Lanthanides + Actinides

Lanthanides and Actinides

Chem 324 Course

Lecture 1: Introduction to the 4f elements, the lanthanides. Shapes and nature

of the f-orbitals. Oxidation states. The lanthanide contraction.

Lecture 2: Extraction and isolation of the lanthanides. Introduction to lanthanide

chemistry. Solid state compounds, halides and oxides.

Lecture 3: Divalent and tetravalent compounds. Electronic configurations,

magnetism and spectroscopy.

Lecture 4: Lanthanide coordination chemistry and shift reagents. Use in organic

synthesis.
Lecture 5-6: Organolanthanide chemistry and organometallic catalysis.

Lecture 7-10: Actinide occurrence and synthesis. The 5f orbitals; comparison to

lanthanide chemistry. Applications of actinide elements. Actinide oxidation
states and coordination chemistry. Spectroscopy. Actinide organometallic
chemistry.
 Introduction to the 4f elements
• Lanthanides are a family of 15 chemical elements whose atomic numbers range
from 57 to 71.

• They are classified as f block elements along with the actinides. They are
commonly called the rare earths. They are characterized by the filling up of the 4f
energy levels which are not usually involved in bonding. These highly
electropositive elements have a common oxidation state of +3 and generally
resemble each other in their chemical and physical properties. The have a generic
symbol “Ln”.

• The lanthanides represent the largest naturally occurring group of elements

in the periodic table.

• They are highly electropositive and reactive metals. Spectral and magnetic
properties of lanthanide ions are remarkable.

• the complexes of lanthanides and the lanthanide salts are getting more and
more applications in biology, biochemistry and medicine.
• The chelates of lanthanide ions are used as labels in
fluorescent immunoassays. The paramagnetic and
luminescent Tb+3- phosphatidylcholine-complexes are unique
evidence for the cation phospholipid interaction.
• Water-soluble La+3 and Eu+3 complexes are effective in
detecting sugars neutral environment and glycolipids and
phospholipids as well.
• Simple lanthanide salts and complexes exhibit an antitumoral
activity.
 4F elements?

The lanthanides comprise the largest naturally-occurring group in the periodic table.
They are belonging to 6-th period
 Location on Periodic Table
• block of two rows of elements located below
the main body of the chart.
4F elements?
Discovery of the f elements and their position in the Periodic
Table
1789
Klaproth shows pitchblende contains a new element,
uranium which was isolated as a metal
in 1841 by Peligot.
1794
J. Gadolin isolates "yttria", but thought it was the pure
oxide of Y

By 1910 – all elements identified

The Rare Earth Elements

(f) TypeTransition Elements
 The Lanthanides

Also known as the rare earths

aside from the radioactive promethium which is produced
artificially, the
lanthanides are not especially rare. e.g. La, Ce and Nd are more
common than Pb.
 Monazite Bastnaesite,
Mixed lanthanide orthophosphates (LnPO4) Fluorocarbonate (LnFCO3)

Major sources of lanthanides are Monazite sand-composed of phosphates of

thorium, cerium, neodymium and lanthanum; the phosphate portion of monazite
contains small traces of other lanthanide ions and the only lanthanide that does
not occur naturally is promethium, which is made artificially by nuclear reaction.
Bastnaesite, found in USA and Madagascar is a mixed fluorocarbonate MIIICO3F
where M is La or the lanthanide metals. It provides 20% total supply of
lanthanides. An also very small amount of xenotime mineral is mined. Monazite
occurs in many countries while the principal sources of bastnaesite are China and
a vast deposit located in the Sierra Nevada mountains of California discovered in
1949
 Physical Properties
• The lanthanides and actinides have many
common properties. This makes them difficult to
separate from each other.
• The metals are silver, silvery-white, or gray
metals.
• The metals are very shiny, but tarnish in air.
• The metals have high ability to conduct with
electricity.
 Chemical Properties
• Very reactive.
• Tarnish when exposed to air, forming their
oxides.
• High melting points and boiling points.
• Reacts with water
• Burns easily in air.
• Reacts with ultraviolet light.
 Uses
• Petroleum products.
• Lanthanides are used in lamps, lasers,
magnets, motion picture projectors, and X-ray
screens.
• Actinides are used in Chemotherapy, power
plants, and nuclear weapons.
Lanthanum is the first element in the
lanthanide series.
 4f orbitals

The difficulties in separating the lanthanides and obtaining the elements

in a pure form were due to the pronounced chemical similarities
between the elements.

The 4f orbitals play a role central in determining the properties of the

elements For any atom, there are seven 4f orbitals
two sets of orbitals in common use.

What do f Orbitals Look Like?

They are generally represented in one of two ways, either as a cubic set, or as a general
set, depending upon which way the orbitals are combined. The cubic set comprises
fxyz; fz(x2−y2), fz(y2−z2) and fy(z2−x2); fz3, fx3 and fy3.
The general set, more useful in non-cubic environments, uses a different combination:
fz3; fxz2 and fyz2; fxyz; fz(x2−y2), fx(x2−3y2) and fy(3x2−y2).
Two distinct shapes
4f orbitals have only limited radial extension (or alternatively are
extremely contracted). Inefficiently shielded from (Zeff) The effective
nuclear charge (It is the net positive charge attracting an electron in an atom.)

