MSC Fe Lem Chapter 1

f - Elements
Gd
Eu
Gd
4fz3
Master degree course, SCGC
Jean-Claude Bünzli
2008
Section of chemistry and chemical engineering

Laboratory of lanthanide supramolecular
chemistry
MSc: f-Elements, Prof. J.-C. Bünzli, 2008 1
Table of contents
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

Pedagogical objective
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

Chapter 1 f-Atoms and Ions
Table of Contents
1.1 Definitions and discovery

1.2 Occurrence of 4f elements
1.3 Basic properties
1.3.1 Electronic configuration
1.3.2 Oxidation states of 4f elements
1.3.3 Oxidation states of 5f elements
1.4 Radioactivity of 5f elements
Nuclear fuel Particle filter

rod assembly for Diesel exhaust
gases
Chapter 1. f-Atoms and 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
Discovery of rare earths

1794 (Y) – 1947 (Pm)
Discovery of actinides
1789 (U) – 1971 (Lr)
Naturally occurring: Ac, Th, Pa, U, (Np, Pu)

1.1 The discovery of 4f-elements
lanthanides: Ce-Lu
lanthanoids: La-Lu
4f rare earths
5f actinides
Yttrium was discovered in 1794 by Johan Gadolin, in Åbo (Turku)
Discovery of yttrium (1794)

1787 Carl Axel Arrhenius, an artillery lieutenant and
amateur geologist, finds a black mineral in a quarry
near Ytterby, 30 km from Stockholm.
1788 B. R. Geijer (Stockholm) describes the mineral
(d = 4.2) and names it ytterbite, presently known
as gadolinite, with formula Be2FeY2SiO10.
1792 J. Gadolin (1760-1852) studies the mineral and
publishes a 19-page report in 1794 in the
Proceedings of the Royal Swedish Academy of
Sciences, concluding to the presence of a new
“earth”, which he names yttrium.
Subsequent work revealed that yttrium contained the oxides of 10

other elements.

Chemical separation
of yttrium
Be2FeY2SiO10
HNO3 / HCl
Fe3+, Be2+, Y3+ SiO2
K2CO3, pH = 4-5
Be(OH)2,FeCO3
Y3+ taken as Al
NH3, pH = 7-8 Fe(OH)3

O2, H2O
Y(OH)3
Johan Gadolin, 1794

Discovery of cerium (1804)
1751 The mineralogist Cronstedt finds a peculiar heavy stone

near Batnäs.
1803 W. Hisinger and J. J. Berzelius analyse this stone and
find it contains an unknown “earth” they name ceria
after the recently discovered planet Ceres. Their
finding is published in 1804 in a 24-page report and
confirmed by the German chemist Klaproth.
The silicate material has a variable composition close

to (Ce,La)3MIIH3Si3O13 and is presently named cerite
(M = Ca, Fe).

Other rare earths (1839-1947)
Most of the other rare earths have been discovered by further

analysing the two initial minerals, gadolinite and cerite.
The main techniques were fractional precipitation and

crystallisation, as well as flame spectroscopy (absorption and
emission).
These operations were tedious: for instance, 20 tons were
needed to produce 82 mg of element 61 by ion-exchange
separation techniques (61 = radioactive promethium), that is a
fraction equal to 4x10-12 !)

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
Main resources (4f elements)
Cerium group (lighter elements)

Bastnasite Ln(CO3)F 65-70%
Monazite LnPO4 50-75%

Cerite (Ce,La)3MIIH3Si3O13 50-70%
Yttrium group (heavier elements)

Xenotime LnPO4 55-65%
Gadolinite Ln2M3Si2O10 35-50%
Euxenite Ln(Nb,Ta)TiO6xH2O 15-35%

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

Gas filtration
CeO2
Soot CeO2
particles
Gaz
Gas produced by
the engine filtrés
EOLYS®
Soot emission of Diesel
engines reduced by 99.9 %

