Topics in

Lanthanides Chemistry
Inner Transition Elements

LANTHANIDES : 4f block elements

Definition: The f- block (inner transition) elements containing partially filled

4f-subshells are known as Lanthanides or Lanthanoides because of their close
similarities with element lanthanum (atomic no: 57). The fourteen elements
from atomic no: 58 to 71 constitute lanthanides.

The informal chemical symbol Ln is used in general discussions of

lanthanide chemistry to refer to any lanthanide. All but one of the
lanthanides are f-block elements, corresponding to the filling of the 4f
electron shell; lutetium, a d-block element, is also generally considered to
be a lanthanide due to its chemical similarities with the other 14. All
lanthanide elements form trivalent cations, Ln3+, whose chemistry is
largely determined by the ionic radius, which decreases steadily from
lanthanum to lutetium.

The lanthanide elements are the group of elements with atomic number
increasing from 57 (lanthanum) to 71 (lutetium). They are termed
lanthanide because the lighter elements in the series are chemically similar
to lanthanum which contains 4fo. Strictly speaking, both lanthanum and
lutetium have been labeled as group 3 elements, because they both have a
single valence electron in the d shell. However, both elements are
often included in any general discussion of the chemistry of the lanthanide
elements.

In presentations of the periodic table, the lanthanides and the actinides are
customarily shown as two additional rows below the main body of the
table, with place holders or else a selected single element of each series
(either lanthanum or lutetium, and either actinium or lawrencium,
respectively) shown in a single cell of the main table, between barium and
hafnium, and radium and Rutherfordium, respectively. This convention is
entirely a matter of aesthetics and formatting practicality; a rarely used
wide-formatted periodic table inserts the lanthanide and actinide series in
their proper places, as parts of the table's sixth and seventh rows (periods).

Electronic configuration of lanthanum and lanthanides. General

features,
The lanthanides are strictly the 14 elements follow in (Table 1) and in
which the 4f electrons are successively added to the La configuration.
- All of the lanthanide from M3+ ions and so do Sc and Y which have
the atomic structures [ Ar ] 3d1 4s2 and [kr] 4d5 5s2 respectively .
- for several of the lanthanides other oxidation states occur although
these are always less stable than the characteristic group valency.
- The +2 ions are readily oxidized and the + 4 ions are readily reduced
to the +3 ion.
- A simplified explanation for the occurrence of these valences is that
empty. half – filled or filled shells are especially stable.
- Sc, Y and La form only the M3+ ions since removal of 3 electrons leaves
the inter configuration [ Ar] 3d1 4s2, [Kr] 4d1 5s2, [Xe]5d16s2
Table (1). Electronic configuration of lanthanum and lanthanides.
Radii
Electronic
Z Name Sym configuration M2+ M3+ M4+ 2 3
bol + +
1 1
57 Lanthanum La [Xe] 4f 5d
o
[Xe] 4f 5do
[Xe] - 1.87 1.06
6s2
58 Cerium Ce [Xe] 4f2 6s2 (4f1 5d1 6s0) 4f1 4f1 1.83 1.03
59 Praseodymium Pr [Xe] 4f3 6s2 4f3 4f2 4f2 1.82 1.01
60 Neodymium Nd [Xe] 4f4 6s2 4f4 4f3 1.81 0.99
61 Promethium Pm [Xe] 4f5 6S2 4f5 4f4 0.98
62 Samarium Sm [Xe] 4f6 6S2 4f6 4f5 1.79 0.96
63 Europium Eu [Xe] 4f7 6s2 4f7 4f6 2.04 0.95
64 Gadolinium Gd [Xe] 4f7 5d1 6s2 4f7 5d1 4f7 1.80 0.94

65 Terbium Tb [Xe] 4f9 6s2 4f9 4f8 4f7 1.78 0.92

66 Dysprosium Dy [Xe] 4f10 6s2 4f10 4f9 4f8 1.77 0.91
67 Holmium Ho [Xe] 4f11 6s2 4f11 4f10 1.76 0.80
68 Erbium Er [Xe] 4f12 6s2 4f12 4f11 1.75 0.83
69 Thulium Tm [Xe] 4f13 6s2 4f13 4f12 1.74 0.84
70 Ytterbium Yb [Xe] 4f146s2 4f14 4f13 1.92 0.85
71 Lutetium Lu [Xe] 4f14 5d1 6s2 4f14 5d1 4f14 1.74 0.86