Electrons accommodated behave in a core-like manner and are thus

relatively uninvolved in bonding and are also unaffected by the ligand
environment to any great degree
Ground state Atomic ‫اﺳم اﻟﻌﻧﺻر‬ Element Symbol electronic config’n
configurations number

21 ‫ﺳﻜﺎﻧﺪﯾﻮم‬ Scandium Sc [Ar]4S23d1

37 ‫ﯾﺘﺮﯾﻮم‬ Yutrium Y [Kr]5s24d1

57 ‫ﻻﻧﺜﺎﻧﻮم‬ Lanthanum La [Xe]5d16s2

58 ‫ﺳﯾرﯾوم‬ Cerium Ce [Xe]4f15d16s2

59 ‫ﺑﺮازادﻣﯿﻮم‬ Praseodymium Pr [Xe]4f36s2

60 ‫ﻧﯿﻮدﯾﻤﯿﻮم‬ Neodymium Nd [Xe]4f46s2

61 ‫ﺑﺮﻣﯿﺜﯿﻮم‬ Promethium Pm [Xe]4f56s2

62 ‫ﺳﻤﺎرﯾﻮم‬ Samarium Sm [Xe]4f66s2

63 ‫ﯾﻮرﺑﯿﻮم‬ Europium Eu [Xe]4f76s2

64 ‫ﺟﺎدوﻟﯿﻨﯿﻮم‬ Gadolinium Gd [Xe]4f75d16s2

65 ‫ﺗﺮﺑﯿﻮم‬ Terbium Tb [Xe]4f96s2

66 ‫دﯾﺴﺒﻮرزﯾﻮم‬ Dysprosium Dy [Xe]4f106s2

67 ‫ھﻮﻟﯿﻮم‬ Holium Ho [Xe]4f116s2

68 ‫ارﺑﯿﻮم‬ Erbium Er [Xe]4f126s2

69 ‫ﺛﻮﻟﯿﻮم‬ Thulium Tm [Xe]4f136s2

70 ‫ﯾﺘﺮﯾﻮم‬ Ytterbium Yb [Xe]4f146s2

71 ‫ﻟﻮﺗﯿﺘﯿﻮم‬ Lutetium Lu [Xe]4f145d16s2

Atomic
number
‫اﺳم اﻟﻌﻧﺻر‬ Element Symbol electronic
config’n
Ln+2 Ln+3 Radius Radus
Ln Ln+2

21 ‫ﺳﻜﺎﻧﺪﯾﻮم‬ Scandium Sc [Ar]4S23d1

37 ‫ﯾﺘﺮﯾﻮم‬ Yutrium Y [Kr]5s24d1

57 ‫ﻻﻧﺜﺎﻧﻮم‬ Lanthanum La [Xe]6s25d1 [Xe] 5d1 [Xe] f0 188 166

58 ‫ﺳﯾرﯾوم‬ Cerium Ce [Xe]4f15d16s2 [Xe]4f2 [Xe]4f1 183 144

59 ‫ﺑﺮازادﻣﯿﻮم‬ Praseodymiu Pr [Xe]4f36s2 [Xe]4f3 [Xe]4f2 182 113
m
60 ‫ﻧﯿﻮدﯾﻤﯿﻮم‬ Neodymium Nd [Xe]4f46s2 [Xe]4f4 [Xe]4f3 181 111

61 ‫ﺑﺮﻣﯿﺜﯿﻮم‬ Promethium Pm [Xe]4f56s2 [Xe]4f5 [Xe]4f4 181 109

62 ‫ﺳﻤﺎرﯾﻮم‬ Samarium Sm [Xe]4f66s2 [Xe]4f6 [Xe]4f5 180 108

63 ‫ﯾﻮرﺑﯿﻮم‬ Europium Eu [Xe]4f76s2 [Xe]4f7 [Xe]4f6 199 107

64 ‫ﺟﺎدوﻟﯿﻨﯿﻮم‬ Gadolinium Gd [Xe]4f75d16s2 [Xe]4f75d1 [Xe]4f7 180 105

65 ‫ﺗﺮﺑﯿﻮم‬ Terbium Tb [Xe]4f96s2 [Xe]4f9 [Xe]4f8 178 104

66 ‫دﯾﺴﺒﻮرزﯾﻮم‬ Dysprosium Dy [Xe]4f106s2 [Xe]4f10 [Xe]4f9 177 103

67 ‫ھﻮﻟﯿﻮم‬ Holium Ho [Xe]4f116s2 [Xe]4f11 [Xe]4f10 176 102

68 ‫ارﺑﯿﻮم‬ Erbium Er [Xe]4f126s2 [Xe]4f12 [Xe]4f11 175 100
69 ‫ﺛﻮﻟﯿﻮم‬ Thulium Tm [Xe]4f136s2 [Xe]4f13 [Xe]4f12 174 99
70 ‫ﯾﺘﺮﯾﻮم‬ Ytterbium Yb [Xe]4f146s2 [Xe]4f14 [Xe]4f13 194 99
71 ‫ﻟﻮﺗﯿﺘﯿﻮم‬ Lutetium Lu [Xe]4f145d16s2 [Xe]4f145d1 [Xe]4f14 173 98
• At start of the series the 5d orbitals are lower in energy than the 4f
orbitals
• ground state of La is [Xe]5d16s2

• Ce is [Xe] 4f15d16s2 not [Xe]4f26s2.

• i.e. 4f and 5d orbitals are of comparable energy at the start of the series.

•As the atomic number (Z) increases the 4f orbitals rapidly contract
and are stabilised relative to the 5d orbitals

•4f set are only poorly shielded by the core electrons

Pr has the ground state [Xe] 4f36s2

trend continues as far as Eu [Xe] 4f76s2.

