CHAPTER TWO

The f-block metals: Lanthanoids and Actinoids

1
 The elements constituting the f-block are those in which the 4f and 5f orbitals are
progressively filled in the latter two long periods.
 There are two series of metals: the lanthanoids (the 14 elements that follow
lanthanum in the periodic table) and the actinoids (the 14 elements following
actinium).
 Scandium, yttrium, lanthanum and the lanthanoids are together called the rare earth
metals.
 Although La and Ac are strictly group 3 metals, the chemical similarity of La to the
elements Ce–Lu, and of Ac to Th–Lr, means that La is commonly classified with the
lanthanoids, and Ac with the actinoids.
 The lanthanoids resemble each other much more closely than do the members of a
row of d-block metals.
 All the actinoids are unstable with respect to radioactive decay, although the half-
lives of the most abundant isotopes of thorium and uranium, naturally occurring
isotopes, (232Th and 238U, t1/2 = 1.4 x 1010 and 4.5 x 109 yr respectively) are so long
that for many purposes their radioactivity can be neglected.
2
 The valence shell of a lanthanoid element contains 4f orbitals and that of an actinoid,
5f atomic orbitals.
 A crucial difference between the 4f and 5f orbitals is the fact that the 4f atomic
orbitals are deeply buried and 4f electrons are not available for covalent bonding.
 Usually for a lanthanoid metal, M, ionization beyond the M3+ ion is not energetically
possible. This leads to a characteristic +3 oxidation state across the whole row from
La to Lu.
 The known oxidation states of the actinoids are shown in Table 2.3. The existence of
at least two oxidation states for nearly all these metals implies that the successive
ionization energies probably differ by less than they do for the lanthanoids.
 The chemistry of the actinoids is much more complicated. The complication arises
partly owing to the occurrence of a wide range of oxidation states in these elements
and partly because their radioactivity creates special problems in their study.

3
 For the higher oxidation states in actinoids, covalent bonding must certainly be
involved. This may occur either because the 5f atomic orbitals extend further from
the nucleus than do the 4f atomic orbitals and are available for bonding, or because
the energy separations between the 5f, 6d, 7s and 7p atomic orbitals are sufficiently
small that appropriate valence states for covalent bonding are readily attained.
 The large size of the lanthanoid and actinoid metals means that in their complexes,
high coordination numbers (> 6) are common.
 Preferences between different coordination numbers and geometries tend to be
controlled by steric effects.

4
Chemistry of the Lanthanide Elements
Electronic Configurations
 It may be noted that atoms of these elements have electronic configuration with 6s2 common
but with variable occupancy of 4f level (Table 2.1).
 However, the electronic configurations of all the tripositive ions (the most stable oxidation
state of all the lanthanoids) are of the form 4fn (n = 1 to 14 with increasing atomic number).
 As shown in Table 2.1, as the atomic number increases, the 5d electron typically
moves into the 4f subshell, with the exceptions of Gd (atomic number 64) and Lu
(atomic number 71). This shift is energetically favorable in most elements, as it leads
to a more stable electronic configuration that is widely accepted.
 In Gadolinium (Gd) such a shift would have destroyed the symmetry of a half filled f-
subshell and the resulting configuration would have been less stable than the probable
configuration i.e., 4f7 is more stable than 4f8 configuration.
 In lutetium (Lu), the f-subshell is already completely filled and cannot accommodate any
additional electron.
 From table 2.1, it may be concluded that the general electronic configuration of lanthanide
elements could be written as [Xe]4f1-145d0,16s2. The three subshells, viz., 4f, 5d and 6s
together form the valence shell of these elements, i.e., 4f.5d.6s = valence shell.
5
Table 2.1: Electronic Configurations and Radii of Lanthanum and Lanthanoids

