Preface

Inorganic chemistry is of fundamental importance not only as a basic science but also
as one of the most useful sources for modern technologies. Elementary substances
and solid-state inorganic compounds are widely used in the core of information,
communication, automotive, aviation and space industries as well as in traditional
ones. Inorganic compounds are also indispensable in the frontier chemistry of organic
synthesis using metal complexes, homogeneous catalysis, bioinorganic functions, etc.
One of the reasons for the rapid progress of inorganic chemistry is the development of
the structural determination of compounds by X-ray and other analytical instruments.
It has now become possible to account for the structure-function relationships to a
considerable extent by the accumulation of structural data on inorganic compounds.
It is no exaggeration to say that a revolution of inorganic chemistry is occurring. We
look forward to the further development of inorganic chemistry in near future.

The authors have tried to describe detailed chemical facts and concepts that are
necessary to understand modern inorganic chemistry and will be helpful for the
examinations such as CSIR-NET, GATE, IIT-JAM, TIFR and BARC.

This text book describes important concepts of INNER TRANSITION ELEMENTS,

BIOINORGANIC CHEMISTRY, INORGANIC SPECTROSCOPY and NUCLEAR CHEMISTRY
systematically. The necessary theories to explain these properties of compounds come
from physical chemistry and basic concepts for learning inorganic chemistry are
presented in volumes of the series.

Numerous books are available which provide guidance to students appearing for
NET/JRF and GATE examinations but there was a dearth of books which provide ample
practice to the students by incorporating numerous exercises. The success of this
book series has been gratifying, it tells us that teachers have found it effective and
that students have been found it useful and informative. Emphasis has been laid to
incorporate a variety of practice problems for the benefit of the students. The unique
feature of the book series is the approach towards inorganic chemistry. It has been
presented in the simplest manner covering all areas.

Our major objective is to develop confidence among the students who are appearing
in NET/JRF and GATE examinations after post-graduation by providing them solved
objective type questions which covers the main aspect of the topic. Keeping in view
the need of the hour authors presented a unique book which aims at further
enhancement of knowledge of the complex topics. The vast range of questions from a
unique perspective gives a real comprehension of the various topics related to the
concerned examinations. Although we have made every effort to make the book error
free, we are under no illusion. We welcome comments, criticism and suggestions from
the readers to evolve the contents.
Tauheed Nadeem
Monika Bhumkar
 Acknowledgement

First of all we would like to thank our entire students at Institute for advanced
Studies (IFAS), who have helped us to learn and practice both the art and science of
chemistry. We would like to thank Er. Radheshyam Choudhary, Founding CEO, IfAS
Edutech Pvt. Ltd. for being a continuous source of inspiration through his positive
strokes.

We also want to thank Dr. Kailash Choudhary, Director at IFAS Publications, for his
valuable support and critical suggestion for completion of the work.

Our special thanks to Mr. Avinash More, Mr. Rajeev Abhyankar and Mr. Amol Pawade
for reviewing and helping us for preparing the systematic layout, your comment were
invaluable in improving the text. We could not have done this without their help and
passion for chemistry.

Furthermore, our special thanks to Prasad Walimbe and Diksha Sawan for helping us
for the layout of book. We could not have done this without your help and passion for
chemistry. An additional thanks to Akash Paswan and Rajesh Sahoo for their creative
diagrammatic help.

We would not forget to thank all the IfAS team where we were able to further
continue our teaching, training, and especially learning the many facets of the
process of building these creative chapters in books.

This book is a team effort, and producing it would be impossible without outstanding
people of IFAS publication. It was pleasure to work with many others dedicated and
creative people of IFAS during the production of this book. Special thanks for Vikendra
Metha who crafted our ideas to wonderful design of cover page and Kuldeep Singh
Rathore for formatting and type setting.

And finally, our humble greetings to all who put their significant efforts and are
unmentioned.
Tauheed Nadeem
Monika Bhumkar
Index

Chapter 1 Inner Transition Elements

1.1 Introduction 1
1.2. Electronic Structure Lanthanides 2
1.3. Physical Properties 3
1.4. Chemical Properties of Lanthanides 7
1.5. Compounds of Lanthanides 8
1.6. Lanthanide contraction and its consequences 9
1.7. Complexes of the lanthanides 10
1.8. Separation of the lanthanide elements 11
1.9. Colour and Spectra 14
1.10. Magnetic properties 16
1.11. Chemistry of Ce (+IV) and its complexes: 18
2+ 2+ 2+
1.12. Chemistry of Sm , Eu and Yb and its complexes 18
1.13. Solubility 19
1.14. Electronic Spectroscopy 19
1.15. Fluorescence / Luminescence 20
1.16. Solid State Chemistry of Lanthanides 20
1.17. Actinides 21
1.18. Comparison between Actinides and Lanthanides 31
1.19. Difference between lanthanoids and actinoids 32
1.20. Summary 35
1.21. HOTS- High Order Thinking Skills 36

Chapter 2 Bioorganic Chemistry

2.1. Introduction 39
2.2. The Need of Inorganic Elements 39
2.3. The Essential Elements and the Essential Metal Ions 40
2.4. Biological Metal - Coordination Sites 44
2.5. Different Role of Metals 45
2.6. Ligands in Common Biological Functions 47
2.7. Oxygen Carrier and Storage Devices 48
2.8. Electron Transfer 55
2.9. Iron Storage and Transport 62
2.10. Transporting Some Toxic Metals 65
2.11. Enzyme 67
2.12. Coenzyme B12 74
2.13. Photosynthesis 76
2.14. Nitrogen Fixation 78
2.15. The Generation and Uses of Metal-Ion- Concentration Gradients 81
2.16. Inorganic Medicinal Compounds 83
2.17 Summary 90
2.18. HOTS- High Order Thinking Skills 93

Chapter 3 Inorganic Spectroscopy

3.1. Introduction 99
3.2. Nuclear Magnetic Resonance (NMR) Spectroscopy 102
3.3. Fluxional Behavior of Molecules 128
3.4. Electron Spin Resonance (ESR) Spectroscopy 135
3.5. Mossbauer Spectroscopy 180
3.6. Summary 209
3.7. HOTS- High Order Thinking Skills 210

Chapter 4 Nuclear Chemistry

4.1. Discovery of Radioactivity 218
4.2. Types of Radioactive Rays 217
4.3. General Properties of Radioactive Radiations 218
4.4. Nuclear Stability and Radioactive Decay 218
4.5. The Band of Stability and Type of Radioactive Decay 220
4.6. Laws of Radioactive Disintegration 223
4.7. Radioactive Equilibria 227
4.8. Decay patterns 231
4.9. Isotopes, Isobars and Isotones 232
4.10. Nuclear Reactions or Nuclear Transmutation or Disintegration 233
4.11. Types of Nuclear Reactions 234
4.12. Nuclear Reactions vs Chemical Reactions 238
4.13. Mass Defect and Binding Energy of the Nucleus 239
4.14. Binding Energies and Stability of Nuclei 240
4.15. Meson Theory of Nuclear Forces 241
4.17. Barriers for Charged Particles 244
4.18. Reaction Cross-Sections 244
4.18. Reaction Cross-Sections 245
4.20. Nuclear Fusion 247
4.21. Uses of Nuclear Fusion 248
4.22. Basic Requirement for Controlled thermonuclear Reactions 250
4.23. Neutron Activation Analysis (NAA) 250
4.24. Artificial or Induced Radioactivity 251
4.25. Preparation of Transuranium Elements 252
4.26. Uses of Radioisotopes 253
4.27. Summary 256
4.28. HOTS – High Order Thinking Skills 257
CHAPTER - 1
INNER TRANSITION ELEMENTS
1.1. Introduction

In this chapter we look at f-block metals and their compounds. There are two series of metals: the lanthanoids (the 14 elements
that follow lanthanum in the periodic table) and the actinoids (the 14 elements following actinium).

