The Chemistry of Lanthanides

B.Sc. Chemistry
Semester IV

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General introduction of Lanthanides
• The term lanthanide was coined by Victor Goldschmidt by 1925.There
are 15 elements in the lanthanide series, which is generally shown at
the bottom of the periodic table. The series of elements are called
the lanthanides because they're so similar to the element lanthanum.
• The general symbol Ln is used when referring to the lanthanides. These
are arranged by their atomic number. (range in atomic number from 57
to 71)
• The lanthanoids and actinoids are collectively known as the inner
transition metals, while scandium, yttrium, lanthanum and the
lanthanoids are together called the rare earth metals. Because the
elements known occurred as oxides (earths) and were available
scarcely.
• In 1985 International Union of Pure and Applied Chemistry "Red
Book" recommends that "lanthanoid" is used rather
than "lanthanide". The ending "-ide" normally indicates a negative
ion. However, owing to their wide current use, "lanthanide" is still
allowed.
Electronic Configuration
 They have a electronic configuration of [Xe] 4f1-14 5d0-1 6s2 of the 14
lanthanides, Promethium (Pm) with atomic number 61 is the only synthetic
radioactive element.
 Note: The energy of 4f and 5d electrons are almost close to each other and so
5d orbital remains vacant and the electrons enter into the 4f orbital.
Element Atomic Expected electronic Real configuration
number configuration
Lanthanum (La) 57 [Xe]5d1 6s2 -
Cerium (Ce) 58 [Xe]4f1 5d1 6s2 [Xe]4f1 5d1 6s2
Praseodymium (Pr) 59 [Xe] 4f2 5d1 6s 2 [Xe]4f3 6s2
Neodymium (Nd) 60 [Xe]4f 3 5d 1 6s 2 [Xe]4f4 6s2
Promethium (Pm) 61 [Xe]4f4 5d 1 6s 2 [Xe]4f 5 6s 2
Samarium (Sm) 62 [Xe]4f 5 5d1 6s2 [Xe]4f6 6s2
Europium (Eu) 63 [Xe]4f 6 5d1 6s2 [Xe] 4f7 6s2
Gadolinium (Gd) 64 [Xe]4f7 5d1 6s2 [Xe] 4f7 5d1 6s2
Terbium (Tb) 65 [Xe]4f8 5d1 6s2 [Xe]4f9 6s2
Dysprosium (Dy) 66 Xe]4f9 5d1 6s2 [Xe]4f10 6s2
Holmium (Ho) 67 [Xe]4f10 5d1 6s2 [Xe]4f11 6s2
Erbium (Er) 68 [Xe]4f11 5d1 6s2 [Xe]4f12 6s2
Thulium (Tm) 69 [Xe]4f13 5d1 6s2 [Xe]4f13 6s2
Ytterbium (Yb) 70 [Xe]4f13 5d1 6s2 [Xe]4f14 6s2
Lutetium (Lu) 71 [Xe]4f14 5d1 6s2 [Xe]4f14 5d1 6s2
General appearance
Oxidation States
They shows +2, +3, and +4 oxidation states. But ionization beyond the M3+ ion is
energetically possible, and this leads to a most stable characteristic +3 oxidation state .
Element Atomic Ground State Electronic M3+
Number Configuration
La 57 4f0 5d1 6s2 4f0
Ce 58 4f1 5d1 6s2 4f1
Pr 59 4f3 6s2 4f2
Nd 60 4f4 6s2 4f3
Pm 61 4f5 6 2 4f4
Sm 62 4f6 6s2 4f5
Eu 63 4f7 6s2 4f6
Gd 64 4f7 5d1 6s2 4f7
Tb 65 4f9 6s2 4f8
Dy 66 4f10 6s2 4f9
Ho 67 4f116s2 4f10
Er 68 4f126s2 4f11
Tm 69 4f136s2 4f12
Yb 70 4f146s2 4f13
Lu 71 4f145d1 6s2 4f14
I. Sm and Ce form Sm2+ and Ce 4+ ions but are easily converted to +3
states. That is why Sm2+ is a good reducing agent while Ce4+ is a good
oxidizing agent.
Sm2+ → Sm3+ + e- (electron provider, a reductant)
Ce4+ + e- → Ce3+ (electron acceptor, an oxidant)
ii. +2 and +4 oxidation states are also shown by the elements particularly
when they lead to:
(a) Noble gas electronic configuration, e.g., Ce 4+ (4f0),
(b) Half-filled f-orbital, e.g., Eu 2+ and Tb 4+ (4f7 ),
(c) Completely filled f-orbital, e.g., Yb2+ (4f14) in the valence shell.
Among the above, +2 and +4 oxidation states, which exist only in
aqueous solutions, are exemplified by Sm2+, Eu2+, Yb2+ and Ce4+.
 It has also been observed that the higher oxidation states of the
lanthanides are stabilized by fluoride or oxide ions, while the lower
oxidation sates are favored by bromide or iodide ions.
 Nd, Sm, Eu, Tm, and Yb shows 2+ and 3+ both oxidation states.
 +4 state is exhibited by Ce, Pr, Nd, Tb and Dy elements.
Ionic Radii and Lanthanide Contraction
• It has been observed that the atomic as well as the ionic radii of
lanthanides decrease (generally increases on moving down in group)
steadily as we move from Ce to Lu due to increasing nuclear charge
and electrons entering inner (n-2)f orbital.
• This shrinking the ionic size of the Ln3+ ions with increasing atomic
number is called lanthanide contraction
• The term steadily decrease means the values decrease regularly and
with a very small difference though the nuclear charge increases by
+14 units from the first to the last element.
• The atomic radii of these elements also decrease from Ce to Lu (Ce :
165 pm, Lu : 156 pm) but the overall shift is only of 165-156 = 9 pm.
These values do not decrease regularly like ionic radii rather there are
some irregularities at Eu and Yb which have abnormally high atomic
radii. (Eu : 185 pm, Yb : 170 pm).
• The atomic radii for the metals are actually the metallic radii which
are recorded for the metal atoms surrounded by 8 or 12 nearest
neighbors (in bulk).
 In case of Eu and Yb only two 6s-electrons participate in metallic bonding, 4f-
subshells being stable. While for other lanthanides, three electrons are
generally available for this purpose. This results in larger atomic volumes for Eu
and Yb because of weaker bonding among atoms. The larger values ultimately
give rise to the larger size to the atoms of the elements.
Ce 3+ Pr 3+ Nd 3+ Pm3+ Sm3+ Eu 3+ Gd3+ Tb 3+ Dy 3+ Ho3+ Er 3+ Tm3+ Yb3+ Lu 3+
103 101 100 98 96 95 94 92 91 90 89 88 86 85