-Lu and Gd form only tripositive ions since the latter then have the
stable 4f14 and 4f7 configurations respectively.
- In All of these s cases removed of less than three electrons under
chemical conditions does occur because the M2+ or M+ ions would be
so much larger than the M3+ ions that the energy saved in the ionization
step would be less than the additional lattice or hydration energies of
the salts of the small M3+ ions as compared with the lattice or hydration
energies of the M2+ or M+ ions.
- The most stable M3+ and M4+ ions are formed by elements which can
attain the f0, f 7 and f 14 configuration.
- Thus Ce and Tb attain the f5 and f7 configuration, respectively, by
going to the oxidation states other than for the lanthanide.
- Whereas Eu and Yb have the f7 and f14 configurations respectively,
in the oxidation states other than, for the lanthanides.
These argument becomes less convincing however, when we note that
Sm and Tm give M2+ specie having f6 and f13 configurations but no
M2+ ions , whereas Pr and Nd give M4+ ions with configurations f1 and
f2 but no penta or hexa valent species .

Admittedly, the Sm(II) and especially Tm(II), Pr(II) and Nd ( II)states

are very unstable indeed , but the idea that stability is favored even by
the more approach to an fo , f7 or f 14 configuration even though such a
configuration is not actually attained , is of dubious validity .
- The existence of Nd2+ , f4 , provides particularly cogent evidence for
believing that although the special , stability of fo . f7 , f14 may be one
factor there are other thermodynamic and kinetic factors .Which are of
equal or greater importance in determining the stability of oxidation
states
Magnetic and Spectral properties:
The Lanthanide ions that generally have unpaired electrons are colored
and are paramagnetic .
In several aspects, the magnetic and spectral behavior of lanthanides is
fundamentally different from that of the difference lies in the fact that
the electrons responsible for the magnetic and spectral properties of
lanthanide ions are 4f electrons , and the 4f orbitals are very effectively
shielded from interaction with external forces by the over lying 6s2 and
6p6 shells .

Hence , there are essentially only very weak effects of ligand fields

Hence the states arising from the various 4f n configurations are only
slightly affected by the surroundings of the ions and remain practically
invariant for a given ion in all of its compounds
- Because the orbitals are so well shielded from the surroundings of the
ions , the various states arising from the fn configurations are split by
external fields only to the extent of 100 cm in to ( 2 J +1) or ( J+1/2)
sublevels , depending on whether J is integral or half integral.

Total angular momentum J = (S+L), (S+L+1) ........... (S-L)

- Thus when electronic transitions, called f–f transitions, occur from

one J state of on fn configuration to another J state of this configuration,
the absorption bands are extremely sharp . They are similar to those for
free atoms and are quite unlike those for the d-d transitions.
- Virtually all of the absorption bands found in the visible and near-
ultraviolet spectral of the lanthanide ions have this line – like character
. There are , However , bands found in some cases which are quite broad
, These may be assigned to transitions in which an f electron is excited
to an outer d , s or p orbital .

- Since these outer levels are very much broadened by external fields , the
breath of the absorption bands due to such transitions is attributable to
the breadth of these upper states .

- The magnetic properties of the ions are litter affected by their chemical
surroundings .

Magnetic properties :

La3+ and Ce4+ have an f 0

configuration and Lu3+ has an f14
configuration. These have no unpaired electrons and are diamagnetic. All
other f states contain unpaired electrons and are therefore paramagnetic.

The magnetic moment of transition elements may be calculated from

the equation.

µ(S + L) =

µ(S + L) is the magnetic moment in Bohr magnetons calculated using

both the spin and orbital momentum contributions. S is the resultant spin
quantum number. For the first-row transition elements, the orbital
contribution is usually quenched out by interaction with the electric
fields of the ligands in its environment. Thus, as a first approximation the
magnetic moment can be calculated using the simple spin only formula.
(µs is the spin only number and n is the number of unpaired electrons.)

µs =

this simple relationship works with La3+ ( f 0 ), and two of the

lanthanides
La3+ (f 7) and Lu3+ (f 14).
La3+ and Lu3+ have no unpaired electrons, n = 0 and
µs = 0
Gd3+ has seven unpaired electrons, n = 7 and µs
= = √63 = 7.9 BM
the other lanthanide ions do not obey this simple relationship. The 4f
electrons are well shielded from external fields by the overlying 5s and 5p
electrons. Thus, the magnetic effect of the electron in its orbital is not
quenched out. Thus the magnetic moments must be calculated taking into
account both the magnetic moment from the unpaired electron spins and
that from the orbital motion . this also happens with the second and third
row transition elements. However, the magnetic properties of the
lanthanides are fundamentally different from those of the transition
elements. In the lanthanides the Spin contribution S and orbital
contribution L couple together to give a new quantum number J .
J=L–S when-the shell is less than half full
and J=L+S when-the shell is more than half full
the magnetic moment µ is calculated in Bohr magnetons (BM) by :
µ=g
where

g= +

Coordination Numbers and Stereochemistry :

