Sc, Y, La subgroup

Ce family (lanthanides)
Th family (actinides)
General properties
Electronic configuration
Compare the electronic config.of these elements (and their +3 ions)
with that of Al and of Ga subgroup (Ga,In,Tl)
Conclusion : the elements of Ga subgroup have a similar atomic structure to Al in the
ground state but sharply different structures of their E3+ ions.
Element, K L M N
Ion/ level
Al 2 8 3
Ga 2 8 18 3
Sc 2 8 9 2
Al3+ 2 8 8
Ga3+ 2 8 18
3+
Sc 2 8 8
As a consequence:
the properties of similar compounds in the series B,Al,Sc….Ac
change uniformly, in contrast to the B,Al,Ga….Tl series
compare for example : - atomic and ionic radii
-the heats of formation of the highest oxides
in the series B-…La ( p and d elements ) with that in B –…. Tl series ( p elements
only). What is observed? Explain
Element B Al Sc Y La Ac
Z 5 13 21 39 57 89
A 10.81 26.88 44.95 88.9 138.9 [227]
Valency 2s22p1 3s23p1 3d14s2 4d15s2 5d16s2 6d17s2
electron
Atomic 0.91 1.43 1.64 1.81 1.87 2.03
radius
Ionic radius, 0.21 0.57 0.83 0.97 1.04 1.11
3+
E
-∆ H298 1461 1670 1715 1841 1902
(kJ/mol)
E2O3
B2O3 Al2O3 Ga2O3 In2O3 Tl2O3
-∆ H298 1461 1670 1071 1004 502
(kJ/mol)
Metallic Increases regularly in the series
properties
Clark 10-3 10-3 10-3 10-9

Electrochemical character
Sc and its analogues are far in front of hydrogen
Sc is slightly more metallic than Al, but resembles it in :
- reacts vigorously with H2O when the protective oxide layer is removed
- hydrous oxide, Sc2O3.x H2O is amphoter
- only compounds in +3 oxidation state are formed
- in its compounds, C.N greater 6 are unknown
 - there is no evidence for a lower O.S although are known phases with unusual
stoichiometrie like:
- ScI2.17,ScBr2.3
- Sc analogues are closer in their properties with alkaline earth metals (Ca)
Occurrence
- are very dispersed, do not form separate minerals
Preparation : 1.- electrolysis of molten chlorides
- 2.- metallothermic reduction :
- ScCl3 + Ca (10000C)→ Sc + CaCl2
- Ln2O3 + La (more 10000C) → Ln + La2O3
Reactivity -
increases down the group (like s group elements)
- with nonmetals –at elevated temperatures
- with diluted acids:
O 2, S M2O3, M2S3
wet air
M(OH)3 X2 MX3

MxEy H2, B, N2 MN
C, Si Sc, Y, La
interstitial C
compounds ionic carbides
0
H2O (t C)
La(OH)3
+
acids
MX3 + H2
(HCl ,HNO3, H2SO4)
the interstitial compounds are high melting compounds of metallic type with low-
active nonmetals

What are high-temperature superconductors?

At ordinary temperatures, metals have some resistance to the flow of electrons, due
to vibration of the atoms which scatter the electrons.
As the temperature is lowered, the atoms vibrate less and the resistance decreases,
until the material’s critical temperature,TC is reached. At this temperature , the
resistance drops abruptly to zero.;
1911 – Onnes,a Dutch physicist discovered that Hg loses all resistance to electrical
flow when cooled to about 4K, a current once started will flow continuously
(superconductivity)
1933 -Superconductors are also perfectly diamagnetic (repel a magnetic field)
Meissner effect
A magnetic field induces a current in a conductor;conversely, a current induces a
magnetic field
When a magnet approches a superconductor, it induces a current in the
superconductor.Because there is no resistance to the current, it continues to flow,
thus inducing its own magnetic field which then repels the magnet’s field.If the
magnet is sufficiently small and strong, the repulsion will be enough to
counterbalance the pull of gravity and the magnet will levitate above the surface of
the superconductor.
Evolution of superconductivity:
1987-Bednorz, Muller – IBM Zurich (noble prize)
92 K-first ceramic superconductor YBCO
(1:2:3-YBa2Cu3O7-δ )
is an oxygen-deficient triple perovskite (ABO3)3
A = central cations Y and Ba ; B= Cu cations
today – 125 K superconductor
 YBCO
YBCO is an oxygen-deficient triple perovskite, A3B3O9-x where Y and Ba are the
central A cations and Cu the B cation. Oxygen is missing from the central Y
layer and from the a-axis of the basal plane.