6
Atomic and Ionic Sizes
 The overall decrease in atomic and ionic radii from lanthanum to lutetium (the lanthanoid
contraction) is a unique feature in the chemistry of the lanthanoids.
 The decrease in atomic radii (derived from the structures of metals) is not quite regular as it
is regular in M3+ ions (Table 2.1).
 The atomic radii values do not decrease regularly like ionic radii rather there are some
irregularities at Eu and Yb which have abnormally high atomic radii.
 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).
 The metallic radius (rmetal) is half of the distance between the nearest neighbour atoms in a
solid state metal lattice, and is dependent upon coordination number. When the coordination
number increases, rmetal also increases.
 Various metal atoms in metal crystal are bonded together by metallic bonding.
 In Eu and Yb, only two 6s-electrons participate in metallic bonding, 4f-subshells being
stable. 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. 7
Cause of lanthanide contraction
 As we move along the lanthanide series from Ce to Lu, the addition of electrons takes place
to the 4f-orbitals, one 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.
 However, the nuclear charge (i.e. atomic number) goes on increasing by one unit at each step
(i.e., each next element). Thus, the attraction between the nucleus and the outermost shell
electrons also goes on increasing gradually at each step.
 The 4f-electrons are not able to shield effectively the attraction of the nucleus (i.e. inward
pull) for the electrons in the outer most shell as the atomic number of lanthanide elements
increases.
 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.
 It may be concluded that the lanthanide contraction among the 4f - series elements and their
ions takes place due to the poor shielding effect of 4f-electrons and gradual increase in the
nuclear charge.

8
Consequences of Lanthanide Contraction
Lanthanide contraction plays an important role in determining the chemistry of
lanthanides
 Basic character of lanthanide hydroxides, Ln(OH)3
Because the size of tripositive lanthanide ions (Ln3+) decreases regularly with
increasing atomic number (or nuclear charge), the process being called lanthanide
contraction, therefore, 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.
 There is very small change in the radii of lanthanides and hence their chemical
properties are quite similar. This makes the separation of these elements using the
usual physical and chemical methods is difficult. Consequently, new methods like ion
exchange technique, solvent extraction etc. have now been used for their separation
which are based on slight difference in the properties like hydration, complex ion
formation, etc.
9
Oxidation States
 It is observed for these elements that +3 (i.e. formation of tripositive ions, Ln3+) is the principal or
common oxidation state exhibited by all of them. This is said to be the most stable oxidation state
of the lanthanides.
 Some of these elements also show +2 and +4 oxidation states but except a few such ions, they have
the tendency to get converted to +3 state. For example, Sm and Ce form Sm2+ and Ce4+ ions but are
easily converted to +3 states. That is why Sm2+ is a good reducing agent while Ce4+ is a good
oxidizing agent, i.e.,
– Sm2+ → Sm3+ + e (electron provider, a reductant)
– Ce4+ + e → Ce3+ (electron acceptor, an oxidant)
 It means Ln2+ and Ln4+ ions are less frequent than Ln3+ ions among the lanthanides. +2 and +4
oxidation states are shown by the elements particularly when they lead to:
(a) Noble gas electronic configuration, e.g., Ce4+ (4f0),
(b) Half-filled f-orbital, e.g., Eu2+ and Tb4+ (4f7), and
(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+.
10
 The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation
states.
 Due to the only one stable oxidation state (i.e., +3), lanthanide elements resemble each other
much more than do the transition (or d-block) elements.
 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 favoured by bromide or iodide
ions.
 In addition to +3 oxidation states, lanthanoid elements may show +2 oxidation states (Eu, Yb
and Sm) and +4 oxidation states (Ce, Pr and Tb).