 The lanthanoids are electropositive metals that commonly occur in their compounds as Ln (III); other oxidation
states are stable only when an empty, half-filled, or full f subshell is produced.
 Lanthanides are characterized by the filling up of the antepenultimate 4f energy levels.
 Actinides are characterized by the filling up of the antepenultimate 5f energy levels.

They are extremely similar to each other in properties, and until 1907 they were thought to be a single element. In the past
they were called the rare earths. This name is not appropriate because many of the elements are not particularly rare.
Furthermore, the name is not precise since in addition to the 14 lanthanides it also includes La, Sc, Y which are d-block
elements, and sometimes Th (an actinide) and Zr (another d-block element).

Fig 1.1: Position in the periodic table

IFAS Publications www.ifasonline.com

2 Inorganic Chemistry

1.2. Electronic Structure of Lanthanides

The electronic structures of the lanthanide metals are shown in Table-1. Lanthanum (the d-block element preceding this series)
0 1 2
has the electronic structure: xenon core 4f 5d 6s . It might be expected that the 14 elements from cerium to lutetium would be
formed by adding 1, 2, 3, ... 14 electrons into the 4f level.However, it is energetically favourable to move the single 5d electron
1
into the 4f level in most of the elements, but not in the cases of Ce, Gd and Lu.The reason why Gd has a 5d arrangement is that
7 1 2 1
this leaves a half filled 4f level, which gives increased stability i.e. [Xe]4f 5d 6s .Lu has a 5d arrangement because the f shell
1 2
is already full. i.e.[Xe] 4f14 5d 6s

The lanthanides are characterized by the uniform (+III) oxidation state shown by all the metals. They typically form compounds
3+ 1 3+ 2 3+ 3 3+ 14
which are ionic and trivalent. The electronic structures of the ions are Ce -f , Pr -f , Nd -f ……..… Lu -f .

Electrons are filled in the 4f subshell which is antepenultimate shell (inside penultimate shell i.e.d subshell) 4f electrons are very
effectively shielded from their chemical environment outside the atom by the 5s and 5p electrons. Consequently, the 4f
electrons do not take part in bonding. They are neither removed to produce ions nor do they take any significant part in crystal
field stabilization of complexes. So the oxidation state shown by these metals is due to loss of electrons from outer d and s
orbitals.

Crystal field stabilization is very important with the d-block elements. The octahedral splitting of f orbitals, 0 is only about I kJ
mo1-1. So, whether the f orbitals are filled or empty has little effect on the normal chemical properties. However, it does affect
their spectra and their magnetic properties.
Table 1.1: Electronic Structures and Oxidation States
3+
Element and their symbols Electronic Structure of Atoms Electronic Structure of M Oxidation States
1 2
Lanthanum La [Xe] 5d 6s [Xe] +III
1 1 2 1
Cerium Ce [Xe]4f 5d 6s [Xe]4f +III +IV
3 2 2
Prascodymium Pr [Xe]4f 6s [Xe]4f +III (+IV)
4 2 3
Neodymium Nd [Xe]4f 6s [Xe]4f (+II) +III
5 2 4
Promethium Pm [Xe]4f 6s [Xe]4f (+II) +III
6 2 5
Samarium Sm [Xe]4f 6s [Xe]4f (+II) +III
7 2 6
Europium Eu [Xe]4f 6s [Xe]4f +II +III
7 1 2 7
Gadolinium Gd [Xe]4f 5d 6s [Xe]4f +III
9 2 8
Terbium Tb [Xe]4f 6s [Xe]4f +III (+IV)
10 2 9
Dysprosium Dy [Xe]4f 6s [Xe]4f +III (+IV)
11 2 10
Holmium Ho [Xe]4f 6s [Xe]4f +III
12 2 11
Erbium Er [Xe]4f 6s [Xe]4f +III
13 2 12
Thulium Tm [Xe]4f 6s [Xe]4f (+II) +III
14 2 13
Ytterbium Yb [Xe]4f 6s [Xe]4f +II +III
14 1 2 14
Lutetium Lu [Xe]4f 5d 6s [Xe]4f +III

Q1. Which of the following carbonate- fluoride mineral contains all the lanthanoids?
a. Monazite b. Bastnasite
c. Pitch blende d. Zicronite
Solution:
Bastnasite mainly represented by (Ce, La, Y) CO3F contains all the lanthanoids, whereas Monazite (Phosphate mineral of
thorium and other rare earth) contains lines ones.

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 3

1.3. Physical Properties:

1.3.1. Ionic Radius

Ionic radii depend on how many electrons are removed. For simplicity, the radii of ions with the same charge are compared in
Table.
3+ 3+ 3+ 3+ 0
Table 1.2: Ionic Radii of Sc , Y and La and the Ln ions (A )

Sc
0.745
Y
0.900
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
1.03 1.02 0.99 0.983 0.97 0.958 0.947 0.938 0.923 0.912 0.901 0.890 0.88 0.868 0.861

A similar change in size across the series is observed if covalent radii are compared (Table 3). Because of this contraction in size
across the lanthanide series, the elements which follow in the third transition series are considerably smaller than would
otherwise be expected. The normal size increase Sc Y La uisappears after the lanthanides. Thus, pairs of elements such as
Zr/Hf, Nb/Ta and Mo/W are almost identical in size. The close similarity of properties in such a pair makes chemical separation
very difficult. The sizes of the third row of transition elements are very similar to those of the second row of transition elements
(see Table). Thus, the second and third rows of transition elements resemble each other more closely than do the first and
second rows.

IFAS Publications www.ifasonline.com

4 Inorganic Chemistry

1.3.2. Oxidation states

The sum of the first three ionization energies for each element is given in Table-4. The values are low. Thus, the oxidation state
3+ 2+ 4+
(+III) is ionic and Ln dominates the chemistry of these elements. The Ln and Ln ions that do occur are always less stable
3+
than Ln . (In this chapter the symbol Ln is used to denote any of the lanthanides).

In just the same way as for other elements, the higher oxidation states occur in the fluorite and oxides, and the lower oxidation
states occur in the other halides particularly bromides and iodides.

Oxidation numbers (+II) and (+IV) do occur particularly when they lead to:
4+ 0
a. A noble gas configuration. e.g. Ce (f )
2+ 4+ 7
b. A half-filledf shell. E.g. Eu and Tb (f )
2+ 14
c. A completely filled f level. e.g. Yb (f )

2+ 2+ 6 13
In addition (+II) and (+IV) states exist for elements that are close to these states. Thus Sm and Tm occur with f and f
2+ 4+ 1 2
arrangements and Pr and Nd have f and f arrangements. The (+III) state is always the most common and the most
4+ 2+ 2+ 2+
stable.The only (+IV) and (+II) states which have any aqueous chemistry are Ce , Sm , Eu and Yb .The lanthanide elements
resemble each other much more closely than a horizontal row of the transition elements.This is because the lanthanides
effectively have only one stable oxidation state, (+III).

The stability of the elements in the different oxidation states givevs the information about the oxidizing power and reducing
power of that particular element. This can be illustrated by the followmg three examples:

4+
a. Ce is a strong oxidising reagent:
1 1 2
Electronic configuration of Ce is 4f 5d 6s . Ce is most stable in +3 state. In +4 state it is most oxidizing because in +4 state it
can give an electron to become more stable at +3 state.
CAN (Ceric Ammonium Nitrate) is a stronger reagent than KMNO4 and K2Cr2O7 in some reactions.