Perovskite structure, ABX3

The A atoms occupy the central positions and are coordinated to 12 X ions
B atoms are at the cell corners and are octahedrally coordinated.
Typically B atoms are transition metals
and A atoms are large, electropositive atoms such as Ba, La

Cu(I) is coordinated to 4 oxygens in a square planar configuration,

corner-sharing to form chains along the b-axis.

Cu(II) is square-pyramidally coordinated, with the CuO5 units

corner-sharing to form buckled sheets in a-b plane.

The oxygen stoichiometry of YBCO can vary over the range 6< z< 7
whilst retaining the triple perovskite structure; properties range
from superconducting (6.5< z< 7) to semiconducting (z< 6.4).
 Lanthanides, 4f2-14 5s25p65d0-16s2 La - [Xe]5d16s2
Element Z Electronic E0(V) Ionic Ionization
3+
config Ln /Ln radius potential
Ce subfamily (Ce-Gd)
Cerium 58 4f2 -2.48 1.034 36.2
Praseodymium 59 4f3 -2.47 1.013 36.4
4
Neodymium 60 4f -2.44 0.995 37.5
Promerhium 61 4f5 -2.42 0.979 38.4
6
Samarium 62 4f -2.42 0.969 -
7
Europium 63 4f -2.41 0.950 40.4
Gadolinium 64 4f75d1 -2.40 0.938 41.8
Th subfamily (Tb-Lu)
Terbium 65 4f9 (7+2) -2.38 0.923 38.8
10(7+3)
Dysprosium 66 4f -2.35 0.908 39.3
Holmium 67 4f11(7+4) -2.32 0.894 40.4
12
Erbium 68 4f -2.30 0.881 40.8
13
Thulium 69 4f -2.28 0.869 40.5
Ytterbium 70 4f14 -2.27 0.858 41.8
14 1
Lutetium 71 4f 5d -2.25 0.848 40.4
Electronic configuration
at lanthanides 4f level have less energy than 5d, but the energetic difference is very
small – one (or two)4f electrons is easily excited, passes to 5d level, becomes
valence e-
Oxidation states
In most compounds have O.S =+3 and not +2 (closeness of the properties to those of
Sc subgroup elements)
All lanthanides form M3+ ions (Gd and Lu only this O.S)
Certain lanthanides show M2+(Eu2+- 4f7 and Yb2+ - 4f14)
M4+ (Ce4+ - 4f0 and Tb4+ - 4f7)
the special stability of other O.S. is associated with
- an empty, half-filled or filled f shell
- other thermodynamic and kinetic factors
O.S. – the elements adjacent to La (4f0), Gd (4f7),Lu(4f14) have variable O.S
Ce Pr Nd Pm Sm Eu Gd
(II),III,IV III,(IV) (II),III, (IV) III III,II III,II III, II
Tb Dy Ho Er Tu Yb Lu
III, (IV) III (IV) III III III (II) III,II III

Conclusion since the difference in structure if the atoms is exclusively in the N-shell
(which does not greatly affect their chemical properties) all lanthanides are extremely
alike, a great similarity of properties

Some differences appear – these are very important for separating lanthanides from
one another:
1. properties which uniformly change
(lanthanide contraction)
- ionic radii – a gradual, linear decrease
- redox potentials
-
 Variation of ionic radii with Z-is the
effect of lanthanides contraction
a low screening of one 4f e- by other 4f
electrons
with Z increasing (and with the
increasing of number of 4f electrons),
each e- suffers a suplimentary attraction
from the nucleus

Variation of atomic radii with Z

a general decreasing like in the case of
ionic radii
exceptions:Eu and Yb – probably in
their metallic lattices there are divalent
ions with greater volumes
Ce as tetravalent ion with smaller
volume

Variation of redox potentials is another proof of the stability of different ionic species
of lanthanides in water solutions

