SEM VI: INORGANIC CHEMISTRY- IV

Module II: Chemistry of transition and inner transition elements (8 hrs)

Transition Metals: General characteristics: Metallic character, oxidation states, size, density,
melting points, boiling points, ionization energy, colour, magnetic properties, reducing
properties, catalytic properties, non-stoichiometric compounds, complex formation and
alloy formation. Difference between first row and other two rows.

Lanthanides: Electronic configuration and general characteristics – Occurrence of

lanthanides -Importance of beach sands of Kerala – Isolation of lanthanides from monazite
sand - Separation by ion exchange method. Lanthanide contraction: Causes and
consequences. Industrial importance of lanthanides.
Actinides: Electronic configuration and general characteristics – Comparison with
lanthanides.
References
1. J. D. Lee, Concise Inorganic Chemistry, 5th Edn., Wiley India Pvt. Ltd. 2008.
2. B. R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry, MilestonePublishers,
New Delhi 2010.
3. J. E. Huheey, E. A. Keiter, R. L. Keiter, O. K. Medhi, Inorganic Chemistry, Pearson 2006.
Furtherreading
1. F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 6thEdn., John Wiley, New York.
1999.
2. D. F. Shriver, P.W. Atkins, Inorganic Chemistry, 3rdEdn., Oxford University Press. 2009. 1
Dr. Ranimol Stephen, SJC, Devagiri, Calicut
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 Inner transition elements

 The elements in which the additional electrons enters (n-2)f orbitals are called inner
transition elements.
 The valence shell electronic configuration of these elements can be represented as (n –
2)f0-14(n – 1)d0-1ns2.

 4f inner transition metals are known as lanthanides (or lanthanoids) because they
come immediately after lanthanum
 5f inner transition metals are known as actinides (or actinoids) because they come
immediately after actinium.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 3

 Electronic Configuration
Element name Symbol Z Ln Ln3+ Radius
Ln3+/ pm
Lanthanum La 57 [Xe] 5d16s2 [Xe]4f0 106
Cerium Ce 58 [Xe]4f15d16s2 [Xe]4f1 103
Praesodymium Pr 59 [Xe]4f36s2 [Xe]4f2 101
Neodymium Nd 60 [Xe]4f46s2 [Xe]4f3 99
Promethium Pm 61 [Xe]4f56s2 [Xe]4f4 98
Samarium Sm 62 [Xe]4f66s2 [Xe]4f5 96
Europium Eu 63 [Xe]4f76s2 [Xe]4f6 95
Gadolinium Gd 64 [Xe]4f75d16s2 [Xe]4f7 94
Terbium Tb 65 [Xe] 4f96s2 [Xe]4f8 92
Dysprosium Dy 66 [Xe] 4f106s2 [Xe]4f9 91
Holmium Ho 67 [Xe] 4f116s2 [Xe]4f10 89
Erbium Er 68 [Xe] 4f126s2 [Xe]4f11 88
Thulium Tm 69 [Xe] 4f136s2 [Xe]4f12 87
Ytterbium Yb 70 [Xe] 4f146s2 [Xe]4f13 86
Lutetium Lu 71 [Xe] 4f145d16s2 [Xe]4f14 85

Energies of 4f and 5d levels are very close, electrons may exchange their positions.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 4

 Atomic and ionic sizes: The Lanthanide Contraction

As the atomic number increases, each succeeding element contains one more electron in
the 4f orbital and one proton in the nucleus. The 4f electrons are ineffective in screening
the outer electrons from the nucleus causing imperfect shielding. As a result, there is a
gradual increase in the nucleus attraction for the outer electrons. Consequently gradual
decrease in size occur. This is called lanthanide contraction.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 5

Lanthanide contraction is due to,
(i) mutual shielding of 4f electrons is imperfect due to more diffuse shapes of
the f-orbitals.
(ii) Increase in atomic number
(iii) Increase in effective nuclear charge
(iv) Reduction in size of the entire 4fn subshell along the series (due to the
increase in nuclear pull experienced by the 4f electrons).

Consequences of lanthanide (lanthanoid) contraction

(i) There is close resemblance between the second (4d) and third (5d) transition series. In
atomic/ionic sizes and properties.

