: TeF6 > SeF6 > SeF6
progressively more covalent down the Group as a result of decreasing – Octahedral anionic complexes [MMX6]2- (X = halide) are more commonly
electronegativity of chalcogens observed for Se, Te, and Po.
4. Thermal stabilities of hydrides EH2 decrease down the column because of 8. Oxygen has strong preference for -2 formal oxidation state, whereas heavier
decreasing EH mean bond enthalpies elements exhibit oxidation states of -2, +2, +4, and +6.
5. Abilities of hydrides to form hydrogen bonds decreases rapidly down the 9. Tendency towards catenation reaches maximum at sulfur which forms wide
Group after oxygen, with dramatic effect on boiling and melting points of range of ring and chain compounds, e.g. S8 and Sn
hydrides (e.g. H2O versus H2S). 67 68
 Group 17: Halogens Group 17 Halogens

Chlorine

Fluorine

69 Bromine Iodine 70

Group 17 trends (1) Group 17 trends (2)

1. All elements are diatomic and molecular (X2); boiling and melting points
increase due to increasing van der Waals interactions between diatomic
molecules for the heavier elements
2. Elements are typical non-metals in their physical and chemical properties
– Form anionic compounds based on X- which is associated with completed octet
– Ionic compounds MX become progressively less ionic as relative atomic mass of X
increases, because of decreasing electronegativity of halogens down in group
– Iodine has greatest tendency to form cationic species, e.g. I2+, I5+, because it has
lowest ionization energy
3. Atoms form strong covalent bonds with other non-metals
– Mean bond enthalpies for E−X bonds are particularly large for F
– Wide range of molecular fluorides is known
– F is particularly effective at bringing out highest valencies of non-metals and
highest oxidation states of metals
4. Oxidising ability of the halogens: F2 > Cl2 > Br2 > I2
Only I2 is oxidised by HNO3
5. Stabilities of HX decreases down the Group, but their acid strengths increase
71
6. Only HF forms strong hydrogen bonds and this is reflected in boiling and
melting points of HX
7. Halogens form many interhalogen compounds with the less electronegative
halogen surrounded by the more electronegative halogens
– ICl and IBr are commercially available
– Most extensive series of compounds exists for iodine, e.g. IF7, IF5, ICl4-, ICl2-
– Fluorine does not form any interhalogen compounds where it occupies central
position within the molecule
8. Oxygen fluorides OnF2 (n = 1 to 6) are extremely strong and reactive oxidants.
Oxides become less reactive down the column
9. Perhalates, XO4- are only known for Cl, Br, and I. They exhibit an alternation
in their oxidizing abilities and the perbromates are particularly strong
oxidizing agents
10. In the highest oxidation state (+7), relative oxidizing ability is: Br > I > Cl and
results in the formation of the corresponding +5 oxoanions (bromates, iodates
and chlorates)
11. +3 oxidation state is only significant for Cl
12. +1 oxidation state is well established for Cl, Br, and I 72
 Second row anomaly (1)
• Marked difference in properties between 2nd row elements (Li−Ne) and the
third row elements (Na − Ar). This difference relates to the elements
themselves and their compounds:
1. Anomalous properties of Li and Be compared to the other remaining alkali and
alkaline earth metals (vide supra)
2. Greater thermodynamic stability of allotropes of p-block metals which have
multiple bonds between atoms, e.g. O2 vs. S8, N2 vs. P4, etc. This characteristic
carries over to compounds of these elements, for instance CO2 (molecular)
versus (SiO2)n infinite lattice, etc.
3. Reduced tendency of compounds of 2nd row p-block elements to exhibit
maximum group valency, e.g. NF3 versus PF5; OF2 versus SF6,
4. Formation of higher coordination numbers for 3rd row elements and ability to
behave as Lewis acids even when octet rule is obeyed
5. Greater lability towards nucleophilic substitution for 3rd row halides, which
makes them more susceptible to hydrolysis
73
Secondary periodicity (1)
• Various chemical and physical properties show zigzag or alternating behavior
instead of the expected regular trend as one descends any group of elements.
• Elements in Group 15 display zigzag pattern in their common oxidation states
75
Second row anomaly (2)
• 2nd row elements are unique in the sense that they are only row which have
core consisting only of filled s shell (1s2):
– valence electrons being exposed to high effective nuclear charge
– relatively high orbital ionization energies
– high electronegativity coefficient
– small radii
– contracted atomic orbitals
• Their orbitals can overlap very effectively, leading to strong covalent bonds
and particularly multiple bonds because 2s and 2p orbitals are more similar in
their energies and rmax than 3s and 3p orbitals
• Additional filled shells which make up core levels for heavier p-block
elements result in greater inner shell repulsions between atoms and prevents
their close approach ⇒ reduces extent of inter-orbital overlap, particularly
pπ−pπ overlaps
• 3rd row elements have higher lying 3d valence orbitals which may contribute
to bonding and which are not available for 2nd row elements.
74
Secondary periodicity (2)
• Traditional explanation:
– Additional electron screening due to 3d10 electrons in the case of atoms in row 4,
such as As, and the even greater screening in atoms in row 6, such as Bi.
– Whereas P can readily lose 5 electrons, at least formally, to form a +5 ion, As
cannot do so because of d electron screening, which acts to `separate' outermost p
electrons from outermost s electrons.
– Similar argument can be made for change from Sb to Bi. Removal of 5 outermost
electrons in Bi is prevented by even greater separation in energy between 6s and 6p
outer-shell electrons due to intervening 4f14 electrons, which are absent in the
atoms of Sb
• Drop in sum of 1st 5 ionization energies between As and Sb is at first sight
surprising since both sets of outermost p and s electrons are screened to the
same extent by 10 d-orbital electrons in each case.
But overall decrease in ionization is normal behavior observed on descending
most groups in the Periodic Table.
76
 Secondary periodicity (3) Early actinide relationships (1)

• Group 13: B2H6 and Ga2H6 are volatile, whereas the intervening (AlH3)x is not. • Heavy actinides have properties similar to lanthanides: +III oxidation state
Stable borohydrides are formed by Al but not by B itself or Ga. Al(CH3)3 and dominates
Al(C2H5)3 are both dimeric in vapor phase, whereas the analogous B and Ga • Early actinides resemble transition metals: different oxidation states
compounds are monomeric. • In the past, thorium, protactinium, uranium, and plutonium were actually
• Group 14: Ge resembles C more than Si does. For example, SiH4 is far more placed as members of a 4th transition metal period
readily oxidized than is either GeH4 or CH4.
• Group 15: Phosphorus and antimony form a pentachloride, whereas arsenic
does not. While N(+V) and As(+V) compounds act as good oxidizing agents,
P(+V) does not. N(+III) and As(+III) compounds are far weaker reducing
agents than are compounds of P(+III)

77 78

Early actinide relationships (2)

Chapter 5
• Uranium forms compounds that are similar to chromium and molybdenum
compounds
diuranate ion, [U2O7]2- dichromate, [Cr2O7]2-
uranyl chloride, UO2Cl2 chromyl chloride, CrO2Cl2
molybdenyl chloride, MoO2Cl2 Horizontal Trends (Period
• Uranium bears the closest similarity with tungsten
+VI most stable oxidation state for U and W
Trends) and Diagonal Trends
form stable hexachlorides UCl6 and WCl6
in the Periodic Table

79 1
 Atomic volumes Densities

2 3

First ionization energies Allred−Rochow electronegativity coefficients

4 5
Bonding character in organometallic compounds Valencies and oxidation states (1)

• Valency (valence): (positive number)

– Number of H atoms which unite with 1 atom of that element
– Number of homopolar covalent bonds an atom is capable of forming
• Oxidation state: (can be positive or negative)
– Oxidation state of atom in molecule gives number of valence electrons it has gained
or lost
– Formal charge remaining on the element when all other atoms have been removed
as their normal ions\
• Mendeleev: close relation between the position of an element in the Periodic
Table and stoichiometry of its simple compounds:

Oxides: M2O, MO, M2O3, ..., M2O7, (MO4)

6 7

Valencies and oxidation states (2) Valencies and oxidation states (3)

8 9
 Valencies and oxidation states (4) Diagonal relationships (1)

• Groups 1 and 2: preferred oxidation state (or valency) = number of valence • Diagonal relationship: similarity in chemical properties between element and
electrons that to lower right of it in the Periodic Table
• Groups 13, 14, and 15: d-subshell is effectively core-like and group valency, • Properties of element and its compounds influenced by:
N, is 10 less than formal group numbering recommended by IUPAC – Atomic size (atomic radius)
• Groups 13−15: alternative N-2 valencies are observed which are associated – Electronegativity
with presence of lone pair of electrons on central atom (lone pair effect) – Strengths of bonds with other elements
e.g. In(I)/In(III), Sn(II)/Sn(IV) • Trend in electronegativity:
• Groups 16, 17, and 18: compounds with N, N-2, and N-4 valencies are – Increases on moving to the right in PT
observed. e.g. SF6, SCl4, SCl2 – Decreases on moving down a column
• Groups 17 and 18 the N-6 valency is also observed. • Trend in atomic size:
ClO4-, ClO3-, ClO2-, ClO- – Decreases on moving to the right in PT
– Increases on moving down a column
• 2 atoms which are diagonally related could have similar electronegativities and
atomic radii
• Comparable electronegativities and atomic radii may lead to similarities in
chemical properties which are apparent even though the 2 elements concerned
have different valencies.
10 11

Diagonal relationships (2) Diagonal relationships: lithium and magnesium

1. Li has enthalpy of vaporization, metallic radius, and electronegativity

coefficient which are more similar to those of Mg than Na ⇒ Many
similarities in chemistry of Li and Mg.
Li has an anomalously high enthalpy of vaporization, melting point, boiling
point, density and hardness
2. LiOH and Li2CO3 are much less soluble in water than the corresponding Na
and K compounds. Fluorides, carbonates, and phosphates of Li and Mg are
insoluble, unlike those of Na and K
3. Oxo-anion salts of Li and Mg (CO32-, NO3-, SO42-) decompose quite readily on
heating to give corresponding oxides
4. Li and Mg are unusual in reacting directly with N2 to form nitrides Li3N and
Mg3N2
5. Neither Li or Mg form stable peroxides when burned in atmosphere of O2
which remains in excess
6. Li and Mg both form organometallic compounds which have considerable
covalent character and are therefore soluble in organic solvents.
Organolithium, LiR, and Grignard reagents, RMgX, are used in analogous
12 fashion in organic syntheses. 13
 Diagonal relationships: beryllium and aluminium
1. Enthalpy of atomisation of Be is much higher than that of Mg ⇒ higher
melting and boiling points, enthalpy of fusion, and density and much harder
2. Bonds in Be and Al compounds are highly covalent due to high
electronegativities. Organometallic and halide compounds of Be and Al are
more soluble in organic solvents than those of other Group 2 elements
3. Be and Al have similar standard reduction potentials: E0 (Be2+/Be0) = -1.85 V
and E0 (Al3+/Al0) = -1.66 V. Compare this to E0 (Mg2+/Mg0) = -2.37 V
4. Be and Al both form amphoteric oxides. Both dissolve in alkali to evolve H2
5. Halides of Be are hygroscopic and fume in air and in water; Al2Cl6 hydrolyzes
to yield [Al(OH2)6]3+. Be2+ and Al3+ have high hydration enthalpies and this
leads to highly soluble salts particularly, for Be. Although Be2+ is smaller than
Al3+, the larger positive charge of the latter leads to a much more negative
value for its hydration enthalpy
6. Be and Al form reasonably stable complexes particularly with oxygen and
nitrogen based ligands
7. Unlike Mg, but similar to Al, Be forms ethynide BeC2 rather than carbide
Be2C.
14
Comparison Groups N and (N+10) (1)
• Elements belonging to the same period, but separated by 10 places in their
periodic groups show similarities in their chemical properties and particularly
in their highest oxidation state compounds
• Connection clear in short periodic table (Mendeleev), but less in medium-long
form with IUPAC numbering 1−18
• Phosphorus(V) and vanadium(V)
– Phosphate PO43- and vanadate VO43- ions are both strong bases
– Form large number of polymeric anions, e.g. P4O124- and V4O124-
– Form analogous oxychlorides: POCl3 and VOCl3
– Form similar fluoro-anions: PF6- and VF6-
• Sulfur(VI) and chromium(VI)
– SO42- and CrO42- salts are isomorphous
– Parallel dimer anions exist: S2O72- and Cr2O72-
– Form volatile oxychlorides: SO2Cl2 (m.p. -54 °C, b.p. = 69 °C) and CrO2Cl2 (m.p.
= -96 °C, b.p. = 117 °C) that decompose in water
– SO3 and CrO3 are both strongly acidic, low-melting solids that react with H2O
16
Diagonal relationships: boron and silicon
1. B is semi-metallic, black, very hard solid with high melting point (2300 °C)
and is chemically inert.
Si is a semi-conductor with metallic appearance, relatively unreactive, and
m.p. = 1410 °C
2. B and Si form solid acidic oxides: B2O3 and SiO2
3. H3BO3 and H4SiO4 are weak acids
4. Numerous polymeric borates and silicates exist
5. B and Si do not exist as aquated ions, [B(OH2)4]3+ and [Si(OH2)6]4+. Both form
wide range of oligomers based on boron-oxygen and silicon-oxygen bonds
6. Halides are molecular covalent solids or liquids which readily hydrolyze and
behave as Lewis acids
7. Hydrides of B (boranes) and Si (silanes) are volatile, flammable covalent
compounds
15
Comparison Groups N and (N+10) (2)
• Chlorine(VII) and manganese(VII)
– ClO4- and MnO4- are both strongly oxidizing and their salts isomorphous
– Cl2O7 and Mn2O7 are highly explosive liquids at room temperature
– ClO2 and MnO2 have both rare oxidation state +4
• Magnesium and zinc
– Sulfates are water soluble
– Carbonates and hydroxides are water insoluble
– Chlorides are hygroscopic, with (partially) covalent bonding
• Aluminium and scandium
– Similarities in ionization energies, electronegativities and boiling points metals
– In solution, both Al3+ and Sc3+ hydrolyze significantly to give acid solutions
containing polymeric hydroxy species
– Al(OH)3 and Sc(OH)3 are both produced as gelatinous precipitates upon addition of
hydroxide and redissolve as anionic species in presence of excess hydroxide
– Fluoro anions formed: AlF63- and ScF63-
17
 Comparison Groups N and (N+10) (3)
• Titanium(IV) and tin(IV)
– TiO2 and SnO2 are isomorphous and show thermochromism
– Ti(NO3)4 and Sn(NO3)4 are isomorphous
– Similarities in melting and boiling points of chlorides: TiCl4 (m.p .= -24 °C, b.p. =
136 °C) and SnCl4 (m.p. = -33 °C, b.p. = 114 °C)
– TiCl4 and SnCl4 are Lewis acids, forming adducts with ethers, and they hydrolyze
in water
• Osmium and xenon
– Form covalent compounds with +8 oxidation state:
– OsO4 and XeO4
– OsO2F4 and XeO2F4
– OsO3F2 and XeO3F2
• (Dis)similarities between Group 1 (alkali metals) and Group 11 (Cu, Ag, Au)
– Alkali metals are soft, low-density metals that react vigorously with water
– Group 11 metals have high density and are unreactive
– Both groups form +1 cations: NaCl, KCl versus CuCl, AgCl
18
Comparison Groups N and (N+10) (5)
• If these elements form compounds resulting either from complete ionization of
these electrons or their complete participation in covalent bond formation then
the compounds have identical stoichiometries.
• O and F are very effective at bringing out highest oxidation states and
valencies ⇒ similarities most obvious in fluorides and oxides
• Similarities in formulae of compounds formed by elements in Groups N and
(N + 10) can be most useful if one is seeking isostructural analogues, but fails
to emphasise the important differences in properties of the elements in other
oxidation states.
20
Comparison Groups N and (N+10) (4)
• Post-transition elements in the (N + 10) groups have valence electrons in s and
p subshells, outside filled d shell which is effectively core-like, because
ionization energies of d electrons are large
• Effective number of valence electrons identical in Groups N+10 and N: (x + y)
• (x+y) valence electrons occupy different valence orbitals: s and d for Groups
N and s and p for groups (N + 10).
19
Differences in N and (N+10) elements:
atomic properties
• Atoms belonging to the same row of the Periodic Table, but connected by N −
(N + 10) relationship, have following important differences in properties:
1. (N+10) atom has much smaller size, because presence of d shell results in
significant increase in effective nuclear charge experienced by its s and p
valence electrons
2. Larger effective nuclear charge also increases ionization energies of atom and
makes it more electronegative
3. Although N and (N+10) atoms both have (x+y) identical, the fact that they are
occupying different valence orbitals can have significant impact on properties
of compounds with these valence orbitals partially occupied
21
 Differences in N and (N+10) elements:
Knight's move relationship (1)
chemical properties
1. (N +10) elements are more noble than N elements, i.e. less reducing
2. Although having same stoichiometry, they can have different solid state
structures and physical and chemical properties
3. (N + 10) metal ions form much more stable complexes than N metal ions
4. (N+10) metal ions show more pronounced soft behavior as Lewis acids
5. Kinetic labilities may be very different
6. In intermediate oxidation states, compounds have very different properties
probably because of differences in orbitals occupied
7. Although d shells behave in core-like manner for elements in Groups 12−18,
in Group 11 they are sufficiently available for elements to form compounds
with partially filled d shells
8. Higher electronegativities of Groups 11 and 12 metals make their compounds
generally more highly colored than corresponding compounds of Groups 1 and
2 metals (lower energies CT transitions)
9. (N + 10) metal ions do not form hydrated metal ions in solution as readily
10. (N + 10) metal ions show greater tendency to disproportionate in a way which
is not possible for N metal ions.
22 23