2+
b. Eu is a strong reducing reagent:
2+ 3+ 2+
Eu is less stable than that of the Eu due to configurational reasons as stated in the above table. Thus Eu acts as a
strong reducing agent.

2+
c. Sm is a strong oxidising reagent:
+2
Whereas in Sm , the lanthanides are more stable in +3 state and hence in +2 state it gets oxidized easily (good reducing
agent) to get to +3 oxidation state.

1.3.3. Ionization Energy

Lanthanides have fairly low ionisation energies. IE1and IE2values are quite comparable with the values of alkaline earthmetals,
particularly calcium. The sum of the first three ionisation energies in kJ/mol for each element is given below. Thevalues are low.
Due to low values of ionisation energies, lanthanides are highly electropositive in nature. The values of standard reduction
0
potential (E values) increase from La to Lu. E values become less negative in the series. Although there are some exceptions, All
the lanthanides are, thus, strong reducing agents. The reducing power decreases from La to Lu.

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 5

The values in volts are given in the following table:

Table 1.3: Ionization Energy and Standard Electrode Potential
Sum of first three
3+ 3+
Elements Symbol ionisation energies Eo Ln / Ln(volts) Radius Ln (Å)
-1
(kJ mol )
Lanthanum La 3493 -2.52 1.032
Cerium Ce 3512 -2.48 1.020
Praseodymium Pr 3623 -2.46 0.99
Neodymium Nd 3705 -2.43 0.983
Promethium Pm - -2.42 0.97
Samarium Sm 3898 -2.41 0.958
Europium Eu 4033 -2.41 0.947
Gadolinium Gd 3744 -2.40 0.938
Terbium Tb 3792 -2.39 0.923
Dysprosium Dy 3898 -2.35 0.912
Holmium Ho 3937 -2.32 0.901
Erbium Er 3908 -2.30 0.890
Thulium Tm 4038 -2.28 0.880
Ytterbium Yb 4197 -2.27 0.868
Lutetium Lu 3898 -2.26 0.861

The point to be noted that is, the first ionization energies of Sm, Dy and Lu are same.
Q. Which statement is incorrect about the lanthanoid metals?
a. Each metal reacts with dilute acid to release H2.
3+ 3+
b. Eu and Yb dissolve in liquid NH3 to give Eu and Yb respectively.
c. Reaction between Ln and H2 give hydrides of formula LnH2 or LnH3.
d. The chemistry of the lanthanoids is dominated by the +3-oxidation state
Solution: 2
3+ 3+
Eu and Yb are formed
2+ 7
Eu has 4f configuration. -very stable
2+ 14
Yb has 4f configuration – appreciably stable

1.3.4. Shielding effect of the lanthanoids

The Lanthanide Contraction is the result of a poor shielding effect of the 4f electrons. The shielding effect is described as the
phenomenon by which the inner-shell electrons shield the outer-shell electrons so they are not affected by nuclear charge. So
when the shielding is not as good, this would mean that the positively charged nucleus has a greater attraction to the electrons,
thus decreasing the atomic radius as the atomic number increases. The s orbital has the greatest shielding while f has the least
and p and d in between the two with p being greater than d. The Lanthanide Contraction can be seen by comparing the
elements with f electrons and those without f electrons in the d block orbital. Pd and Pt are such elements. Pd has 4d electrons
while Pt has 5d and 4f electrons. These 2 elements have roughly the same atomic radius. This is due to Lanthanide Contraction
and shielding. While we would expect Pt to have a significantly larger radius because more electrons and protons are added, it
does not because the 4f electrons are poor at shielding. When the shielding is not good there will be a greater nuclear charge,
thus pulling the electrons in closer, resulting in a smaller than expected radius.

IFAS Publications www.ifasonline.com

6 Inorganic Chemistry

1.3.5. Hydration energy and lattice energy: -

 Hydration energy (also hydration enthalpy) is the amount of energy released when one mole of ions
undergo hydration which is a special case of solvation. It is a special case of dissolution energy, with the solvent being
water.
 Lattice energy is a measure of the energy contained in the crystal lattice of a compound, equal to the energy that
would be released if the component ions were brought together from infinity.
 It is found that- “Small elements have high lattice and hydration energy. As the size increases, lattice energy and
hydration energy are found to be decreased.”

Thus from La to Lu, Lattice energy and hydration energy decreases as expected.

1.3.6. Abundance and Isotopes

The lanthanide elements are not particularly rare. Cerium is about as abundant as copper. Apart from promethium, which does
not occur in nature, all the elements are more abundant than iodine. The abundance of the elements and the number of
naturally occurring isotopes varies regularly (Table 5). Elements with an even atomic number (i.e. an even number of protons in
the nucleus) are more abundant than their neighbours with odd atomic numbers (Harkins' rule).

Elements with even atomic numbers also have more stable isotopes. Elements with odd atomic numbers never have more than
two stable isotopes. Throughout the periodic table the stability of a nucleus is related to both the number of neutrons and the
number of protons in the nucleus (Table 6). Element 61, promethium, does not occur naturally. It was first made and studied
at Oak Ridge in Tennessee, USA, in 1946. Its absence may be explained by Mattauch's rule.

This states that if two elements with consecutive atomic numbers each have an isotope of the same weight, one of the isotopes
will be unstable. Since elements 60 and 62 have seven isotopes each, there are not many stable mass numbers available for
promethium, element 61 (Table 6). According to Matrauch’s rules, if promethium is to have a stable isotope, it must have a
mass number outside the range 142-150. The only isotopes of Pm which have been made so far are radioactive.
Table 1.4: Abundance of the elements in the earth's crust by weight and number of natural isotopes

Atomic number Element Abundance (ppm) Relative Naturally occurring

in earth’s crust abundance isotopes
58 Ce 66 26 4
59 Pr 9.1 37 1
60 Nd 40 27 7
61 Pm 0 32 0
62 Sm 7 40 7
63 Eu 2.1 49 2
64 Gd 6.1 41 7
65 Tb 1.2 56 1
66 Dy 4.5 42 7
67 Ho 1.3 55 1
68 Er 3.5 43 6
69 Tm 0.5 61 1
70 Yb 3.1 44 7
71 Lu 0.8 59 2

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 7

Table 1.5. Numbers of stable nuclei with odd and even numbers of neutrons and odd and even atomic number
Atomic number Number of neutrons Stable nuclei
Even Even 164
Even Odd 55
Odd Even 50
Odd Odd 4

Q1. What is the difference between lanthanoids and lanthanides?

Solution: Fifteen elements from La-Lu are lanthanoids. (Preferred by IUPAC).Furthermore, fourteen element Ce-Lu
without lanthanum are lanthanides (meaning the elements similar to lanthanum).

1.4. Chemical Properties of Lanthanides

The metals are all soft and silvery white. They are electropositive and therefore they are very reactive.The heavier metals are
less reactive than the lighter ones because they form a layer of oxide on the surface. Thechemical properties of the group are
3+
essentially the properties of trivalent ionic compounds. The sum of the first three ionization energies varies with minima at La ,
3+ 3+ 3+ 3+
Gd and Lu which are associated with attaining an empty, half full or full f shell. Maxima occur at Eu and Yb associated
with breaking a half full or full shell.