Trend of decrease in ionic radii

Cause of Lanthanide Contraction
• On moving from Ce to Lu, the addition of one electrons takes place to
the 4f-orbitals, at each step. The mutual shielding effect of f-electrons is
very little, being even smaller than that of d-electrons, due to the
scattered or diffused shape of these orbitals.
• The nuclear charge (i.e. atomic number) goes on increasing by one unit
at each step . So the attraction between the nucleus and the outermost
shell electrons also goes on increasing gradually at each step.
• The 4f-electrons shields less effectively the attraction of the nucleus (i.e.
inward pull) for the electrons in the outer most shell with increase of
the atomic number. This results in the increased inward pull of the outer
most electrons by the nucleus, finally causing the reduction in the
atomic or ionic size of these elements. The sum of the successive
reductions gives the total lanthanide contraction.

Conclusion- lanthanide contraction among the 4f-sereies elements and in

their ions takes place due to the poor shielding effect of 4f-electrons and
gradual increase in the nuclear charge.
Consequences of Lanthanide Contraction
 Basic character of lanthanide hydroxides- Because of lanthanide
contraction the covalent character between Ln3+ ion and OH- ions
increases from La(OH)3 to Lu(OH)3 (Fajans’ rules). As a result, the basic
character of the hydroxides decreases with increasing atomic number.
Consequently, La(OH)3 is the most basic while Lu(OH)3 is the least basic.
 Resemblance between the atomic radii of the second and third transition
series elements-
 On comparing the atomic radii the elements of Group 3, i.e. Sc, Y and La
in terms of their atomic radii with the elements of 4d and 5d series in the
next group, viz. Group 4, 5....12, it is observed that the values are
unexpectedly almost equal.
 This similarity is found because of the inclusion of 14 lanthanides
between La (Z = 57, Group 3) and Hf (Z = 72, Group 4) of third transition
series which due to “lanthanide contraction”. (Which cancel the increase
in the values of atomic radii).
 The examples of the pairs of elements (first and second transition series)
which show similar properties and hence are difficult to separate are Zr-
Hf, Nb-Ta, Mo-W, Ru-Os, Rh-Ir, Pd-Pt and Ag-Au.
 3d
series