2. properties which periodically change

O.S.
magnetic properties
spectral (optic) properties
The colour of ions changes in accordance with greater or lower stabilization of the 4f
states
4f0, 4f1, 4f7, 4f13 qnd 4f14 – colouless
the rest are more or less intensely coloured – is observed a repetition of colours ;
ions with n electrons have the same colours as ions with ( 14-n ) electrons
Ion Number of Colour Number of Ion
- -
unpaired e even e
La3+(4f0) 0 colourless 0 Lu3=(4f14)
Ce3+(4f1) 1 colourless 1 Yb3+(4f13)
3= 2
Pr (4f ) 2 green 2 Tu3+(4f12)
Nd3+(4f3) 3 reddish-violet 3 Er3+(4f11)
3+ 4
Pm (4f ) 4 pink-yellow 4 Ho3+(4f10)
Sm3+(4f5) 5 yellow 5 Dy3+(4f9)
3+ 6
Eu (4f ) 6 pale yellow 6 Tb3+(4f8)
Gd3+(4f7) 7 colourless
0 14
All the f states, except f and f contain unpaired electrons
lanthanides are paramagnetic elements
at these elements – magnetic effect arrising from the motion of the electron in its
orbital (orbital motion) contributes to the paramagnetism, as well as, that arising from
the electron’s spinning on its axis (spin motion)
magnetic susceptibilities are calculated on the basis of spin and orbital contributions:
(J = L + S –orbital and spin
momemta)
Ng 2 µ 2 J ( J +1)
χM = 3 KT

C.N. and stereochemistry – lanthanide

- In contrast to the d elements, the f elements may have C.N higher 9 (11, 12, 13,
etc.)
- lanthanide ions form (in comparation with d block elements
few complexes with ligands other than oxygen, and even those with nitrogen ligands
are often readily hydrolyzed

Occurrence and separation of lanthanides

Lantahanides are always found in nature together
Clark is comparable to that of I2, Sb, Cu –but lanthanides are very dispersed
More than 250 minerals containing lanthanides are known
Main ores for manufacturing are:
- phasphates – monazite : (Ln,Th)PO4
- fluorides; fluoride-carbonates; silicates
Separation of the individual lanthanide elements is one of the most difficult problem
of inorganic chemistry. Explain.
Steps :
- mineral concentration (by classical methods (magnetic or weight separations)
- chemical tretment (acidic or basic decomposition)
- separation of lanthanides as a group
- separation of the individual lanthanide elements
-
The lanthanides properties which are used in eparation and the corresponding
separation methods
Property Separation method
Oxidation state Oxido-reduction procedure
Different solubility of some compunds Fractional crystallization (double salts)
Repartition coefficient Liquid-liquid extraction
Ionic change coefficient Ion exchange
Pressure of decomposition Thermal decomposition
Magnetic properties of ions Separation in magnetic field
Velocity of ions Electrophoresis
Constant of stability of complex Combined procedures
compounds (crystallization,ion exchange
extraction
 Monazite (SiO2)
(Ln,Th)PO4
+H2SO4 conc

insoluble in solution
residue Th(SO4)2, Ln2(SO4)3
SiO2, TiO2 H3PO4
+ (NH4)2C2O4
Ln2(C2O4)3 solution
Th(C2O4)2 C2O42-,PO43-
+(NH4)2C2O4
in solution Ln2(C2O4)3 as a group
Th4+ t0C

Ln2O3

+H2SO4 + (NH4)2SO4

Ln2(SO4)3 . (NH4)2SO4
Fractional
crystallization

Ion exchange - from citrate complexes

Cation exchange resin (Resin-H) :
3ResinH + Ln3+ → (Resin)3Ln + 3H3O+
citric acid, buffered with ammonia to constant pH is added
Ln-(Resin)3 + 3 Hcit → 3HResin + Lncit3
The heavier ions are smaller, they will
be more strongly complexed by the
cytrate and the heavier lanthanide
elements are washed down the column
first and will be eluted. If the conditions
are correct , the different elements will
be separated into pure components

Reactivity. Compounds
-lanthanides (like La) come after the alkali and aline earth metals in chemical activity
-are stable in dry air; at 200-4000C ignite in air and burn forming mixtures of oxides
and nitrides
- form alloys with most metals and intermetallic compounds
- react energetically with acids (but are stable in HF, H3PO4
-are covered with insoluble salts films)
do not dissolve in alkalis
Compounds are practically ionic – a direct consequence of relatively high sizes of Ln
ions in all O.S
The majority of lanthanides compounds (halides, nitrates, perchlorates,etc.) have
high m.p.,
high solubility in polar solvents,
electricalconductivity in solution
Oxides, Ln2O3- are basic oxides, refractory (m.p ≈ 20000C), practically insoluble in
water , react with it → hydroxides