Knight's move relationship (2) Knight's move relationship (3)

• Zinc and tin • Gallium and antimony

– Similar melting points of chlorides: ZnCl2 (m.p. 275 °C) − SnCl2 (m.p. 247 °C) – Similar melting points fluorides: GaF3 (m.p. = 77 °C) − SbF3 (m.p. = 77 °C)
– Both elements are commonly used for plating steel (tin for food cans) – Similar boiling points chlorides: GaCl3 (b.p. = 200 °C) − SbCl3 (b.p. = 221 °C)
– Nonpoisonous (except organotin compounds)
– Form alloys with copper (Zn: brass and Sn: bronze)
• Cadmium and lead
– Toxic
– Closely lying boiling and melting points of chlorides, bromides, and iodides
– CdCrO4 and PbCrO4: yellow (used as pigments) and insoluble in water
– CdI2 and PbI2 have similar unusual crystal structure
• Silver and thallium
– Matches in melting points: AgNO3 (m.p. = 212 °C) − TlNO3 (m.p. = 206 °C);
AgCl (m.p. = 455 °C) − TlCl (m.p. = 430 °C)
– Ag(I) and Tl(I) ions have similar chemical properties; (although in many cases Tl(I)
is more similar than K(I))
– Ag2CrO4 and Tl2CrO4: brick-red and insoluble
– Insoluble halides (except fluorides)
– AgCl and TlCl are both photosensitive 24 25
 Chapter 6
Noble gases

1 2

History and occurrence (1) History and occurrence (2)

• 1785: Henry Cavendish • Names:

– Observed in classic work on composition of air that, after repeatedly sparking – Helium: helios (sun)
ample of air with excess of O2, there was small residue of gas (1/120th of original – Neon; neos (new)
volume) – Argon: argos (inactive)
– Failed to further characterize the compound (unreactive) – Krypton: kryptos (hidden)
• 1868: Lockyear, Frankland, Lockwood – Xenon: xenos (strange)
– New yellow line was observed close to Na D lines in spectrum of sun's – Radon: after radium (formed by radioactive decay of Ra)
chromosphere
• Helium
– Attributed to new element unknown on earth
– 23 wt.% of Universe and Sun (second most abundant element after hydrogen)
– Named helium (helios = sun)
– Rare in atmosphere because He atoms travel fast enough to escape from the Earth;
• 1885: He atoms are too light to be retained by Earth's gravitational field
– Ramsay and Crookes identified terrestrial He, formed by dissolution of uranium – Most of He on Earth (5 ppm by volume) is product of α-decay of radioactive
mineral cleveite in acids elements
– Kayser showed by spectroscopy that He also occurs in the earth's atmosphere – He concentrations up to 7 wt.% are found in certain natural gas deposits (USA,
• 1884 to 1889: discovery of Ne, Ar, Kr, Xe by Rayleigh, Ramsay and Travers Eastern Europe)
• 1900 to 1904: discovery of Rn by Rutherford – Some He arrives from the Sun as solar wind of α- particles

3 4
 History and occurrence (3)
• All other noble gases occur in atmosphere
– Noble gases make up about 1 % of earth's atmosphere
– Mainly argon (0.94 vol.%) and neon (0.0015%)
Argon and neon are more abundant than arsenic and bismuth
– Xenon and radon are rarest noble gases
– Radon is product of radioactive decay and is radioactive itself
– Neon, argon, krypton, and xenon are extracted from liquid air by low-temperature
distillation
• Oganesson (Og, Z = 118)
– Synthetic element
– Belongs to group 18, but it is not clear yet whether it behaves like noble gas; it can
be reactive
– Only few atoms of this element have been produced so far; its chemistry remains
unexplored
5 6
The elements (2)
• Very low boiling points of lighter noble gases follow from weakness of
dispersion forces between the atoms and absence of other forces
• Dispersion forces directly proportional to polarisability and inversely
proportional to ionisation potential of atoms
• Boiling points proportional to square root of polarisibility
• Van der Waals forces: general term for weak intermolecular interactions
• London dispersion forces: attractive interaction between any pair of
molecules, including non-polar atoms, arising from interactions of
instantaneous multipoles (instantaneous dipole–induced dipole forces)
7 8
The elements (1)
• Elements are all mono-atomic gases at room temperature
• Low concentrations of dimers in liquid state, held together by London
dispersive forces
• Non-polar, spherical atoms: physical properties vary regularly with atomic
number
– Enthalpy of vaporization increases from He to Rn by >200×
– Regular increase in boiling and melting points He → Rn
The elements (3)
• Liquid and solid 3He and 4He exhibit unique properties:
– Only elements that do not possess a triple point
– Remain liquid down to absolute zero upon cooling under their own vapor pressure
– Solid helium can be obtained only under high pressure
– Below 2.178 K, 4He undergoes transformation into second liquid phase (4He-II)
• 4He-II
– Superfluid (zero viscosity)
– Flows over obstacles that lie above miniscus to reach lowest attainable level
– If vessel is filled by dipping into bath of 4He-II and
then raised above surface of bath, 4He-II flow as
film up the inner wall of vessel, over the edge,
down the outer wall, and drips from bottom of
vessel back into bath
– Anomalous behavior results from quantum effects
(4He-II is a quantum fluid)
 The elements (4) Electric discharge in noble gases

• All Group 18 elements are very unreactive: noble gases

(“noble gases” is preferred over “inert gases”
• Unreactivity can be understood in terms of their atomic properties: ground-
state electronic configurations, ns2np6 (1s2 for He) are closed-shell
configurations
• High ionization energies:
– very low tendency to release electrons
– 1st ionization energy is high because effective nuclear charge is high at far right of
helium neon argon
the period
– He has highest ionization energy of all elements (2373 kJ/mol)
– Value decreases down group as result of increasing size of atoms
– Value for heavier noble gases is smaller than values of O and F
• Negative electron affinities:
– No tendency to take up extra electrons
– Incoming electron needs to occupy orbital belonging to new shell
• He diffuses through rubber, PVC and most glasses (Dewar vessels for liquid
He should not be made of glass) krypton xenon
• Characteristic colors for electric discharges of noble gases 9 http://images-of-elements.com 10

Chemistry of the noble gases (1) Chemistry of the noble gases (2)

• Discovery of noble gases was direct result of their unreactive nature
• It was long believed that noble gases were incapable of forming chemical
compounds
• Until 1962, only compounds of noble gases which could be prepared were
clathrates
• 1962: N. Bartlett prepared xenon hexafluoroplatinate ‘XePtF6’ by reaction of
Xe with PF6 ⇒ first noble gas compound
XePtF6 itself is unstable and quickly disproportionates into XeFPtF5,
XeFPt2F11, and Xe2F3PtF6
• Noble gas compounds can be divided into 3 general types:
1. short-lived molecules containing noble gas atoms
2. inclusion compounds (clathrates and intercalation compounds)
3. valence compounds
• Valence compounds are only formed with most electro-negative elements (so
far, F, Cl, Br, N, and C), whereby thermodynamically stable compounds with
fluorine are formed only by Xe and Rn
• Thermodynamic stability of noble gas compounds, e.g., halides, follows the
following general rules:
1. Stability of compounds EX2 increases with increasing atomic number of noble gas
and with decreasing atomic number of halogen:
ArF2 < KrF2 < XeF2 < RnF2
XeF2 > XeCl2 > XeBr2
2. Stability of compounds decreases as oxidation state of noble gas increases:
XeF2 > XeF4 > XeF6
• Valence compounds of xenon do not involve new type of chemical bonding.
Atoms are bound in same manner as in long-known interhalogen compounds,
such as IF7, and in TeF6

11 12
 Clathrates (1) Clathrates (2)

• Clathrate: chemical substance consisting of crystal lattice that traps or

contains molecules
• Clathrates with hydroquinone, l,4–C6H4(OH)2
– Formed by Ar, Kr and Xe
– Not formed for He or N: too small or insufficiently polarizable to be retained
– Obtained by crystallizing hydroquinone from aqueous solution in presence of noble
gas at pressure of 10–40 atm
– Lattice of which is held together by hydrogen bonds in such a way as to produce
cavities in ratio 1 cavity: 3 molecules of hydroquinone
– Molecules of gas (G) are physically trapped in these cavities, by weak van der
Waals interactions between ‘guest’ and ‘host’ molecules
– Clathrates are non-stoichiometric, but have ‘ideal’ or ‘limiting’ composition of
[G{1,4–C6H4(OH)2}3]
– Once formed, the clathrates have considerable stability, but gas released on
dissolution or melting

13 14

Clathrates (3) Chemistry of xenon

• Noble gas clathrate hydrates • Chemistry of Xe is much the most extensive in this group and the
– Formed by Ar, Kr and Xe but not by He or Ne • Known oxidation states of Xe range from +II to +VIII.
– Obtained when water is frozen under high pressure of gas. • Rich variety of stereochemistries
– They have ideal composition, [G8(H2O)46]
• Clathrates provide a means of storing noble gases and of handling various
radioactive isotopes of Kr and Xe which are produced in nuclear reactors

15 16
 Xenon fluorides (1) Xenon fluorides (2)

• Xenon fluorides XeF2, XeF4 and XeF6 are synthesized by direct reaction • XeF2 has linear structure, with 3 lone pairs
between the elements
• Reaction done in Ni reaction vessel that has been passivated by exposure to F2
to form a thin protective NiF2 coating. Treatment also removes surface oxide,
which would react with xenon fluorides
• Formation of higher halides is favored by higher proportion of fluorine and
higher total pressure:
XeF2 crystals

• XeF4 has square-planar structure, with 2 lone pairs

• Crystals of XeF2 are formed by exposing dry Xe and F2 gas to sunlight in a

sealed glass flask (photochemical reaction). On exposure to light, F2
XeF4 crystals
dissociates into reactive fluorine atoms. 17 18

Xenon fluorides (3) Reactions of xenon fluorides (1)

• XeF6 is fluxional molecule in gas phase. Structure is distorted octahedron (C3v) • Chemistry of xenon fluorides is dominated by redox and metathesis reactions
with lone pair on 1 face. Lone pair moves from face to face, leading to • Important reaction of XeF6 is metathesis with oxides:
dynamic distortion of octahedron

• Xenon fluorides are strongly oxidizing reagents:

• Solid XeF6 consists of F- bridged [XeF5]+ units • Xenon fluorides react with strong Lewis acids to form xenon fluoride cations:
• In solution, XeF6 occurs as Xe4F24 tetrameren

19
cations are associated with counterion by F- bridges 20
 Reactions of xenon fluorides (2) Reactions of xenon fluorides (3)

• XeF4 reacts with Lewis base F- in acetonitrile solution to produce [XeF5]- ion: • Another route to Xe–N bonds is reaction of xenon fluoride with strong Lewis
acid:

followed by introduction of Lewis base, such as CH3CN to yield

• Xenon fluorides can be used for preparation of compounds of noble gases [CH3CNXe]+[AsF6]-
with elements other than F and O. Reaction of nucleophiles with xenon
fluoride is useful strategy for synthesis of such bonds.
• Reaction

is driven forward by stability of product HF and energy of formation of Xe–N

bond

21 22

Xenon oxides (1) Xenon oxides (2)

• Xenon oxides are endergonic (∆fG∅ > 0) and cannot be prepared by direct • In basic aqueous solution, Xe(VI) oxoanion HXeO4- slowly decomposes in
interaction of the elements coupled disproportionation and water oxidation to yield Xe(VIII) perxenate,
• Oxides and oxofluorides are prepared by hydrolysis of xenon fluorides: XeO64- and xenon:

• Perxenates of several alkali metal ions have been prepared by treatment of

XeO3 with O3 in alkaline conditions
• Perxeneate ion is powerful oxidizing agent in acidic aqueous solution:

• Pyramidal xenon trioxide, XeO3 presents serious hazard because this

endergonic compound is highly explosive
• XeO3 is very strong oxidizing agent in acidic solution: E0(XeO3,Xe) = +2.10 V • Treating Ba2XeO6 with concentrated H2SO4 produces the only other known
oxide of xenon, XeO4, which is an explosively unstable gas

23 24
 Xenon oxofluorides
• Xenon forms the oxofluorides XeOF2, XeO3F2, and XeOF4
• When alkali metal fluorides are dissolved in XeOF4 , solvated fluoride ions are
formed of composition F-·3XeOF4. Attempted removal of XeOF4 from solvate
yields XeOF5-, which is a pentagonal pyramid.
Coordination compounds of xenon
• 1st stable noble-gas coordination compound to be synthesized was
[AuXe4]2+[SbF11]2-, which contains square-planar [AuXe4]2+ cation
• Made by reduction of AuF3 by HF/SbF5 in elemental xenon to yield dark red
crystals that are stable up to -78 °C
• During the reduction of Au3+ to Au2+, the extreme Brønsted acidity of HF/SbF5
is essential and overall reaction indicates the role of protons:
• Green crystals of [Xe2]+[Sb4F21]- are also produced at -60 °C. Xe–Xe bond
length is 309 pm and is longest homonuclear bond known for main-group
element.
Xenon insertion compounds
• Number of noble gas hydrides have been isolated at low temperatures with
general formula H–E–Y, where E is Group 18 element and Y is an
electronegative element or fragment.
• Examples: H–Xe–Cl, H–Xe–Br, H–Xe–I, and H–Kr–Cl
• Prepared by UV photolysis of HY precursors in solid noble gas at low T
• Xenon reacts in this way with water, with formation of HXeOH and HXeO •
radical. Radical can react further with another Xe atom and H2 to form
H–Xe–O–Xe–H, which is the smallest molecule to contain 2 Xe atoms
• Xenon atoms have been successfully inserted into H–C bonds of hydrocarbons
by photolysis and annealing of solid mixture of C2H2 (acetylene) and Xe.
Noble gas hydrides H–Xe–C≡C–H and H–Xe–C≡C–Xe–H have been prepared
in this way.
25 26
Compounds of other noble gases
• Radon has lower ionization energy than xenon, so it can be expected to form
compounds even more readily
• Evidence exists for the formation of RnF2, and cationic compounds, such as
[RnF]+[SbF6]-, but detailed characterization is very difficult due to
radioactivity of radon
• Krypton has much higher ionization energy than xenon and its ability to form
compounds is more limited
• Krypton difluoride, KrF2, is prepared by passing an electric discharge or
ionizing radiation through a fluorine–krypton mixture at low temperatures
(-196 °C)
• KrF2 is and endergonic and highly reactive compound that must be stored at
low temperatures
• When monomeric HF is photolysed in solid argon and annealed to 18 K, HArF
is formed. Stable up to 27 K and contains HAr+ and F- ions.
27 28
 29 30

Applications (1) Applications (2)

• Helium • Krypton:
– Cryogenic cooling liquid (4.2 K); coolant for superconducting magnets used for – Gas mixture of krypton and argon is used in energy-saving lamps
NMR spectroscopy and magnetic resonance imaging (MRI) – Krypton-ion lasers
– Non-flammable filling gas for balloons and lighter-than-air craft • Xenon:
• Neon: – Xenon lamps (continuous spectrum, resembling daylight)
– As (red) neon light for advertising purposes – Stroboscopic lamps and flash lamps
– In helium-neon laser – Anesthetic
• Argon: – Isotopes of xenon are used in medical imaging
– Inert atmosphere for synthesis of air sensitive compounds (heavier than air)
– Inert atmosphere for protection of metal against oxidation in arc welding
– To fill the gap between panes in sealed double-glazed windows as its low thermal
conductivity reduces heat loss
– Was used as inert atmosphere in incandescent light bulbs, where it reduced burning
of the W filament.