The 14 lanthanide elements lie between the first member La and the second member Hf of
the 5d series.
The lanthanide contraction wipes out the expected increase in atomic/ionic size from the
second transition series to third.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
(ii) The ionization energies of the third row transition elements are greater than those of
the corresponding elements of the second row.
Move down a group from second to third transition series, the size remains almost
same due to lanthanide contraction whereas nuclear charge increases to a very large
extent.

(iii) Separation of the lanthanides are difficult, separated by ion- exchange method.

Lanthanides have similarity in most of their properties makes their separation by

chemical method is difficult.
It shows some difference in certain properties such as ability to form complexes.. So it is
utilized to separate lanthanide ions by ion- exchange methods.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
(iv) The basic strength of the hydroxides decreases along the lanthanide series.

Size of the lanthanide ion (Ln3+) decreases regularly with increase in atomic number, La3+ to
Lu3+.
Polarizing power increases La3+ to Lu3+.
Covalent character of the interaction between Ln3+ and OH- increases from La3+ to Lu3+.
So, basic strength of hydroxides decreases along the lanthanide series.
La(OH)3 is the most basic, Lu(OH)3 is the least basic.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Oxidation States

Predominantly +3 oxidation state.

 Some lanthanides show +2 and +4 oxidation states.

 Arises mainly from the extra stability of empty, half filled or filled f subshell.

(i) Cerium (Ce) attains stable f0 configuration in its +4 oxidation state

Ce: [Xe]4f15d16s2 Ce4+: [Xe]4f05d06s0
It has a tendency to reduced to common oxidation state +3, indicated by the positive Eo
value of +1.74 V for the Ce4+/Ce3+ couple.
Ce(IV) is a good oxidizing agent in aqueous solution and is used as a good analytical oxidant
in titrimetry (Cerimetry).

(ii) Terbium (Tb) attains stable half filled f7 configuration in its +4 oxidation state.
Tb: [Xe]4f96s2 Tb4+: [Xe]4f76s0
TB(IV) also has a tendency to get reduced to the common +3 state and hence is a good
oxidising agent.
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(iii) Europium (Eu) attains stable f7 configuration and ytterbium (Yb) attains stable f14
configuration in their +2 oxidation states.
Eu: [Xe]4f76s2 Eu2+: [Xe]4f76s0
Yb: [Xe]4f146s2 Yb2+: [Xe]4f146s0
They have a tendency to get oxidised to common oxidation state +3, hence, Eu(II) and Yb(II)
are good reducing agents in aqueous solution.

Some elements exhibits other oxidation states , eg: Sm(II), Tm(II), Pr(IV), Nd(IV), Dy(IV)
etc, which do not have empty, half filled or completely filled stable configuration.
It s based on the complicated thermodynamic and kinetic factors.

Why Sm2+, Eu2+, and Yb2+ ions in solutions are good reducing agents but an aqueous solution
of Ce4+ is a good oxidizing agent?

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Properties of lanthanides

 Silvery white soft metals and tarnish rapidly in air.

 Hardness increases with increasing atomic number.
 Sm being steel hard.
 Their melting points range fro 1000 to 1200 K, Sm melts at 1623 K.
 It has metallic structure.
 Good conductors of heat and electricity.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Magnetic properties

 The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f14 type
(Yb2+ and Lu3+) are all paramagnetic.
 Lanthanides have very high magnetic susceptibilities due to their large
number of unpaired f-electrons.

The total magnetic moment is the sum of the spin moment and the orbital moment.
total = orbital + spin

 total  g J(J  1)
J(J  1)  S(S  1) - L(L  1)
g 1 
2J(J  1)
g is called the magnetogyric ratio.

Lanthanide complexes are used in MRI (magnetic resonance imaging), eg. Gd(III)
complexes. -
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Colour

 Trivalent lanthanide ions are coloured in the solid state and aqueous solution.
 Colour is due to the presence of partly filled f- orbitals and the consequent f-f
electronic transitions.
 F- f transition is due to the lifting of degeneracy by crystal field effects.
 Absorption bands are narrow and pale colours are yielded.
 La3+ and Lu3+ do not show any colour due to f0 and f14 configuration.