• Optics and lighting

- Polishing powders
- Protection against sun (sunglasses)
- Lasers, particularly Nd YAG
- Phosphors for displays (incl. electrolumin. displays)
- Fluorescent lamps
• Medicine
- Seasickness (Ce oxalate), thromboses (Nd oxalate)
- Renal insufficiency (La2(CO3)3.4H2O)
- X-ray intensifying screens
- NMR imaging
- Cancer radio- and photo-therapy
- Laser surgery (Nd YAG laser)
- Luminescent immunoassays
• Science
- Shift reagents, luminescent and magnetic probes
- Catalysts for organic chemistry
fluorescent lamps
Er amplifier
for optical fibers rechargeable batteries
Re-inforced
pigments cast Al pistons
MRI images

1.3 Basic properties

1.3.1 Electronic configuration
4f-orbitals
x(x2–3y2)
y(3x2–y2) xyz z(x2–y2)
xz2 yz2 z3

4f-orbitals (in octahedral symmetry)
T2u
A2u
z(x2-y2) y(z2-x2) x(z2-y2)
xyz
T1u
z
y x
z3 y3 x3
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)
• The energy of the 4f orbitals decreases abruptly

beyond La: -0.95 eV for La, -5 eV for Nd !
which leads to the filling of the 4f shell
• The 4f orbitals lie outside the Xe electronic structure

for La, but inside the Xe electronic structure for the
other Ln elements
Actinides
• Similarly, the 5f orbitals are also “inner orbitals”

inner nature of
4f (Nd3+) and
5f (U3+) orbitals

1.3.2 Oxidation states

of 4f elements
Ln0 4fN-1 5d1 6s2

La, Ce, Gd, Lu
4fN 6s2
Pr-Eu,Tb-Yb
LnII 4fN-1 5d1

La, Gd
4fN
Ce-Eu, Tb-Yb
4fN-1 6s1
Lu
LnIII 4fN-1 (no exception)
Slide 210 MSc: f-Elements, Prof. J.-C. Bünzli, 2008 24
Oxidation states of 4f elements

• The more stable oxidation state of Ln is +3
-2.7
-2.6 Eored : Ln3+(aq) + 3 e- D Ln(s)

La
-2.5
Volts
Tb
-2.4
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
Main reason: the fourth ionization energy is larger

than the sum of the first three ones;
this extra energy cannot, in most cases,
be compensated by bond 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

4600
I1 + I2 + I 3
4400 I4
4200
-1
I / kJmol
4000
3800
3600
3400
Ce Pr Pm Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Oxidation states of 4f elements
• Ce, Pr, Nd and Tb may have +4 oxidation state

E 0red for Ln4+(aq) + e- D Ln3+(aq) in acidic solutions:
+1.72 V for Ce4+, stable in water
+3.20 V for Pr4+, oxidizes water
+3.10 V for Tb4+, oxidizes water
• Sm, Eu, and Yb have a relatively stable +2 state

E 0red for Ln3+(aq) + e- D Ln2+(aq) in acidic solutions:
-0.35 V for Eu2+, stable in water
-1.15 V for Yb2+, reduces water
-1.56 V for Sm2+, reduces water

Ln3+ + e- D Ln2+ In water

In thf
0.0 Calculated
-0.5
-0.83
-1.0
-1.5
/V
-2.0
red
0
-2.5
E
-3.0
-3.5
-4.0
-4.5
-5.0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb

2500
I3
2400 YbII 4f14
EuII 4f7
2300
-1
I3 / kJmol
2200
2100
2000
GdII 4f75d1 LuII 4f145d1
1900
Ce Pr Pm Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Ionic radii: lanthanide contraction
1.25 ri / Å Ionic radii, CN = 9

La
1.20
II
Ca : 1.18 Å
II
1.15 Sr : 1.31 Å
Gd
0.18 Å
1.10
1.05 Lu
Z
1.00
56 58 60 62 64 66 68 70 72