4d
series

5d
series
 Difficulty in the separation of lanthanides: As there is an only small
change in the ionic radii of Lanthanides, their chemical properties are
similar. This makes the separation of elements in the pure state
difficult.
 Complex formation: Because of the smaller size but higher nuclear
charge, tendency to form coordinate complexes increases from La3+ to
Lu3+.
 Electronegativity: It increases from La to Lu.
 Ionization energy: Attraction of electrons by the nuclear charge is
much higher and hence Ionization energy of 5d elements are much
larger than 4d and 3d. In 5d series, all elements except Pt and Au have
filled s-shell.
Complexes of Lanthanides
The lanthanides have low charge density due to their larger size in spite of
having high charge (+3). Hence, they do not cause much polarization of the
ligands and have a weak tendency for complex formation.
This reluctance for complex formation may be attributed mainly to:
 The unfavorable electronic configuration on the lanthanide ions.
 The larger size which leads to little attraction for electron rich species.
 So only the high energy 5d, 6s and 6p-orbitals are available for
coordination, the 4f-orbitals being screened, so that only strong (usually
chelating) coordinating groups can interact.
 Few complexes with unidentate ligands are formed but stable complexes
are formed by Ln3+ ions with chelating ligands such as - (i) oxygen
containing, viz., EDTA, β-diketones, citric acid, oxalic acid, acetyl acetone,
oximes, (ii) nitrogen containing, viz., ethylene diamine, NCS.
 The Ln3+ ions do not form complexes with π-bonding ligands such as CO,
NO, CNR, etc., at all.
 Ce(IV) complexes are relatively common, an example of high oxidation
state ion seeking stabilization through complexation.
Few more facts about complexation of Lanthanides
 The amine complexes are prepared in non-aqueous medium.
 The most stable complexes are with chelating oxygen ligands such as
citric acid, oxalic acid, EDTA, acetylacetone.
 β-diketone complexes of Eu+3 and Pr+3 are used as lanthanide shift
reagents in nmr spectroscpy.
 Coordination number 6 is uncommon and occur with bulky ligands such
as (2,6-dimethylphenyl) and [N(SiMe3)2].
 Coordination number 10, 12 is reported with higher lanthanides and
with smaller ions viz. SO4-2, NO3- respectively.
 The most important class of lanthanide complexes are the anionic type.
Note : Complexation with hydroxycarboxylic acids such as citric and tartaric
acid is used in the separation procedure of lanthanides.
Some complexes of lanthanides
Chemical Reactivity of Lanthanides
I. All the lanthanides show similarity in the reactivity. This is due to
the shielding of unpaired electrons of the inner 4f-orbital by the
outer 5s, 5p, and 5d orbital’s.
II. Get readily tarnished with oxygen and forms the oxides of M2O3
except for CeO2 which reacts with hydrogen forming solid
hydrides at 300-400 °C.
III. Hydrides get decomposed by water.
IV. Halides can be made by heating metal with halogen or the oxide
with ammonium halide. Chlorides are deliquescent while
fluorides are insoluble.
V. Nitrates, acetates, sulphates are soluble while carbonate,
phosphate, chromates and oxalates are insoluble in water.
Compounds of Lanthanides
 Oxides: If lanthanide elements are ignited in air or O2, they readily form
the oxides of Ln2O3 (Ce -gives a dioxide, CeO2) . The oxides are ionic
and basic. The basic nature of oxides decreases along the series with
decreasing ionic size.
2Ln + O2 → Ln2O3
Ce + O2 → CeO2