Standard reduction potential (EoLn3+/Ln)

 EoLn3+/Ln values are in the range -2.25 to -2.52 V.
 High negative values of EoLn3+/Ln indicate that the metals have a strong tendency to
lose three electrons to undergo oxidation.
 They are good reducing agents and can be used to reduce oxides of other metals
 They are highly electropositive.
 They can displace H2 from dilute acids and forming hydroxides (hydroxides are basic
like alkaline earth metals.
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Chemical Properties

 Metal combines with hydrogen when gently heated in the gas.

 The carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated with
carbon.

 They liberate hydrogen from dilute acids and burn in halogens to form halides.

 They form oxides and hydroxides, M2O3 and M(OH)3, basic like alkaline earth metal
oxides and hydroxides.
Ln2O3 B H2
ur
n
w
ith i ds
O ac
2 it h
W
Ln2S3 Heated with S With helogens LnX
Ln 3
N2 W
ith
ith H
w 2O
ed
at C 2773 K
He
LnN LnC Ln(OH)3 +H2
2
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Complex formation

Lanthanides do not easily form complexes.

Poor tendency to form complexes is mainly due to:
- Eventhough the tripositive lanthanide cations have high charge of +3, their
size is large when compared to transition metals like Fe, Ni, Cr, Co etc. So small charge –
to- radius ratio. Lower charge density makes it difficult to accept electron pairs from
ligands.
- 4f orbitals are buried deep inside, they are unavailable for complex
formation.
Lanthanides can form stable complexes with chelating ligands containing oxygen or
nitrogen like acetylacetone, eg: [Yb(acetylacetone)H2O]3+ .

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 15

Occurrence of lanthanides
Some examples of minerals

(i) Monazite: Monazite sand is a mixture of lanthanide phosphates, LnPO4

Certain samples contain even up to 30% of thorium phosphate and some
zirconium phosphate.
Monazite sand occurs mainly in the sand beaches of Travancore ( Kerala),
Brazil, S. Africa and USA.
(ii) Bastnaeesite: These minerals are mainly mixed fluorides and carbonates of lanthanides,
(Ln)FCO3.
The minerals are found in USA, Mexico and Sweden.
(iii) Fluocerite: Fluocerite minerals are fluoride minerals, LnF3.
These minerals are found in Sweden, Kazakhstan etc

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Beach sands of Kerala

 The coastal sands of Kollam and Alappuzha districts in Kerala between Neendakara and
Kayamkulam contain deposits of minerals.
 Also known as Chavara deposit.
 127 million tonnes of heavy minerals in the Chavara deposit.
 Ilmenite (FeTiO3) is the dominant component.
 Deposit also contains leucoxene and rutile, which are titanium minerals (TiO2).
 These minerals are primarily used for the production of white titanium dioxide pigment.
 29 million tonnes of Chavara deposit is sillimanite, an aluminosilicate mineral (Al2SiO5).
 5 million tonnes of zircon (ZrSiO4 with ZrO2 and some HfO2).
 Another deposit is garnet ( a silicate mineral X3Y2(SiO4)3 where X is divalent Ca, Mg, Fe
or Mn and Y is trivalent Al, Fe or Cr).

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
 Around ~ 1 million tonnes of Chavara deposit contains the monazite mineral.
 Monazite is an important mineral which contains mainly the phosphates of lanthanides
and thorium.
 It is represented as Ln(PO4)3.Th3(PO4)4.
 Monazite is the significant source of commercial lanthanides.
 Thorium extracted from the monazite mineral is used in the manufacture of fuel rods in
nuclear reactors.
 Different kinds of monazite mineral,
- Monazite-(Ce)- (Ce, La, Nd, Th, Y)PO4
- Monazite- (La)- (La, Ce, Nd)PO4
- Monazite- (Nd)- (Nd, La, Ce)PO4
- Monazite-(Sm)- (Sm, Gd, Ce, Th)PO4
The first element listed in the parenthesis is the element with the greater percentage in
the mineral.
 Most common one is Monazite-(Ce).
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
The discovery process for this huge Indian deposit was accidentally initiated in the year 1908
when Herr Schomberg, a German chemist identified the presence of monazite in the sand
remnants of contaminants of coir imported from Kerala.
Encouraged by the great demand in those days for thorium oxide in gas mantle, Schomberg
established the first plant at Manavalakurichi (MK) in 1910 for separation of monazite and
later another plant at Chavara.