1.4.1. Reduction potential

0
The standard reduction potentials (E ) are all high (Table 29.2). They vary in a regular way over a small range from -2.48 to -
0
2.26volts depending on the size of the ions. The lanthanides are all much more reactive than is Al (E = -1.66 volts) and are
0
slightly more reactive than Mg (E = -2.37 volts). Thus, they react slowly with cold water but more rapidly on heating.

2Ln + 6H2O 2Ln (OH) 3 + 3H2

1.4.2. Basicity of hydroxides and oxides

The hydroxides Ln(OH)3 are precipitated as gelatinous precipitates by the addition of NH4OH to aqueous solutions. These
hydroxides are ionic and basic. They are less basic than Ca(OH)2 but more basic than Al(OH)3 which is amphoteric.The metals,
oxides and hydroxides all dissolve in dilute acids, forming salts.Ln(OH) 3 are sufficiently basic to absorb CO2 from the air and
form carbonates. The basicity decreases as the ionic radius decreases from Ce to Lu. Thus Ce(OH)3 is the most basic, arid
Lu(OH)3, which is the least basic, is intermediate between scandium and yttrium in basic strength. The decrease in basic
properties is illustrated by the hydroxides of the later elements dissolving in hot concentrated NaOH, forming complexes.

+ 3-
Yb (OH) 3 + 3NaOH 3Na + [Yb (OH) 6]
+ 3-
Lu (OH) 3 + 3NaOH 3Na + [Lu (OH) 6]

IFAS Publications www.ifasonline.com

8 Inorganic Chemistry

The metals tarnish readily in air, and on heating in O 2 they all give oxides Ln2O3. Yb and Lu form a protective oxide film which
IV
prevents the bulk of the metal forming the oxide unless it is heated to 1000°C. The one exception is Ce which forms Ce O2
rather than Ce2O3.The oxides are ionic and basic. Basic strength decreases as the ions get smaller.

All Ln elements form basic oxides and hydroxides (strictly not the acidic oxides and hydroxides). Thus the trends in the
basicity of the basicity of the hydroxides and oxides can be generalized as:

a. As the size of the lanthanide element increases, basicity is found to be enhanced.

E.g. Ce(OH)3 is the most basic, arid Lu(OH)3
b. Effective nuclear charge is inversely proportional to the basicity.
c. Alkali metal hydroxides are more basic than Ln metal hydroxides and they both are more basic than p-block elements.

1.5. Compounds of Lanthanides

1.5.1. Hydrides
 The metals react with H2, but often require heating up to 300-400°C to start the reaction.
 The products are solids of formula LnH2. Eu and Yb both have a tendency to form divalent compounds and EuH 2 and
2+ -
YbH2 are salt-like hydrides and contain M and two H . The others all-form hydrides LnH2 which are black metallic and
conduct electricity.
3+ -
 These are better formulated as Ln . 2H and an electron which occupies a conduction bandIn addition Yb forms a
nonstoichiometric compound approximating to YbH2.5. The hydrides are remarkably stable to heat, often up to 900°C.
 They are decomposed by water, and react with oxygen.
CeH2 + 2H2O CeO2 + 2H2
3+
 These 'dihydrides' take up H if heated under pressure and all except Eu form salt-like hydrides LnH3 made up of Ln
-
and three H .
 These do not have a delocalized electron and do not show metallic conduction

1.5.2. Halides
The anhydrous halides MX3 can be made by heating the metal and halogen, or by heating the oxide with the appropriate
ammonium halide.

Ln2O3 + 6NH4Cl → 2LnCl3 + 6NH3 + 3H2O

3+ + -
The fluorides are very insoluble, and can be precipitated from solutions of Ln by addition of Na F or HF. This is used as a. test
-
for the lanthanides in qualitative analysis. However, with excess F , the smaller lanthanide ions may form soluble complexes
2+
[LnF(H2O)n) . The chlorides are deliquescent and soluble, and crystallize with six or seven molecules of water of crystallization.
If the hydrated halides are heated, they form oxohalides instead of dehydrating to anhydrous halides.

LnCl3.6H2O → LnOCl + 5H2O + 2HCl

Heating CeX3· (H2O)n results in CeO2. The bromides and iodides are similar to the chlorides. These dihalides can be made by
reducing the trihalide with hydrogen, with the metal, or with sodium amalgam, The dihalides such as LaI2 and NdI2 tend to be
nonstoichiometric.

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 9

1.5.3. Borides, carbides, nitrites

At elevated temperatures, the lanthanides react with B, giving LnB 4 and LnB6.On arc-melting the metals with C in an inert
atmosphere they form carbides. The carbides can also be made by reducing Ln2O3 with C in an electric furnace. LnC2 are more
reactive than CaC2. They react with water, giving ethyne and also some hydrogen, C 2H4 and C2H6. They also show metallic
3+
conductivity. They do not contain Ln (+II) and are best described as acetylides of Ln and with the extra electron in a
conduction band.
2LnC2 + 6H2O 2Ln (OH) 3 + 2C2H2 + H2

C2H2 + H2 C2H4→ C2H6

At elevated temperatures the metals also react with N, P, As, Sb and Bi giving LnN etc. The latter is hydrolysed by water in a
similar way to AlN:
LnN + 3H2O Ln (OH) 3 + NH3
A wide variety of oxosalts are known, including nitrates, carbonates, oxalates, sulphates, phosphates and also salts of strongly
oxidizing ions such as perchlorates.

1.6. Lanthanide contraction and its consequences:

Covalent and ionic radii normally increase on descending a group in the periodic table due to the presence of extra filled shells
of electrons. On moving from left to right across a period, the covalent and ionic radii decrease. This is because the extra orbital
electrons incompletely shield the extra nuclear charge. Thus, all the electrons are pulled in closer. The shielding effect
ofelectrons decreases in the order s >p >d >f. The contraction in size from one element to another is fairly small.

However, the additive effect over the 14 lanthanide elements from Ce to Lu is about 0.2 Å, and this is known as the lanthanide
contraction. The hardness, melting points and boiling points of the elements all increase from Ce to Lu. This is because the
attraction between the atoms increases as the size decreases. The properties of an ion depend on its size and its charge. The
3+
Ln lanthanide ions change by only a small amount from one element to the next (Table), and their charge is the same, and so
3+
their chemical properties are very similar. Since Lu is the smallest ion it is the most heavily hydrated. Though the lanthanides
3+ 3+
do not form complexes very extensively; since Lu is the smallest ion the complexes formed by Lu are the are the strongest.
3+ 3+
La and Ce are the largest ions so La(OH)3 and Ce(OH)3 are the strongest bases.The lanthanide contraction reduces the radii
of the last four elements in the series below that for Y in the preceding transition series. Since the size of the heavier lanthanide
3+ 3+ 3+
ions, particularly Dy and Ho , are similar to that of Y it follows that their chemical properties also very similar. As a result,
the separation of these elements is very difficult.

Consequences of Lanthanide contraction:

3+
 Basicity of ions: Due to lanthanide contraction, the size of Ln ions decrease regularly with increase in atomic
number. According to Fajan's rule, decrease in size of Ln3+ ions increase the covalent character and decrease the
3+
basic character between Ln and OH− ion in Ln(OH)3. Since the order of size of Ln3+ ions are
3+ 3+ 3+
La >Ce ...>Lu
 There is regular decrease in their ionic radii as we have already discussed
 Regular decrease in their tendency to act as reducing agent, with increase in atomic number.
 Due to lanthanide contraction, second and third rows of d-block elements (transition elements) are quite close in
their properties.
 Due to lanthanide contraction, these elements occur together in natural minerals and are difficult to separate.