Gd - 4f orbitals are half filled - electron is added to a 5d orbital –

[Xe] 4f75d16s2

pattern resumes Tb [Xe] 4f96s2 until

the 4f shell is filled at Yb [Xe] 4f146s2

Lu configuration is [Xe] 4f145d16s2

Note: 5d has one electron on the following elements:

La: [Xe], 4f0 5d1 6s2

7 1 2 Stable, because half-filled 4f
Gd : [Xe] , 4f 5d 6s
Lu : [Xe] , 4f14 5d1 6s2 Stable, because completely filled 4f
Ionisation energies and oxidation states

chemistry of lanthanides is dominated by the +3 oxidation state

sum of the first three ionaisation energies greater than the energy of Ln4+

Ln3+ Ln4+ +e
(g) (g)

Once three electrons removed

stabilization of the 4f orbitals is
so large that the 4f electrons
are so tightly held as to be
inaccessible
Oxidation states of Ln:
1. Ln2+ (Second oxidation state):
only well characterized Ln2 ions
Eu2+ (4f7),
Yb2+ (4f14) and
Sm2+ (4f6 ) s

Stability is achieved at half-filled (Eu2+) and completely filled 4f shells

(Yb2+) reflected in the variation of the third ionization energy of the
lanthanides feature very high values for Eu and Yb very low values for
subsequent elements
Pr+2 [Xe]4f36s2 [Xe]4f3
Nd+2 [Xe]4f46s2 [Xe]4f4

Sm+2 [Xe]4f66s2 [Xe]4f6

TM+2 [Xe]4f136s2 [Xe]4f13

 Preparation of Ln2+ compounds Nd,Sm,Tm,Eu,Yb,Lu
1. Reduction of Ln salts using free atoms or compound (Ln-
salts like F-, Cl- and oxides

2EuCl3 + H2 2EuCl2 + 2HCl

2SmCl3 + H2 2SmCl2 + 2HCl
6SmCl3 + 8NH3 6SmCl2 + 6NH4Cl + N2

3SmCl3 + Al 3SmCl2 + AlCl3

2. Reduction using Zn/Hg, only for EU

2Eu 3+ (aq) + Zn + Hg 2Eu2+ (aq)

3. Heat Reduction using for Iodides

∆
2LnI3 (s) 2LnI2 (s) + I2 (g) ( Ln = Sm, Eu, Yb)

4. By oxidation
2Ln + Oxidizing agent Ln2+
(Ln = Sm, Eu, Yb)
 Properties of Ln2+ compounds:

*There is similarities between Ln-compounds and some alkaline elements like:

Sr, Ba, Eu, Yb in solubility and crystal structure

*Some Ln2+ has good stability due half and completely filled 4f:
Eu2+ (4f7),
Yb2+ (4f14) and
2+ 2+ 2+ 2+
Pr ,Nd ,Sm ,Tm

*Some Ln2+ are strong reduced agents

2+ 2+ 2+
Eu >Yb >Sm
2+ 2+
Sm ,Yb oxidized in the presence of hydronium ion:

2Sm2+ (aq)+2H3O+ 2Sm3+ (aq)+2H2O+H2(g)

2+
Eu , neesds oxygen plus the hydronium ion:
2+ + 3+
4Eu (aq)+4H3O + O2 4Eu (aq)+6H2O
2. Ln3+
Most thermodynamically stable oxidation state is Ln3+

La [Xe]6s25d1 [Xe] f06s05d0

Gd [Xe]4f75d16s2 [Xe]4f76s05d0

Lu [Xe]4f145d16s2 [Xe]4f146s05d0

Properties of Ln3+ compounds:

1. Oxidation and Reduction

a. Oxidation: Ln3+ can be oxidized easily in the presence of oxidizing agents, e.g.

2Ln 3+ (aq) + O2(g) + 2H+ (aq) 2 Ln4+ (aq) +2 H2O (aq)

(Ln = Ce, Pr, Tb)

 Ce 3+ (aq) -e Ce4+ (aq)

Ce4+ : strong oxidizing agent in aqueous solution

Ce [Xe]4f15d16s2 [Xe]4f2 [Xe]4f1 [Xe]4f0

Pr 3+ (aq) -e Pr4+ (aq) [Xe]4f4 [Xe]4f3

Tb 3+ (aq) -e Tb4+ (aq) [Xe]4f8 [Xe]4f7

b. Reduction of Ln3+

Ln 3+ (aq) + ½ H2 (g) Ln2+ (aq) + H+ (aq)

Eu 3+ (aq) + e- Eu2+ (aq) [Xe]4f76s2

Eu2+ (4f7)

Xe]4f146s2
Yb 3+ (aq) + e- Yb2+ (aq)
Yb2+ (4f14)
 Stability of Ln3+ ions: They are stable due to the following reasons:

1. Low inonization energy ‫اﻻﻧﺨﻔﺎض ﻓﻲ طﺎﻗﺔ اﻟﺘﺎﯾﻦ‬

2. High lattice energy ‫ اﻻرﺗﻔﺎع ﻓﻲ ﻓﻲ طﺎﻗﺔ اﻟﻄﺎﻗﺔ اﻟﺒﻠﻮرﯾﺔ‬.

3. Stable electronic configuration ‫اﻟﺘﺮﺗﯿﺐ اﻻﻟﻜﺘﺮوﻧﻲ اﻟﻤﻤﯿﺰ‬

Gd0 Gd2+ Gd3+ Lu0 Lu2+ Lu3+

[Xe]4f75d16s2 [Xe]4f75d1 [Xe]4f7 [Xe]4f145d16s2 [Xe]4f145d1 [Xe]4f14

4. Strong ionic bond: Ln3+ compounds have high melting and boiling
points due to high strong ionic bond, ( Formation energy (∆f) high)

Lnx+

‫طﺎﻗﺔ اﻟﺗﺎﯾن‬
‫طﺎﻗﺔ اﻟﺷﺑﻛﺔ اﻟﺑﻠورﯾﺔ‬
Ln
E

Hf
1. The stability of oxidation state depends on many factors such as ionisation energy, lattice
energy, solvation or hydration energy etc. In case of lanthanides the first three ionisation
energies are very comparable. Thus they can easliy attained +3 oxidation sate by the loss
of three electrons from their outermost shell.
2. All of these lanthanides show stable +3 oxidation state in aq soln. The reason behind the
stability of +3 oxidation state is hydration energy. The stability of aqueous or hydrated
form of any compound increases with the hydration energy. M+2 ion will have lower
hydration energy than M+3 ion as Hydration energy ά 1/size.
3. Generally, the higher oxidation state than +3 is not observed due to the stabilization of 4f
orbitals compared to 5d and 6s. The order of penetration of the orbitals into the inner
electron core is 4f greater than 5d greater than 6s. The 4f electrons are the closest to the
nucleus, thus 4f electrons are strongly pulled by nucleus.
 3. Ln4+ Ce
Pr
Despite high I4 energies, five lanthanides have some tetravalent chemistry
Ce Nd, Dy, Tb and Pr - restricted to solid-state fluorides and some dioxides Nd
(i.e. very highly oxidizing ligands.) Tb
Dy

only extensive chemistry is shown by Ce4+ chemically accessible due to the

higher energy of the 4f orbitals at the start of the series not sufficiently stable to
prevent the loss of the fourth electron.