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Separation of lanthanides

Separation consists of two steps:

(a) Isolation of lanthanides from monazite sand- acidic method using H2SO4.
(b) Separation of the individual lanthanides using the ion-exchange method.

(a) Isolation from monazite sand , Ln(PO4)3.Th3(PO4)4

Ln = La, Ce, Pr, Nd, Sm, Dy, etc.

1. Concentration of minerals by,

(i) washing in a forceful stream of water (Levigation) followed by blowing an air blast, and
(ii) applying a magnetic field ( magnetic separation of its magnetic impurities).
(iii) Digestion with conc.H2SO4
 Concentrated monazite sand is digested with conc. H2SO4 at 150-200oC.
 Convert the phosphates into corresponding sulphates.
 Thorium and lanthanide sulphates pass into solution to remove insoluble impurities like
SiO2, TiO2 and ZrSiO4 etc, filtered off.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
 Th 3 (PO 4 ) 4  6H 2SO 4  3Th(SO 4 ) 2  4H 3 PO 4
2LnPO 4  3H 2SO 4  Ln 2 (SO 4 ) 3  2H 3 PO 4 ( Ln  La, Ce etc..)

 Make the solution alkaline, by adjusting the pH Th (HPO4) get precipitated and removed
by filteration.

Th(SO 4 ) 2  2H 3 PO 4  Th(HPO 4 ) 2  2H 2SO 4

 The filterate containing lathanide ions is collected and is then separated by ion-exchange
method.
Cold water

Monazite 150-200oC Grey mud Solution Made alkaline by adding

sand several hours Solution
oxides of lanthanides
H2SO4, 98% Ln3+
Residue (Sand, SiO2, TiO2,
ZrSiO4 etc.)

Th- containing mud

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
(b) Separation of the individual lanthanides using ion-exchange method

1 In this process of solution of the lanthanides in ionic, soluble form is passed down a long
column containing resin.
[Link] lanthanide ions are stick to the resin with various strengths based on their size .
3. Then the lanthanides are washed out of the ion exchange column with various
solutions emerging one at a time and so are separated.

Different steps
(i) Sample introduction

 Aqueous solution containing the mixture of lanthanide ions [Ln3+(aq)] is paased through a
column packed with a suitable synthetic cation- exchange resin (H-Resin).
 H+ ions exchangeable with te Ln3+ (aq) ions present in the solution and get fixed on it.

Ln 3aq  3H - Resin (s)  Ln(Resin)3(s)  3H  (aq) [Ln  lanthanides]

 The smaller the size of the aquated lanthanide ion, Ln3+(aq), the stronger is the
attachment of ion to the resin. 22
Dr. Ranimol Stephen, SJC, Devagiri, Calicut
  Size of non-hydrated Ln3+ decreases from La3+ to Lu3+.
 Smaller ions are hydrated more, so Lu3+ is the most hydrated and La3+ is the least
hydrated.
 Among the Ln3+ hydrated ions, Lu3+(aq) has the largest size and La3+ (aq) the smallest.
 La3+(aq) is the most strongly bound and Lu3+(aq) is the least strongly bound ions on the
resin.

(ii) Elution

 Ln3+ ions on the resin are eluted using a suitable eluent (or eluant).
 A preferred eluent is a buffer solution containing citric acid and ammonium citrate.
 Ln3+ ions get displaced from the resin by the NH4+ ions in the increasing order of their
strength of binding to the resin.
 It forms soluble complexes with the citrate ions.