31 32
 lanthanides = elements with atomic numbers 57-71 (La-Lu)
Ln: general symbol
rare earths = lanthanides + Sc, Y REEs = rare-earth elements
f-block elements = lanthanides + actinides

Chapter 7
Lanthanides

1 2

Rare earths: names and symbols Ytterby (Sweden)

3 4
 Rare earths: How do they look like?
Occurrence and abundance of the lanthanides (1)

Source: US Geological Survey

5 6

Occurrence and abundance of the lanthanides (2) Electronic configurations (1)

• Rare earths are not rare (Ce is as abundant as Cu)
• Elements become scarcer with increasing atomic number Z
(abundance decreases over lanthanide series)
• Elements with even Z are more abundant than elements with odd Z
(Oddo-Harkins rule)
• Promethium does not occur in Nature: radioactive element with only
short-lived radioisotopes
• Lanthanides (actinides): gradual filling of 4f (5f) orbitals
• Lanthanum: 5d subshell lower in energy than 4f ⇒ [Xe]6s25d1
• If Z increases, 4f orbitals contract rapidly and become more stable than 5d, 4f
orbitals penetrate `xenon core' more
• Cerium: [Xe]6s25d14f1
• Deviations from normal filling pattern due to (half-)filled 4f shell
• Lutetium: [Xe]6s25d14f14 (filled 4f shell)
• Electronic configurations are those of neutral atoms in gas phase; not relevant
to most chemists (work in liquid and solid phase)
• All Ln3+ ions have a [Xe]4fn electronic configurations

7 8
Electronic configurations (2) Electronic configurations (3)

9 10

4f-orbitals

11 12
Patterns in ionization energies (1) Patterns in ionization energies (2)

13 14

Atomic and ionic radii (1) Atomic and ionic radii (2)

• Atomic radii = metallic radii

• Atomic radii exhibit a smooth trend across the series (except Eu and Yb)
Most lanthanides: [Ln3+(e-)3]
Eu and Yb: [Ln2+(e-)2]
• Ionic radii of Ln3+ ions exhibit a smooth decrease across series
• Divalent ions compare in crystal radii with the Ca2+ and Sr2+ ions

15 16
 Lanthanide contraction Consequences of lanthanide contraction

• 4f electrons are `inside' 5s and 5p shells:
– core-like
– shielded from ligands
– no participation in bonding
– spectroscopic and magnetic properties largely independent of environment
• Decrease in size of 4f shell with increasing Z due to:
– Imperfect shielding of 4f electron by another 4f electron (radial contribution)
– Imperfect shielding occasioned by the directed nature of f-orbitals
• 5s and 5p orbitals penetrate 4f subshell and are not well shielded from
increasing nuclear charge
• Lanthanide contraction
– Decrease in sizes of atoms and ions, with increasing atomic number
– Due to combined effect of contraction of 4f, 5s and 5p shells
• Reduction in size from one Ln3+ ion to the next makes their separation
possible, but the smallness and regularity of the reduction makes the
separation difficult
• By the time holmium is reached, Ln3+ radius has been sufficiently reduced to
be almost identical with Y3+ radius
– Y is invariably associated with HREEs (HREE = heavy REE)
– Difficult to separate Y from HREEs
– Close similarity between Y and HREE compounds ions in all properties that are
determined by cation charge − cation size relationships (e.g. crystal structure,
degree of covalency, stability of complex species)
– yttrium earths: Y + HREEs (Y more abundant than HREE)
• Similarities in atomic and ionic radii of 4d and 5d elements
– Interpolation of lanthanides almost exactly cancels anticipated increase of
occupation of next shell
– Hf is extremely similar to Zr
– Similarities Nb-Ta, Mo-W,… Pd-Pt

17 18

Oxidation states Why are Ln3+aq ions so stable? (1)

• Textbook authors often give impression that lanthanides are dull, unimportant
and to be ignored

“Lanthanum has only one important oxidation state in aqueous solution, the
+3 state. With few exceptions, this tells the whole boring story about the other
lanthanides.”

Ref. G.C. Pimentel, R.D. Sprately, Understanding Chemistry; Holden-Day, 1971, San Francisco, CA, p. 862

• However, this is by no means the whole story and oxidation states +2 and +4
are known for several lanthanides, especially in solid state

19 20
 Why are Ln3+aq ions so stable? (2) Standard reduction potentials

• Trivalent oxidation state owes it general stability to a somewhat fortuitous

combination of ionization and hydration energies, rather than to any particular
electronic configuration
• Ionization energies: I1 < I2 < I3 < I4
• Hydration energies: Ln4+ > Ln3+ > Ln2+
• Extra energy required to ionize Ln2+ to Ln3+ is compensated by extra energy
release when Ln3+ is hydrated, compared to hydration of Ln2+ ion
• Eu2+ relatively stable to high value I3
• Extra energy release due to hydration of Ln4+ does not compensate for I4
• Ce4+ relatively stable to low value I4
• Ln3+ is stable in solid state due to balance between ionization energies and
lattice energy
• Energy conditions are more favorable to existence of non-trivalent species in
solid state than in solution
• Empty, half-filled and completely filled 4f-shells can stabilize some non-
trivalent oxidation states (e.g. Ce4+ 4f0, Eu2+ 4f7, Yb2+ 4f14)
21 22

Lanthanide metals: physical properties Melting point of lanthanide metals

• Physical properties usually show smooth transition across the series, except
that discontinuities are observed for Eu and Yb
• Metals are soft, malleable and ductile
• Relatively high melting points and boiling points
• Mischmetal: mixture of lighter lanthanides, cerium in particular, which is
manufactured from `unseparated‘ mixture of REE oxides

23 24
 Boiling point of lanthanide metals Lanthanide metals: chemical properties

• When freshly cut, silvery lustre, which tend to tarnish on exposure to air
• Electrochemical behaviour comparable to Mg: (E0(Mg2+/Mg0) = -2.37V)
• Similar values for E0(Ln3+/Ln0)
• Vigorous oxidation in dilute acids to trivalent oxidation state
• Slow reaction with water at RT, faster when heated
• Dry oxygen (air) attacks the pure metals very slowly at RT, but at higher
temperature the metals ignite and burn
• Impure metals and alloys rich in cerium are pyrophoric
• Moist air attacks Eu very rapidly, and La, Ce, Pr, Nd quite rapidly
• Similar reaction with halogens as with oxygen
• Eu and Yb dissolve in liquid ammonia to yield dark blue, strongly reducing
solutions, that are believed to contain solvated electrons e(NH3)y-

25 26

Lanthanide metals: production Metallothermic reduction (1)

• Metals have similar reactivities to magnesium
– Cannot be extracted by methods like carbon reduction of oxides
– Cannot be electrodeposited from aqueous solutions
• Methods:
– Metallothermic reduction
– Electrowinning from molten salts (cfr. Hall−Héroult process for Al and Mg)
• Reduction of anhydrous halides with calcium metal (calciothermic reduction)
• Mixture of LnF3 and Ca is heated in Ta crucible at 50 °C above melting point
in Ar atmosphere:
• Fluorides are preferred:
– LnF3 are non-hygroscopic
– CaF2 produced is stable, unlike other calcium halides which are liable to boil at
temperatures reached in process
• Main impurity is Ca which is removed by melting under vacuum
• Method not suitable for Eu, Yb, Sm: LnF2 formed
• Metallothermic reduction with La metal:

• Eu, Yb, Sm can be separated from La and La2O3 by vacuum distillation

• Operated in batch mode (slow and expensive); used for smaller quantities
27 28
 Metallothermic reduction (2) Electrowinning (1)

• Electrolysis of molten chlorides

– Fused mixture of LnCl3 with either NaCl or CaCl2 (to reduce melting point) at 950 °C
– Electrolysed in graphite or refractory-lined steel cell, which serves as cathode, with
graphite rod as anode
– Cathode: molten Ln Anode: Cl2 gas
– Primarily used for Ce and Mischmetal

29 30

Electrowinning (2) Electrowinning (3) – PR China

• Oxide feed−fluoride electrolyte electrowinning

– Lanthanide oxide (e.g. Nd2O3) dissolved in molten fluoride electrolyte, a mixture
of LiF, NaF and BaF2 at about 1050 °C.
– Direct electric current is passed through electrolyte from graphite anode to
tungsten cathode
– Cathode: molten Ln Anode: CO2 gas
– Oxide feed can be handled safely and easily
– Formation of chlorine gas is avoided
– For Nd metal, NdFe alloys (NdFeB magnets)
• Always designed to produce molten metal:
molten product is easily tapped, poured, or
syphoned from the electrowinning furnace
• Quasi-continuous process

31 32
 Electrowinning (4) – Less-Common Metals (UK)
33
Oxidation state +2
• Lanthanide dihalides are usually made by reduction using H2 (e.g. EuX2,
YbX2, or SmI2) or by comproportionation reaction:
• In few cases, thermal decomposition is applicable, e.g. LnI2 (Ln = Sm, Yb)
and EuBr2:
• Another method, used especially for LnI2, involves heating metal with HgX2:
• SmI2 and YbI2 can be conveniently prepared by reacting metal with 1,2-
diiodoethane in anhydrous tetrahydrofuran at RT:
35
Oxidation state +2
• Sm(II), Eu(II) and Yb(II) are the only divalent lanthanide ions that exist in
aqueous solution and form series of metal complexes
• Strong reducing agents
• Reducing ability: Sm2+ >>Yb2+ >>Eu2+
• Reaction with acidified H2O (fast for Sm, Yb, slow for Eu):
• Reaction with acidified H2O + O2 (fast):
• Hydrated water-soluble Sm(II) and Yb(II) salts are oxidized by their own
water of crystallization, but those of Eu(II) are relatively stable
• Water-insoluble compounds (e.g., the sulfates, carbonates, fluorides) resist
oxidation even in presence of H2O
• More extensive stabilization is noted when ions are trapped in inert solid
matrix (e.g., EuO in SrO, LnF2 in LnF3)
• EuSO4 is poorly soluble in water, just like SrSO4 and BaSO4 34
Oxidation state +2
• Iodides of Nd, Sm, Eu, Dy, Tm, and Yb are definitely compounds of +2 ions,
with salt-like properties, are insulators, and have magnetic and spectroscopic
properties expected for the M2+ ions
• SmI2 is an important reagent in synthetic organic chemistry for selective
reduction reactions (Kagan's reagent)
• LaI2, CeI2, PrI2, and GdI2 have metallic sheen and are very good conductors of
electricity (delocalized electrons): M3+(I-)2(e-)
36
 Oxidation state +3 Oxidation state +3

• Characteristic oxidation state of the lanthanides • Halides can be obtained as hydrates from reaction of metal oxides or
• All lanthanides have this oxidation state as the most stable one carbonates with aqueous acids
• Properties of this state very largely determine the chemistry of lanthanides • hydrates are hydrolyzed on heating to oxyhalide and thus anhydrous halides
• Similar chemical properties, with gradual change across lanthanide series cannot be made that way:
(lanthanide contraction)
• Chemical bonding is mainly ionic, very limited covalent effects
• They do not form Ln=O or Ln≡N multiple bonds of type known for many • Trifluorides, being very insoluble, can be precipitated as LnF3⋅1/2H2O by
transition metals and certain actinides. action of HF on aqueous Ln(NO3)3
• Gradual filling of 4f orbitals across lanthanide series • Hydrates dehydrated by heating in current of anhydrous HF gas (or in vacuo):
• 4f electrons well shielded from environment by closed 5s2 and 5p6 shells
• 4f orbitals do not participate in chemical bonding
• Ligand field effects are small compared to d-block elements
Atomic-like absorption and emission spectra (narrow lines or bands) • Anhydrous halides can generally be made by heating metal with halogen
• Pale colours from weak, narrow forbidden f-f optical transitions. (except for EuI3) or gaseous HCl:
• Magnetic and optical properties are largely independent of environment (e.g.
similar spectra in gas/solution/solid).
37 38

Oxidation state +3 Oxidation state +3

• Another method for chlorides involves refluxing the hydrated chlorides with • Coordination number of trihalides changes with radii of ions, from 11 (9+2)
thionyl dichloride (SOCl2): for trifluorides of large lanthanides to 6 for triiodides of smaller lanthanides

• Thermal decomposition of ammonium halogenometallates (300 °C)

39 40
 Oxidation state +3 Oxidation state +3

• Sesquioxides Ln2O3
– Final products of combustion of metals or ignition of hydroxides, carbonate,
nitrate, etc. for all Ln except Ce, Pr, Tb (CeO2, Pr6O11, Tb4O7)
– Ce2O3, Pr2O3 and Tb2O3 formed by reduction of higher oxides by H2
– Three structural types: A, B and C
– Strongly basic and the lighter, more basic, ones resemble oxides of Group 2
– Insoluble in water but absorb it to form hydroxides
– Dissolve readily in aqueous acids to yield solutions which, providing they are kept
< pH 5 to avoid hydrolysis, contain [Ln(H2O)x]3+ ions
• Trivalent chalcogenides Ln2Z3 (Z = S, Se, Te)
– Obtained by direct combination between the elements
– Sulfides by action of H2S on chloride or oxide

• Ln3+ are hard Lewis acids

• Prefer to bind to O-donor ligands

41 42

Oxidation state +3 Oxidation state +3

• Sesquioxides Ln2O3 • [Ln(H2O)n]3+

– Final products of combustion of metals or ignition of hydroxides, carbonate, – CN = 9 for early lanthanides (La − Eu)
nitrate, etc. for all Ln except Ce, Pr, Tb (CeO2, Pr6O11, Tb4O7) – CN = 8 for the later metals (Dy − Lu)
– Ce2O3, Pr2O3 and Tb2O3 formed by reduction of higher oxides by H2 – With intermediate metals exhibiting mixture of species
– Three structural types: A, B and C • [Ln(H2O)9]3+ tricapped trigonal prism
– Strongly basic and the lighter, more basic, ones resemble oxides of Group 2
– Insoluble in water but absorb it to form hydroxides
– Dissolve readily in aqueous acids to yield solutions which, providing they are kept
< pH 5 to avoid hydrolysis, contain [Ln(H2O)x]3+ ions
• Trivalent chalcogenides Ln2Z3 (Z = S, Se, Te)
– Obtained by direct combination between the elements
– Sulfides by action of H2S on chloride or oxide

• Ln3+ are hard Lewis acids

• Prefer to bind to O-donor ligands

43 44
 Oxidation state +3 Oxidation state +3

• Aqua ions hydrolyze: increasingly so from La to Lu

[Ln(H2O)n]3+ + H2O → [Ln(H2O)n-1(OH)]2+ + H3O+

• Insoluble hydroxides precipitate at neutral pH unless complexing agents are

present
• Soluble in water: chloride, bromide, bromate, perchlorate, nitrate, acetate, and
iodide salts
• Insoluble in water: fluorides, carbonates, oxalates and phosphates
• Complex formation with water molecules is very common
Hydrated compounds are often formed
• Stable complexes with polydentate ligands (e.g. EDTA)
• Stability constants increase from La3+ → Lu3+ (increase in charge density)
• High coordination numbers: most often 8 of 9, but up to 12
• Coordination polyhedra are determined by steric factors, not by orbital overlap
• Coordination polyhedra are often ill-defined
• Fast ligand exchange in solution (kinetically labile)
45 46

Oxidation state +3 Oxidation state +4

• Cerium: only lanthanide with extensive chemistry in oxidation state +IV

• Ce4+ aqua ion: thermodynamically unstable, but kinetically stable
• Standard reduction potential depends on anion due to complex formation
E0 = +1.61 V in 1M HNO3
E0 = +1.44 V in 1M H2SO4
E0 = +1.70 V in 1M HClO4
• Ce3+ can be oxidized to Ce4+ only by strongly oxidizing agents: S2O82- or O3
or can be prepared electrolytically
• Ce4+ is reduced by many reagents: Fe2+, Sn2+, I- , H2O2, organic compounds
• Tetravalent cerium forms complexes with high coordination number:
– CN = 10 [Ce(CO3)5]6-
– CN = 11 [Ce(NO3)4(H2O)3]
– CN = 12 [Ce(NO3)6]2-
• Best known salts:
– CeSO4⋅4H2O
– (NH4)2[Ce(NO3)6] (CAN) selective oxidizing agent in organic chemistry