 Hydroxide: The lanthanides react slowly with cold water but readily
with hot water:
Ln + 6H2O → 2Ln (OH)2 + 3H2
Yb(OH)3 + 3NaOH → 3Na+ + [Yb(OH)6]
Lu(OH)3 + 3NaOH → 3Na+ + [Lu(OH)6]3-
 Lanthanides form oxo-salts such as nitrates, sulphates, perchlorates and
salts of oxoacids which are soluble in water but carbonates and oxalates
are insoluble. The difference in basicity is responsible for the difference in
thermal stability of the oxosalts which decreases along the series. Thus,
La(NO3)3 is more stable than Lu.
LnCl3.6H2O → LnOCl +5H2O + 2HCl
2LnC2 + 6H2O → 2Ln(OH)3 + 2C2H2 + H2
LnN + 3H2O → Ln(OH)3 + NH3
 Halides and Hydrides: The lanthanides also burn in halogens to produce
LnX3 type halides and combine with H2 at high temperature to give stable
MH2 or MH3 type hydrides. Among halides, fluorides are insoluble but
other halides are soluble in water.
CeH2+ 2H2O →CeO2 +2H2
Ln2O3 +6NH4Cl →2LnCl3 + 6NH3 + 3H2O
Physical Properties of Lanthanides
• Density: Among the inner transition series, the trend in density will be
reverse of atomic radii, i. e. density increases, with an increasing atomic
number along the period. They have a high density ranging between 6.77
to 9.74 g cm-3.
• Melting and Boiling Points: They have a fairly high melting point but
there is no definite trend in the melting and boiling point of lanthanides.
Magnetic Properties
• La3+ and Ce3+ have f0 configuration, and Lu3+ has an f14
configuration. Hence, these are diamagnetic.
• Rest of other ions are paramagnetic in nature due to unpaired
electrons in orbitals.
• µ(S+L) = √[4S(S+1)+L(L+1)]
• µ (S+L) is the magnetic moment in Bohr magneton calculated using
both the spin and orbital momentum contributions.
• S is the resultant spin quantum number and L is the resultant orbital
momentum quantum number.
• For the first row transition elements, the orbital contribution is
usually quenched out by the interaction with electrical fields of the
ligands in its environment.
• Hence, for the first transition series the magnetic moment is
calculated by spin only formula. µS = √[4S(S+1) or µS = √[n(n+2)
• µS = √[4S(S+1) or µS = √[n(n+2)
• The abovementioned simple relationship works with La3+ (f =
0) and two of the lanthanides Gd3+ (f7) and Lu3+ (f14).
• For Gd3+ comprising of seven unpaired electrons n =7; µS =
√[7(7+2) = √(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 overlaying 5s and 5p electrons.
• Thus the magnetic effect of the motion of the electron in its
orbital is not quenched out.
• This phenomenon also happens for 4d and 5d transition
series.
• However, the magnetic properties of lanthanoides are
fundamentally different from transition elements.
• In lanthanoides, the spin contribution S and
orbital contribution L couple to each other to
give new quantum number J.
• J = L – S when the shell is less than half filled
• J = L + S when the shell is more than half filled
• The magnetic moment μ is calculated in Bohr
magneton by μ = g√J(J+1)
𝑆 𝑆+1 −𝐿(𝐿+1)
• Where g = 3/2 +
2𝐽(𝐽+1)
The Fig. shows the calculated magnetic moments for the lanthanoides using
both the simple spin only formula (broken line) and the coupled spin plus
orbital momentum formula (solid line).
• For most of the elements, there is excellent agreement between the
calculated values using the coupled spin + orbital momentum formula and
the experimental values measured at 300 K. The range of experimental
values are shown as bars.
• The agreement for Eu3+ is poor and that for Sm3+ is not very good.
• The reason is that Eu3+ the spin orbit coupling constant is only
about 300 cm-1. This means that the difference in energy between
the ground state and the next state is small.
• Thus, the energy of thermal motion is sufficient to promote some
electrons and partially populate the higher state.
• Because of this the magnetic properties are not solely determined
by the ground state configuration.
• But, the measurement of magnetic moment at a low temperature
prevents the population of the higher energy levels. The magnetic
moment of Eu3+ at low temperature is close to zero as expected.
Occurrence and isolation
Lanthanides (elements 57–71) are fairly abundant in the earth's crust,
despite their historic characterization as rare earth elements.
Thulium, the rarest naturally occurring lanthanoid, is more common in
the earth's crust than silver (4.5 × 10−5 % versus 0.79 × 10−5 % by mass).
Oddo Harkin’s Rule
Elements with an even atomic (i.e. an even number of protons in the
protons in the nucleus) are more abundant than their neighbours with
odd atomic numbers.
 Elements with even atomic number also have more stable isotopes.
 Elements with odd atomic number never have more than two stable
isotopes.
Naturally Occurring Isotopes
Le Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
0 4 1 7 0 7 2 7 1 7 1 6 1 7