IFAS Publications www.ifasonline.com

10 Inorganic Chemistry

1.7. Complexes of the lanthanides:

3+
The lanthanide ions Ln have a high charge, which favours the formation of complexes.

3+ 3+
However, the ions are rather large (1.03 - 0.86 Å) compared with the transition elements (Cr = 0.615 Å, Fe = 0.55 Å (low
spin)) and consequently they do not form complexes very readily. Complexes with amines are not formed in aqueous solution
because water is a stronger ligand than the amine. However, amine complexes can be made in nonaqueous solvents. few stable
-
complexes are formed with CO, CN and organometallic groups. This is in contrast to the transition metals. The difference arises
because the 4f orbitals are well shielded and are 'inside the atom'. Thus, they are not taking part in π back bonding, whereas in
thetransitionelements the d orbitals are involved in π bonding. The most common and stable complexes are those with
4-
chelating oxygen ligands such as citric acid, oxalic acid, EDTA and acetylacetone.

These complexes frequently have high and variable coordination numbers, and water or solvent molecules are often attached
3+ 3+
to the central metal. -Diketone complexes of Eu and Pr dissolved in organic solvents are used as lanthanide shift reagents
in nmr spectroscopy. Coordination numbers below 6 are uncommon, and occur only with bulky ligands such as (2,6-
- -
dimethylphenyl) and [N(SiMe3)2] . In contrast to the transition elements, the coordination number 6 is not common.

The most common coordination numbers are 7. 8 and 9 and these give a variety of stereochemistries. Coordination numbers 10
and 12 occur with the larger (lighter) lanthanides and small chelating ligands N and S (Table 7).

Complexes with monodentate oxygen ligands are much less stable than the chelates, and tend to dissociate in aqueous
solution.

-
There are hardly any complexes with nitrogen donor ligands except ethylenediamine and NCS , and these are decomposed by
2+
water. Fluoride complexes LnF are formed particularly by the smaller ions, but chloride complexes are not formed in aqueous
media or concentrated HCl. This is an important distinction between the lanthanide and actinide groups.

4+ 2-
Ce is smaller and more highly charged, and [Ce(NO3)6] is formed in the non-aqueous solvent N2O4, and is 12-coordinate. Each
N uses two oxygen atoms to coordinate to the metal.

The lanthanides form no complex with π bonding ligands, and the lack of π bonding is attributed to the unavailability of the f
orbitals for bonding.

It is difficult to explain the bonding in complexes with high coordination numbers.

If one s orbital, three p orbitals and all six d orbitals in the valency shell are used for bonding, this accounts for a maximum
coordination number of 9. The higher coordination numbers of 10 and 12 presents a problem.

They imply either participation of f orbitals in bonding, or bond orders of less than one.

There are few organic compounds of the lanthanides. Alkyls and aryls can be made with lithium reagents in ether solution:
LnCl3 + 3LiR LnR3 + 3LiCl
3-
LnR3 + LiR Li [LnR4] and [LnMe6]

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 11

Table 1.6: Some Lanthanide Complexes

Coordination Number Complex Shape
-
4 [Lu(2,6-dimethylphenyl)4] Tetrahedral
IV 2-
6 [Ce Cl6] Octahedral
6 [Er(NCS)6] Octahedral
7 [Y(acctylacetone)3H2O] Mono-capped trigonal prism
8 [La(acctylacetone)3(H2O)2] Square Antiprism
8 [Eu(acctylacetone)3(phenanthroline)] Square Antiprism
-
8 [Ho(tropolonate)4] Dodecahedral
3+
9 [Nd(H2O)9] Tri-capped trigonal prism
IV
10 [Ce (NO3)4(Ph3PO)2] Complex(each N is bidentate)
IV 2-
12 [Ce (NO3)6] Icosahedral (each N is bidentate)

Note:
1. Cyclopentadienyl compounds [Ln(C5H5)3], [Ln(C5H5)2CI) and [Ln(C5H5) Cl2] are known but are sensitive to water and air.
2. The compounds La2O3 and Lu2O3 have coordination number 7 and 6 respectively.
3. In CN = 8, the complexes of Ho and No are always dodecahedral in geometry.

Q1. Which statement is NOT correct about complexes formed by lanthanoides?

a. hard donor ligands are favoured over soft donor ligands.
b. The 4f atomic orbitals do not play a significant part in metal-ligand bonding.
c. High coordination numbers are often observed.
d. Aqua ions are typically 6-coordinate.
Solution:
3+
 Ln ions have larger radii. They are typical hard Lewis acid and the bonding in their complexes is electrostatic and
non-directional.
 As a result, steric factor determines geometry of lanthanide complexes.
 Cordination numbers are generally high (>6 and up to 8) and coordination geometries are often irregular.
 Even low coordination numbers (like 3) can be achieved with very bulky ligands.

1.8. Separation of the lanthanide elements

The properties of metal ions are determined by their size and charge. The lanthanides are all typically trivalent and are almost
identical in size, and so their chemical properties are almost identical. The separation of one lanthanide from another is an
exceedingly difficult task, almost as difficult as the separation of isotopes of one element. The classical methods of separation
exploit slight differences in basic properties, stability or solubility. These are outlined below. However, in recent years the only
methods used are ion exchange and valency change.

1.8.1. Precipitation
With a limited amount of precipitating agent, the substance with the lowest solubility is precipitated most rapidly and most
completely. Suppose hydroxyl ions are added to solution conyaining a mixture of Ln(NO 3)3. The weakest base Lu (OH)3
precipitated first, and the strongest base La(OH)3 is precipitate last. The precipitate contains more of the elements at the right
of the series.
Thus, the solution contains more of the elements at the left of the series. The precipitate can be filtered off. Only partial
separation is affected, but the precipitate can be redissolved in HNO3 and the process repeated to obtain greater purity.

IFAS Publications www.ifasonline.com

12 Inorganic Chemistry

1.8.2 Thermal Reaction

If a mixture of Ln(NO3)3 is fused, a temperature will be reached when first least basic nitrate changes to the oxide. Then the
mixture is leached with water. The nitrates dissolve in water and can be filtered off, leaving the insoluble oxides. The oxides are
dissolved in HNO3 and the process repeated.

1.8.3. Fractional Crystallization

This can be used to separate lanthanide salts. The solubility decreases from La to Lu. Thus, salts at the Lu end of the series will
crystallize out first. Nitrates, sulphates, bromates, perchlorates and oxalates have all been used as also have double salts such
as Ln(NO3)3 3Mg(NO3)2.24H2O because they crystallize well. The process needs repeating many times to obtain good
separations. Non-aqueous solvents such as, diethyl ether have been used to separate Nd(NO3)3 and Pr(NO3)3,

1.8.4. Complex Formation

A mixture of lanthanide ions is treated with a complexing agent such as EDTA (ethylenediaminetetraacetic acid). All the ions
3+
form complexes. The ions at the right-hand side of the lanthanide series such as Lu form the strongest complexes as they have
the smallest ions. Oxalates of the lanthanides are insoluble.However addition of oxalate ions to this solution does not give a
3+
precipitate since the Ln ions are all complexed with EDTA.If some acid is added to the solution, the least stable EDTA
3+ 3+ 3+
complexes are dissociated.This releases ions at the left hand side of the series Ce , pr , Nd which is immediately precipitated
as the oxalates.

These are filtered off. Separation is not complete, so the oxalates are redissolved and the process repeated many times.