47 48
 Oxidation state +4 Oxidation state +4

• Pr4+, Nd4+, Tb4+, Dy4+ do not occur in aqueous solution

E0(Pr4+/Pr3+) = +2.86 V (estimated) oxidizes water
• Tb4+ has been reported as carbonato complexes in water
• LnX4 occur only as fluorides of Ce4+, Pr4+ and Tb4+: CeF4, PrF4 and DyF4
• Can be formed by direct reaction between Ln and F2
• TbF4 from TbF3 and F2 at 320 °C
• PrF4 prepared by rather complex procedure of fluorinating a mixture of NaF
and PrF3 with F2 (yielding Na2PrF6) and then extracting NaF from reaction
Ceric ammonium nitrate Pr6O11
mixture with liquid HF
• CeO2: stable oxide of cerium
• Pr and Tb form mixed valence oxides Pr6O11 and Tb4O7
• PrO2 and TbO2 can be obtained by reaction between Pr and Tb in O2
atmosphere at high T and p

Ceric ammonium sulfate Tb4O7

49 50

Occurrence of the actinides

• Actinides: elements with atomic number 89−103 (Ac − Lr)

• Actinium, thorium, protactinium and uranium occur in Nature
• Actinium and protactinium occur only in very small amounts as decay

Chapter 8 •
products as decay products of 235U and 238U
Uranium (Z = 92) is heaviest element in Nature
• All other actinides are synthetic elements (transuranium elements)
Actinides • All actinides are radioactive, often very intensively

1 2
 Overview Discovery of thorium and uranium

• Uranium: discovered in 1789 by Martin Heinrich Klaproth

(discovered also zirconium and cerium)

• Thorium: discovered in 1828 by Jöns Jakob Berzelius

(discovered also selenium and independently of Klaproth
cerium)

3 4

Synthesis (1) Synthesis (2)

• Most actinides can be prepared by neutron irradiation of a suitable target • For elements beyond plutonium, successive neutron capture is required:
• Neutron capture is followed by β- decay
• In β- decay, mass number A remains the same, but Z increases by +1 (next
element in periodic table
• Synthesis of actinium (Ac) and protactinium (Pa)

• Successive neutron capture is slow process: starting with 1 kg of 239Pu, using a

• Synthesis of neptunium (Np) and plutonium (Pu) neutron flux of 3 × 1014 neutrons cm−2s−1 (high, but experimentally feasible
value), around 1 mg of 252Cf is obtained after 5–10 y
• Limit of this process in nuclear reactor is 257Fm; product of next neutron
absorption is 258Fm, which undergoes spontaneous fission (t1/2 = 0.38 ms)

5 6
 Synthesis (3) Synthesis (4)

• Heavy actinides were first produced by using more intense neutron flux than
can be obtained in reactor, in form of thermonuclear explosion, resulting in
multiple neutron capture and a whole series of rapid decays
• Einsteinium (Es) and fermium (Fm) were first produced during ’Ivy Mike’,
the world’s first thermonuclear test, at Eniwetok atoll on 1st November 1952

7 8

Synthesis (5)

• For obvious reasons, synthesis of actinides with thermonuclear bombs are

unlikely to be followed in the future
• Instead, heavy-ion-bombardment, using particles such as 4He, 11B, 12C, 15N,
16O and 18O, is used

• Disadvantages:
– suitable actinide target required
– 1 atom-at-a-time route
9 10
 Electronic configurations (1) Electronic configurations (2)

• Actinides are characterized by gradual filling of 5f shell

• Early in actinide series, electrons in 6d orbitals are lower in energy than in 5f
orbitals
• Ground-state electronic configurations show that 6d orbitals are filled before
5f
• 5f orbitals are starting to be filled at protoactinium, and with exception of
curium (5f7), 6d orbitals are not occupied again
• 5f orbitals are not shielded by filled 6s and 6p subshells as 4f orbitals
• of lanthanides are (by corresponding 5s and 5p subshells)
• 5f orbitals less ‘inner orbitals’ in sense that 4f orbitals are for lanthanides, and
thus more perturbed in bonding
• Energy gap between 5fn 7s2 and 5fn−1 6d 7s2 configurations is less than for
corresponding lanthanides
• Near-degeneracy of 5f, 6d, and 7s electrons means that more outer-shell
electrons can be involved in compound formation (and wider range of
oxidation states is observed)
11 12

Electronic configurations (3) Electronic configurations (4)

• For the earlier actinides, higher oxidation states are available and, as for d-
block transition elements, several are often available for each metal
• This resemblance to the transition metals was noted for Ac–U nearly a century
ago and initially made people think that actinides were another block of
transition metals
• As 5f electrons do not shield each other from the nucleus effectively, energies
of 5f orbitals drop rapidly with increasing atomic number, so that electronic
structures of later actinides and their ions become more and more like those of
the lanthanides
• Starting round about Bk, most elements tend to exhibit one stable oxidation
state, +3 in nearly all cases, thus resembling the lanthanides

13 14
 Reduction potentials (1)
15
Reduction potentials (3)
• Large negative values of E0 for M4+/M3+ for Th and Pa indicate that reduction
to form (+3) species for these metals will be difficult, whilst for U, Np, and Pu
the smaller E0 values indicate that both +3 and+4 states will have reasonable
stability
• From Am onwards, E0 > +2V for all these elements (except Bk), suggesting
that for all these metals the (+3) state will be more favored (as observed)
• Tendency for E0 values for both M4+/M3+ and M3+/M2+ to become more
positive, and for the reduction to be more favored, on crossing the series from
left to right, shows that overall lower oxidation states become more stable with
increasing atomic number.
17
Reduction potentials (2)
• Negative reduction potentials for the M3+/M potentials indicate that the
following process is energetically favorable
Actinide metals react with dilute acid solutions and even with water in some
cases
• Large negative reduction potentials for the M3+/M2+ process early in series
indicate that for these metals no aqueous chemistry of M2+ ions is to be
expected.
• Potentials become less negative with increasing atomic number, indicating
increasing stability of M2+, and positive value for nobelium reflects that No2+ is
most stable ion for this metal in aqueous solution
• Several compounds have been isolated in solid state for Am2+ (5f7), Cf2+, and
Es2+ (as might be expected from reduction potentials) and the (+2) ion is
known in solution for Fm and Md too
16
Relativistic effects
• For lighter chemical elements, velocity of electrons is negligible compared
with velocity of light. However, for actinides this is not the case
• As velocity of electrons increases towards c, then their mass increases too
• For a 1s electron in a uranium atom:
Mass increase of 1s electron:
• Mass increase produces contraction of 1s orbital and stabilization of 1s
electrons. Similar but smaller effects occur for p electrons.
• In contrast, d and f electrons tend to be expanded and destabilized (compared
with imaginary, ‘non-relativistic’ atoms), due to increased shielding of nucleus
by (increasingly stabilized) outer core s and p electrons.
• Important ‘relativistic effect’ is that 5f orbitals of actinides are larger and their
electrons more weakly bound than predicted by non-relativistic calculations,
hence 5f electrons are more chemically ‘available’. This leads to:
– bigger range of oxidation states than with lanthanides
– greater tendency to covalent bond formation (but maybe involving 6d rather than 5f
orbitals) in ions like MO2+ and MO22+ (most notably the uranyl ion, UO22+)
18
 Chemistry of actinides Reactions of thorium

• Studies of chemistry of actinides have been limited by number of factors:

– care needed in handling radioactive materials
– toxicity (especially Pu)
– very small quantities available and very short half-lives of later actinides
– radiation and heating damage to solutions
– radiation damage (defects and dislocations) to crystals
• Vast majority of studies reported have concerned thorium and uranium, due to
accessibility of raw materials, ease of handling, and the long lifetimes of the
relatively weakly α-emitting elements Th and U.
• In many cases, compounds of Np and Pu with similar formulae to U and Th
analogues have been made and found to be isomorphous and thus presumably
isostructural

19 20

Reactions of uranium General patterns

• Chemistry of thorium is essentially confined to +4 state (to an even greater

degree than Zr or Hf)
• Uranium exhibits oxidation states of +3, +4, +5, and +6, with most compounds
being in either +4 or +6 state
• Uranium(III) compounds tend to be easily oxidized:

• Under aqueous conditions the UO2+ ion readily disproportionates to mixture of

U4+ and UO22+, although there is chemistry of uranium(V) in non-aqueous
solvents
• As actinide series is crossed, it becomes harder to involve f electrons in
compound formation, so that later actinides increasingly show chemistry in +3
state, resembling the lanthanides, but with more prominent +2 state.

21 22
 Coordination numbers (1) Coordination numbers (2)

• As for the lanthanides, actinide complexes display high coordination numbers

• Best characterized aqua ion is the hydrated uranyl ion [UO2(OH2)5]2+
• Similar ions are firmly believed to exist in cases of [MO2(aq)]2+ (M = Np, Pu)
and [MO2(aq)]+ (M = U, Np, Pu)
• Ions like UO22+ are unprecedented in lanthanide chemistry, both in respect of
+6 oxidation state and also in presence of strong and non-labile U=O bonds
• Coordination numbers of hydrated +3 actinide ions appear to be higher than
those of Ln3+ ions (9 for early lanthanides, 8 for later ones), explicable on
account of slightly higher ionic radii of actinide ions

23 24

Stability of complexes Oxides

• Pattern of oxidation state here is very different to that of the lanthanides,

where common oxides are Ln2O3
• Uranium–oxygen phase diagram is very complicated, with some of the 14
reported phases not being genuine and several phases showing variable
composition. The important phases are UO2, U4O9, U3O8, and UO3

• Thorium(IV) forms stronger complexes with fluoride, ‘hardest’ halide ion,

than with chloride and bromide; this is behaviour expected of ‘hard’ Lewis
acid
• Thorium(IV) forms strong complexes with oxygen-donor ligands like nitrate
• Hexadentate ligand EDTA4- forms very stable complexes, due largely to
favourable entropy change when 6 water molecules are replaced.
25 26
 Uranyl compounds (1)

• great majority of uranium(VI) compounds contain the UO2 group and are
known as uranyl compounds
• Exceptions: halides UOF4, UF6, and UCl6, and some alkoxides such as
U(OMe)6
• Uranyl compounds characteristically have a yellow fluorescence under UV
light
• From the early 19th century, glass manufacturers added uranium oxide when
making yellow and green glass (it is sometimes known as Vaseline glass)

27 28

Uranyl compounds (2) Uranyl compounds (3)

• Uranyl complexes can be thought of as derivatives of the UO22+ ion

• Many uranyl complexes are known
• They may be cationic, such as [UO2(OH2)5]2+ ions; neutral, e.g.
[UO2(OPPh3)2Cl2]; or anionic, such as [UO2Cl4]2-
• All feature a trans-UO2 grouping with the characteristic short U–O bonds
(1.7–1.9 Å)
• Essentially linear geometry of UO2 unit is invariable feature of uranyl
complexes
• Uranium d–p and f–p π bonding have both been proposed to explain bonding

29 30
Uranyl complexes (4): MO scheme Uranyl complexes (5)

• Electron count takes 6 electrons from uranium, 4 from each oxygen (4+4),
deducting 2 for the positive charges, giving 12 valence electrons in total
• Alternatively, if uranyl ion is thought of as combination of U6+ and two O2−,
taking 6 electrons from each oxide and none from U6+, the total is again 12
• 12 electrons completely occupy the six σu, σg, πu, and πg molecular orbitals:

• Addition of further electrons puts them in the essentially non-bonding δu and

φu orbitals, accounting for existence of rather less stable MO22+ (M = Np, Pu,
Am) ions
• Uranium(V) species UO2+ exists, but is less stable than UO22+, possibly owing
to weaker overlap; it readily decomposes by disproportionation:

31 32

Transactinides in the periodic table

Chapter 9
Transactinides

1 2
 Discovery of transuranium elements and
Overview
transactinides

3 4

Synthesis (1) Synthesis (2)

• After synthesis of lawrencium in 1961, there seemed few prospects of • Nuclei with closed shells of nucleons are stabilized, particularly against
extending Periodic Table into another series spontaneous fission.
• Experience with actinides had shown that half-lives for α-decay of each • Nuclei where the numbers of protons and neutrons are both magic numbers
element were steadily growing shorter as atomic number increased, whilst (‘double-magic’ nuclei) are particularly stable: 4He, 16O, 40Ca, and 208Pb.
drop in half-lives for spontaneous fission was even more dramatic • After 208Pb, next ‘double-magic’ nucleus would be 298114
• Extrapolation to elements with atomic numbers around 107–108 indicated that • Stability of nuclei can be represented on 3-D maps, with peaks corresponding
half-lives would be so short (t1/2 = 10−3 s) that it would be impossible to isolate to the stablest ‘magic number’ nuclei
further elements
• Theoreticians thought that stable heavier elements might be in prospect
• Stability is determined by the inter-nucleon forces (nucleons are protons and
neutrons):
– Attractive force between all nucleons
– Coulombic repulsion force between protons
(becoming more important as number of protons increases)
• Extra stability is associated with filled shells of nucleons, ‘magic numbers’:
– for neutrons: 2, 8, 20, 28, 50, 82, 126, 184, and 196
– for protons: 2, 8, 20, 28, 50, 82, 114, and 164.
5 6
 Synthesis (3) Synthesis (4)

• Discovery of these elements has largely resulted from researches by a few

research groups:
– Russian scientists at Joint Institute for Nuclear Research (JINR), Dubna
– German scientists at Gesellschaft für Schwerionenforschung (GSI), Darmstadt
– Americans at Lawrence Berkeley National Laboratory, Berkeley, California
– Japanese workers at the RIKEN Linear Accelerator Facility
• Approach used is to bombard target nucleus (generally an actinide) with
positively charged nuclei of other elements, using particle accelerator
(cyclotron or linear accelerator) to supply high energy needed to overcome
Coulomb repulsion between positively charged target nucleus and positive
projectile nucleus
• Atoms are produced 1 at a time, obviating ‘normal’ chemical experiments on
bulk samples
• Chance of collision producing combined nucleus is best about 1 in 109
collisions

7 8

Synthesis (5) Synthesis (6)

• New atomic nucleus produced is in excited nuclear state, it has excess of

energy to get rid of. If energy of bombarding particles is too low, they do not
possess enough energy to overcome Coulombic repulsion between them
• In most cases, high excitation energy leads to prompt fission of compound
nucleus and fusion product is lost
• Rarely, excitation energy is dissipated by evaporation of neutrons. Each
evaporation step competes with prompt fission.
• After the evaporation of 2 to 5 neutrons, the compound nucleus has cooled
sufficiently to dissipate further energy by emission of gamma rays
• Newly formed nucleus of heavy element now survives sufficiently long to
allow its detection by radioactive decay

9 10
 Synthesis (7) Synthesis (8)

• First transactinides were produced by using light nuclei as targets, in the same
way as heavy actinides were produced:
• Heavier projectile atoms and concomitantly lighter targets were used for
synthesis of elements from 107 to 112 (‘cold-fusion’ approach)
• Method uses projectile particles with minimum kinetic energy to just result in
fusion so that product nucleus has little excessive energy to get rid of, so that
not only probability of fission minimized, but few neutrons ‘evaporate’ from
‘hot’ nucleus, so that mass number of resulting product is as high as possible
• Pb, Bi, Ni targets have (near)-magic-number structures, so that large part of
projectile energy is consumed in breaking into filled shell and this also reduces
possibility of new nucleus undergoing fission

11 12

Synthesis (9) Synthesis (10)

• Bombardment of 244Pu with neutron-rich 48Ca for several weeks led to 1 atom
of element 114. Atom had lifetime of about 30 s before decaying to form atom
of element 112:
• 48Ca has been used as projectile for synthesis of other transactinides:
• Complete nuclear fusion process of heavy ions with irradiated target atoms is
exceptionally rare process leading to production rates of transactinides in
range from several atoms per minute up to single atoms per several days
• Half-lives of the produced transactinide isotopes known today range from
milliseconds up to several seconds only, rarely to minutes and hours
• Availability of heavy actinide target materials is one of the key issues for
synthesis of superheavy elements
• New superheavy elements with Z = 114 through 118 have been synthesized in
bombarding actinide targets of 242,244Pu, 243Am, 245,248Cm, 249Cf and 249Bk with
48Ca beams