11
Complex Formation by Lanthanides
 Although the lanthanide ions have high charge (+3), yet the size of their ions is very
large (charge/size = small). 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:
(i) The unfavourable electronic configuration on the lanthanide ions.
(ii) The larger size which leads to little attraction for electron rich species.
 Because of the above reasons, 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.
 Thus, only a few complexes with unidentate ligands are formed but stable complexes are
formed by Ln3+ ions with chelating ligands such as (i) oxygen containing, e.g., EDTA,
β-diketones, oxalic acid, acetyl acetone, (ii) nitrogen containing, e.g., ethylene diamine.
 The Ln3+ ions do not form complexes with π-bonding ligands such as CO, NO, etc., at
all.
12
 The complex forming tendency and the stability of the complexes increases with
increasing atomic number. This fact is taken as a basis to take advantage in their
separation from one another. Ce(IV) complexes are relatively common, an example of
high oxidation state ion seeking stabilization through complexation.
 It is characteristic of the lanthanide ions (Ln3+) ions that coordination numbers
exceeding six are common.
 Very few six-coordinate species are known but coordination numbers of seven, eight,
and nine are important.
 In the ion [Ce(NO3)6]2-, the Ce is surrounded by 12 oxygen atoms of chelate NO3
groups.

13
Occurrence and separation of the lanthanoids
 All the lanthanoids except promethium (Pm) occur naturally. The most stable isotope
of promethium, 147Pm (β-emitter, t1/2 = 2.6 year) is formed as a product of the fission
of heavy nuclei and is obtained in mg amounts from products of nuclear reactors.
 Bastnäsite and monazite are the main ores for La and the lanthanoids.
 All the metals (excluding Pm) can be obtained from monazite, a mixed phosphate
(Ce, La, Nd, Pr, Th, Y . . .)PO4.
 Bastnäsite, (Ce, La . . .)CO3F, is a source of the lighter lanthanoids.
 The first step in extraction of the metals from monazite is removal of phosphate and
thorium (≈30 % of the monazite).
 The ore is heated with caustic soda, and, after cooling, Na3PO4 is dissolved in water.
 The residual hydrated Th(IV) and Ln(III) oxides are treated with hot, aqueous HCl;
ThO2 is not dissolved, but the Ln(III) oxides give a solution of MCl3 (M = La, Ce. . .)
which is then purified.
 The similarity in ion size and properties of the lanthanoids make separation difficult.
Modern methods of separating the lanthanoids involve solvent extraction using
[nBuO]3PO or ion exchange.
14
 A typical cation-exchange resin is sulfonated polystyrene or its Na+ salt.
 When a solution containing Ln3+ ions is poured on to a resin column, the cations exchange
with the H+ or Na+ ions

 The equilibrium distribution coefficient between the resin and the aqueous solution
([Ln3+(resin)] /[Ln3+(aq)]) is large for all the ions, but is nearly constant.
 The resin bound Ln3+ ions are now removed using a complexing agent such as EDTA4-.
 The formation constants of the EDTA4- complexes of the Ln3+ ions increase regularly from
1015.3 for La3+ to 1019.2 for Lu3+.
 If a column on which all the Ln3+ ions have been absorbed is eluted with dilute aqueous
H4EDTA, and the pH adjusted to 8 using NH3, Lu3+ is preferentially complexed, then Yb3+,
and so on.
 By using a long ion-exchange column, 99.9% pure components can be separated (figure given
below).

15
Figure: A representation of the order in which EDTA4- complexes of the heavier lanthanoids are eluted from a cation-
exchange column.
16
Isolation of Individual Lanthanide Elements:

The following methods have been used to separate lanthanides from one another.

1. 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. The separation
can be achieved by repeating crystallization process a number of times.

17
2. Fractional Precipitation Method:

 This method is also based on the difference in solubility of the precipitate formed,
which is formed on addition of the precipitant, i.e. Precipitating agent.

 If a little amount of precipitant is added, the salt with lowest solubility is precipitated
most readily and rapidly. For example, 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 precipitating the hydroxides a number of

times, it is possible to get the complete separation of lanthanide elements.

18
3. Valency change Method:
 This method is based on the change of chemical properties by changing the oxidation
state of the lanthanide elements. The most important application of this method is made
in the separation of cerium and europium elements from mixture of lanthanides.
i. The mixture containing Ln3+ ions if treated with a strong oxidizing 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.
ii. 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. 19
4. Complex Formation Method:

 This 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. However, 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.