(EDTA)

1.8.5. Solvent Extraction

3+ 3+
The heavier Ln ions are more soluble in tri-n-butylphosphate than are the lighter Ln ions. Their solubilities in water and ionic
solvents, however, are reversed. The ratios of the partition coefficients of La(NO 3)3 and Gd(NO3)3 between a solution of the
metal ions in strong HNO3 and tri-n-butylphosphate is 1 : 1.06. This difference is quite small, but by using a continuous counter-
current apparatus a very large number of partitions can be performed automatically. This is much less tedious than performing
10 000 or 20 000 crystallizations. Kilogram quantities of 95% pure Gd have been obtained by this method. The technique was
originally developed in the early days of atomic energy to separate and identify the lanthanide elements produced by fission of
uranium.

Q. What is the principle involved in solvent extraction of lanthanoids by using tri-n-butylphosphate?

Solution:
3+ n
 The solubility of Ln ions in tri-butylphosphate. (Bu O)3PO, solvent increased with increase in atomic weight of
Ln.
 Thus, the separation of lanthanoides is achieved on large scale by extracting an aqueous containing mixture of
nitrates of lanthanoids with the solvent tri-n-butylphosphate. This is the commercial method.

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 13

1.8.6. ValencyChange
4+ 2+ 3+
A few lanthanides have oxidation states of (+IV) or (+II). The properties of Ln or Ln are so different from those of Ln that
separation is fairly easy. Cerium can be separated from lanthanide mixtures quite easily as it is the only lanthanide which has
4+ 3+
Ln ions stable in aqueous solution. Oxidizing a solution containing a mixture of Ln ions with NaOCl under alkaline conditions
4+ 4+ 3+ 3+ 4+
produces Ce . Because of the higher charge, Ce is much smaller and less basic than Ce or any other Ln . The Ce is
separated by carefully controlled precipitation of CeO2 or Ce(lO3)4, leaving the trivalent ions in solution.

4+ 3+
Alternatively, Ce can readily be extracted from other Ln lanthanides by solvent extraction in HNO3 solution using tributyl
phosphate. Ninety-nine percent pure Ce can be obtained in one stage from a mixture containing 40% Ce. In a similar way the
2+ 3+ 2+
properties of Eu are very different from those of Ln . Europium sulphate Eu S resembles the Group 2 sulphates and is
3+ 3+
insoluble in water. Ln sulphates are soluble. If a solution of Ln ions is reduced electrolytically using a mercury cathode, or by
2+ 2+ 2+
using zinc amalgam then Eu will be produced. In H2SO4, EuSO4 will be precipitated. This can be filtered off. (Sm and Yb may
also be produced in the same way, but these are oxidized slowly by water.) Valency change is still a useful method for purifying
Ce and Eu despite the advent in recent years of ion exchange.

1.8.7. Ion Exchange

This is the most important, the most rapid and most effective general method for the separation and purification of the
lanthanides.

A solution of lanthanide ions is run down a column of synthetic ion-exchange resin such as Dowex-50. This is sulphonated
3+
polystyrene and contains the functional groups -SO3H. The Ln ions are absorbed onto the resin and replace the hydrogen
atom on -SO3H.
+ 3H(resin)(s) ⇌ Ln(resin)3(s) + 3

+
The H ions produced are washed through the column. Then the metal ions are eluted, that is are washed off the column in a
selective manner. The eluting agent is a complexing agent, for example a buffered solution of citric acid/ammonium citrate or a
dilute solution of (NH4)3(H · EDTA) at pH 8. Consider the citrate case, equilibrium is set up:

+ 3-
Ln(resin)3 + 3H + (citrate) ⇌ 3H(resin) + Ln(citrate)

3+
As the citrate solution flows down the column Ln ions are removed from the resin and form the citrate complex. A little lower
3+
down the column the Ln ions go back onto the resin. As the citrate solution runs down the column the metal ions form
complexes alternately with the resin and the citrate solution many times. The metal ion gradually travels down the column, and
3+
eventually passes out of the bottom of the column as the citrate complex. The smaller lanthanide ions such as Lu form
3+
stronger complexes with the citrate ions than do the larger ions like La , Thus the smaller and heavier ions spend more time in
solution, and less time on the colournn, and are thus eluted from the column first. The different metal ions present separated
into bands which pass down the column. The progress of the bands may be followed spectroscopically by atomic fluorescence.
The solution leaving the column is collected by means of an automatic fraction collector in separate containers. By this means
the individual elements can be separated. The metals may be precipitated as insoluble oxalates, and then heated to give the
oxides. The chromatographic process is analogous to carrying out many separations or much crystallization steps, but the
separation is carried out on a single column. By using a long ion-exchange column the elements may be obtained 99.9% pure
with one pass.

IFAS Publications www.ifasonline.com

14 Inorganic Chemistry

Q1. Describe the ion exchange method of separation of lanthanides.

Solution:
 The ore (monazite or bastnaesite) is dissolved in HCl and converted to a solution of LnCl3.
+
 Ion Exchange: First the solution is eluted onto the cation exchange column to replace the resin bound Na ions in a band at
the top of the column
3+ + 3+ +
Ln (aq) + 3Na (resin) ⇌ Ln (resin) + 3Na (aq)

4- 3+
 Then elute with a complexing agent such as EDTA and adjust pH. The Ln with the smallest radii (and ofcourse heavier)
4-
are most strongly bound to the anionic ligand (EDTA ) and so are eluted first.

3+ + 3- +
Ln (resin) + 3Na (aq) + [EDTA-H] (aq) ⇌ Ln[EDTA-H] (aq)+ 3Na (resin)

3+
Note: Ln = trivalent lanthanoid ionIon exchange method is not useful for commercial largescale separation. But highly pure
lanthanoids are obtained (up to 99.99%)

1.9. Colour and Spectra:

3+
Spectra of Ln ions often contain large numbers of absorptions. Since the 4f electrons are well shielded and not affected by the
environment of the ion, bands arising from f–f transitions are sharp (rather than broad like d–d absorptions) and their positions
in the spectrum are little affected by complex formation. Intensities of the absorptions are low, indicating that the probabilities
of the f–f transitions are low, i.e. little d–f mixing. Absorptions due to 4f–5d transitions are broad and are affected by ligand
environment.

Many trivalent lanthanide ions are strikingly coloured both in the solid state and in aqueous solution, The colour seems to
depend On the number of unpaired f electrons. Elements with (n) f electrons often have a similar colour to those with (14 - n) f
electrons. (See Table1) However, the elements in other valency states do not all have colours similar to their isoelectronic 3+
counterparts (Table 9).Colour arises because light of a particular wavelength is absorbed in the visible region.The wavelength
absorbed corresponds to the energy required to promote an electron toa higher energy level. In the lanthanides spin orbit
coupling is more important than crystal field splitting. In the spectra of transition metals, crystal field splitting is of major
importance.All but one of the lanthanide ions show absorptions in the visible or near- UV region of the spectrum.