• Target materials are available in very limited quantities and require specialized
production and processing facilities.
• As a typical facility for such irradiations, there is the High Flux Isotope
• Synthesis of oganesson (Z = 118): Reactor (HFIR) at Oak Ridge National Laboratory, USA, where actinide
materials, Am/Cm, are exposed to intense thermal neutron flux
• Up to 200 mg of 252Cf is produced in each campaign, and this process
produces ~20 mg of 249Bk, micrograms of 254Es, and picograms of 257Fm
13 14
Synthesis (11)

15 16

17 18
 Isolation of the elements (1)

• Classical chemical routes are impractical with ultra-small quantities of very

radioactive, short-lived atoms.
• Once a heavy element has been synthesized in nuclear fusion reaction, it has to
be immediately separated from plethora of other reaction products so that it
can be identified via its radioactive decay.
• Due to the kinetic energy imparted by projectile, fusion-evaporation residue
carries momentum of beam and is ejected from target nucleus with well-
defined velocity. Thus, the newly formed nucleus carries a distinctive charge
and kinetic energy.
• Separation is accomplished within few microseconds with aid of kinematic
separators, which are filtering reaction products in flight by velocity, mass, or
energy or mass/charge ratio

19 20

Isolation of the elements (2) Identification (1)

• Detection relies on studying radioactive decay, which is usually either

α-emission or spontaneous fission.
• Superheavy nuclei can be detected very sensitively down to single atom level
• Superheavy nuclei are frequently characterized by decay chains, rapid
emission of several alpha particles in a short time period and often terminated
by spontaneous fission. These signatures are unique.
• To detect such signatures, highly efficient particle detectors have been
developed that even offer spatial resolution.
• Time-correlation process is used: solid-state detector monitors both time and
position of arrival of fusion products
• Subsequent decay events at this position give not just the decay information of
atom (half-life, α-particle energy), but also corresponding information for its
decay products, which are recognizable and thus ‘known’ nuclei

21 22
 Identification (2)
• Reaction of 209Bi with 54Cr led to very short-lived nuclei (t1/2 = 4.7 ms)
emitting α-particles with energy of 10.38 MeV
• α-emitter correlated with decay chain composed of 3 successive α-emitters,
identified as:
258105 (4.4 s; α-particles of 9.17 MeV)
254Lr(13 s; α-particles of 8.46 MeV)
250Md (52 s; α-particles of 7.75 MeV)
• Product of fusion reaction was thus 262107
• Limiting factor in detecting reaction product is thus time of flight of product
from target to detector, which is of order of microseconds
23
Rutherfordium (Z = 104)
• Chemical properties of Rf are similar to those of Zr and Hf
• Behaviour of Rf on cation-exchange resins resembles that of Zr and Hf.
This supports assignment of a (+4) oxidation state
• Coordination number of 6 for Rf4+(aq) has been suggested
• Extracted from concentrated HCl as anionic chloride complexes, unlike
trivalent actinides and group I and II metals, but similarly to Zr and Hf
Formation of [RfCl6]2- complex has been suggested
• Like Zr and Hf, however, it forms stable anionic fluoride complexes, and a
complex ion [RfF6]2- has been proposed
• Volatility of RfCl4 (condensing ∼220 °C) is similar to that of ZrCl4 but greater
than that of HfCl4. It is much greater than that of actinide tetrachlorides
25
Predicting chemistry of the transactinides
• Elements from 104 to 112 are believed to have electron configurations
resulting from filling 6d orbitals, so they are predicted to transition metals
• For elements with Z > 112, it is assumed that 7p orbitals are filled first
• Elements 119 and 120 involve filling 8s orbital;
• For elements 121 to 153, one electron is first placed in 7d (or 8p) orbital, then
5g and 6f orbitals
• Relativistic effects can cause the elements to have properties differing from
those predicted by simple extrapolation
24
Dubnium (Z = 105)
• Aqua ion of Db is readily hydrolysed, even in strong HNO3, and resembles
those of Nb(V), Ta(V) and Pa(V)
+4 ions of the Group IV elements don’t do this, so this is argument in favour
of +5 oxidation state in aqueous solution
• Study of complex formation in HCl indicates resemblances to Nb(V) and
Pa(V) rather than Ta(V)
• It forms anionic fluoride complexes which, like those of Nb, Ta, and Pa, are
strongly adsorbed on anion-exchange resins
• Study of volatility of halides (assumed to be pentahalides) indicates that DbBr5
is less volatile than NbBr5 and TaBr5 (in contradiction of recent theoretical
predictions) and RfBr4
26
 Seaborgium (Z = 106)
• Comparative study of reaction of 263Sg, Mo, and W with SOCl2 in air suggests
that SgCl2O2 is formed, with similar volatility to the Mo and W homologues
• Investigations of Sg in aqueous solution indicate +6 to be most stable
oxidation state and that it forms neutral or ionic oxo and oxohalide
compounds, species possibly including [SgO4]2−, [SgO3F]−, or [SgO2F4]2−
• Chromatographic study of solutions in very dilute HF indicates formation of
SgO42−, analogous to MoO42− and WO42−
• So far, Sg behaves as a 6d transition metal, similar to Mo and W, with no
evidence for deviations due to relativistic effects and little resemblance to
uranium
27
Natural limits to expansion of periodic table (1)
• Chemical and nuclear physics arguments limit maximum size of PT of
elements (maximum number of elements)
• Shortest time period element needs to exist to be recognized as member of PT
is defined as >10-14 s, which is time needed for formation of electron shell
• However, inflight separation with kinematic separator requires times of
microseconds
• The recipe so far successful to synthesize superheavy elements involved fusion
of doubly magic 48Ca with an actinide target
• Unfortunately, only few micrograms or even nanograms of Es and Fm
respectively will be available in the near future (needed for elements 119 and
120)
• Synthesis elements 119 and 120 has to rely on new, less favorable
combinations of projectile and target. So far, several experiments have failed
to find evidence for the synthesis of elements beyond Z = 118
29
Bohrium (Z = 107) and hassium (Z = 108)
• Some 6 atoms of bohrium were detected as a volatile oxychloride, believed to
be BhO3Cl, by analogy with Tc and Re
• Hassium atoms were oxidized to a very volatile oxide (thought to be HsO4 by
analogy with Ru and Os – its absorption enthalpy is comparable with that of
OsO4), and deposited on NaOH surface. Six correlated α-decay chains of Hs
were observed and attributed to Na2[HsO4(OH)2], sodium hassate(VIII), by
analogy with osmium, the 5d homologue of Hs
28
Natural limits to expansion of periodic table (2)
• Theoretical predictions of nuclear fusion reactions indicate that synthesis of
elements 119 and 120 lies within reach of present day technologies. To be
expected in the near future
• Concerning synthesis of elements beyond Z = 120, the outlook is less
optimistic
• Half-life limit of microseconds may be reached rather quickly. According to
theoretical predictions all isotopes of elements 119–124 have half-lives < 1 ms
• From the chemical point of view, boundary conditions are less stringent.
• Number of electrons that can be arranged around nucleus is limited. Modern
relativistic electronic structure theory that takes into account quantum
electrodynamic effects (QED) predicts this to happen at element Z = 173
30
 Overview

• Electronic structure

Chapter 10
– Crystal-field theory
– Ligand-field theory
• Electronic spectra
– Electronic spectra of atoms

Electronic structure of
– Electronic spectra of complexes
– Charge-transfer bands

d-metal complexes –
–
Selection rules and intensities
Luminescence
• Magnetism
– Paramagnetism
– Spin-crossover complexes
– Cooperative magnetism

1 2

Crystal-field theory

• Metal-ligand bond is considered as being 100% ionic

• More primitive theory; strictly speaking it applies only to ions in crystals
• Ligand lone pair is modelled as a negative point charge that repels electrons in
d-orbitals of central metal ion.

Electronic structure • Theory concentrates on resulting splitting of d-orbitals into groups with
different energies
• Uses splitting to rationalize and correlate optical spectra, thermodynamic
stability, and magnetic properties of complexes.
• Will be applied to octahedral, tetrahedral and square-planar complexes

3 4
Octahedral complexes: orientation of d-orbitals Splitting of d-orbitals in octahedral complex

5 6

Absorption spectrum of [Ti(H2O)6]3+ Crystal-field splitting parameters ∆O

• [Ti(H2O)6]3+ is d1 complex
• Absorption band corresponds to
transition t2g0eg1 ← t2g1eg0
• ∆O = 20300 cm-1
• For complexes with more than 1
d-electron it is not so straightforward
to extract ∆O: energy of transition
does not depend only on orbital
energies but also on electron-electron
repulsion energies.

7 8
 Spectrochemical series Gradual filling of d-orbitals

• Spectrochemical series of ligands: ligands are arranged in order of increasing

energy of transitions that occur when they are present in complex

- Ligands at the left: weak-field ligands d2 d3

- Ligands at the right: strong-field ligands

• Spectrochemical series of metals:

or
-Smaller size of highly charged ions results in shorter metal-ligand distances and
hence in stronger interaction energies
d4 d4
- Larger size of 4d and 5d orbitals compared to compact 3d orbitals results in
stronger interactions with ligands
9 10

Low-spin and high-spin complexes (1) Low-spin and high-spin complexes (2)

P = electron pairing energy (Coulombic repulsion experienced by 2

electrons when they are forced in one orbital and have to pair)
Strong field: ∆O > P Weak-field: ∆O < P
11 12
 Low-spin and high-spin complexes (3) Low-spin and high-spin complexes (4)

• Strength of crystal field (as measured by value of ΔO) and the spin-pairing • 4d4 complex [RuCl6]2- has t2g4 configuration, typical of strong crystal field
energy (as measured by P) depend on identity of both metal and ligand despite Cl- being low in spectrochemical series
⇒ not possible to specify universal point in spectrochemical series at which • [Ru(ox)3]3- has low-spin configuration t2g5
complex changes from high-spin to low-spin • [Fe(ox)3]3- has high-spin configuration t2g3 eg2
• For 3d-metal ions:
– low-spin complexes commonly occur for ligands high in spectrochemical series
(such as CN-)
– high-spin complexes are common for ligands that are low in series (such as F-)
• For octahedral dn complexes with n =1−3 and 8 − 10 there is no ambiguity
about configuration and designations high-spin and low-spin are not used
• Values of ΔO for complexes of 4d- and 5d-series metals are typically higher
than for 3d-series metals
• Pairing energies for 4d- and 5d-series metals are lower than for 3d-series
metals because orbitals are less compact and electron−electron repulsions
weaker
• Complexes of 4d- and 5d-series metals metals generally have electron
configurations that are characteristic of strong crystal fields and have low spin
13 14

Crystal-field stabilization energies Tetrahedral complexes: orientation of d-orbitals

LFSE = ligand field stabilization energy

15 16
Splitting of d-orbitals in tetrahedral complex Tetrahedral complexes

All tetrahedral complexes are high-spin because of small value of ∆T.

17 18

Square-planar complexes (1) Square-planar complexes (2)

• d8 configuration, coupled with strong ligand field, favours formation of

square-planar complexes. Tendency is enhanced with 4d and 5d metals due to
their larger size and greater ease of electron pairing
• Many square-planar complexes are found for complexes of large 4d8 and 5d8
Rh(I), Ir(I), Pt(II), Pd(II), and Au(III) ions, in which unfavourable steric
constraints have less effect and there is large ligand-field splitting associated
with 4d- and 5d-series metals
• Small 3d-series metal complexes such as [NiX4]2- with X a halogen, are
generally tetrahedral because ligand-field splitting parameter is generally quite
small and will not compensate sufficiently for unfavourable steric interactions
• 3d8 Ni(II) forms square-planar complex only with strong-field ligands such as
in [Ni(CN)4]2-

19 20
 Jahn-Teller effect Jahn-Teller effect

• Tetragonal distortion can be expected when ground state electronic

configuration of complex is orbitally degenerate
• Complex will distort so as to remove the degeneracy and to achieve a lower
symmetry.
• Explains why 6-coordinate d9 complexes of Cu2+ usually depart considerably
from octahedral symmetry and show pronounced tetragonal distortions.

"for a non-linear molecule in an electronically degenerate state,

distortion must occur to lower the symmetry, remove the
degeneracy, and lower the energy"
(Jahn and Teller, Proc. Roy. Soc., 1937, A161, 220)

21 22

Jahn-Teller effect Octahedral versus tetrahedral coordination

• Most pronounced for six-coordinate d9 (Cu2+) , high-spin d4 (Mn3+), • LFSE predicts that d3 and d8
low-spin d7 (Ni2+) complexes ions strongly prefer octahedral
geometry over tetrahedral one
• Also possible for other complexes than octahedral complexes with d9, high-
Cr3+ d3
spin d4 and low-spin d7:
Ni2+ d8
– Octahedral complexes: d1, d2, low-spin d4, low-spin d5, high-spin d6, d7 • For other configurations
– Tetrahedral complexes: d1, d3, d4, d6, d8, d9 preference is less pronounced
• Because neither t2g orbitals in octahedral complex nor any of d-orbitals in • Strongest tendency to form
tetrahedral complex point directly to ligands, the Jahn-Teller effect is too small tetrahedral complexes is found
to induce measurable distortion in structure of complex for d2 and d7 ions
V2+ d2
Co2+ d7

• LFSE = 0 for d0, high-spin d5

and d10 ions: geometry of these
ions is not influenced by LFSE
effects

23 24
 Variation of the hydration enthalpy Ligand field theory

• Metal-ligand bond is considered as being 100% covalent.

• MOT applied to d-metal complexes
• Ligand field theory gives a more complete description of the electronic
structure and accounts for a wider range of properties. Explains order of
ligands in spectrochemical series
• Principle: valence orbitals of ligands are used to form symmetry-adapted linear
combinations (SALCs). SALCs of a given symmetry can overlap with metal
atomic orbitals of same symmetry and build in this way molecular orbitals
• Molecular orbitals are filled by electrons in order of relative energy
• First consider effects of σ bonding in octahedral complexes. Then consider
additional effects of π bonding.

25 26

Symmetry labels of orbitals in Oh point group +

SALCs

SALCs for σ-bonding

27 28
 MO scheme for octahedral complex
29
π-donor ligands
• Ligands with local π-symmetry and without
empty low-energy p or π* orbitals
• Decrease ∆O
• Result in ligand-to-metal π-bonding
• Decrease stability of complex, and favour
high-spin complexes
• Examples: F-, Cl-, Br-, I-, en H2O
31
π-bonding
• Several metal complexes form π-bonds with ligands besides the σ-bonds
• Effect of π-bonding on ∆O depends whether π-orbitals of ligands act as
electron donor or electron acceptor.
30
π-acceptor ligands
• Ligands with filled π-orbitals and empty
π*-orbitals of a relatively low energy
• Increase ∆O
• Result in metal-to-ligand π-bonding
• Increase stability of complex, and favour
low-spin complexes
• Examples: CO, PR3
32
 π-bonding and spectrochemical series

• Order of ligands in spectrochemical series is partly that of strength with which

they can participate in M−L σ-bonding
• CH3- and H- are strong σ-donors and arevery high in the series
• When π-bonding is significant, it has a strong influence on ∆O :
– π-donor ligands decrease ∆O
– π-acceptor ligands increase ∆O
Electronic spectra
Therefore CO (strong π-acceptor ) is high in series and OH- (strong π-donor) low in
series
• Spectrochemical series can be interpreted as follows:

33 34

Electronic absorption spectrum of d3 complex

[Cr(NH3)6]3+
3 types of transitions:
- 2 types of d-d or
ligand-field transitions
- spin forbidden
- spin allowed
- Charge-transfer
Why do we observe multiple transitions? transitions (CT)
35
Spectroscopic terms (1)
• First we have to look at energy levels of free ion, before we introduce
ligand-field (crystal-field) effects
• Electronic configuration is incomplete description of arrangement of electrons
in atoms
• Example: configuration 2p2
– 2 electrons might occupy orbitals with different orientations of their orbital angular
momentum: ml = -1, 0, +1 for l =1
– designation 2p2 tells nothing about spin orientations of the 2 electrons: ms = -1/2 or
+1/2
• Atom may have several different states of total orbital and spin angular
momenta, each one corresponding to occupation of orbitals with different
values of ml by electrons with different values of ms
• Different ways in which electrons can occupy orbitals specified in
configuration are called microstates (or quantum states) of configuration
• Examples of microstates of 2p2: (1+,1-) and (-1+,0+)
• Microstates of given configuration have same energy only if electron−electron
repulsions on atom are negligible
36
 Spectroscopic terms (2) Spectroscopic terms (3)

