Chem 435

Lanthanides, Dr. Usama El-Ayaan

s block

Electronic Structure
p block

d block

105

Db

107

Bh

f block

Lanthanides, Dr. Usama El-Ayaan

Lanthanides, Dr. Usama El-Ayaan

Atomic No.

Name

Symbol

Ce

58

58

Cerium

Ce

Pr

59

59

Praseodymium

Pr

Nd

60

60

Neodymium

Nd

Pm

61

61

Promethium

Pm

Sm

62

62

Samarium

Sm

Eu

63

63

Europium

Eu

Gd

64

64

Gadolinium

Gd

Tb

65

65

Terbium

Tb

Dy

66

66

Dysprosium

Dy

Ho

67

67

Holmium

Ho

Er

68

68

Erbium

Er

Tm

69

69

Thulium

Tm

Yb

70

70

Ytterbium

Yb

Lu

71

71

Lutetium

Lu

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Lanthanides, Dr. Usama El-Ayaan

Lanthanides, Dr. Usama El-Ayaan


Element

Symbol

Atomic Number

Electronic Configuration

Cerium

Ce

58

[Xe]4f15d16s2

Praseodymium

Pr

59

[Xe]4f36s2

Neodymium

Nd

60

[Xe]4f46s2

Promethium

Pm

61

[Xe]4f56s2

Samarium

Sm

62

[Xe]4f66s2

Europium

Eu

63

[Xe]4f76s2

Gadolinium

Gd

64

[Xe]4f75d16s2

Terbium

Tb

65

[Xe]4f96s2

Dysprosium

Dy

66

[Xe]4f106s2

Holmium

Ho

67

[Xe]4f116s2

Erbium

Er

68

[Xe]4f126s2

Thulium

Tm

69

[Xe]4f136s2

Ytterbium

Yb

70

[Xe]4f146s2

Lutetium

Lu

71

[Xe]4f145d16s2

4f electrons are very effectively shielded by the 5S and 5p electrons, consequently the 4f electrons do not take
part in bonding.
Lanthanides, Dr. Usama El-Ayaan


14
4f.
(
1907 ).

The Rare Earth Elements (.
La, Ce & Nd .)Pb

Lanthanides, Dr. Usama El-Ayaan


Monazite
)(LnPO4
78%

Ce, Pr,
Nd.

bastnaesite
)(LnCO3F
.22%

Lanthanides, Dr. Usama El-Ayaan

Natural Abundance

.
Lanthanides, Dr. Usama El-Ayaan

Lanthanides, Dr. Usama El-Ayaan


: Extraction

: Separation

Lanthanides, Dr. Usama El-Ayaan

----

Extraction

Alkali
Digestion

 Acid
Dissolution


f
,d,p,s

) (III


Y, Sc

SOLUBILITY

BASICITY

STABILITY

) Ce(IV), Eu(II )(III





2Ln(NO3)3.3Mg(NO3)2.2H2O
( )
( )
Ln(NO3)3.2NH4NO3.4H2O
( )

( Lns
) )(like dissolves like

( )

OH-

Ln(OH)3

M+




( )

the binding constants of the Ln(EDTA) complexes

-------Lu+3

La+3 --------

mixture
p
r
o
c
e
s
s

ppt
(more pure)
process

ppt pure

Triangle

separation technique

ppt
(Mixture)

Soln.
(Mixture)

process

process

Soln.
(more pure)

ppt
(more pure)
process

Soln.
(more pure)
process

Soln.pure

fractional crystalization

Solvent Extraction

Ln(NO3)3

(BuO)3PO4 tributylphosphate

) ( (distribution coefficient (

Fractional precipitation

Ln(OH)3

NaOH

HCl
NaOH

( )

.

Lu

La

Thermal dissociation

Lu+3

La+3

Ion exchange chromatography

column
stationary phase :

( , R--M+ ) R+-X-

: eluent
rate of flow

sample
effluent

Ion exchange chromatography

.......


e.g. the binding constants of the Ln(EDTA) complexes

Elution order

is Lu La

Change in oxidation state

)(III

) (II), (IV
) (III

Change in oxidation state

Ce
Ce+4

KMnO4

Ce(OH)4

CeO2

Ln+3


Eu
Eu+2

(
) Ca, Sr, Ba

Change in oxidation state

Zn/Hg

H2SO4

EuSO4

Ln+3