3+
Table 1.7: Colour of Ln ions

No of 4f electrons Colour No of 4f electrons Colour

3+ 3+
La 0 Colourless Lu 14 Colourless
3+ 3+
Ce 1 Colourless Yb 13 Colourless
3+ 3+
Pr 2 Green Tm 12 Pale Green
3+ 3+
Nd 3 Lilac Er 11 Pink
3+ 3+
Pm 4 Pink Ho 10 Pale Yellow
3+ 3+
Sm 5 Yellow Dy 9 Yellow
3+ 3+
Eu 6 Pale Pink Tb 8 Pale Pink
3+ 3+
Gd 7 Colourless Gd 7 Colourless

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 15

4+ 2+ 3+
Table-1.8 Colours of Ln , Ln and their isoelectronic Ln counterparts:
3+
Electronic configuration Isoelectric M
4+ 0 3+
Ce Orange-red 4f La Colourless
2+ 6 3+
Sm Blood-red 4f Eu Pale pink
2+ 7 3+
Eu Pale greenish yellow 4f Gd Colourless
2+ 14 3+
Yb Yellow 4f Lu Colourless

3+
The exception is Lu which has a full f shell. These colours arise from transitions. Strictly these transitions are Laporte forbidden
(since the change in the subsidiary quantum number is zero). Thus the colours are pale because they depend on relaxation of
the rule. The f orbitals are deep inside the atom. Thus, they are largely shielded from environmental factors such as the nature
and number of ligands which form the complexes, and from vibration of the ligands. Thus the position of the absorption band
(i.e. the colour) does not change with different ligands. Vibration of the ligands changes the external fields. However, thisonly
-1
splits the various spectroscopic states by about l00cm , so the absorption bands are unusually sharp.

The lanthanides are used for wavelength calibration instruments because of their sharp absorption bands. For an f electron the
subsidiary quantum number l = 3, so m1may have values 3, 2, 1, 0, -1, -2, -3. Thus a large number of transitions are usually
possible.

This is in marked contrast to the transition elements where d-d spectra give absorption bands whose position changes from
ligand to ligand, and the width of the peak is greatly broadened because of the vibration of the ligands.It is also possible to get
transitions from the 4f to the 5d level.Such transitions give broader peaks and their position is affected by the nature of the
ligands.

Absorption spectra of lanthanide ions are useful both for the qualitative detection and the quantitative estimation of
lanthanides.

Lanthanide elements are sometimes used as biological tracers for drugs in humans and animals.This is because lanthanide
elements can quite easily be followedin the body by spectroscopy, because their peaks are narrow and very characteristic.

3+ 3+
Ce and Yb are colourless because they do not absorb in the visible region However, they show exceptionally strong
absorption in the UV region, because of transitions from 4f to 5d. Absorption is very strong for two reasons. Since l = l This is
an allowed transition and so gives stronger absorption than forbidden f-f transitions. Furthermore, promotion of electrons in
3+ 1 3+ 8
these ions is easier than for other ions. The electronic configuration of Ce is f and Yb is f Loss of one electron gives the
extra stability of an empty or half full shell. f-d peaks are broad, in contrast to the narrow f-f peaks. Charge transfer spectra are
possible due to the transfer of an electron from the ligand to the metal. This is more probable if the metal is in a high oxidation
4+
state or the ligand has reducing properties. Charge transfer usually produces intense colours. The strong yellow colour of Ce
2+
solutions arises from charge transfer rather than f-f spectra. The blood red colour of Sm is also due to charge transfer.

3+ 1 3+ 1
Q1. Why is the Ce (4f ) ion colorless, whereas Ti solution (3d ) are purple?
Solution:
3+ 2 2
The 4f configuration of Ce has only two multiplets: the ground state F5/2 and the excited state F7/2. The transition between
3+ 1
these states absorbs only infrared radiation and no visible light. The Ti ions have d configuration. It absorbs green and yellow
3+
color and transmits the complementary colors rich in red and violet. Hence the hydrated Ti is pink color. This transition is only
spin allowed and Laport forbidden.

IFAS Publications www.ifasonline.com

16 Inorganic Chemistry

Table-1.9: Ground term symbols for lanthanides:

III n 2S+1
Ln 4f , n = Ground term LJ
2
Ce 1 F5/2
3
Pr 2 H4
4
Nd 3 I9/2
5
Pm 4 I4
6
Sm 5 H5/2
7
Eu 6 F0
8
Gd 7 S7/2
7
Tb 8 F6
6
Dy 9 H15/2
5
Ho 10 I8
4
Er 11 I15/2
3
Tm 12 H6
2
Yb 13 F7/2

1.10. Magnetic properties

3+ 4+ 3+ 14
 La and Ce have an f° configuration, and Lu has an f configuration. These have no unpaired electrons, and are
diamagnetic.
 All other fstates contain unpaired electrons and are therefore paramagnetic. The magnetic moment of transition
elements may be calculated from the equation:
μ(S+L) = √
 μ(S+L) is the magnetic moment in Bohr magnetons calculated using both the spin and orbital momentum contributions.
 S is the resultant spin quantum number and L is the resultant orbital momentum quantum number.
 For the first-row transition elements, the orbital contribution is usually quenched out by interaction with the electric
fields of the ligands in its environment. Thus, as a first approximation the magnetic moment can be calculated using
the simple spin only formula. (μs is the spin only magnetic moment in Bohr magnetons. S is the resultant spin
quantum number and n is the number of unpaired electrons.)
μS = √ OR
μS = √
3+ 0 3+ 7 3+ 14 3+ 3+
 This simple relationship works with La (f ), and two of the lanthanides Gd (f ) and Lu (f ).La and Lu have no
unpaired electrons, n = 0 and μs = √ =0
3+
 Gd has seven unpaired electrons. n = 7 and
μs = √ =√ = 7.9BM
 The other lanthanide ions do not obey this simple relationship.
 The 4f electrons are well shielded from external fields by the overlying 5s and 5p electrons. Thus, the magnetic effect
of the motion of the electron in its orbital is not quenched out. Thus, the magnetic moments must be calculated
taking into account both the magnetic moment from the unpaired electron spins and that from the orbital motion.
This also happens with the second and third row transition elements. However, the magnetic properties of the
lanthanides are fundamentally different from those of the transition elements. In the lanthanides the spin
contribution S and orbital contribution L couple together to give a new quantum number J.
J = L-SWhenthe shell is less than half full
and

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 17

J = L+Swhen the shell is more than half full

The magnetic moment μ is calculated in Bohr magnetons (BM) by:
μ= √
Where,
g=1 +

Figure shows the calculated magnetic moments for the lanthanides using both the simple spin only formula and the coupled
spin plus orbital momentum formula. For most of the elements there is excellent agreement between the calculated values
using the coupled (spin + orbital) momentum formula and experimental values measured at 300 K. The ranges of experimental
3+ 3+ 3+
values are shown as bars. The agreement for Eu is poor, and that for Sm is not very good. The reason is that with Eu the
-1
spin orbit coupling constant is only about 300 cm . This means that the difference in energy between the ground state and the
next state is small.

3+
Fig 1.2: Paramagnetic moments of Ln lanthanide ions at 300K. Spin-only values are shown as a broken line and the spin plus
orbital motion as solid lines.

Table 1.10: Magnetism & Spectra

3+
Ln Ln Ground No. of Colour gJ√ Observed
configuration state Unpaired e-
0 1
La 4f S0 0 Colorless 0 0
1 2
Ce 4f F5/2 1 Colorless 2.54 2.3-2.5
2 3
Pr 4f H4 2 Green 3.58 3.4-3.6
3 4
Nd 4f I9/2 3 Lilac 3.62 3.5-3.6
4 5
Pm 4f I4 4 Pink 2.68 -
5 6
Sm 4f H5/2 5 Yellow 0.85 1.4-1.7
6 7
Eu 4f F0 6 Pale pink 0 3.3-3.5
7 8
Gd 4f S7/2 7 Colorless 7.94 7.9-8.0
8 7
Tb 4f F6 6 Pale pink 9.72 9.5-9.8
9 6
Dy 4f H15/2 5 Yellow 10.65 10.4-10.6
10 5
Ho 4f I8 4 Yellow 10.6 10.4-10.7
11 4
Er 4f I15/2 3 Rose-pink 9.58 9.4-9.6
12 3
Tm 4f H6 2 Pale green 7.56 7.1-7.6
13 2
Yb 4f F7/2 1 Colorless 4.54 4.3-4.9
14 1
Lu 4f S0 0 colorless 0 0

IFAS Publications www.ifasonline.com

18 Inorganic Chemistry

Thus the energy of thermal motion is sufficient to promote some electrons and partially populate the higher state. Because of
this the magnetic properties are not solely determined by the ground state configuration. Measuring the magnetic moment at a
3+
low temperature prevents the population of higher energy levels. The magnetic moment of Eu at low temperature is close to
zero as expected. The unusual shape of the spin plus orbital motion curve arises because of Hund's third rule. When the f level
is less than half full the spin and orbital momenta contributions work in opposition (J= L - S). When the f shell is more than half
full they work together (J = L + S).