• Because atoms and most molecules are compact, interelectronic repulsions are • Russel-Saunders coupling: process of combining electron angular momenta
strong and cannot always be ignored by summing first the spins, then orbital momenta, and finally combining the
• As a result, microstates that correspond to different relative spatial two resultants
distributions of electrons have different energies • Possible values of L and S are:
• If we group together microstates that have same energy when
electron−electron repulsions are taken into account, spectroscopically
distinguishable energy levels are obtained: terms
• For 3d complexes: most important property of microstate that determines its
energy is relative orientation of electron spins
• For configuration d2 (l1 = 2, l2 = 2, s1 = ½, s2 = ½)
• Next in importance is relative orientation of orbital angular momenta of
electrons
• Terms can be put in order of energy by sorting microstates according to:
1. Total spin quantum number S (determined by relative orientation of individual
spins)
2. Total orbital angular momentum quantum number L (determined by relative • To find values of L and S for atoms with 3 electrons, we continue process by
orientation of individual orbital angular momenta of electrons) combining l3 with the value of L just obtained, and likewise for s3

37 38

Spectroscopic terms (4) Spectroscopic terms (5)

• Once L and S have been found, allowed values of quantum numbers ML and • Total orbital angular momentum of atomic term is denoted as:
MS can be determined:

in analogy with s, p, d, f for orbitals with l = 0, 1, 2, 3

• ML and MS give orientation of angular momentum relative to arbitrary axis:
there are 2L +1 values of ML for a given value of L and 2S+1 values of MS for • Total spin is normally reported as value of 2S+1 ( = multiplicity of term)
given value of S
• For 2 electrons:

• Term symbol: 2S+1L

• Example: (0+,-1-) is microstate with ML = 0 -1 = -1 and MS = +1/2 + (-1/2) = 0
and it may contribute to any term for which these two quantum numbers apply. • 2S+1 = 1, 2, 3, 4, … singlet, doublet, triplet, quartet, …

39 40
 Spectroscopic terms (6) Classification of microstates (1)

• For heavy atoms, such as those of 4d and 5d series, relative orientations of • Allowed terms of configuration are found by identifying values of L and S to
orbital momenta or of spin momenta are less important which microstates of atom can contribute
• Spin and orbital angular momenta of individual electrons are strongly coupled • Pauli principle restricts microstates that can occur in configuration and
together by spin-orbit coupling consequently affects terms that can occur
• Relative orientation of spin and orbital angular momenta of each electron is • Example: 2 electrons cannot both have same spin and be in d orbital with ml =
most important feature for determining the energy +2. Therefore, microstate (2+,2+) is forbidden and so are values of L and S to
• Terms of heavy atoms are therefore sorted on basis of values of total angular which such a microstate might contribute
momentum quantum number j for an electron in each microstate: jj-coupling • Set up table with only microstates allowed by Pauli principle included
• Use process of elimination to classify all microstates
• Start with state of highest ML value
• 3d2 configuration:
45 microstates
Terms allowed: 1G, 3F, 1D, 3P, 1S

41 42

Classification of microstates (2) Term energies (1)

• Once values of L and S that can arise from a given configuration are known, it
is possible to identify the term with lowest energy (ground term) by using
Hund’s rules:
1. For a given configuration, term with greatest multiplicity lies lowest in energy
2. For term of given multiplicity, term with greatest value of L lies lowest in energy
• Hund’s rules applied to d2 configuration (Ti2+):
• Rule 1: ground state will be either 3F or 3P
• Rule 2: 3F term is lower in energy than 3P term
⇒ 3F is ground term of d2 configuration
• ‘Greatest L’ rule is reliable only for predicting ground term, but there is
generally little correlation of L with order of higher terms
• Predicted order for d2 terms:

• Experimental order:

43 44
Term energies (2) Term energies (3)

• In general, all we want to know is the identity of ground term of atom or ion
• Procedure:
– Identify microstate that has highest value of MS.
⇒ Gives highest multiplicity of the configuration
– Identify highest permitted value of ML for that multiplicity
⇒ Gives highest value of L consistent with the highest multiplicity

45 46

Term energies (4) Term energies (5)

47 48
 Racah parameters (1)
• Different terms of configuration have different energies on account of
repulsion between electrons
• Racah parameters A, B and C summarize effects of electron−electron
repulsion on energies of terms that arise from single configuration:
– A corresponds to average of total interelectron repulsion
– B and C relate to repulsion energies between individual d electrons
– Empirical quantities obtained from gas-phase atomic spectra
• Energy of a term can be expressed as linear combination of the 3 Racah
parameters
• For d2 configuration:
• A is common to all terms; if we are interested in relative energies we do not
have to know its value
• Racah parameters are positive as they represent electron −electron repulsions
49
Racah parameters (3)
51
Racah parameters (2)
• If C > 5B, energies of terms of d2 configuration lie in order that is largely
determined by Hund’s rules:
• If C < 5B, advantage of having occupation of orbitals that corresponds to high
orbital angular momentum is greater than the advantage of having high
multiplicity, and 3P term lies above 1D (as is in fact the case for Ti2+)
In this case, Hund’s rules can be used only to predict ground state
• C appears only in expressions for energies of states that differ in multiplicity
from ground state
• If we are interested only in relative energies of terms of same multiplicity as
ground state (that is excitation without change in spin state), we do not need to
know value of C
• Parameter B is of the most interest
50
Electronic spectra of complexes
• Main transitions observed in UV-VIS spectra of d-block transition metal
complexes are transitions between orbitals that are predominantly metal d
orbital in character, with separation characterized by strength of ligand-field
splitting parameter ΔO (d-d transitions or ligand field transitions)
• Electron−electron repulsion splits ligand-field transitions into components
with different energies
52
 Ligand-field transitions (d-d transitions)
• d3 complex [Cr(NH3)6]3+
• Ground state: (t2g)3 or xy1 xz1 yz1
• 2 bands at 25000 cm-1 are intraconfigurational
transitions (d-d): (t2g)2(eg)1 ← (t2g)3.
• Energetic position is determined by ∆o and electron
repulsion.
• For contribution of electron repulsion, 2 groups of
excitations have to be considered:
(a) z2 ← xy, x2-y2 ← xz, x2-y2 ← yz more repulsion
(b) z2 ← xz, z2 ← yz, x2-y2 ← xy same repulsion
53
Nephelauxetic series (2)
• Values of β depend on identity of metal ion and ligand
• List of ligands ordered by value of β gives nephelauxetic series:
• Small value of β indicates large measure of d-electron delocalization on to
ligands and hence significant covalent character in complex
• Series shows that Br- ligand results in greater reduction in electron repulsions
in ion than an F- ligand, which is consistent with greater covalent character in
bromo complexes than in analogous fluoro complexes
• Example: B = 843 cm-1 for [NiF6]4-
B = 600 cm-1 for [NiBr4]2-
• The softer the ligand, the smaller the nephelauxetic parameter
55
Nephelauxetic series (1)
• For [Cr(NH3)6]3+, Racah parameter B = 657 cm-1, which is 64% smaller than
value of B for Cr3+ in gas phase
• Reduction is general observation and indicates that electron repulsions are
weaker in complexes than in free atoms and ions
• Weakening occurs because occupied molecular orbitals are delocalized over
ligands and away from metal
• Delocalization increases average separation of electrons and hence reduces
their mutual repulsion
• Reduction of B from its free ion value is normally reported in terms of
nephelauxetic parameter β:
54
Charge-transfer bands (CT bands)
• CT bands arise from the movement of electrons between orbitals that are
predominantly ligand in character and orbitals that are predominantly metal in
character.
• CT transitions can be identified by their high intensity and the sensitivity of
their energies to solvent polarity (solvatochromism)
• Two types:
– Ligand-to-metal charge-transfer transition (LMCT transition)
– Metal-to-ligand charge-transfer transition (MLCT transition)
56
Charge-transfer bands LMCT transitions

• Most common type of CT transitions

• LMCT transitions are observed in visible region of spectrum when metal is in
high oxidation state and ligands contain non-bonding electrons.
• Typical examples are tetraoxo anions of transition metals (Td symmetry) e.g.
MnO4- and CrO42-
• Transition of e- from O2- to e-orbital of Mn+
(initially d0)
• Lowest LMCT for metals that can be
easiest reduced
• Trends in LMCT energy are:

57 58

KMnO4 LMCT transitions

NH3 → M
ε = 5570 L mol-1 cm-1 at 525 nm

Cl- → M
59 60
 LMCT transitions Optical electronegativities

• General observation: ∆E(LMCT) NH3 > Cl- > Br- > I-

• Variation in position of LMCT bands can be expressed in terms of optical
electronegativities of metal χM and ligand χL.
• Wavelengths of transition can be written as difference between 2
electronegativities:

• Optical electronegativities have values comparable to those of Pauling

electronegativities
• If LCMT terminated in eg orbital, ∆O must be added to energy predicted by this
equation
• Electron pairing energies must be taken into account if transition results in
population of orbital that already contains electron
• Values for metals are different in complexes of different symmetry
• Ligand values are different if transition originates from π orbital rather than σ
orbital. 61 62

MLCT transitions MLCT transitions

• MLCT transitions are observed when metal is in low oxidation state and
ligands have low-lying acceptor orbitals (low-lying π* orbitals).
• Much less common than LMCT transitions
• Typically for ligands with aromatic groups
• Transition occurs at low energy and appears in visible region if metal ion is in
low oxidation state, as its d-orbitals are than relatively close to empty ligand
orbitals

63 64
 Selection rules and intensities Selection rules and intensities

• Strength of electronic transition (expressed by molar absorptivity ε) is • No centre of inversion in tetrahedral complexes (Td symmetry)
determined by transition dipole moment d-d transitions are allowed
ε ≈ 500 L mol-1 cm-1

• If transition dipole moment = 0 → forbidden transition, ε = 0

• Octahedral complexes have centre of inversion
d-d transitions: ground state is g, excited state is g, but r(x,y,z) is u
Therefore: g × u × g = u spectrum [CoCl4]2-

• d-d transitions in octahedral complexes are Laporte-forbidden • CT transitions are allowed; very intense transitions
ε ≈ 1000−50000 L mol-1 cm-1
• Asymmetric vibrations relax this selection rule (vibronic coupling).
• For spin-forbidden transitions: ε < 1 L mol-1 cm-1
• ε ≈ 10-100 L mol-1 cm-1 for d-d transitions in octahedral complexes 65 66

Selection rules and intensities Selection rules and intensities

• Electronic transitions with change of multiplicity are forbidden. • Electronic transitions with change of multiplicity are forbidden.
• Intensities of spin-forbidden transitions are greater for 4d and 5d complexes • Intensities of spin-forbidden transitions are greater for 4d and 5d complexes
than for the comparable 3d complexes (heavy atom effect, due to stronger than for the comparable 3d complexes (heavy atom effect, due to stronger
spin-orbit coupling). spin-orbit coupling).

67 68
 Luminescence Luminescence of ruby (Al2O3:Cr3+)

• Luminescent complex re-emits radiation after it has been electronically

excited.
• Fluorescence occurs when there is no change in multiplicity.
∆S = 0 allowed transition
• Phosphorescence occurs when an excited state undergoes intersystem
crossing to a state of different multiplicity and then undergoes radiative decay.
∆S ≠ 0 forbidden transition
• Luminescence is more general term than fluorescence or phosphorescence
because no mechanism need to be considered

Absorption spectrum of ruby

69 70

Luminescence of ruby (Al2O3:Cr3+)

Magnetism

71 72
 Magnetic measurements Diagmagnetism versus paramagnetism

• Experimental distinction between high-spin and low-spin octahedral

complexes is based on determination of their magnetic properties
• Compounds are classified as diamagnetic if they are repelled by magnetic
field and paramagnetic if they are attracted by magnetic field
• Magnitude of paramagnetism of a complex is commonly reported in terms of
magnetic dipole moment it possesses: the higher the magnetic dipole moment
of complex, the greater the paramagnetism of sample

73 74

Paramagnetic compounds Oxygen is paramagnetic!

75 76
 Magnetisation Magnetic permeability and susceptibility

• When a sample is placed in a magnetic field, the magnetic field inside the • Ratios I/H0 and B/H0 are constant for given compound.
sample will be larger or smaller than the external magnetic field, depending
whether the sample is paramagnetic or diamagnetic
• B/H0 is magnetic permeability
• ∆H: difference between the internal and external magnetic field:
Ratio of density of magnetic field lines in presence of sample to density of
∆H = B − H 0 magnetic field lines in absence of sample

B = induced magnetic field inside sample, H0 = free-field value B/H0 = 1 in vacuo

diamagnetic compounds: B < H0 , paramagnetic compounds: B > H0
• Difference between the applied magnetic field and the induced magnetic field • I/H0 is magnetic susceptibility per unit volume or volume magnetic
is often expressed in terms of I, the intensity of magnetisation: susceptibility (κ)
Expresses extent to which material is magnetised
4π I = B − H 0
• both B and I are proportional to the strength of the external magnetic field. B
4πκ = −1
H0

77 78

Magnetic permeability and susceptibility Magnetic susceptibility

• Ratios I/H0 and B/H0 are constant for given compound. • Specific magnetic susceptibility or mass magnetic susceptibility:

κ
• B/H0 is magnetic permeability χg =
Ratio of density of magnetic field lines in presence of sample to density of ρ
magnetic field lines in absence of sample • Molar magnetic susceptibility:

B/H0 = 1 in vacuo
χM = χg ⋅ M
• I/H0 is magnetic susceptibility per unit volume or volume magnetic
susceptibility (κ) • Paramagnetic susceptibility
Expresses extent to which material is magnetised

B χ para = χ M − χ dia
4πκ = −1
H0

79 80
 Curie’s law Magnetic moment

• Curie’s law: paramagnetic susceptibility is inversely proportional to absolute • Magnetic moment is connected to intrinsic
temperature: electron spin

NA µ 2 NA2 µ 2 C • magnetic moment µ = vector that connects

χ para = = ≡ torsion τ that object experiences in
3kT 3RT T magnetic field to magnetic field itself:

τ=µ×B

• Magnetic moment µ can be derived from magnetic susceptibility:

3RTχ para
µ=
NA

81 82

Magnetic moment Spin-only magnetic moment

• µ is expressed in Bohr magnetons • In 3d transition metals, it is sufficient to consider only spin contribution to
magnetic moment; contribution by orbital angular momentum can be neglected
Bohr magneton β (= eh/(4πmc)) is natural unit for magnetic moment (due to quenching of orbital angular momentum)
• Instead of effective magnetic moment, spin-only magnetic moment µS can be
considered:
• Effective magnetic moment µeff
µ S = g S (S + 1)
µ = µeff β
g is the Landé g factor (2.00023 ≈ 2); S = n/2

µ S = 2 S (S + 1) = 4S (S + 1)
3RTχ para
µ eff =
NA β µ S = n(n + 2)

n is number of unpaired electrons

83 84
 Gouy-balans
Calculated versus experimental magnetic moments

85 86

Faraday-balans Spin-crossover effect

Temperature dependence of magnetic moment of [Fe(phen)2(NCS)2].

High-spin to low-spin transition

87 88
 Spin-crossover effect Cooperative magnetism

• In solids, spins on neighbouring metal centres may interact to produce

magnetic behaviour, such as ferromagnetism and antiferromagnetism, that are
representative of the whole solid.

89 90

Paramagnetism versus ferromagnetism Ordering of magnetic dipoles

91 92
 Temperature dependence of
Hysteresis loop of ferromagnetic material
magnetic susceptibility

Critical temperatures: Curie temperature (TC) and Néel temperature (TN)

93 94

Electronic structure of Ln3+ ions (1)

• Ground state for given lanthanide ion is largely unaffected by ligands bound to
Chapter 11 it
• Crystal field splittings are weak because of shielding of 4f electrons by filled
5s and 5p orbitals

Electronic structure of
• Orbital angular moment is unquenched (unlike in d-block metal complexes)
• Electronic structure may be accounted for using Russell–Saunders coupling

f-block elements scheme in which electron spins are coupled together separately from coupling
of orbital angular momenta of electrons
• Spins of individual electrons(s) are coupled together (added vectorially) to
give total spin quantum number S
• Orbital angular momenta (l) of individual electrons are coupled similarly
• For f electron, l = 3, so that magnetic quantum number ml can have any one of
7 integral values between +3 and −3.
• Vectorial addition of the ml values for f electrons for the multi-electron ion
affords total orbital angular momentum quantum number L

1 2
 Electronic structure of Ln3+ ions (2) (4  + 2) ! 14 !
Number of levels
=
N !(4  + 2 − N ) ! N !(14-N )!