20
5. Solvent Extraction Method:
 This method is based on the differences in the solubility of lanthanides salts in
water and an immiscible or partially miscible organic solvent. The organic
solvents are called extracting solvents or extractants.
 In this method, the aqueous solution of lanthanide salts is passed through the
organic solution which extracts the lanthanides from water. Tri-butyl
phosphate (TBP) is the most commonly used solvent for extraction of
lanthanides from dilute nitric acid solution. The solubility of Ln(III) elements
increases slightly with increasing atomic number.
 When TBP is used as extracting solvent and aqueous solution of lanthanide
salts are passed through it, the TBP form complexes with the Lu3+(aq) ions in
presence of NO3– ions.
Lu3+(aq) + 3NO3–(aq) + 3TBP (org)→ Lu(NO3)3(TBP)3(org) 21
6. Modern Ion-Exchange Method:
 This is the 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 Dowex-50).
 The resin is the sulphonated polystyrene containing-SO3H as the functional group. As the
solution of mixture moves through the column, Ln3+ (aq) ions replace H+ ions of the resin
and get themselves fixed on it:
Ln3+(aq) + 3H(resin) → Ln(resin)3 + 3H+(aq)
 The H+(aq) ions are washed through the column. The Ln3+(aq) ions are fixed at different
positions on the column. Since, Lu3+ (aq) is largest (Lu3+ anhydrous is smallest and is
hydrated to the maximum extent) and La3+(aq) ion is the smallest (La3+ anhydrous is largest
and is less hydrated). As a result, Lu3+(aq) ion is attached to the column with minimum
firmness remaining at the bottom and La3+(aq) ion with maximum firmness remaining at the
top of the resin column.
 In order to move these Ln3+(aq) ions down the column and recover them, a solution of
anionic ligand such as citrate or 2-hydroxy butyrate is passed slowly through the column
(called elution).
22
 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
 As the citrate solution (buffer) runs down the column, the metal ions get attached alternately
with the resin and citrate ions (in solution) many times and travel gradually down the column
and finally pass out of the bottom of the column as the citrate complex.
 The Ln3+(aq) cations with the largest size are eluted first (heavier Ln3+(aq) ions) because
they are held with minimum firmness and lie at the bottom of the column. The lighter
Ln3+(aq) ions with smaller size are held at the top of the column (with maximum firmness)
and are eluted at last. The process is repeated several times by careful control of
concentration of citrate buffer in actual practice.

23
Lanthanoid metals
 All the lanthanoids are soft white metals.
 Lanthanum and the lanthanoids, except Eu, crystallize in one or both of the close-
packed structures. Eu has a bcc structure and the value of rmetal given in Table 2.1 can
be adjusted to 205 pm for 12-coordination.
 It is important to notice in Table 2.1 that Eu and Yb have much larger metallic radii
than the other lanthanoids, implying that Eu and Yb (which have well-defined lower
oxidation states) contribute fewer electrons to M-M bonding. This is consistent with
the lower values of ΔaHo: Eu and Yb, 177 and 152 kJ mol-1 respectively, compared
with the other lanthanoids.
 The metal with the next lowest enthalpy of atomization after Eu and Yb is Sm.
 Like Eu and Yb, Sm has a well-defined lower oxidation state, but unlike Eu and Yb,
Sm shows no anomaly in its metallic radius. Further, Eu and Yb, but not Sm, form
blue solutions in liquid NH3 due to reaction.

24
Table 2.2 Standard enthalpies of atomization and hydration† (at 298 K) of the Ln3+ ions, sums of the first three ionization
energies of Ln(g), and standard reduction potentials for the lanthanoid metal ions.

25
 The later lanthanoid metals are passivated by an oxide coating and are kinetically more inert than the
earlier metals. Values of Eo for half-reaction lie in the range –1.99 to –2.38 V (Table 2.2).

