Ifas F Block
Ifas F Block
Ifas F Block
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.
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
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
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
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
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).
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.
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.
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.
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.
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
Thus from La to Lu, Lattice energy and hydration energy decreases as expected.
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
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
+ 3-
Yb (OH) 3 + 3NaOH 3Na + [Yb (OH) 6]
+ 3-
Lu (OH) 3 + 3NaOH 3Na + [Lu (OH) 6]
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:
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.
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.
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.
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.
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.
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]
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.
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.
These are filtered off. Separation is not complete, so the oxalates are redissolved and the process repeated many times.
(EDTA)
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.
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.
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%)
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
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.
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.
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).
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.
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.
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