Ionic radii: variation with coordination number CN

III
1.4 r / Å La
i
II
Ca
1.3 Eu
III
1.2
III
1.1 Yb
1.0
0.9
CN
0.8
6 7 8 9 10 11 12
Oxidation states in the 4f metals

2.10
Eu Atomic radii / Å
2.05 for CN = 12
2.00 +2
Yb
1.95
1.90
La
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
1.3.3 Oxidation states of 5f elements An
7 common
other
Formal oxidation state
6 solid state only
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
• The stability of AnIV decreases along the series

Quite stable for Th, Pa, U, Np.
Only found in solution with fluoride for Am, Cm, Bk
The drop in E 0 (An4+/An3+) at Bk reflects the stability
of [Rn]5f7 (BkIV).
• The trend in E 0 (An3+/An2+) parallels the one in

E 0 (An4+/An3+).
The stability of AnII increases across the series.
Note that the discontinuity appears at Cm, reflecting
the stability of [Rn]5f7 (CmIII).
• The greater range of oxidation numbers of An elements

compared with Ln is due to the nature of 5f orbitals

4500
4000 I4
3500
3000 I3
-1
I / kJmol
2500
2000
1500 I2
1000
I1
500
0
Ac Th Pa U Np Pu AmCm Bk Cf Es Fm Md No Lr

Reduction potentials of 5f elements
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

Influence of relativity on f-orbitals

m0
m  mass of a particle moving
v 2 with velocity v
1 ( )
c
Effects are important for heavy elements
For U(1s) : m = 1.35m0, leads to contraction of 1s

On the contrary d and f orbitals are expanded and destabilized.
5f orbitals are more destabilized than 4f; they are more weakly
bound and more chemically active, henceforth the larger range of
oxidation numbers (and, also, larger covalency of the bonds)

Ionic radii: actinide contraction

115
r / pm
110
105
An3+
100
95
90 An4+
85
80
75 An5+
70
65
Th Pa U Np Pu Am Cm Bk Cf Es
1.4 Radioactivity of the actinides

All of the An isotopes are radioactive, mostly a emitters.
Z El. A t1/2 (* b-, EC) Z El. A t1/2
90 Th 232 1.401010 y 96 Cm 244 18.11 y

91 Pa 231 3.25104 y 97 Bk 247 1.38103 y
92 U 235 7.04108 y 98 Cf 249 351 y
238 4.47109 y 99 Es 252 472 d
93 Np 236 1.55105 y* 100 Fm 257 100.5 d
94 Pu 239 2.41104 y 101 Md 258 56 d
244 8.26107 y 102 No 259 1 h (a + EC)
95 Am 241 4.32102 y 103 Lr 262 3.6 h

Nuclear fission
91
Kr
36
235
92 U
1
0n
thermal neutron
ca. 2 kJmol-1
142
36 Ba
A large nucleus is split into two smaller (and more stable)

ones by collision with a thermal neutron.
The process releases several neutrons, which in turn
collide with other nuclei, initiating “chain reaction”,
provided a “critical mass” exists, i.e. a minimum amount of
the fissile product.
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
1.6´10-13 J
fission
fusion

Nuclear power generation

Control rods Best natural isotope: 235U
Steam Natural abundance: 0.72 %,
henceforth the need for
enrichment.
Fuel: UO2 enriched to 2-3%
235U, under the form of
Fuel rods
pellets stuffed into Zr tubes
Control rods: boron nitride or
graphite (absorb neutrons)
The cooling fluid also acts as
moderator, slowing down the
Cooling fluid produced neutrons (boric acid
(H2O, D2O) added).
Isotope separation
• Gaseous diffusion of UF6 through Al or Ni membranes
(pore size 10-25 nm). Graham’s law:
1
235
v ( UF6 ) 352
vdiff  a   1.0043
diff
MW
238
vdiff ( UF6 ) 349
3000 passes needed (large and expensive fluorine-
resistant chemical plants) for 90% enrichment
• Centrifugation of UF6 (238UF6 concentrates near the

walls)
• Laser separation (now abandoned)