Ln(Resin)3 (aq)  Citrate 3- (aq)  3NH 4 (aq)  Ln - citrate complex (aq)  3NH 4 - Resin (s)

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
 Lu3+ , the least tightly bound to the resin comes out first as its citrate complex.
 All lanthanides comes out in the increasing order of binding strength to the resin.
 La3+, the most strongly bound to the resin would be the last to come out.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Industrial importance of lanthanides
 Used for the production of alloys, alloys termed as mischmetals (mixed metals).
Mischmetal is an alloy of rare earth elements Eg: cerium mischmetal, contains 50%
cerium, 25% lanthanum and small amounts of neodymium and praseodymium.
Alloy of cerium and iron (ferrocerium) called Auer metal, which produced a brilliant
spark when struck, so used as a flint in cigarette and gas lighters.
Mg- mischmetal used to produce bullet shells.
Ce-Mg alloys are used in the production of flash light powders.
Used as oxygen removers in vacuum tube production.
 Mixed oxides of lanthanides are used as catalysts in petroleum cracking.
 Oxides of Eu and Yb are used as phosphors in television screens and computer monitors.
 Cerium oxide is used to polish glass and also used in gas mantles.
 Mixed oxides used in the ceramic industry to colour ceramics and glasses.
 Lanthanide compounds used in street lights, search lights, and in the flood- lights of
stadia.
 Found application in nuclear reactor components and in the production of lasers.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
The Actinides ( Actinoids)
 The elements in which the extra electron enters 5f- orbitals of (n-2)th main shell are
known as 5f-block elements, actinides or actinoids.
 Actinides include the fourteen elements from Th ( Z=90) to Lr (Z=103).
 Only Th, Pa and U are naturally occurring.
 The actinide elements lying beyond U are all synthetic and referred as transuranium
elements or transuranic elements.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Electronic configuration

 General electronic configuration is [Rn]5f2-146d0-27s2.

 5f and 6d levels are very close in energy and the electrons exchange their positions.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 27

Actinide contraction

 The shielding of one f-electrons are less due to its diffused shape.
 With increasing atomic number, the effective nuclear charge experienced by each 5f-
electrons as well as the outer electrons increases in each step.
 This causes shrinkage in the radius of atoms or ions as one proceed from Ac to Lr.
 This accumulation of successive shrinkage is called actinide contraction.

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Oxidation states
 Actinides show greater range of oxidation states than the lanthanides.
 Because the 5f, 6d and s levels in actinides are much closer in energy than the 4f, 5d
and 6s levels of lanthanides.

Element Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Oxidation +2 +2
state +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7

 Higher oxidation states are shown by the actinides in the first half of the series.

Complex formation
 Easily form complexes due to the greater participation of 5f- orbitals in bonding. ( Eg:
[Th(acac)4])
 They form complexes with chelating ligands like EDTA and also with - acceptor
ligands.
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Metallic properties

 Dense metals
 Moderately high melting point
 Highly electropositive
 Silvery white in appearance

Reactivity

 Highly reactive metals.

 React with boiling water to release hydrogen gas.
 Combine with hydrogen to form their hydrides.
 Combine with halogens to form halides

5f electrons of actinides are less firmly held and as a result, more available for bonding
than the 4f- electrons of the lanthanides.

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Magnetic properties
 Actinide ions containing unpaired 5f- electrons are paramagnetic.
 Experimental values are generally found to be lower than the theoretical values.
 Magnetic properties of the actinide ions are more complex.
 Ions which contain no unpaired electrons are diamagnetic, Eg: f0 (Ac3+ and Th4+) and
f14 (Lr3+).

Colour

 Tripositive actinides are coloured.

 Ions having 5f0, 5f7 and 5f14 configurations are colourless.
 Colour arises due to f-f transition.
 Due to greater availability of 5f- orbitals for bonding, they are more influenced by the
ligand fields and more intense colours.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Comparison of lanthanides and actinides

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 32

Questions

1. Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and U. Why?
2. Although +3 oxidation states is the characteristic oxidation state of lanthanoids but
cerium shows +4 oxidation state also. Why?
3. Why do actinides show greater range of oxidation states than the lanthanides?
4. What is the difference in the electronic structures of transition and inner transition
elements?
5. What are transuranic elements?
6. Write a short note on the existence of rare earth elements in the beach sands of Kerala.
7. Why Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents but an aqueous
solution of Ce4+ is a good oxidising agent?
8. Comment on the oxidation state of Ce.
9. Why are La3+ and Lu3+ compounds colourless?

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 33

10. Briefly explain the isolation and separation process of lanthanides.
11. What is lanthanide contraction? How does it originate and what are the important
consequences of lanthanide contraction?
12. Explain the basicity of Ln(OH)3.
13. What is misch metal?

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