Isolation of Lanthanides
 All the metals (excluding Pm) can be obtained from monazite sand ,
a mixed phosphate (Ce,La,Nd,Pr,Th,Y . . .)PO4. Bastnӓsite, (Ce, La .
..)CO3F, is a source of the lighter lanthanoids.
 Monazite sand is the best known and most important mineral of
lanthanide elements which is essentially a mixture of
orthophosphates, LnPO4 containing upto 12% thorium, the
element of 5f series, small amounts of Zr, Fe and Ti as silicates,
lanthanum and about 3% yttrium. Among lanthanides contained in
monazite, the bulk is of Ce, Nd, Pr and others occur in minute
quantities.
Separation of lanthanides from Monazite Sand
• Monazite is treated with hot conc. H2SO4 when thorium,
lanthanum a dissolve as sulphates and are separated from
insoluble material (impurities).
• On partial neutralisaion by NH4OH, thorium is precipitated as
ThO2. Then Na2SO4 is added to the solution.
• Lanthanum and light lanthanides are precipitated as
sulphates leaving behind the heavy lanthanides in solution.
• To the precipitate obtained as above, is added hot conc.
NaOH. The resulting hydroxides of light lanthanides are dried
in air at 1000 °C to convert the hydroxides to oxides.
• The oxide mixture is treated with dil. HNO3/HCl. This brings
CeO2 as precipitate and other lanthanides in solution
Separation/Extraction of Individual Lanthanides
Role of solubility in the separation
 To separate respective lanthanides the solubility of salts plays very
important role.
 Solubility depends upon on small difference between the lattice
energy and the solvation energy and there is no obvious trend in the
group.
 Many lanthanides forms double salts, like Na2SO4Ln2(SO4)3.8H2O
these salts are used to separate lanthanides from each other.
Separation of Lanthanides
Fractional Crystallization Method: This method is based on the difference in
solubility of the salts such as nitrates, sulphates, oxalates, bromates, perchlorates,
carbonates and double salts of lanthanide nitrates with magnesium nitrate which
crystallize well and form crystals.
• Since, the solubility of these simple and double salts decreases from La to Lu,
the salts of Lu will crystallize first followed by those of lighter members.
• A non-aqueous solvent, viz., diethyl ether has been used to separate Nd(NO3)3
and Pr(NO3)3 .
Fractional Precipitation Method: Based on the difference is solubility of the
precipitate formed.
When NaOH is added to a solution of Ln(NO3)3, Lu-hydroxide being the weakest
base and having the lowest solubility product is precipitated first while La-
hydroxide which is the strongest base and has the highest solubility product is
precipitated last. By dissolving the precipitate in HNO3 and reprecipitating the
hydroxides a number of times, it is possible to get the complete separation of
lanthanide elements.
Valency change Method
Based on the change of chemical properties by changing the oxidation
state. The most important application of this method is made in the
separation of cerium and europium elements from mixture of lanthanides.
• The mixture containing Ln3+ ions if treated with a strong oxidising agent
such as alkaline KMnO4, only Ce3+ ion is oxidized to Ce4+ while other Ln3+
ions remain unaffected. To this solution alkali is added to precipitate
Ce(OH)4 only, which can be filtered off from the solution.
• Eu2+ can be separated almost completely from Ln3+ ions from a solution
by reducing it with zinc-amalgam and then precipitating as EuSO4 on
adding H2SO4 which is insoluble in water and hence can be separated.
The sulphates of other Ln3+ ions are soluble and remain in solution.
Complex Formation Method
Method is generally employed to separate heavier lanthanide elements
from the lighter ones by taking the advantage of stronger complexing
tendency of smaller cations with complexing agents.
• When EDTA is added to Ln3+ ion solution, lanthanides form strong
complexes. If oxalate ions are added to the solution containing EDTA
and Ln3+ ions, no precipitate of oxalates is obtained.
• On adding small amount of acid, the least stable complexes of lighter
lanthanides are dissociated and precipitated as oxalates, but the
heavier lanthanides remain in solution as EDTA complexes
Modern Ion-Exchange Method
Most rapid and most effective method for the isolation of individual lanthanide elements
from the mixture.
 An aqueous solution of the mixture of lanthanide ions (Ln3+aq) is introduced into a
column containing a synthetic cation exchange resin such as DOWAX-50 [abbreviated
as HR (solid)].This cation-exchange resin is also called sulfonated polystyrene or
where its Na+ salt is used. When a solution containing Ln3+ ions is poured on to a resin
column, the cations exchange with the H+ or Na+ ions.
Ln3+ (aq) + 3H+ (resin) ↔ Ln3+ ( resin) + 3H+ (aq)
Ln3+ (aq )+ citrate ions → Ln-citrate complex
 The resin bound Ln3+ ions are now removed using a complexing agent such as EDTA4-.
 By using a long ion-exchange column, 99.9% pure components can be separated.
Where Lu3+aq. ion is attached to the column with minimum firmness remaining at
the bottom and Ce3+aq. ion with maximum firmness remaining at the top of the resin
column.
 Likewise if the citrate solution (a mixture of citric acid and ammonium citrate) is used
as the eluant, during elution process, NH4+ ions are attached to the resins replacing
Ln3+aq. ions which form Ln-citrate complexes:
Ln (resin)3 + 3NH4+ → 3NH4- resin + Ln3+aq
Ln3+aq + citrate ions → Ln-citrate complex
 The Ln3+aq cations with the largest size are, eluted first (heavier Ln3+aq ions)
 Lighter Ln3+aq ions with smaller size are held at the top of the column.
Colour property of Lanthanides
• Some trivalent ions (M3+) are coloured in solid as well as in
solution.
• The colour of lanthanide ion is due to absorption in visible region
of the spectrum resulting f-f transitions because they have partly
filled orbitals. The colour of ions having nf electrons is about
same with those having (14 – n)f electrons.
• f0, f7, f14 are colourless. Ce3+ (f1) and Tb3+ (f8) shows 4f→5d
transition, loss of one electron.
• Gives the extra stablity of an empty and half filled shell.
Ce4+ = Ligand → Metal Charge Transfer
Sm2+ = Metal → Ligand Charge Transfer
Main Smith Colour Sequence- Sequence is arranged to learn
simply the colour trend.