 The following thermochemical cycle illustrates the factors that contribute to the enthalpy change for
the reduction of Ln3+(aq) to Ln(s):

 Values of ΔHo (defined above) for the lanthanoid metals can be determined using the data in Table 2.2.
The trend in ΔhydHo (Ln3+, g) is a consequence of the lanthanoid contraction, and offsets the general
increase in the sum of the ionization energies from La to Lu.
 The variations in ΔhydHo(Ln3+, g), sum of IE and ΔaHo(Ln) effectively cancel out, and values of ΔHo
are similar for all the metals with the exception of europium.
 The trend in values of Eo follows from the trend in ΔHo. However, actual Eo values must (i) be
determined from ΔGo rather than ΔHo and (ii) be related to Eo (defined as 0 V) for the reduction of
H+(aq) to 1/2H2(g).
26
1
 For +
(H / H2); ΔHoHyd = -1091 KJ/mol, IE1=1312 KJ/mol, ΔaHo = 218 KJ/mol.
2
Therefore its overall ΔHo = -439 KJ/mol the reduction potential (Eo) calculated from
these values are taken as 0 V.
 In addition to values of Eo for the Ln3+/Ln couple, Table 2.2 lists values of Eo for
half-reaction Ln2+/Ln couple, this being of greatest importance for Sm, Eu and Yb.

 As a consequence of the negative reduction potentials (Table 2.2), all the metals
liberate H2 from dilute acids or steam.

27
Lanthanide Compounds
 The lanthanides are very electropositive and reactive metals, the reactivity depends on the
size. Europium with the largest size is most reactive. All the lanthanides generally give
normal and complex compounds.
Oxides:
 If lanthanide elements are ignited in air or O2, they readily form the oxides of Ln2O3 type
except Ce which gives a dioxide, CeO2. The oxides are ionic and basic. The basic nature of
oxides decreases along the series with decreasing ionic size.

Hydroxides:
The lanthanides react slowly with cold water but readily with hot water:
2 Ln + 6 H2O → 2 Ln(OH)3 + 3H2

28
 On adding aqueous ammonia to this aqueous solution, hydroxides are precipitated as
gelatinous precipitate. These hydroxides are also ionic and basic, the basic nature decreasing
with increasing atomic number.
 La(OH)3 is most basic and Lu(OH)3 is least basic. Their basic character is more than that of
Al(OH)3 but less than that of Ca(OH)2.
Oxo-salts:
 Lanthanides form oxo-salts such as nitrates, sulphates, perchlorates and salts of oxo-acids
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 oxo-salts which decreases along the
series.
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.
 Reactions of F2 with Ln give LnF3 for all the metals and, for Ce, Pr and Tb, also LnF4.
Carbides:
 The carbides Ln2C3 and LnC2 are formed when the metals are heated with carbon. 29
Color
Table: Colours of aqua
 Most lanthanoid ions are only weakly coloured because their absorptions complexes of La3+ and Ln3+
in the visible region of the spectrum are commonly f-f transitions which
are symmetry forbidden.
 The exhibited color generally depends upon the number of unpaired
electrons
 Usually (but not invariably) f n and f 14-n species have similar colours.
 The ions having configuration f 0 and f 14 are colourless as they are
diamagnetic; and if any colour is present it is not due to f–f transition.
 Lanthanoid ions typically display weak but sharp absorption spectra
because the f orbitals overlap only weakly with the ligand orbitals.

 The spectra of their complexes generally show

much narrower and more distinct absorption
bands than those of d-metal complexes.
 The 5s and 5p orbitals are expected to shield the
4f electrons from the ligands.

Figure: The splitting of f orbitals in an octahedral crystal field. 30

Magnetic properties
 The magnetic moments of lanthanoid compounds arise from both spin and orbital contributions.
 From Ce3+ to Gd3+, the paramagnetic behaviour increases, then decreases and finally becomes
diamagnetic for Lu3+.
 Ce4+, Yb2+ and Lu3+ are diamagnetic.

