Professional Documents
Culture Documents
Elements
Gd
Eu
Gd
4fz3
Master degree course, SCGC
Jean-Claude Bünzli
2008
Pedagogical objective 3
Chapter 1 f-Atoms and ions 4
Chapter 2 Physico-chemical properties 52
Chapter 3 Coordination chemistry 121
Chapter 4 Organometallics 205
Chapter 5 Selected applications 247
Appendices
1 2 3 4 5 6 7 8
• Overview of f-elements 1
S P
properties, with 2
D
reference to their uses 3
in daily life and high 4 3d
technology applications 5 4d
6 5d
7 6d
• Mainly focused on
4f-elements F
4f
Pre-requisites 5f
Coordination chemistry
Quantum chemistry
Table
Table of
of Contents
Contents
Chapter
Chapter 1.
1. f-Atoms
f-Atoms and
and Ions
Ions
1.1 Definitions and discovery
Lanthanides: 58-71 Ln
Actinides: 90-103 An
Parent elements La and Ac often included in Ln and An
Rare earths: Sc, Y, La + Ce-Lu
lanthanides: Ce-Lu
lanthanoids: La-Lu
4f rare earths
5f actinides
Chemical separation
of yttrium
Be2FeY2SiO10
HNO3 / HCl
K2CO3, pH = 4-5
Be(OH)2,FeCO3
Y3+ taken as Al
1.2 Occurrence of
4f elements Abundance in cosmos
relative to silicon:
The elements are “rare” Si = 106
but not rarer than many
others, such as Au, Pt,
Pd, Rh, for instance
La-Lu
Natural abundance
50 Ce 50
Abundance in earth’s crust
40 expressed in ppm (g/ton) 40
30 Nd 30
Odd/even effect
20 20
La Sm Gd
10 Dy Er Yb 10
0 Pr 0
Eu Tb Ho Tm Lu
56 58 60 62 64 66 68 70 72
Atomic number
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 12
Chapter 1 f-Atoms and Ions
Main resources
World resources are estimated to 83 million metric tons
for a present usage of about 40’000 metric tons a year
China 50 % (?)
Russia 25 % (?)
USA 10 %
Australia 5 %
Other 10 %
Baotou (Inner
Mongolia)
Applications of 4f-elements
• Catalysts
- cracking of hydrocarbons
- conversion of exhaust gases (gasoline and diesel)
• Metallurgy
- Steel production (removal of O, S)
- Nodular graphite
- Hardener (e.g. in magnesium)
• Materials
- High temperature superconducting ceramics
- Electronic devices (capacitors, O2-sensors)
- Magnets (Sm5Co, Nd5Fe)
- Neutron moderators in nuclear reactors
- Hydrogen storage with metal hydrides
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 15
Chapter 1 f-Atoms and Ions
Gas filtration
CeO2
Soot CeO2
particles
Gaz
Gas produced by
the engine filtrés
EOLYS®
Soot emission of Diesel
engines reduced by 99.9 %
fluorescent lamps
Er amplifier
for optical fibers rechargeable batteries
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 18
Chapter 1 f-Atoms and Ions
Re-inforced
pigments cast Al pistons
MRI images
xz2 yz2 z3
T2u
A2u
xyz
T1u
z
y x
z 3
y 3
x 3
Lanthanides
• Sc, Y and La introduce the 3d, 4d and 5d transition
series: nd1(n+1)s2 n=3 (Sc), 4 (Y) and 5 (La)
inner nature of
4f (Nd3+) and
5f (U3+) orbitals
Y (Z = 39)
-2.3 Lu
Sc (Z = 21, E ored = -2.08 V )
atomic number
-2.2
55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 25
Chapter 1 f-Atoms and Ions
Main
Main reason:
reason: the
the fourth
fourth ionization
ionization energy
energy isis larger
larger
than
than the
the sum
sum of
of the
the first
first three
three ones;
ones;
this
this extra
extra energy
energy cannot,
cannot, inin most
most cases,
cases,
be
be compensated
compensated by by bond
bond formation
formation
Explanation:
Upon ionization, all of the valence orbitals (4f, 5d, 6s)
are stabilized, but to variable degrees.
4f orbitals are stabilized most and 6s least.
After removal of three electrons, the remaining are very
tightly bound
YbII 4f14
EuII 4f7
Gd II
4f 5d
7 1 LuII 4f145d1
1.2
III
1.1 Yb
1.0
0.9
CN
0.8
6 7 8 9 10 11 12
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 32
Chapter 1 f-Atoms and Ions
1.85 Ce Pr Nd
PmSm Gd
Tb Dy
1.80 +3 Ho Er
Tm Lu
1.75
atomic number
1.70
56 58 60 62 64 66 68 70 72
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 33
Chapter 1 f-Atoms and Ions
common
other
solid state only
I4
I3
I2
8 E0 / V
[Rn]4f7
6
4 An4+ / An3+
2 An3+ / An2+
0
-2
-4
-6
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
r / pm
An3+
An4+
An5+
Nuclear fission
91
Kr
36
235
92 U
1
0n
thermal neutron
ca. 2 kJmol-1
142
36 Ba
The nucleus mass is smaller than the sum of the masses of its
constituting particles (neutrons, protons), due to the nuclear forces.
Henceforth the concept of “cohesion energy”, usually given per
nucleon:
Kr
1 MeV = Ba
1.610-13 J
fission
fusion
Isotope separation
• Gaseous diffusion of UF6 through Al or Ni membranes
(pore size 10-25 nm). Graham’s law:
235
1 v ( UF6 ) 352
v diff ∝
diff
α= = = 1.0043
MW
238
vdiff ( UF6 ) 349
[UO2(NO3)2(TBP)2]
Plutonium-Uranium
PUREX [Pu(NO3)4(TBP)2 Refining by EXtraction
FeII
[UO2(NO3)2(TBP)2] PuIII(aq)
HNO2
PuIV(aq)
UO3 oxalic acid
H2 300 oC
UO2 PuO2
0.8
0.8 kg
kg minor
minor 957
957 kg
kg UU 33
33 kg
kg fission
fission
actinides
actinides 10 products
products
10 kg
kg Pu
Pu
Np, Am, Cm Zr 3.6 kg
420 g 30 g of which Cs 2.7 kg
2 kg Tc 0.8 kg
320 g radioactive Sm 0.8 kg
Se, Sn, I 0.3 kg
Radioactive Xe, 3H2
Other non radioactive
MSc: f-Elements, Prof. J.-C. Bünzli, 2008
24.8 kg
47
Chapter 1 f-Atoms and Ions
Other
Other fission
fission
products
products DIAMEX
Glass Am,
Am, Cm,
Cm, Ln
Ln
LnIII(aq) SANEX
Am
AmIII,, Cm
III III
CmIII N
Selective Actinide N N
EXtraction N
Am Cm N N
N S
P O O
N N SH P
N
N
N N
calix[4]arene-CMPO
OCH3
O O
O O
O
OCH3
H3CO
P
O
H
N O
OR 4 separation
R = C3H7 MSc: f-Elements, Prof. J.-C. Bünzli, 2008 50
Chapter 1 f-Atoms and Ions
Future developments
Grouped separation allowing
separation of all An which
are then inserted into a
matrix and irradiated by
high- velocity neutrons
(breeder reactor) – if
politically accepted.
Ionic liquids
N N
X-
Reprocessing
plant in La Hague