1.11. Chemistry of Ce (+IV) and its complexes:

4+
The only (+IV) lanthanide which exists in solution and has any aqueous chemistry is Ce . It is rare to find 4+ ions in solution.

4+
The high charge on the ion leads to it being heavily hydrated, and except in strongly acidic solutions the hydrated Ce
+
ishydrolysed, giving polymeric species and H .Ce (+IV) solutions are widely used as an oxidizing agent in volumetric analysis
4+
instead of KMnO4 and K2Cr2O7.In classical analysis burettes containing Ce must be washed with acid since washing with water
3+
giyes the hydrated ion.Aqueous cerium(IV) solutions can be prepared by oxidizing a Ce solution with a very strong oxidizing
agent such as ammonium peroxodisulphate(NH 4)2S2O8. Ce (+ IV) is also used in organic reactions, for example the oxidation of
alcohols, aldehydes and ketones at the α-carbon atom. The common compounds are CeO2 (white when pure) and CeO2 · (H2O)n
(a yellow gelatinous precipitate). CeO2 can be obtained by heating the metal, or Ce(OH)3 or C (oxalate) in air.

3+
CeO2 has a fluorite type of structure. It is insoluble in acids and alkalis, but dissolves if reduced, giving Ce solutions.

Ce + O2 CeO2
2Ce (OH) 3 + O2 2CeO2 + 3H2O
Ce2 (C2O4)3 + 2O2 2CeO2 + 6CO2

Ce (SO4)2 (formerly called cerie sulphate) is well known and is yellow like K2CrO4. CeF4 is obtained from CeF3 and F2.It is white,
and is rapidly hydrolysed by water. It has a three-dimensional crystal structure with the metal at the centre of square antiprism.
A number of complexes are stable, for example ammonium cerium (IV) nitrate (NH4)2[Ce (NO3)6]. The crystal structure is
unusual and contains bidentate N groups. The Ce atom has a coordination number of 12 and the shape is an icosahedron.
This structure is stable even in solution. Two of the N ions may be replaced by phosphine ligands Ph3PO, giving a neutral 10-
IV
coordinate complex [Ce (NO3)4(Ph3PO)2]. The other (+IV) compounds are not stable in water and are known only as oxides,
fluorides and a few fluoro complexes. Thus PrO2, PrF4, Na2 [PrF6], TbO2, TbF4, TbO2, DyF4 and Cs3(DyF7] are all known. The
elements Pr, Nd Tb, and Dy also form (+IV) states. These are generally unstable, occur only as solids, and are found as fluorides
or oxides which may be nonstoichiometric.

1.12. Chemistry of Sm2+, Eu2+ and Yb2+ and its complexes:

2+ 2+ 2+ 2+
The only (+II) states which have any aqueous chemistry are Sm , Eu and Yb .The most stable divalent lanthanide is Eu .

11
This is stable in water, but the solution is strongly reducing. Eu SO4 can be prepared by electrolysing E solutions, when the
II III
divalent sulphate is precipitated. Eu Cl2 can be made as a solid by reducing Eu Cl3 with H2.

2EuCl3 + H2 2EuCl2 + 2HCl

IFAS Publications www.ifasonline.com

 Inner Tansition Elements 19

3+ 2+
Aqueous Eu solutions can be reduced by Mg, Zn, zinc amalgam or electrolytically to give Eu .EuH2 is ionic and similar to CaH2.
Eu(II) resembles Ca in several ways:The insolubility of the sulphate and carbonate in water. The insolubility of the dichloride in
strong HCI. The solubility of the metals in liquid NH3.One major difference between Eu and Ca is that the dihalides EuX2 have a
magnetic movement of 7.9 Bohr magnetons corresponding to seven unpaired electrons, whereas Ca compounds are
dimagnetic.

3+/ 2+ 3+
The couple Eu Eu has a standard reduction potential of -0.41 volts. This is about the same as for Cr and these are both
2+ 2+
about the strongest reducing agents that do not reduce water.Yb and Sm can be prepared by electrolytic reduction of their
2+
trivalent ions in aqueous solution.However, the Ln ions are readily oxidized by air. These two elements form hydroxides,
carbonates, halides, sulphates and phosphates. The states Nd(+II), Pm(+II), Sm(+II) and Gd(+II) are only found in solid dihalides
LnCl2 and LnI2.

These dihalides can be made by reducing the trihalide with hydrogen, with the metal, or with sodium amalgam, The dihalides
3+ -
such as LaI2 and NdI2 tend to be nonstoichiometric. They show metallic conduction, and are better represented as La + 2I +
electron, A detailed study of the third ionization energy shows the stability of a half-filled and completely filled shell. The
ionization energies also suggest that there may also be extra stability associated with three quarters filled shell.

Q1. Which oxidation states correctly represented the usual range exhibited by the stated metal?
a. Ce: +3 and +4 b. Th: +2 and +4
c. Pu: +3, +4, +5 and + 6 d. U: +2, +3 and +4
Ans: 1 is correct. Uranium can show up to +6.

1.13. Solubility
Salts of the lanthanides usually contain water of crystallization. Solubility depends on the small difference between the lattice
energy and the salvation energy, and there' is no obvious trend in the group. The solubility of many of the salts follows the
pattern of Group 2 elements. Thus, the chloride and nitrates are soluble in water and the oxalates, carbonates and fluorite are
almost insoluble.

Unlike Group 2, however, the sulphates are soluble. Many of the lanthanides form double salts with the corresponding Group 1
or ammonium salts, e.g. Na2SO4Ln2(SO4)3· 8H2O, and as these double salts crystallize well, they have been used to separate the
lanthanides from one another

1.14. Electronic Spectroscopy

Transitions which involve only a redistribution of electrons within the 4f orbitals (f-f transitions) are orbitally-forbidden by the
III
Selection Rules.Colours of Ln compounds are usually not very intense. Crystal/Ligand field effects in lanthanide 4f orbitals are
2 6
virtually insignificant.4f electrons are well shielded from external charge by 5s & 5p shells. f-f absorption bands are very sharp
III
(useful fingerprinting and quantisation of Ln ).*d↔d transitions in transition metal compounds are also orbitally forbidden, but
gain intensity from and are broadened by the effects of molecular vibrations in distorting the crystal field ].Optical spectra are
virtually independent of environment - similar spectra in gas/solution/solid (sharp lines like typical gas atom
III III
spectra).Insensitivity of f-f transitions means of limited use in study of lanthanide materials.Ce and Tb have high intensity
n n n-1 1
bands in the UV due to 4f 6s 4f 5d transitions, i.e. f-d and therefore not orbitally forbidden.

IFAS Publications www.ifasonline.com