Summary of the properties of lanthanoids

 They typically form compounds which are ionic and trivalent.
 Ionization energies are fairly low and comparable to alkaline earth metals. Hence, they are good
reducing agents.
 Complex formation tendencies are less. However, Lu3+ forms several complexes due to its small
size.
 Basic nature gradually decreases from La(OH)3 to Lu(OH)3 due to high polarization caused by
gradual decrease in size of M3+ ion. The hydroxides of lanthanoids, Ln(OH)3 are less basic than
Ca(OH)2 and more basic than Al(OH)3.
 Other reaction of lanthanoids can be summarized as shown in Figure 2.1.
31
Figure 2.1 Some important reactions of lanthanoids.
32
USES OF LANTHANIDES
 Use as catalysts: Lanthanide catalysts have been repeatedly recommended for use in numerous
organic reactions, including the hydrogenation of ketones to form secondary alcohols, the
hydrogenation of olefins to form alkanes, the dehydrogenation of alcohols and butanes.
 Use in the glasses industry: Cerium oxide has been found to be a more rapid polishing agent for
glass, and are used in the polishing of lenses for cameras and eyeglasses, as well as in polishing
mirrors and television faceplates. Very pure neodymium oxide, when added in sufficient
quantities (1–5 percent), gives a beautiful purple glass. Again CeO2, La2O3, Nd2O3 and Pr2O3 are
used as decolourizing agents for glasses.
 Cerium molybdate and cerium tungstate are used in paints and dyes.
 Cerium sulfide is used for making crucibles that can withstand temperatures up to 1950°C (as the
melting point is 2000 °C).
33
 Use in the metallurgical industry: Small amounts of misch metal (50 % Ce, 25 % La, 15 % Nd
and 10 % other rare-earth metals and iron) and cerium have long been added to other metals or
alloys to remove their nonmetallic impurities such as H, O, S, and As (by forming very stable
lanthanoid oxysulfides), which reduce the mechanical strength and ductility of steel. Misch metal
added to cast iron makes a more malleable nodular iron. Added to some steels, it makes them less
brittle. The addition of misch metal to certain alloys has been reported to increase the tensile
strength and improve the hot workability and the high-temperature oxidation resistance. The
flints of cigarette lighters and bullets are an alloy of misch metal and iron. The addition of misch
metal or pure rare-earth elements to magnesium increases its high-temperature strength and its
creep resistance — that is, resistance to slow deformation under prolonged use.
 Use in the television industry: It has been found that if a small amount of europium oxide
(Eu2O3) is added to yttrium oxide (Y2O3), it gives a brilliant-red phosphor. Colour television
screens utilize red, green, and blue phosphors. Compounds of the lanthanoids find a wide range
of applications, many of which depend on the optical properties associated with their f-f
electronic transitions: europium oxide and europium orthovanadate are used as red phosphors in
displays and lighting.

34
 Other applications: Another significant industrial application of rare earths is in the
manufacture of strong permanent magnets. Alloys of cobalt with rare earths, such as cobalt–
samarium, produce permanent magnets that are far superior to most of the varieties now on
the market. The alloys SmCo5 and Sm2Co17 of samarium and cobalt have very high magnetic
strengths, more than ten times that of iron and some magnetic iron oxides (Fe3O4). They also
have excellent corrosion resistance and good stability at elevated temperatures.

35
Chemistry of the Actinide Elements
 The group of fourteen elements from thorium (Th, Z = 90) to lawrencium (Lr, Z = 103) are
called actinides, actinoids or actinons. These are named so because these elements succeed
the element actinium (Ac, Z = 89). These elements are also known as inner-transition
elements as they lie between actinium and rutherfordium (Rf, Z =104), i.e., the elements of
fourth transition series. Thus, they constitute the second inner-transition series of which
actinium is the prototype.
 They are radioactive, and therefore of the greatest importance in the study of nuclear
chemistry and of the principles which underline the conversion of mass into energy.
 In these elements 5f-subshell of the antepenultimate shell (n = 7) is successively filled by the
additional or differentiating electrons, one at a time in each step, which are embedded in the
interior while 6d- and 7s-electons are exposed to the surroundings.
 The actinides lying beyond uranium, i.e., the elements with Z = 93 to 103 are called
transuranium elements.