Element Configuration Element Configuration

La3+ Colourless Lu3+ Colourless
Ce3+ Colourless Yb3+ Colourless
Pr3+ Green Tm3+ Pale green
Nd3+ Lilac Er3+ Rose-pink
Pm3+ Pink Ho3+ Pale yellow
Sm3+ Yellow Dy3+ Yellow
Eu3+ Pale pink Tb3+ pale pink
Gd3+ Colourless Gd3 + Colourless
Ceric Ammonium Sulphate and its analytical use
• Ceric sulfate is used in analytical chemistry for redox titration, often together
with a redox indicator. A related compound is ceric ammonium sulfate. The
solubility of Ce(IV) in methanesulfonic acid is approximately 10 times the
value obtainable in acidic sulfate solutions.
• Formula: (NH4)4Ce(SO4)4·2H2O

• A crystallographic study shows that the compound contains the

Ce2(SO4)88− anion, where the cerium atoms are 9 coordinated by oxygen
atoms belonging to sulfate groups, in a distorted tricapped trigonal prism.
The compound is thus sometimes formulated as (NH4)8[Ce2(SO4)8]·4H2O.
Applications
References
I. J. D. Lee, Concise, Inorganic Chemistry, 5th Edition.
II. Catherine E. Housecroft and Alan G. sharpe, Inorganic
chemistry, Second Edition.