Ce 3+ (aq) -e Ce4+ (aq)

Ce [Xe]4f15d16s2 [Xe]4f2 [Xe]4f1 [Xe]4f0

Tb4+

Tb 3+ (aq) -e Tb4+ (aq) [Xe]4f8 [Xe]4f7

 Preparation of Ln4+ compounds

1. Oxidation
Heating the oxides of Ce, Pr, Tb at high temperature:

2Pr2O3 + O2 500 ₀C
4 PrO2
100 atm

450 ₀C
2Tb2O3 + O2 4 TbO2

2. Burning Ce metal or Ce-oxalate directly in air

∆
Ce + O2 CeO2

∆
Ce (C2O4) 3 + O2 CeO2 + 6 CO2
3. Oxidation using Florine

300- 500 ₀C
Ce F3 + ½ F2 CeF4

3. Exchange Oxidation

Ce (OH)4 + 4 HNO3 Ce(NO)3 + 4H2O

2Ln2O 3 + 3 CCl4 4 LnCl3 + 3CO2

2LnCl 3 + 3 NaF 4 LnF3 + 3NaCl

Ce4+ : Used as oxidizing agents, is very stable in both
aqueous and solide state . Is found in two compounds:

Hydrated cerium oxide, CeO2. X H2O Which is easily dissolve in acid

CeO2. X H2O + HCl CeCl4 + (2+X) H2O

Unhydrous cerium oxide, CeO2weak base and does not react with acid
lanthanide contraction

The radius of tripositive lanthanide cations, (M3+) reveals that

these values decrease as we move from La3+ to Lu3+ in the
lanthanide series. “The steady decrease in the values of the radii
of M3+ cations in the lanthanide series is called as Lanthanide
contraction.”
The Lanthanide Contraction
Reduction of Ln metal and Ln3+ radii is referred to as the lanthanide contraction

Atomic number Symbol Radius Ln ,Å Radus Ln+3 ,Å

Arises from the poor ability of
the 4f electrons to screen the
21 Sc 1.641 0.68 other valence electrons from
37 Y 1.801 0.88 the increasing nuclear charge
57 La 1.877 1.061
58 Ce 1.832 1.034 i.e: The effective nuclear
59 Pr 1.828 1.013
60 Nd 1.821 0.995
charge increases across the
61 Pm 1.821 0.979
series
62 Sm 1.802 0.964
63 Eu 2.042 0.950
64 Gd 1.802 0.938
65 Tb 1.782 0.923
66 Dy 1.773 0.908
67 Ho 1.766 0.994
68 Er 1.757 0.881
69 Tm 1.746 0.869
70 Yb 1.940 0.858
71 Lu 1.734 0.848
Metallic and Ionic Radii

Metallic and ionic radii show a gradual reduction with increasing atomic number
exceptions - metallic radii of Eu and Yb

Ie: Other electrons are not pulled so near to the nucleus

Shielding Effect Trend-Cause of lanthanide contraction
On proceeding from one element to the next in the lanthanide series, the
nuclear charge (atomic number) increases by 1. The additional electron
enters the ‘4f’ shell of the elements. Also, the shielding of one electron
residing in the 4f orbital, by the other present in the same orbital, is poor.
Due to negligible amount of mutual shielding effect between the electrons
residing in 4f orbital, the increase in nuclear charge by +1 at each next
element in the lanthanide series brings the valence shell nearer to the
nucleus and hence, the size of M3+ cations goes on decreasing as we move
from one element to another.
Effects of lanthanide contraction on properties:
Lanthanide contraction plays an important role in determining the
chemistry of lanthanides and heavier transition elements.
1. There is a decrease in the basic character of M(OH)3 bases or the
hydroxides of lanthanides, with increase in atomic number. Thus,
La(OH)3 is the most basic while Lu(OH) 3 is the least basic. Due to
lanthanide contraction, the decrease in size of M3+ cations increases the
covalent character (i.e, decrease in ionic character) between the M3+ ion
and OH- ion(according to Fajan's rules), thereby reducing the basic
character of the lanthanide hydroxides.
2. Because of the lanthanide contraction, the post lanthanide elements
have higher density, and are smaller in size

The importance of the lanthanide contraction arises from its consequences:

The reduction in size from one LuIII to the next could make their separation
possible, but the smallness and regularity of the reduction makes the
separation difficult;
 Chapter 2

1. Extraction and isolation of the lanthanides.

2. Introduction to lanthanide chemistry. Solid state

compounds, halides and oxides, coordination and

organometallic chemistry
 Extraction

The extraction of the Lanthanides from minerals by:

Ø Alkali Digestion of Monazite/Xenotime.