- It is characteristic of the M3+ ions that coordination numbers exceeding

six are common very few 6-coordination species are known but
coordination numbers of 7 &8 and 9 are important. In the ion [ Ce
(NO3)6 ]2- , the Ce is surrounded by 12 oxygen atoms of chelate NO 3
groups .
- The decrease in raids from La to Lu also has the effect that different
crystal structures and coordination numbers may occur for different
parts of the lanthanide group . For example , the metal atoms in the
trichlorides La – Gd are 9 coordinate , where as the chlorides of Tb–
Lu have an AlCl3 type structure with the metal being octahedrally
coordinated .Similar difference in coordination numbers occur for ions
in solutions. [ Nd ( H2O)9 ]3+

Cl Cl Cl

Al Al

Cl Cl Cl
The lanthanide contraction.

Consists of a significant and steady decrease in the size of the atoms and
ions with increasing atomic number, that is, La has the greatest and Lu his
smallest , radius ( Table 1 ) Note that the radius of La3+ is about 0.18Ao
larger than that of Y3+ so that if the 14 lanthanide elements did not
intervene we might have expected Hf 4+ to have a radius 0.2Ao greater than
that of Zr 4+ .

- Instead, the lanthanide contraction, amounting to 0.12Ao almost exactly

wipes out this expected increase and results in almost identical radii or
Hf 4+ and Zr 4+ as noted previously.

- The cause of the lanthanide contraction is attributed to the imperfect

shielding of one electron by another in the same subshell.

- As we go along the lanthanide series, the nuclear charge and number of

4f electrons both increase, but owing to the shape of the f orbitals, there
is little screening from the nucleus of an electron in one f orbital by
electrons in other f orbitals, hence each of these electrons experiences
as an increasing elective nuclear charge, and the ions state decreases.

- It should be noted also that the decrease through steady, is not quite
regular, the biggest decreases occurring with the first f electrons added.

- There, also appears to be a larger decrease after f7, that is between Tb

and Gd.
- Some physical properties of lanthanide compounds sometimes show
similar divergence from regularity as a consequence of the ionic size,
this for ion exchange elution there is a break in the regularity in the
separations between Gd and Tb and in the extraction of lanthanides
from strong nitric acid solutions by tributy phosphate in CCl4 , there are
change in the distribution constants at Gd

- A half – filled shell effect has also been noted from stabilities of
lanthanide complexes of ED TA.

The Metals:

- In recent years all of the metals have been obtained in a state of high purity.

- The lighter metals (La, Ce, Pr, Nd, and Gd) are obtained by reduction of the
trichlorides with Ca. at 1000 Co. or more.

- For Tb, Dy, Ho, Er, Tm and Tb (heavier) the trifluorides are used
because the chlorides are too volatile.

- Pm is made by reduction of PmF3 with Li.

- Eu, Sm, and Tb Trichlorides are reduced only to the dihalides by Ca

- Reduction of +3 oxides with La at high temperatures gives the metals .

- The metals are silvery – white and highly electro positive.

They react with H2O slowly in the cold, rapidly on heating to liberate H2 .

2M + 3H2O M2O3 + 3H2

- They tarnish in air and burn easily to give the oxide M2O3 , Ce is the
exception giving CeO2 .

- Yttrium is resistant to air even up to 1000o owing to formation of a

protective oxide coating.

- The metals react with H2 at elevated temperature to give stable MH2 and
MH3 phases, which usually occur in a defect condition.

- The hydrides react readily with oxygen and water.

- the Metals also react readily with C, N2, Si, P, S, halogens and other
nonmetals at elevated temp.

- They all react directly with water, slowly in the cold rapidly on heating
, to liberate hydrogen.

- Their high oxidation potentials are in accord with their electropositive

character .

- It is interesting that the atomic volumes, densities and some other

properties of the metals change.

- Smoothly except for Eu and Yb, and occasionally Sm and Tm .

- It obvious that the deviations occur with just these lanthanides which have
the greatest tendency to exist in the divalent state.

- Presumably these elements and to donate only two electrons to the

conduction bands of the metals this leaving larger cores and affording
lower binding forces.
Chemistry of the trivalent lanthanides and Yttrium.
- All of the metals are detained by reduction of halides or oxides .

- The trivalent state is the characteristic one for all of the lanthanides.

- They form oxides M2O3 , which resemble the Ca , Sr , Ba group oxides

and absorb CO2 and water from air to form carbonates and hydroxides
respectively .

M2O3 + CO2 M2(CO3)3

M2O3 + H2O M(OH)3

- The hydroxides, M(OH)3 , are definite compounds , having hexagonal

structures , and not merely hydrous oxides .