Ionization energy of 235U slightly different from 238U
Laser with wavelength tuned for ionizing 235U produces
235U+ which is collected on an electrode

Fuel reprocessing and treatment

238U produces 239Pu, which can also be used as fuel
238
92 U + n 
1
0
239
92 U  239
93 Np + -10 e (b-, t1/2  24 min)
Np 
239
93
239
94 Pu + -10 e (b-, t1/2  2.4 days)
1st stage: extraction of U and Pu

Other fission
products + An
HNO3 7 M
nitrates Np
[UO2(NO3)2(TBP)2]
[Pu(NO3)4(TBP)2
TBP extraction
in kerosene (PUREX)
[UO2(NO3)2(TBP)2]
[Pu(NO3)4(TBP)2 Plutonium-Uranium
PUREX
Refining by EXtraction
FeII
[UO2(NO3)2(TBP)2] PuIII(aq)
HNO2
PuIV(aq)
UO3 oxalic acid
H2 300 oC
UO2 PuO2

2nd stage: separation of radioactive wastes
1000 kg irradiated fuel
0.8 kg minor 957 kg U 33 kg fission

actinides 10 kg Pu products
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
24.8 kg
Other fission
products DIAMEX
Glass Am, Cm, Ln
LnIII(aq) SANEX
AmIII, CmIII N
Selective Actinide N N
EXtraction
Am Cm
N
N N

Some extraction molecules for An/Ln separation

exploiting the difference in hard/soft behavior
tptz Cyanex 301 CMPO
N S
P O O
N N SH P
N
N
N N

Some extraction molecules for selective separation
calix[4]arene-CMPO
OCH3
O O
O O
O
OCH3
H3CO
P
O
H
N O
CH2
calix-crown for 137Cs
OR 4 separation
R = C 3H 7 MSc: f-Elements, Prof. J.-C. Bünzli, 2008 50
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

MSC Fe Lem Chapter 1

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f - Elements

Section of chemistry and chemical engineering

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 2

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 3

1.1 Definitions and discovery

Nuclear fuel Particle filter

Chapter 1. f-Atoms and Ions

Discovery of rare earths

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 5

1.1 The discovery of 4f-elements

Discovery of yttrium (1794)

Subsequent work revealed that yttrium contained the oxides of 10

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 7

Fe3+, Be2+, Y3+ SiO2

NH3, pH = 7-8 Fe(OH)3

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 8

Discovery of cerium (1804)

1751 The mineralogist Cronstedt finds a peculiar heavy stone

The silicate material has a variable composition close

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 9

Other rare earths (1839-1947)

Most of the other rare earths have been discovered by further

The main techniques were fractional precipitation and

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 10

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 11

Main resources (4f elements)

Cerium group (lighter elements)

Monazite LnPO4 50-75%

Yttrium group (heavier elements)

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 13

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 14

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 15

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 16

• Optics and lighting

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 19

1.3 Basic properties

y(3x2–y2) xyz z(x2–y2)

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 20

4f-orbitals (in octahedral symmetry)

z(x2-y2) y(z2-x2) x(z2-y2)

• The energy of the 4f orbitals decreases abruptly

• The 4f orbitals lie outside the Xe electronic structure

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 22

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 23

1.3.2 Oxidation states

Ln0 4fN-1 5d1 6s2

LnII 4fN-1 5d1

Oxidation states of 4f elements

-2.6 Eored : Ln3+(aq) + 3 e- D Ln(s)

Main reason: the fourth ionization energy is larger

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 26

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 27

Oxidation states of 4f elements

• Ce, Pr, Nd and Tb may have +4 oxidation state

• Sm, Eu, and Yb have a relatively stable +2 state

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 28

Ln3+ + e- D Ln2+ In water

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 29

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 30

Ionic radii: lanthanide contraction

1.25 ri / Å Ionic radii, CN = 9

MSc: f-Elements, Prof. J.-C. Bünzli, 2008 31

Ionic radii: variation with coordination number CN