Monazite and Xenotime can also be opened-out through an

Acid Route

Ø Acid Dissolution of Bastnaesite

Extraction from native ores
alkali digestion of monazite/xenotime or acid dissolution of bastnaesite

After initial concentration by crushing, grinding and

froth flotation, bastnasite is treated with 10% HCl to
remove calcite, by which time the mixture contains
around 70% lanthanide oxides. This is roasted to oxidize
the cerium content to CeIV; on further extraction with
HCl, the Ce remains as CeO2, whilst the lanthanides in
the (+3) state dissolve as a solution of the chlorides.
Monazite is usually treated with NaOH at 150 ◦C to
remove phosphate as Na3PO4, leaving a mixture of the
hydrated oxides, which are dissolved in boiling HCl at
pH 3.5, separating the lanthanides from insoluble ThO2.
Sulfuric acid can also be used to dissolve the lanthanides.
 Separation
1. Chemical separation:
Chemical separations rely on using stabilities of unusual oxidation states
For example:
Cerium and europium may be extracted chemically :
Oxidise only Ce3+ to M4+ by HClO3 or KMnO4, then precipitate as CeO2 or
Ce(IO3)4.
Ce3 + Ce4+ Ce(IO3)4
ppt

e.g Oxidize only Ce3+ to Ce4+ (4f0) by HClO3 or KMnO4

On action of Zn/Hg, only Eu forms a stable M2+ that does

not reduce H2O, then isolate by precipitation as EuSO4

Eu3 + Eu2+ EuSO4

ppt
• Today, the separation of lanthanides on a technical
scale relies on two technologies:

• Ion exchange chromatography (small quantities of fast

and high purity materials)

• Solvent extraction (large quantities).

Ion exchange chromatography

It was found that if Ln3+ ions were adsorbed at the top of a cation-
exchange resin, then treated with a complexing agent such as
buffered citric acid, then the cations tended to be eluted in reverse
atomic number order.The anionic ligand binds most strongly to
the heaviest (and smallest) cation, which has the highest charge
density. A disadvantage of this approach when scaled up to high
concentration is that the peaks tend to overlap.
Ion exchange chromatography
To perform an ion-exchange separation, a solution of lanthanide ions is
induced at the top of the a cation-exchange column in the sodium form.
The Ln3+ ions readily undergo ion exchange displacing H+ or Na+ ions, thus
forming a band of the lanthanide ions bound to the top of the cation exchange
column. To remove these ions down the column and effect a separation,
a solution consisting ligands (complexing agent) such as citrate, lactate or
(NH4)3 EDTA-H . These ligands form complexes with the lanthanides.
Moreover, because the complexes possess lower positive charge than the
initial Ln3+, they are less tightly held by the resin Ln3+, and are displaced
from the ion exchange material into the surrounding solution. The equilibria
that are established between cations on the ion exchange resin (res) and
neutral or anionic complexes in solution can be summarized as follows. Initial
ion exchange displacement of the H+/Na+ and La3+ in a band at the top of the
column:
Ln3+ (aq) + 3Na+ (res) <----> Ln3+ (res) + 3Na+ (aq)
Subsequent elution with a solution of a complexing agent leads to formation
of neutral or negatively charged lanthanide complexes. To maintain
electroneutrality with the ion exchange resin sodium cations take place of
the neutral or negative lanthanide complex:
3Na+ (aq ) + Ln3+ (res) + 3 RCO2-(aq) <----> 3Na+ (res) + Ln(RCO2)3(aq)
The heavier, smaller lanthanide ions form stronger EDTA complexes so that
they are removed from the resin first, thus the lanthanides are eluted in order
of decreasing atomic number; with long columns, complete separations can
be achieved.
 2- Ion-exchange Chromatography methods
Ion-exchange methods makes use of the lanthanide contraction
The mixed lanthanides are loaded on to a cation-exchange resin and then
eluted with a suitable complexing agent like EDTA or citric acid
When a solution containing Ln3+(ions is poured onto a resin column,
the cation exchange with H+ ions

3H+(resin) + Ln3+(aq) Ln3+(resin) +3H+(aq)

The equilibrium distribution cofficient between the resin and aqueous solution
[Ln3+(resin) / Ln3+(aq)] is large for all ions. The resin bound Ln3+ are now
removed using a complexing agent such as EDTA4-. The formation constants
Of the EDTA4- complexes of the Ln3+ ions increase regularly from 1015.3 for
La to 1019.2 for Lu. Elute with H4EDTA, PH = 8, use long column, 99.9% pure
component can be separated
Heavier, smaller lanthanides are better Lewis acids removed from the resin
first in the order of their stability constants i.e. decreasing atomic number [The
cations tended to be eluted in reverse atomic number order]

The order in which as EDTA4- complexes of the heavier lanthanoids are

eluted from the column
A disadvantage of Ion exchange chromatography, when scaled up to high
concentration is that the peaks tend to overlap

Overlap of peaks at high concentration.

• Solvent extraction is used o give material with up to 99.9% purity.
• In 1949, it was found that Ce4+ could readily be separated from Ln3+ ions
by extraction from a solution in nitric acid into tributyl phosphate
[(BuO)3PO].

• The heavier lanthanides form complexes which are more soluble in the
aqueous layer. After the two immiscible solvents have been agitated
together and separated, the organic layer is treated with acid and the
lanthanide extracted. The solvent is recycled and the aqueous layer put
through further stages.
 Aqueous solution of the mixed lanthanide(3+) cations extracted into a non-polar
organic liquid (kerosene) - contains ca. 10% of bis(2-ethylhexyl)phosphinic
acid (DEHPA)

or
tri-n-butylphosphine oxide (TBPO)
(nBu3O)3P=O

DEHPA

As in the chromatographic process, smallest/heaviest lanthanides form the most

stable TBPO complexes and are extracted most efficiently in a series of
continuous counter-current extractions
For a lanthanide LnA distributed between two phases, a distribution coefficent
DA is defined:

DA = [LnA in organic phase] / [LnA in aqueous phase]

For two lanthanides LnA and LnB in a mixture being separated,

a separate on factor can be defined, where

β is very close to unity for two adjacent lanthanides in the Periodic Table
(obviously, the larger β is, the better the separation).
 Extraction is a separation technique based on differences in solubilities of
substances in two immiscible solvents (usually water and a water insoluble
organic solvent).

solubility in solvent 1
Kc = partition coefficient = ------------------------
solubility in solvent 2

Qustion-1
Given compound A, K (ether:water) = 4.0, how much of A can be extracted
from a solution of 10.0 g of A in 100 mL of water with a single portion of 100
mL of ether?

