CHEM 252 : Lanthanides

Lecture 2
 What are Lanthanides?
• The elements with Z=58-71
NAME SYMBOL ATOMIC ELECTRONIC ELECTRONIC EO/V RADIUS
NUMBER CONFIGURATION CONFIGURATION OF M3+
OF ATOM OF M3+ ION ION/Å
Lanthanum La 57 [Xe]5d6s2 [Xe] -2.37 1.17
Cerium Ce 58 [Xe]4f15d6s2 [Xe] 4f1 -2.34 1.15
Praseodynium Pr 59 [Xe] 4f36s2 [Xe] 4f2 -2.35 1.13

Neodynium Nd 60 [Xe] 4f46s2 [Xe] 4f3 -2.32 1.12

Promethium Pm 61 [Xe] 4f56s2 [Xe] 4f4 -2.29 1.11
Samarium Sm 62 [Xe] 4f66s2 [Xe] 4f5 -2.30 1.10
Europium Eu 63 [Xe] 4f76s2 [Xe] 4f6 -1.99 1.09
Gadolinium Gd 64 [Xe] 4f75d6s2 [Xe] 4f7 -2.29 1.08
Terbium Tb 65 [Xe] 4f86s2 [Xe] 4f8 -2.30 1.06
Dysprosium Dy 66 [Xe] 4f106s2 [Xe] 4f9 -2.29 1.05
Holmium Ho 67 [Xe] 4f116s2 [Xe] 4f10 -2.33 1.04
Erbium Er 68 [Xe] 4f126s2 [Xe] 4f11 -2.31 1.03
Thulium Tm 69 [Xe] 4f136s2 [Xe] 4f12 -2.31 1.02
Ytterbium Yb 70 [Xe] 4f146s2 [Xe] 4f13 -2.22 1.01
Luthetium Lu 71 [Xe] 4f145d6s2 [Xe] 4f14 -2.30 1.00
 What are Lanthanides?
• The lanthanides are all very reactive and
electropositive.
• The chemistry is dominated by the +3
oxidation state.
• Despite the high charge, the large size of the
Ln(III) ions results in low charge densities and
their compounds are predominately ionic in
character.
 What are Lanthanides?
• Abundance & Distribution
– They are naturally occuring and abundant except
Prometheum (147Pm, t1/2 = 2.6 years) which is
produced artificially.

• e.g. La, Ce & Nd are more common than Pb

 What are Lanthanides?
• Most-common minerals from which they are
obtained:
– monazite & xenotime (mixed La, Th, Ln
phosphates)
• widely-distributed, concentrated in sand & river beds
due to relative insolubility
– bastnaesite (a La, Ln fluorocarbonate MIIICO3F)
 What are Lanthanides?
• Elemental Proportions of Rare Earth-Content
of Minerals

% of Ln as: La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

monazite 22 45 5 17 4 0.1 2 0.2 1 0.1 0.4 - 0.2 -

xenotime 0.5 5 0.7 2.2 1.9 0.2 4 1 8.6 2 5.4 0.9 6.2 0.4

basnaesite 32 49 4.4 13.5 0.5 0.1 0.3 - - - 0.1 - - -

 What are Lanthanides?
Abundance of lanthanides in nature
 What are Lanthanides?
Abundance of lanthanides in nature
– abundance shows even-odd alternation with
atomic number

– mirrored by several/few alternation of

number of stable isotopes with even/odd Z
 Extraction of Lanthanides?
Alkali Digestion of Acid Dissolution of Bastnaesite
Monazite/Xenotime
 Separation of lanthanides
1. Cerium & Europium may be extracted
Chemically:
• Oxidize only Ce to M4+ by adding HClO or
KMnO4, then precipitate as CeO2 or Ce(IO3)4
• On action of Zn/Hg only Eu forms a stable M2+
that doesn't reduce H2O, then isolate by
precipitation as EuSO4
 Separation of lanthanides
2. Separation by Fractionation:
• Small Scale methods used originally include:
– Fractional Crystallization of e.g.
Ln(NO3)3.2NH4NO3.4H2O
or
Ln(BrO3)3

– Fractional Thermal Decomposition of e.g. Ln(NO3)3

 Separation of lanthanides
• Current Small Scale Lab. Separation:
– Ion-Exchange Displacement Column
• Ln3+(aq) are strongly adsorbed by a cation-exchange
resin
– Add an eluant ligand

EDTA HIB{[[alpha]]-hydroxyisobutyric acid}

Separation of lanthanides

Ion-exchange chromatography
 Separation of lanthanides
• Ligand binds most strongly to smallest ion
– e.g. the binding constants of the Ln(EDTA)
complexes

Elution order is Lu to La
 Separation of lanthanides
Current Large Scale Industrial Separation:
• Solvent Extraction
– Ln3+(aq) is extracted in a continuous counter-
current process into a non-polar organic liquid
(e.g. kerosene)
• the kerosene contains ca. 10% of bis(2-ethylhexyl)
phosphinic acid (DEHPA) or
• tri-n-butylphosphine oxide (TBPO) (nBu3O)3PO

• solubility of Ln3+ in organic solvent increases

with its Relative Atomic Mass
 Production of elemental metals

La, Ce, Pr, Nd, Gd:

2MCl3 + 3Ca 2M + 3CaCl2 (T > 1000 °C)

Tb, Dy, Ho, Er, Tm, Y:

2MF3 + 3Ca 2M + 3CaF2 (MCl3 is too
volatile)
 Production of elemental metals

Pm:
PmF3 + 3 Li Pm + 3LiF

Eu, Sm,Yb:
M2O3 + 2La 2M + La2O3 (MCl3 reduced to MCl2
by Ca)