Number of f Number of Number of Number of LF

electrons terms levels sublevels
2S+1L 2S+1L 2S+1G
J x

1 13 1 2 14
2 12 7 13 91
• There is weaker coupling, spin–orbit coupling, between S and L
• Vector addition of L and S affords resulting quantum number, J 3 11 17 41 364
• J can have values of (L + S), (L + S) − 1; . . . . . . . . (L − S)
Example: if L = 6 and S = 2, J values of 8, 7, 6, 5, and 4 are possible 4 10 47 107 1001
• Partly filled 4f shell – multiple configurations
5 9 73 198 2002
• Eu3+ 4f6 → 6 electrons for 7 f-orbitials (2 possible spin orientations)
14!/(6!(14-6)!) = 3003 different arrangments 6 8 119 295 3003
7 119 327 3432

3 4

Electronic structure of Ln3+ ions (3) Example: ground state of Sm3+ (f5)

• Ground state can be determined using Hund’s rules (in this order):
1. spin multiplicity (2S + 1) is as high as possible
2. If there is more than one term with same spin multiplicity, term with highest
L-value is the ground state
3. For shell less than half-filled, J for ground state takes lowest possible value;
for shell more than half-filled, J for ground state is highest possible
• First complete ‘box diagram’, representing orbitals by boxes (7 boxes for 7 f
orbitals) and electrons by arrows
• Put electrons in separate orbitals when shell is less than half-filled, i.e.
choosing maximum number of unpaired electrons, and choosing to maximize
values of ml to give the highest L-value (check Hund’s rule 2)

• Since the shell is less than half-filled, the state with the lowest J -value is
ground state (Hund’s rule 3), so this is J = 5/2
• Term symbol for the ground state of Sm3+ is thus 6H5/2
5 6
 Magnetic properties of Ln3+ ions (1) Magnetic properties of Ln3+ ions (2)

• With exception of La3+ and Lu3+ (and of course Y3+), Ln3+ ions all contain • Formula for magnetic moment of lanthanide ions is different from that of
unpaired electrons and are paramagnetic. transition metal ions, because orbital angular momentum is not quenched
• Magnetic properties are determined entirely by ground state (with 2 • Magnetic moments in second half of series are greater than moments in first
exceptions: Sm3+ and Eu3+), as excited states are so well separated from half, as J = L + S for a shell greater than half-filled and J = L − S for a less than
ground state (owing to spin–orbit coupling) and thus thermally inaccessible half-filled shell
• Magnetic moment of Ln3+ ions is essentially independent of environment, so
that one cannot distinguish between coordination geometries as is sometimes
possible for transition metals – in the case of octahedral and tetrahedral Co2+
complexes, for example
• Magnetic moments are given by equation:

where Landé g-factor is defined by:

7 8

Magnetic properties of Ln3+ ions (3) Magnetic properties of Ln3+ ions (4)

• Strength of spin–orbit coupling means that ground state is well separated from
• excited states, except for Sm3+ and Eu3+, where contributions from low-lying
paramagnetic excited states contribute to magnetic moment
• If magnetic properties of Eu3+ ion were solely determined by 7F0 ground state,
its compounds would be diamagnetic, whereas contributions from thermally
accessible levels such as 7F1 and 7F2 [using Boltzmann factor of exp(−E/kT )]
lead to observed room-temperature magnetic moments of about 3.5μB
• In case of Sm3+, thermal population of 6H7/2 state leads to moments around
1.6 μB, rather than value of 0.845 μB that would be expected if just the 6H5/2
ground state were responsible

9 10
Energy level structure of trivalent lanthanide ions
Splitting of 4f6 levels of Eu3+

• Partly filled 4f shell – multiple configurations

Eu3+ 4f6 → 6 electrons for 7 f-orbitials (2 possible spin orientations)
14!/(6!(14-6)!) = 3003 different arrangments
• 4f shell well shielded from the environment by closed 5s2 and 5p6
shells
• Energy level splitting due to:
– Electrostatic interactions
– Spin-orbit coupling
– Crystal-field (CF) interactions

11 Ref. J.C.G. Bünzli, Inorg. Chim. Acta 139 (1987) 2019. 12

Dieke (1968)
Free-ion levels of Eu3+

Ref. : K. Binnemans, Bull. Soc. Chim. Belg. 105 (1996) 793. 13 14

 ANL report – Carnall, Crosswhite & Crosswhite
energy levels in LaF3 - 1977
Extension to VUV

Ref.: R.T Wegh et al. J. Lumin. 66-68 (2000) 1002.

15 16

Types of transitions f-f transitions

• f-f transitions • Narrow bands

• f-d transitions • Weak intensities: ε < 10 M-1cm-1
• charge-transfer (CT) transitions • Barycenters of CF sublevels are not much
dependent on the nature of the Ln3+ environment; therefore energy of
the transitions is more or less constant
(but not CF splitting!)
• Electric dipole transitions (ED) are forbidden
Magnetic dipole (MD) transitions are allowed, but very weak
• Number of components for a given (2S’+1)L’J’←2S+1)LJ transition depends
on the site symmetry
• Some transitions are hypersensitive, i.e. very sensitive to small
changes in the Ln3+ environment.

17 18
 Selection rules for f-f transitions Typical absorption spectrum of Eu3+

Electric dipole transitions Magnetic dipole transitions

2.8 ε / M-1cm-1
∆l = ± 1 Laporte’s rule ∆l = 0
5L
∆S = 0 spin rule ∆S = 0 2.4 6
∆L ≤ 6 0, 2, 4, 6 ∆L = 0 EuCl3 0.05 M
2.0
∆J ≤ 6 0, 2, 4, 6 ∆J = 0, ± 1, except 0-0 in H2O
5G
4
1.6
5H
J
(2S+1)Γ
J ←7F0,1
Relaxed by J-mixing 1.2 5G
3
5H
6
5K 5F 6 5G
4
0.8 6
5D
6
5G
5G
2
4 4
4
0.4 3
5D 5D 5D
3 2 1

250 300 350 400 450 500 nm

19 20
Ref. : J.C.G Bünzli, Lanthanide course

f-d transitions
f-d transitions
E / 103 cm-1
Allowed by Laporte’s rule, ≈ 100-1000 M-1cm-1
n.obs.
Highly energetic, except for Ce3+, Pr3+, and Tb3+ [Ce(H2O)9]3+, D3h symmetry
48.0 2D
102 ε 225 250 300 nm 5/2
80 E / 103 cm-1
8
70 6 44.0
60 4
2D
50 2 E / 103 cm-1 40.0 3/2

40 0
48 44 40 36 32
30 4f to 5d transition
2 2F
7/2
Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Ce3+ [Xe]5d1 generates two
levels, 2D3/2 and 2D5/2 0 2F
5/2
21
Ref. : J.C.G Bünzli, Lanthanide course Ref. : J.C.G Bünzli, Lanthanide course 22
 Charge-transfer (CT) transitions Red phosphor Y2O3:Eu3+
Allowed by Laporte’s rule, » 200-500 M-1cm-1
Voor Eu3+: LMCT (formal reduction to Eu2+)

48 5D
0→
7F
2
4 III
YPO Eu (CT state)
LMCT
46
44 YOF 3 in 103 cm-1
42 Y2O Excitation spectrum
E /103 cm-1

40
4
38 LaPO Emission spectrum
36 3
34 La2O LaOCl f-f transitions
32 Host Y2O
2S
30 λ /nm
28
230 280 330 380 430 480 530 580 630 680 730
23 24
Ref. : J.C.G Bünzli, Lanthanide course Ref. : J.C.G Bünzli, Lanthanide course

4f emission spectra Characteristic of lanthanide luminescence

Gd Tb Dy Ho Er Tm Yb
40 40
3P
0
• Narrow emission lines (high chromatic purity)
35 35 • Every spectroscopically active lanthanide ion has a typical
Pr Nd Sm Eu luminescence color
6P
30 7/2 30 • Emission color is not very dependent on ion’s environment
1D

25 5D
3
2
25 • Large Stokes shift
-1

2
• Long-lived excited states (several ms in inorganic matrices)
E / 10 cm

20 3P
0 1 5D
4
4F
9/2
1G
4 20 • Direct excitation in 4f-levels is not efficient
3

0 5S 4S
1D
4G 5D 5F
2 3/2 Sensitized luminescence is preferred
15 2
5/2 5 15
1G
4
10 4F
3/2 2F 10
3F 5/2
4

5 4I
13/2 5

0 0
3H 4I 6H 7 8 7F 6H 5 4I 3H 2F
4 9/2 5/2 F0,1 S7/2 6 15/2 I8 15/2 6 7/2
25 26
Ref. : J.C.G Bünzli, Lanthanide course
 Luminescence of lanthanide ions Transitions in europium(III) luminescence spectra

Tb Eu Transitions with ∆J = 0, 2 are hypersensitive (exception 0−0), i.e. very

sensitive to minute changes in the environment of metal ion
Transitions from 5D0 to 7FJ for J =
0 ED 577-581 nm non-degenerate, highly forbidden
Visible luminescence observed
for Eu3+, Tb3+, Sm3+, Dy3+ Dy Sm allowed in some symmetries
1 MD 585-600 nm allowed, weak intensity almost
independent from environment
2 ED 610-625 nm hypersensitive, forbidden if
inversion centre i is present
500 600 700 nm
3 ED 640-655 nm forbidden, very weak
Pr3+ (1.33 mm), Nd3+ (1.06 mm), Er3+ (1.54 mm), and Yb3+ (0.98 mm) have 4 ED 680-710 nm allowed (except if i)
interesting emission bands in the NIR range, some of them are in the 5 ED 740-770 nm forbidden, very weak
telecommunication window (1 – 1.6 mm) 6 ED 810-840 nm allowed, weak (except if i)
27 28

Luminescence of [Eu(tta)3(phen)] 5D
0  7F2

30000
30000
25000

25000
Intensity /counts

20000

Intensity /counts
15000
7
F2
20000
10000

7
15000
5000 7
F0 F1 7 7 7
F3 F4 F2
0 10000
575 600 625 650 675 700 725
Wavelength /nm 7
5000 7
F0 F1 7 7
F3 F4
F3C 0
O N 575 600 625 650 675 700 725
Eu
O Wavelength /nm
N
S
3 29 30
 5D  7F2
0

• Induced electric dipole transition (ED transition) Na3[Eu(oxydiacetato)3]⋅2NaClO4⋅6H2O

• “hypersensitive transition”: intensity is much more influenced by the local (D3)
symmetry of the Eu3+ ion and nature of ligands than intensities of other
ED transitions
Selection rules: |∆S| = 0, |∆L| ≤ 2 and |∆J| ≤ 2
(selection rules for quadrupole transition: “pseudo-quadrupole” transition
• 5D0  7F2 is responsible for typical red luminescence observed in
Cs2NaEuCl6 (Oh)
europium(III) phosphors such as Y2O3:Eu3+ or Y2O2S:Eu3+
• In case transition 5D0  7F2 is very weak, luminescence spectrum is
dominated by 5D0  7F1 and orange luminescence is observed.
Examples: Na9EuW10O36⋅18H2O (D4d symmetry), YF3:Eu3+ (D4d),
GdB3O6:Eu3+ (D4d), Na3[Eu(oxydiacetato)3]⋅2NaClO4⋅6H2O (D3), Eu(antipyrene)6I3 (S6)
SnO2:Eu3+ (D2h)

31 Ref.: F. Kirby et al. Chem. Phys. Lett. 95 (1983) 507 32

[Eu(dbm)3(H2O)] (C3v)
SnO2:Eu3+ (D2h)

[Eu(dbm)3(H2O)] (C3v)

Na3[Eu(oxydiacetato)3]⋅2NaClO4⋅6H2O
(D3)
Ref.: M. Ma et al. J. Alloys Compds. 509 (2011) 3441
Ref.: F. Kirby et al. Chem. Phys. Lett. 95 (1983) 507 33 34
 Number of emission lines for Eu3+ in different Antenna effect (1)
symmetries
• Weak light absorption by forbidden f-f transitions; molar absorption
coefficients ε are < 10 L-1 mol cm-1.
• Indirect excitation via attached ligands or via host lattice in order to get
sensitized luminescence.
• Excitation energy is transferred from ligand to lanthanide ion.

Ref. : P.A. Tanner, Chem. Soc. Rev. 42 (2013) 5090.

35 36

Antenna effect (2) Other routes to sensitization

S1 ISC • Sensitization is not only possible via energy transfer from triplet state
of organic ligands, but also by:
ET
T1 – Inorganic chromophores (e.g. MoO42-, VO42-)
– Charge-transfer bands

A F P L

S0

ligand lanthanide ion

A = absorption, F = fluorescence, P = phosphorescence,

L = lanthanide-centered luminescence, ISC = intersystem crossing,
37 38
ET = energy transfer; S = singlet, T = triplet.
 Quenching (2)
Quenching (1)

• One problem with luminescence in aqueous solution is that another pathway is • Energy gap law: the larger the gap between the excited state and the
available for deactivation of the excited state of lanthanide, in form of more energetic component of the ground state multiplet, the more
vibrational energy transfer to water molecules in particular intense the luminescence
• ‘quenching’ of luminescence can be minimized (apart from working in solid (less non-radiative deactivation)
state, or using non-aqueous solvents) by using multidentate ligands which
exclude waters from coordination sphere of metal, and also by using ligands
which tend to encapsulate lanthanide ion
Gd 32100 cm-1 Yb 10400 cm-1 Tm 6200 cm-1
Tb 14800 cm-1 Dy 7800 cm-1 Er 5900 cm-1
Eu 12300 cm-1 Sm 7400 cm-1 Nd 4400 cm-1

• Gd3+ is the best emitter, but the 6P7/2→8S7/2 transition occurs in the UV
(around 310 nm).
• Eu3+, Tb3+ have often large intrinsic quantum yields and are used as
luminescent probes.

39 40

Quenching (3) Lanthanide phosphors

41 42
 Fluorescent lamps Fluorescent lamps

W filament Hg

∆V e-

Fill gas: Ar UV (254 nm)

Coating

UV photons excite phosphor coating. White light is emitted by

43
blend of phosphors 44

Producing white light: trichromatic stimuli Lamp phosphors

CRI / % Year Phosphors

There are three “prime”
80 colors corresponding to the 1960 Ca5(PO4)3Cl:Sb3+,Mn2+ (white)
60 three spectral responses of
human vision 1974 BaMg2Al16O27:Eu2+ CeMgAl10O19:Tb3+ Y2O3:Eu3+
40
TbIII
20
(EuII) EuIII 1990 BaMgAl10O17:Eu2+ (La,Ce)PO4:Tb3+ Y2O3:Eu3+
0 (Sr,Ca)5(PO4)3Cl:Eu2+ CeMgAl10O19:Tb3+
(Gd,Ce)MgB5O10:Tb3+
-20
400 500 600 nm 2005 BaMgAl10O17:Eu2+ (La,Ce)PO4:Tb3+ Y2O3:Eu3+

Color rendering index obtained

by mixing the three prime colors
Ref. : J.C.G Bünzli, Lanthanide course
400 500 600 nm
45
Ref. : J.C.G Bünzli, Lanthanide course
46
 Red phosphor Y2O3:Eu3+ Green phosphor LaPO4:(Ce3+,Tb3+)

5D
0→ F2
7
LMCT 4f-5d
transition Emission spectrum
Excitation spectrum
Excitation spectrum
Hg 254 nm Emission spectrum
Hg 254 nm
Ce3+→Tb3+
f-f transitions transfer

λ /nm λ (nm)
230 280 330 380 430 480 530 580 630 680 730 240 290 340 390 440 490 540 590 640 690
47 48
Ref. : J.C.G Bünzli, Lanthanide course Ref. : J.C.G Bünzli, Lanthanide course

Blue phosphor Sr4Al4O25:Eu2+ Tricolor lamps

Spectral distribution 80 P /µW·nm-1·lm-1

of a luminescent lamp
with the following
Emission phosphors: 60
excitation (d-f transition)
BaMg2Al16O27:Eu2+ 40
Hg 254 nm CeMgAl11O19:Tb3+
Y2O3:Eu3+
20

0
200 300 400 500 600 nm 400 500 600 700

49 50
Ref. : J.C.G Bünzli, Lanthanide course Ref. : J.C.G Bünzli, Lanthanide course
 Nd-YAG laser (1) Nd-YAG laser (2)

• Laser = Light Amplification by Stimulated Emission of Radiation

• Various lanthanide ions can be used in lasers, different ions operating
at different frequencies from UV to IR
• Most popular laser material: YAG: Nd3+ (Nd-YAG)
(emission at 1064 nm)
• YAG = yttrium aluminium garnet, Y3Al5O12
• Laser functions by increasing light emission by stimulating the release
of photons from excited Nd3+ ions
• Typical device consists of YAG rod a few cm long (containing about
1% neodymium in place of yttrium) that is fitted with mirror at each
end, one being Ag-coated partly transmitting mirror
• Xe flash lamp is used to ‘pump’ the system
• Laser system needs to be (water-)cooled to dissipate heat

52

Nd-YAG laser (3) Nd-YAG laser (4)

• Pumping that excess of Nd3+ ions is in excited state (e.g. 4F5/2 or 4F7/2) • 4I1
1/2 state is excited level of ground state, which is not thermally
so that more ions can emit electrons than can absorb; populated and so undergoes rapid relaxation to ground state,
• Excited ions decay rapidly (or ‘cascade’) to long-lifetime 4F3/2 state maintaining the ‘population inversion’ (whereupon laser process can
non-radiatively, so that high proportion of Nd3+ ions are in this state recommence)
rather than ground state: ‘population inversion’ • Nd-YAG is said to act as ‘four-level’ laser
• If photon of correct energy (at wavelength of laser transition) hits Nd3+ • By frequency doubling with NLO crystal, Nd-YAG laser can emit at
ion in 4F3/2 state, Nd3+ ion is stimulated to release another photon of 532 nm (green light)
same wavelength, as it drops to 4I11/2 state
• As photons are reflected backwards and forwards in rod, more and
more ions are stimulated into giving up photons (thus depopulating the
4F
3/2 state) and eventually the build up of photons is so great that they
emerge from rod as intense beam of coherent monochromatic light
(wavelength 1064 nm, in near-IR)

53 54
 Nd-YAG laser (5) Nd-YAG laser (6)

55 56

MRI contrast agents: What is MRI? MRI contrast agents: Why MRI?