CeO2 obtained : Ce + O2→CeO2

Ce(C2O4)2 → CeO2 + 2CO2 (decomp in O2)
Inert, insoluble in strong acids or alkalis
Hydroxides, Ln(OH)3 –are amorphous precipitates
Basic character , thermal stability and solubility decrease from Ce(OH)3 to Lu(OH)3
Oxosalts (double salts) are very common, used for the separation by fractional
crystallization methods
Complex compounds
The tendency of lanthanides to from complex compounds is determined by factors:
- the 4f orbitals screening by the 5s25p6 octet infront of ligands interaction; so 4f
orbitals are not used to-from bonds and the bonds with (compounds can be regarded
as containing Ln3+ ions surrounded by anions) ligands are especially ionic
- each lanthanide ions in its O.S. (Ln3+, Ln2+, Ln4+) has relatively great size (in
comparison with its electrical charge) so the strenght of bands (especially
electrostatic bands) is small
- crystal field splitting of the 4f orbitals is minimal
The lanthanide elements are often six-coordinated in complexes, but higher
coordinations (7, 8, 9, 10 and 12) are known.The C.N =8 is the most characteristic for
heavier lanthanide ions.
The tendency of lanthanides to have C.N. up to 12, is due to a combination of
- their large size,
- no directional requirements of the 4f orbitals (ionic bonding) and
- minimal crystal field stabilization energy.

C.N Example Shapes

 8 La(acac)3(H2O)2 antiprismatic form

Y(CF3COOHCOOCF3)4- dodecahedral form

9 [Nd(h2O)9](BrO3)3
[La(H2O)4EDTA]⋅ 3 H2O EDTA occupies six
10 position
[M(NO3)5]2-
(M = Ce, Y, Ln) NO3-are present at the
apices of a trigonal
bipyramid
[Ce(NO3)6]3- almost regular
12
La(C6H9N3)43+ icosaedron

Uses of lanthanides
- mischmetal (alloy of lanthanides with a predominant content of Ce and La)
-fabrication of special steels (pyroforic steels) – the elements are not
separated ; the naturally occuring mix is converted to the chloride and then
reduced electrolytically to mischmetal
- mixed lanthanides addition to zeolites to increase catalytic activity, (in
petroleum crackers)
- Gd, Sm, Eu – as control rods in atomic piles (neutron capture)
- La2O3 – glass industry
- Lasers of high intensity (Nd oxide in yttrium aluminium garnet )
- Ytrium in manufactory of warm superconductors
What are high-temperature superconductors?
At ordinary temperatures, metals have some resistance to the flow of electrons, due
to vibration of the atoms which scatter the electrons.
As the temperature is lowered, the atoms vibrate less and the resistance decreases,
until the material’s critical temperature,TC is reached. At this temperature , the
resistance drops abruptly to zero.;
1911 – Onnes,a Dutch physicist discovered that Hg loses all resistance to electrical
flow when cooled to about 4K, a current once started will flow continuously
(superconductivity)
1933 -Superconductors are also perfectly diamagnetic (repel a magnetic field)
Meissner effect
A magnetic field induces a current in a conductor;conversely, a current induces a
magnetic field
When a magnet approches a superconductor, it induces a current in the
superconductor.Because there is no resistance to the current, it continues to flow,
thus inducing its own magnetic field which then repels the magnet’s field.If the
magnet is sufficiently small and strong, the repulsion will be enough to
counterbalance the pull of gravity and the magnet will levitate above the surface of
the superconductor.
Evolution of superconductivity:

1987-Bednorz, Muller – IBM Zurich (noble prize)

92 K-first ceramic superconductor YBCO
(1:2:3-YBa2Cu3O7-δ )
is an oxygen-deficient triple perovskite (ABO3)3
A = central cations Y and Ba ; B= Cu cations
today – 125 K superconductor

YBCO

YBCO is an oxygen-deficient triple perovskite, A3B3O9-x where Y and Ba are the

central A cations and Cu the B cation. Oxyen is missing from the central Y layer and
from the a-axis of the basal plane.

Cu(I) is coordinated to 4 oxygens in a

square planar configuration, corner-
sharing to form chains along the b-axis.
Cu(II) is square-pyramidally coordinated,
with the CuO5 units corner-sharing to
form buckled sheets in a-b plane.
The oxygen stoichiometry of YBCO can
vary over the range 6<z<7 whilst
retaining the triple perovskite structure;
properties range from superconducting
(6.5<z<7) to semiconducting (z<6.4).

Perovskite structure, ABX3

The A atoms occupy the central
positions (1/2, ½, ½) and are coordinated
to 12 X ions

B atoms are at the cell corners and are

octahedrally coordinated.
Typically B atoms are transition metals
And A atoms are large, electropositive
atoms such as Ba, La