Qustion-2
same as above, but extract two times with 50 mL of ether each time

Question-3
Which is more efficient multiple extractions with smaller amounts of solvent or
a single extraction with the same total amount of solvent?
For electronic or spectroscopic use (‘phosphor grade’) 99.999% purity is
necessary, and currently ion-exchange is used for final purification to these
levels. The desired lanthanides are precipitated as the oxalate or hydroxide and
converted into the oxides by thermal decomposition

• The Gd-DEHPA complex is 12 times more soluble in

Kerosene than in water. What mass of the complex
will be extracted from 1.00 dm3 of aqueous solution
containg 25.00 g by shaking with 100 cm3 of
kerosene?
 • The Gd-DEHPA complex is 12 times more soluble in Kerosene than in
water. What mass of the complex will be extracted from 1.00 dm3 of
aqueous solution containg 25.00 g by shaking with 100 cm3 of
kerosene?

• The Kc (Hexane:water) = 8.0, how much of lanthanide salt can be

extracted from a solution of 10.0 g of lanthanide salt in 100 mL of water
with a single portion of 50 mL of Hexane?
4- Production of elemental metals
Ø Individual lanthanides prepared by metallothermic reduction of the
anhydrous lanthanide fluorides or chlorides with calcium metal

Ø Reaction is performed under argon and the product is a Ca/Ln alloy, from
which the Ca is removed by distillation.
Ø Metals with a tendency to form a divalent state (Sm, Eu, Yb) cannot be
made this way (only reduced to the 2+ state)

Ø Obtained by reduction of their oxides with lanthanum

Ø The divalent lanthanides are more volatile and can be removed by

distillation
(b.p.s of La, Sm, Eu, Y are 3457, 1791, 1597 and 1193oC respectively)
Properties of the Metals
metals are rather soft (later Ln are harder) and silvery white tarnish in air
due to their highly electropositive character
Mischmetal is the lanthanide alloy with the longest history. It is a
mixture of the lighter lanthanides, cerium in particular, which is
manufactured from an ‘unseparated’ mixture of the oxides.
CHEMICAL PROPERTIES OF THE COMPOUNDS OF VARIOUS
OXIDATION STATES Oxidation State (+3)
The trivalent state is characteristics of all the lanthanides.

Hydroxides:
Based on their reactivity, they react slowly with cold water, but more rapidly
on heating to form the hydroxide.

2Ln (s) + 6H2O (l) 2Ln(OH)3(aq) + 3H2 (g)

§ The hydroxides are precipitated as gelatinous precipitates by the

addition of NH4OH to aqueous solutions.

§ They can be obtained in the crystalline form by aging Ln2O3 in strong

alkali at high temperature and pressure.

§They are ionic and basic.

§ They are less basic than Ca(OH)2 but more basic than Al(OH)3

which is amphoteric.

§ The hydroxides are basic enough as to absorb CO2 and form

carbonates.

§ Ce(OH)3 is the most basic while Lu(OH)3 is the least basic.

§ The decrease in basic properties can be seen by dissolving the

hydroxides of the later members in hot concentrated sodium hydroxide

which produces complexes

Oxides:

§ The metals readily tarnish in air and on heating in oxygen, they

all give the oxides, Ln2O3 which resembles Ca to Ba group.

§ Cerium alone forms CeO2.

§ Their oxides are also ionic and basic and readily reacts with

water to give the hydroxides.

 Preparation Oxides

The common sesquioxides, Ln2O3, can be made by heating lanthanide

metals in air or heating oxy-compounds such as nitrate or carbonate

Ce, Pr and Tb form LnO2 (i.e. Ln4+) under these conditions but may be
reduced to Ln2O3 with H2.
Oxide superconductors
1986 Bednorz and Müller (Nobel Prize)
La2-xBaxCuO4 became superconducting (i.e. zero resistivity) at 30
K (23 K Nb3Ge was the ‘record’ at that time.)

Niobium-germanium (Nb3Ge) is an intermetallic chemical

compound of niobium (Nb) and germanium (Ge).
Ln2O3 may be divided into three structural types
A-type - light Ln B-type - middle Ln
unusual LnO7 capped-octahedra LnO7 units

LnO7 capped-octahedra

LnO7 units

C-type - heavy Ln
LnO6 units, but not octahedra
(face & body - divacant cubic)

LnO6 units
Divalent oxides, LnO
LnO of (Nd), Sm, Eu and Yb prepared by reduction of Ln2O3 with
the elemental lanthanide at high temperature (800-2000 oC).
EuO and YbO insulating (i.e. genuine Ln2+ O2-)
lustrous golden yellow NdO and SmO are electrically conducting

Tetravalent oxides LnO2

§ LnO2 known for Ce, Pr and Tb - adopt the fluorite structure
CeO2 (Ceria), white when pure but is usually pale yellow (sub-
stoichiometry)
§ catalytic converters catalysing the oxidation of unburnt hydrocarbons
and converting CO to CO2.
In solid state chemistry, the fluorite structure refers to a common motif for
compounds with the formula MX2. The X ions occupy the eight tetrahedral interstitial
sites whereas M ions occupy the regular sites of a face-centered cubic (FCC) structure
Halides:

The anhydrous halides LnX3 can be prepared by heating the metal and

the halogen. It can also be prepared by heating the oxide with an excess

of ammonium halide.

Ln2 O3 + 6NH4Cl 300 C 2LnCl3 + 6NH3 + 3H2 O

 LnF3

§ The fluorides are of particular importance among the halides, because

of their insolubility. Addition of HF acid or Na+F- precipitates the fluorides
from the Ln3+ solutions and this is a characteristic test for lanthanides.