- The basicity of hydroxides decreases with increasing atomic number as

would be expected because of the decrease in ionic radius.

Lu(OH)3 weak base

La(OH)3 strong base

- The hydroxides are precipitated from aqueous solutions by ammonia or

dilute alkalis as gelatin us precipitates.

- They are not amphoteric .

- Among the halides, the fluorides are of particular importance because

of their insolubility.

- An addition of hydrofluoric acid or fluoride ions precipitates the

fluorides are of particular importance because of their insolubility.
- Addition of hydrofluoric acid or fluoride ions precipitates the fluorides
from lanthanide ion solution.

Even 3M in nitric acid and is a characteristic test for lanthanide ions .

- The fluorides, particularly of the heavier lanthanides are slightly

soluble in excess HF owing to complex formation.

- They may be dissolved in 3N nitric acid saturated with boric acid

which removed as BF4 .

- The chlorides are soluble in water, from which they crystallize as

hydrates .

- The anhydrous chlorides cannot easily be obtained from the hydrates

because these lase hydrochloric acid on heating to give the ox
chlorides, MOCl – more readily than they lose water ( Sc and Ce give
Sc2O3 and CeO2 respectively ) .

- The anhydrous chlorides are best by heating oxides ( or oxalates , etc)

with ammonium chlorides at ca. 300oC .

M2O3 + 6NH4Cl 300 2MCl3 + 3H2O + 6NH3

- The bromides and iodides are rather similar to chlorides.

- Lanthanides salts of most oxyacid – sulfates, nitrates, perchlorates,

bromate, etc… are known.

- They are generally soluble and crystallize as hydrates.

- The carbonate, phosphates and oxalates are insoluble, and precipitation
of the fairly specific separation procedure for the lanthanides,
lanthanides can be determined gravimetrically in this way.

- Double salte are very common, the most important ones being the
double nitrates and double sulfates, such as

2M(NO3)3 Mg(NO3)2.24H2O, M(NO3)2(NH4)2NO3.4H2O and

M2(SO4)3.3Na2SO4.12H2O, ……

- The solubility’s of the double sulfates of the latter type fall in to two
rough classes: The cerium group

La – Eu, and the yttrium group Gd – Lu and Y.

- These of the Ce group are only sparingly soluble in Na2SO4 , where are
those of Y group are appreciable soluble .

- This a fairly rapid separation of the entire group of lanthanides in to

two Main group is possible.

- Various of the double nitrates were used in the past for further
separations by fractional crystallization procedures.

- The lanthanides from many well defined compounds with nonmetals

and metalloids other than O2 and halogens.

- The general preparation of all of these compounds is by direct

combination of the elements at elevated temperatures.

- Among these are sulphides, M2S3 (not for Eu), Selenide, M2 Se3, and
oxysulphides, M2O2S .
- Nitrides , phosphides , arsenides , antmonides and bismuthides MN,
MP, Mas, MSb and MBI , Crystallize in the NaCl structure (cubic)

- Borides of the types MB6 and MB4 are well characterized as the
carbides, MC2 , and hydride phases MH2 and MH3 .

- the aqueous M3+ ions are slightly hydrolysed according to :

M(H2O)n3+ + H2O M(H2O)n-1(OH)2+ + H3O+

and the tendency to hydrolysis increases with increasing atomic number

as would be expected from the contraction in radix ( Lu→ La)

- The lanthanides from few complexes , and these are mostly with
oxygen compound .

- This is due in part to the unavailability of the f orbitals to from hydride

orbital (which might lead to covalent bond strength, and also to the
fact that the lanthanide ions are rather large (radii 0.85 –1.06 Ao )
compared with those of the transition elements ( e.g Cr3+ and Fe3+ with
radius of 0.6 – 0.65 Ao ) which lower electrostatic forces of attraction .

- The only stable complexes which are at all common or important are
those with chelate ligands. Diketones such as acetone (I) and
dibenzoyl methane (II).
form complexes of type.

R1

C O
HC M

C O 3

R2

(i) R1 = R2 = CH3 (ii) R1 = CF3 & R2 = CH – CH (iii) R1 = R2 = 6H5

Which are insoluble in water but soluble in organic solvents.

- The lanthanides can also be extracted from aqueous solution in to

organic solvents using certain complexion agents, such as tributyl
phosphate (TBP) in the presence of concentrated hydrochloric acid and
chelate ligands giving water soluble complexes are polyfunctional organic
acid and hydroxy acids such as tartaric, and citric, and various amino
acids.
- Since the lanthanides are highly electropositive, they have little or no
tendency to from complexes with π-bonding ligands and none are
known.