• Gadolinium(III) complexes are used to enhance contrast between • Non-invasive diagnosis

different tissues in MRI scans • Brain Imaging! (multiple sclerosis, brain lesions)
• MRI = Magnetic Resonance Imaging • 3D imaging of organs, imaging of soft tissues (tumors)
• Diagnostic technique in hospitals • Not harmful to patient (unlike X-ray imaging)
• Known as ‘the scanner’ • Superior Images
• Patient-sized NMR spectrometer • Easy to analyse
• Large patient sized magnet • (Safe contrast agents)
(0.5 –1.5 T)
• Measures 1H-NMR parameters
of water and fat protons

57 58
 MRI contrast agents: functional MRI (f-MRI)
• When brain activity occurs, blood flow to that region increases, which
causes contrast change between active and inactive regions
• Very often used in neurosciences: functional MRI (f-MRI)
59
MRI contrast agents: T1 and T2 relaxation
Return of magnetization vector to its original value.
During this process, excess of energy is dissipated to
surroundings.
Field imperfections of static magnetic field (B0) cause
inhomogeneities that make nuclei precess at slightly
different rates.
Nuclei differ in phase, coherence will be lost.
61
MRI contrast agents: physical principles of MRI
• Protons (H2O) are very tiny magnets
• Strong magnetic field (B0, z-axis) aligns protons with
field
z z
y y
• Transmit radio waves into sample, tissue protons
(H2O) will absorb (Excitation) 60
MRI contrast agents: MRI measurement
• In order to make diagnoses about different parts of the body, it is
necessary to obtain 2D image of signals
• Patient is placed in magnetic field gradient (using gradient coils to
create different fields at many points in piece of tissue) so that
otherwise identical H2O molecules yield resonances as slightly
different frequencies at each point, depending upon their position in
field
• Computer processing of data gives digitized image of spatially
organized signal
• Signal intensity depends upon relaxation times of protons
• To enhance contrast to differentiate between healthy and diseased
tissue, paramagnetic contrast agents are used (MRI contrast agents)
62
 MRI contrast agents: basis of contrast (1) MRI contrast agents: basis of contrast (2)

• Measurement of water proton relaxation rates (T1 and T2)

• Proton relaxation of water molecules is tissue-dependent!
Everything that increases proton
relaxation rates of water protons will
increase quality of image
• Agents administered to the patient (intravenous, oral…)
• Enhancing image contrast
• Increasing the relaxation rate of water (and fat) protons
(i.e. they affect T1 and/or T2 relaxation times)
• Most contrast agents shorten T1 relaxation times
• Paramagnetic metal centre (Gd3+, Mn2+…)
• Complexed with organic chelating ligand
• Interactions between metal electrons and (water) protons
causes relaxation enhancement

tumor
63 64

MRI contrast agents: requirements MRI contrast agents: gadolinium (1)

• High magnetic moment • Gadolinium(III) compounds are especially suited as MRI contrast
• Long electron-spin relaxation time agent, because its properties are favorable for nuclear spin relaxation
• Osmolarity similar to serum – Gd3+ ion has large number of unpaired electrons (S = 7/2)
• Low toxicity – Its magnetic properties are isotropic
• High solubility in water – It has relatively long electron-spin relaxation time, ∼10-9 s, which
• Targeting tissue makes it more suitable than other very paramagnetic ions such as
Dy3+ (∼10-13 s).
• Coordinated water molecules
• Free Gd3+(aq) ion is toxic, with LD50 ∼ 0.1 mmol/kg, < imaging dose
• Large molecule with long rotational correlation times (normally of the order of 5 g for a human)
• Gadolinum(III) complexes with ligands that form very stable in vivo
complex are used
• Water molecules must be present in first coordination sphere because
relaxation times are shorter the nearer water molecules are to Gd3+

65 66
 MRI contrast agents: gadolinium (2) MRI contrast agents: gadolinium (3)

• Ideally the more water molecules present the better, since more solvent
waters can readily be exchanged with coordinated water molecules Gd3+
-OOC
COO-
• Balance needs to be found between number of coordinated water N N N [Gd(dtpa)]2-
-OOC
COO-
molecules and stability
COO-
• Most contrast agents have 1 coordinated water molecule Magnevist®
• Best known MRI contrast agents:
[Gd(dtpa)(H2O)]2- Magnevist®
[Gd(dota)(H2O)]- Dotarem ® O O
-

N N O
-
[Gd(dota)]-
Gd3+
N N
Dotarem®
-
O

O
-O O

67 68

REE permanent magnets (1) REE permanent magnets (2)

• REE magnets dominate world of industrial strong and permanent magnets

• 2 main families of RE magnets: NdFeB and SmCo
• NdFeB
– 1 type: Nd2Fe14B
– Srongest commercially available permanent magnets
– Maximum energy product (BH)max :512 kJ/m3
– Have low Curie temperature
(temperature at which thermal motion leads to loss of magnetization)
– Dy or Tb added to increase resistance to demagnetization
– Microstructure plays a crucial role on the magnetic properties
– Poor corrosion resistance (surface plating required)
• SmCo
– 2 main types: SmCo5 and Sm2Co17
– Maximum energy product (BH)max :130 to 260 kJ/m3
– Have much higher Curie temperature
– Are selected for applications requiring high temperatures
– Good corrosion resistance
– Expensive (Co): niche applications (2 to 5% of REE magnet market) 69 70
REE permanent magnets (3) Ferromagnetism (1)

• Ferromagnetism is cooperative phenomenon resulting from long range

interactions between spins of unpaired electrons.
• Each atom produces its own magnetic field which strongly interacts with the
neighbors.
• Spontaneous alignment of spins within magnetic domains below Curie
temperature Tc
• Above Tc, thermal motion destroys the coupling: material is paramagnetic
• Below Curie temperature and in absence of any applied magnetic field H,
ferromagnetic domains are oriented in all directions
⇒ external magnetic flux is zero

71 72

Ferromagnetism (2) Hysteresis loop (1)

73 74
 Hysteresis loop (2) Magnetic units

• Saturation magnetic induction (Bs) • Magnetic flux density B: Tesla (T)

– All magnetic dipoles are aligned and magnetic flux density reached maximum – Historically: Gauss (G) or oersted (Oe)
value – 1 T = 10,000 gauss or oersted
– Strong magnetic flux Bs is created in magnet – 1 gauss =1 oersted in vacuum or in a nonmagnetic substance like air
• Remanence (Br) • Applied field H: ampere per meter (A/m)
– Remaining magnetization in absence of external magnetic field – 1 Oe = 103/4π A/m
– Characterizes strength of permanent magnet
• Energy product (BHmax): megagauss oersteds (MGOe) or kJ/m3
• K (for kneerepresents region where performances of permanent magnet start – Values in MGOe need to be multiplied by 7.96 to be converted into kJ/m3
to degrade in presence of external magnetic field with opposite magnetization
• Coercitivity (Hc)
– Value of H needed for total demagnetization of permanent magnet
– Measures resistance of magnet to demagnetization
– RE magnets are characterized by highest value of coercitivity among all solid-state
magnets. They retain their magnetization indefinitely in normal conditions.
• Energy product (BHmax)
– Quality factor of permanent magnets (to compare performance of magnets)
– Maximum product of Br and Hc
– Corresponds to maximum density of magnetic energy which is stored into magnet 75 76

Dependence of magnetization on temperature (1) Dependence of magnetization on temperature (1)

• Magnetization is very sensitive to thermal agitation which tends to destroy • Magnetization is very sensitive to thermal agitation which tends to destroy
magnetic coupling magnetic coupling
• Ferromagnetism disappears totally at temperature superior to Curie • Ferromagnetism disappears totally at temperature superior to Curie
temperature Tc temperature Tc
• High Tc values are desirable • High Tc values are desirable
– Tc = 310 °C for NdFeB magnets – Tc = 310 °C for NdFeB magnets
– Tc = 750 °C SmCo magnets – Tc = 750 °C SmCo magnets
• It is observed that far below Tc there is degradation of magnetization versus • It is observed that far below Tc there is degradation of magnetization versus
temperature temperature
• Temperature maximum of utilization (Tmax) • Temperature maximum of utilization (Tmax)
• Maximum usage temperature for magnet which ensures a full recovery of its • Maximum usage temperature for magnet which ensures a full recovery of its
properties when T is decreased properties when T is decreased
– Tmax = 80 °C for NdFeB magnets – Tmax = 80 °C for NdFeB magnets
– Tmax = 300 °C SmCo magnets – Tmax = 300 °C SmCo magnets
• Properties of magnet are significantly deteriorating between Tmax and Tc • Properties of magnet are significantly deteriorating between Tmax and Tc

77 78
 Dependence of magnetization on temperature (2)
79
Requirements for exceptional magnets (2)
• Several other parameters also characterize the quality, durability, and
commercial potential of a magnet:
– Resistance to corrosion especially in humid conditions
– Physical strength such as brittleness, hardness
– Available size and shape
– Different potentialities for magnetic polarization
– Raw materials cost and availability
81
Requirements for exceptional magnets (1)
• High magnetic flux density Br
– Highest values of remanence for RE magnets are Br =1.4−1.6 T
• Steep first magnetization curve
– Indicates that magnetic dipoles aligned easily along some crystalline directions
• Strong resistance to demagnetization with high Hc coercitivity values
– Typical values for bestRE magnets coercitivities are ∼25 kOe (25 kG or 2.5 T or
2000 kA/m)
• High energy product BHmax
– Corresponds to maximum density of magnetic energy which is stored into magnet
– Values as high as 400 kJ/m3 are obtained with NdFeB magnets
• High maximum temperature of utilization (Tmax)
– For applications in electric generators and electric motors: > 150 °C
80
Codification of the magnets
• In order to normalize magnet specifications, producers have assigned code to
each magnet which represents material grade
• Codification of Nd magnet is for instance N30, M40, H35, SH40, EH35, and
UH35
• Numerical value corresponds to maximum energy product and is expressed in
MGOe
• Letters codify maximum utilization temperature:
N = 80 °C, M = 100 °C, H = 120 °C, SH = 150 °C, UH = 180 °C, EH = 200 °C
82
Effect of Dy on performance NdFeB magnets (1) Effect of Dy on performance NdFeB magnets (2)

• Decay in magnet strength with increasing temperature is critical factor in many

applications
• For many important applications stable performances are required >150 °C
• Strongest magnets, NdFeB have maximum working temperature Tmax = 80 °C
Too low for many applications
• Tmax can be increased by partially substituting Nd with Dy or Tb
• Direct substitution of Nd by Dy in NdFeB alloys permits to raise Tma up to 220
°C for substitution level of 12 wt%
• Dy substitution also simultaneously yields linear increase in coercivity (Hc)
and linear decrease in remanence (Br), BHmax is not significantly altered
• Major penalty of this substitution is in more expensive alloy due to
significantly higher price of Dy.
Hence novel approaches have been thought out to minimize its fraction while
retaining its beneficial properties

83 84

Effect of Dy on performance NdFeB magnets (3) Effect of Dy on performance NdFeB magnets (4)

• Novel generations of RE magnets require high remanence, high coercitivity, • Grain boundary diffusion method
and high resistance to temperature. – NdFeB powder is coated with a thin layer of oxides such as Dy2O3 or fluoride TbF3
• For economic reasons they must have lowest content of heavy rare earths – Coating is made by dipping the samples into a slurry consisting of the Dy or Tb
(HRE) such as Dy or Tb compounds in suspension into an aqueous or organic solvent
• Optimum performances are observed when HRE are concentrated at grain – Drying and heat treatment result in diffusion of HRE which concentrates at grain
boundaries.
boundaries of ferromagnetic domains
– This process is even more effective at improving coercivity and enhancing heat
• High accumulations of Dy or Tb at grain boundaries prevent nucleation of resistance
reverse magnetic domains which is initial source of magnet degradation
– Suitable for mass production and is consuming considerably smaller amount of
• Two alloying processes have therefore been devised to localize HRE at grain HRE
boundary thereby reducing their overall fraction while retaining superior
magnetic properties
• Two alloys process
– 2 powders are prepared separately, 1 corresponding to pure Nd alloy and 1 to alloy
containing Dy or Tb
– 2 powders are mixed and then sintered at high temperature.
– During sintering HRE diffuse through interface of grains which results in selective
distribution of HRE near grain boundary
85 86
Effect of Dy on performance NdFeB magnets (5) Effect of Dy on performance NdFeB magnets (6)

87 88

Preparation of sintered REE magnets (1) Preparation of sintered REE magnets (2)

• Sintered REE magnets are prepared by powder metallurgy

• Fabrication is complex process which involves several steps including:
– Production of component metals
– Induction melting in appropriate composition ratio
– Milling into fine powder
– Compacting and magnetic alignment of grains
– Sintering into dense solid and pulsed magnetization
• Strongest type of magnets, but not easy to produce in complex shape

89 90
Preparation of sintered REE magnets (3) Preparation of sintered REE magnets (4)

91 92

Preparation of sintered REE magnets (5) Preparation of sintered REE magnets (6)

93 94
 Preparation of sintered REE magnets (7) Preparation of sintered REE magnets (8)

• Final complex shape of NdFeB magnets is obtained by grinding, slicing, holes

drilling, and/or machining
• Not an easy process since sintered Nd-Fe-B magnets behave like ceramic and
have tendency to crack and chip when drilled
• Powder produced when machining these magnets is flammable.
• NdFeB magnets are produced under huge varieties of shapes and designs
• NdFeB alloys are very easily oxidized; hence, commercial magnets must be
protected from corrosion by surface coating
• Epoxy coating can be used for low temperature applications while metal
coating by electrodeposition is most common for high T applications.
• High-grade NdFeB magnets are most commonly plated with Ni. Ni provides a
hard and shiny coating that is corrosion resistant. In addition to Ni, other
metals such as Cu, Sn, Zn, Ag and
• Multimetal deposition such as Ni/Cu/Ni provides a very efficient barrier
against corrosion
• SmCo magnets are very resistant to corrosion. They do not need to be coated,
but are sometimes coated for aesthetical reasons
95 96

Bonded REE magnets

• Bonded magnets are polymer-based magnets.

• They are obtained by mixing powder of magnetic materials with various
polymers
• Once magnetic powder has been mixed with polymer it can be injection
molded or cast into flexible magnetic sheets
• Advantages:
– Gain in materials flexibility for complex shaping
– Good protection of magnetic grains against corrosion
• Drawback:
– Low energy product (about ¼ of energy density of sintered magnet)

97 98