§ The fluorides, particularly of the heavier lanthanides (with smaller Ln

ions) are slightly soluble in excess HF owing to formation of soluble
complex,
[LnF (H2 O)n] 2+ .
 LnCl3

The chlorides are deliquescent, soluble in water from which they crystallize

as hydrates (with Ce to Nd having 7H2O and Nd to Lu having 6H2O). If the

hydrated halides are heated, they form oxohalides instead of dehydrating to

anhydrous halides. However cerium gives CeO2. The bromides and iodides

are similar to chlorides.

LnCl3.6H2O Heat LnOCL + 5H2O + 2HCl

Oxohalides
Larger lanthanides LnF3 (Ln = La–Pm) ‘tysonite’ (LaF3) structure
Ln3+ is coordinated by nine F-, further two F- at a slightly longer
distance.

tricapped
trigonal prism

Post-Pm all LnF3 have the YF3 structure eight close contacts, one
longer Ln-F distance

bicapped
trigonal prism
Divalent halides LnX2
Occurrence of dihalides parallels the high values for the third ionisation
energy depends upon the oxidizing power of the halogen (iodides most
numerous!)
Synthetically useful iodides of the ‘divalent’ lanthanides (Sm,Eu,Yb)I2 are
obtained from thermal decomposition of LnX3 or by reaction of NH4I and the Ln
metal in liquid NH3

Ln + 2LnX3 3 LnCl2
All LnX2 are easily oxidized liberate H2 from H2O (Except for EuX2
which is stable in aqueous solution.)
The diiodides of Eu, Sm and Yb are common and very useful starting
materials in further (e.g. organometallic) syntheses
Tetravalent halides LnX4
Fluorides of Ce(IV), Pr(IV) and Tb(IV) - only CeF4 is thermally stable.
Coordination chemistry of the lanthanides

Ln3+ forms complexes of high coordination numbers. The

coordination numbers for [Ln(OH2)n] 3+ in aqueous solution are up to

9 for the early lanthanoids and 8 for the later smaller members.

The Ln3+ ions readily form complexes with F- and O-donor ligands

with H2O, EDTA, β-diketonate, citric acid, oxalic acid ligands

4f orbitals are deep-seated and hence little involved in ligand binding.

Bonding in lanthanide complexes:

- ionic in nature

- largely non-directional
1) Lanthanide ions behave as hard Lewis acids - high affinity for hard
bases such as F- and H2O.

2) Bonding is largely non-directional and electrostatic in origin.

Coordination geometries are determined by the size and shape (steric
demands) of the coordinating ligands.

3) The f-elements form large cations and thus support high coordination
numbers - size of the Ln3+ cations decreases across the series leading to
higher charge densities and stronger ionic bonds for the heavier
members
Stability constants of lanthanide complexes

A stability (formation) constant, K1, can be written for any

complexing reaction between a Ln3+ ion and a ligand Ln–.
Complexes with water

LnCl3 in H2O forms of [Ln(H2O)x]3+ x = 8 or 9 (coordination numbers up to 12 have

been found)

Aqueous solutions are acidic (at pH < 7) as a result of hydrolysis

Due the highly polarising nature of the Ln3+ cations occurs increasingly as the Ln3+
ions reduce in size (i.e. from La to Lu increasing charge density)
 Chelate and macrocyclic complexes

Polydentate ligands form especially stable complexes chelate effect

Coordination complexes
no (or negligible, 100 cm-1 vs 10000 – 20000 cm-1 for typical d element
complexes)crystal field stabilization can occur between the lanthanide 4f
and ligand orbitals.

no particular shape or coordination geometry is preferred

Coordination geometries therefore are largely determined by the size and
shape(steric demands) of the ligands.

Coordination numbers between extremes of 3 and 12 have been

observed in Ln3+complexes higher coordination numbers being the more
common.
‫ﻣرﻛﺑﺎت ﻣﻌﻘدة ﺑﻌدد ﺗﻧﺎﺳﻘﻲ )‪ :(6‬ﻣن اﻷﻣﺛﻠﺔ ﻋﻠﻰ ھذا اﻟﻧوع ‪-‬‬

‫ﺣﯾث ﺗرﺗﺑط ذرة اﻟﻣﻌدن ﺑﺳت ذرات أﻛﺳﺟﯾن ﻣن ﺛﻼث مرﻛﺑﺎت‪ ,‬وﻻ ﯾذوب ھذا اﻟﻣﻌﻘد ﻓﻲ اﻟﻣﺎء ‪-‬‬
‫وإﻧﻣﺎ ﯾذوب ﻓﻲ اﻟﻣذﯾﺑﺎت اﻟﻌﺿوﯾﺔ‪.‬‬
‫‪O‬‬ ‫‪O‬‬ ‫ﻣرﻛﺑﺎت ﻣﻌﻘدة ﺑﻌدد ﺗﻧﺎﺳﻘﻲ )‪- :(6‬‬

‫‪acetylacetone‬‬
‫‪acac‬‬

‫ﺣﯾث ﺗرﺗﺑط ذرة اﻟﻣﻌدن ﺑﺳت ذرات أﻛﺳﺟﯾن ﻣن ﺛﻼث ﻣرﻛﺑﺎت‪ ,‬وﻻ ﯾذوب ھذا اﻟﻣﻌﻘد ﻓﻲ اﻟﻣﺎء وإﻧﻣﺎ ﯾذوب ﻓﻲ ‪-‬‬
‫اﻟﻣذﯾﺑﺎت اﻟﻌﺿوﯾﺔ‪.‬‬
‫‪H‬‬
‫‪H3 C‬‬

‫‪C‬‬
‫‪C‬‬ ‫‪CH3‬‬
‫‪H 3C‬‬ ‫‪O‬‬

‫‪C‬‬ ‫‪O‬‬
‫‪O‬‬
‫‪La‬‬
‫‪H‬‬
‫‪C‬‬ ‫‪O‬‬ ‫‪O‬‬

‫‪O‬‬ ‫‪C‬‬ ‫‪CH 3‬‬

‫‪H 3C‬‬
‫‪C‬‬

‫‪H3 C‬‬
‫‪H‬‬
 ‫ھذا اﻟﻣﻌﻘدات ﺗذوب ﻓﻲ اﻟﻣﺎء‬

La(H2O)93+ (aq) + EDTA4-(aq) La(EDTA)(H2O)3– + 6H2O

 - :(3) ‫ﻣرﻛﺑﺎت ﻣﻌﻘدة ﺑﻌدد ﺗﻧﺎﺳﻘﻲ‬

Requires the use of very bulky ligands

 - :(12-9) ‫ﻣرﻛﺑﺎت ﻣﻌﻘدة ﺑﻌدد ﺗﻧﺎﺳﻘﻲ‬

All-faced capped trigonal prism

Bicapped square antiprism

Three-face centred trigonal prism,

Organometallic compounds
The organometallic compounds of the lanthanoids are dominated by good donor
ligands, with complexes of acceptor ligands being rare. This is attributed to

♦ The lack of orbitals because the 5d orbitals are empty and the 4f orbitals are
buried so this restricts the number of bonding modes that are available to the
lanthanoid ions.
♦ The strong electropositive nature of the lanthanoids means they need good
donor (eg alkoxide and halide ligands which are both σ and π donors), not
good acceptor ligands(eg CO and phosphine ligands which are both σ donors
and π acceptors)
♦ The bonding in the organometallic lanthanoid complex that do form is mostly
ionic
♦ All organometallic complexes are strong Lewis acids and are very sensitive to
air and moisture.
Examples of organometallic lanthanoid compounds:

Ln(Cp)3 compounds (Cp-cyclopentadienyl compounds)

Sm(η5-Cp)3 Sm(η1-Cp)(η5-Cp)2 this exists in equilibrium

Sm(η5-Cp*)3

These complexes contain Ln3+ ion with a limited number of Ln2+ compounds. Cp groups are

electrostatistically bound to a central cation.

Other examples are η8- Cyclooctatetraene ligands eg Ce(C8H8)2.
 •C

cyclopenta-1,3-diene Cyclopentadienyl
 Applications of lanthanide complexes ‫اﻟﻣرﻛﺑﺎت اﻟﺣﺎﻓزة‬

‫اﻛﺎﺳﯾد اﻟﻼﻧﺛﺎﻧﯾدات ﺗﺳﺗﺧدم ﻻﻛﺳدة ﻏﺎز اﻟﻣﯾﺛﺎن‬

Oxides of the lanthanides

LnO7 capped-octahedra LnO7 units LnO6 units

 ‫اﻣﻼح اﻟﻼﻧﺜﺎﻧﯿﺪات ﺗﺴﺘﺨﺪم ﻻﻛﺴﺪة اﻟﻤﺮﻛﺒﺎت اﻟﻌﻀﻮﯾﺔ‬

‫‪H‬‬

‫‪MeO‬‬ ‫‪C‬‬ ‫‪C‬‬ ‫‪OMe‬‬

‫‪OH O‬‬

‫‪-H+‬‬ ‫‪Ln(NO3)3‬‬

‫‪MeO‬‬ ‫‪C‬‬ ‫‪C‬‬ ‫‪OMe‬‬

‫‪O‬‬ ‫‪O‬‬
 ‫ا ﻛﺳدة اﻟﻛﺣول اﻟﺛﺎﻧوﯾﺔ‬

[Ce(NH4)2(NO3)6] (CAN)

Ceric ammonium nitrate

NMR SHIFT REAGENTS
Most Ln3+ complexes are strongly paramagnetic
do not give useful NMR spectroscopic data - unusual shifts and
broadened

• PARAMAGNETIC MATERIALS
• Paramagnetic materials by shortening relaxation times cause
line broadening.
• They also cause a shift in signals.
• Co and Ni cause severe line broadening thus cannot be used.
• Lanthanide ions are found to cause shifts without line
broadening
lanthanide shift reagents – can be added to diamagnetic samples and
induce chemical shift changes via through space interactions

• SHIFT REAGENETS
• The shift reagents reduce the shielding of all protons.
• The shift increase with the proximity of the protons to the
shift reagents.
• The OH proton may be shifted more than 20 ppm.

R = t-butyl, -CF2CF2CF3,
 Magnetic resonance imaging (MRI)

contrast in a magnetic resonance image (MRI) is due to

the different relaxation times of water protons in
different environments within the body

What Makes a Good MRI Agent?

The choice is dictated by a combination of several factors:
1. High magnetic moment;
2. Long electron-spin relaxation time;
3.Low toxicity;
4. High solubility in water;
5. Targeting tissue;
6. Coordinated water molecules;
Gadolinium(III) compounds are especially suited to this. The Gd3+ ion has a large number of unpaired electrons (S = 7/2)
and moreover its magnetic properties are isotropic. It has a relatively long electron-spin relaxation time, ∼10−9 s, which
makes it more suitable than other very paramagnetic ions such as Dy3+, Eu3+, and Yb3+ (∼10−13 s). These factors are very
favourable for nuclear spin relaxation.
Protons with short relaxation times give rise to
brighter images enhance the contrast in a

magnetic resonance image with ‘contrast agent’

 Protons with short relaxation times
give rise to
brighter images enhance the
contrast in a magnetic resonance

image with ‘contrast agent’

MRI of breast without contrast agent MRI of breast after injection of 0.1
mmol kg-1 [Gd(DTPA)]2-
Q2
• Suggest structures for CN10 and 9.
• Which element will have a higher coordination number, Ce or Yb?
• Which one has more stability constant
Ln with OH or Ln with EDTA, why?