36
Electronic Configurations
Table 2.3: Electronic configurations of Actinium and Actinoids and their ions

37
 The electronic configuration of actinium (Z = 89) which is followed by fourteen
actinides is [Rn]5f06d17s2, the last electron entering the 6d-subshell.

 It has been observed that the electronic configuration of actinides does not follow
the simple pattern as is observed for the lanthanides.

 For the first four actinide elements, viz., Th, Pa, U and Np, due to almost equal
energies of 5f and 6d, the electrons may occupy the 5f or 6d subshells or sometimes
both. From Pu (Z = 94) onwards, 6d1 electron gets shifted to 5f-subshell except for
Cm (Z = 96) and Lr (Z = 103) in which 6d1 electron does not shift to 5f due to stable
5f7 and 5f14 configurations.

 In view of the above considerations, the general valence shell electronic

configuration of the actinide elements may be written as: 5f0-146d0-27s2.
38
Oxidation States
 There is a greater range of oxidation states, which is in part attributed to the fact that the 5f,
6d and 7s levels are of comparable energies.
 The important oxidation states exhibited by actinides are given on table 2.4. The +3
oxidation state is exhibited by all the elements and it becomes more and more stable as the
atomic number increases. The +4 oxidation state is shown by the elements from Th to Cf, the
+5 oxidation state by Pa to Am, the +6 state by the elements from U to Am and the +7 state
is exhibited by only two elements, viz ., Np and Pu. Np in the +7 state acts as an oxidizing
agent.
 The principal cations given by actinide elements are An3+, An4+ and oxo-cations such as
AnO2+ (oxidation state of An = +5) and AnO22+ (oxidation state of An = +6). The examples
of oxo-cations are UO2+, PuO2+, UO22+ and PuO22+ which are stable in acid and aqueous
solutions.
39
 Most of the An3+ ions are more or less stable in aqueous solution. Np3+ and Pu3+ ions in
solution are oxidized to Np4+ and Pu4+ by air. The latter ions are further oxidized slowly to
NpO22+ and PuO22+ by air.
 The lighter elements up to Am show variable oxidation states, but the heavier elements show
maximum oxidation state of +3.
 Table 2.4 shows that a wide range of oxidation states is exhibited by the earlier actinoids, but from Cm
to Lr, the elements resemble the lanthanoids. This follows from the lowering in energy of the 5f
atomic orbitals on crossing the period and the stabilization of the 5f electrons.
 The most stable oxidation state is +3.

Table 2.4: Oxidation states of actinium and the actinoids.

40
Atomic and Ionic Radii
 There is no data for their atomic radii due to unstability. The ionic radii for M3+ and M4+
(according to data available) gradually decrease due to actinoid contraction as the number of
5f electrons increase. This is because the extra charge on the nucleus is poorly shielded by
the f-electrons.
Element Th Pa U Np Pu Am Cm Bk Cf Es Fm
Ionic radius of M3+ ion (pm) 108 105 103 101 100 99 99 98 - - -
Ionic radius of M4+ ion (pm) 96 93 92 91 90 89 88 87 - - -

 The values of ionic radii for both types of ions go on decreasing. This steady fall in the ionic
radii along the actinide series is called actinide contraction which is analogous to lanthanide
contraction found in lanthanides.
 The cause of actinide contraction is the same as has been discussed for the lanthanides. Here
also, increasing nuclear charge and poor shielding effect of 5f-electrons play an important
role.
 It is clear from above table that there is only a small variation in the ionic radii of the
actinide elements; hence they show similar chemical properties.
41
Occurrence and nature of the actinoids
 Of the actinoids, only the first four elements, viz., Ac, Th, Pa and U occur in nature. Among them
only uranium and thorium occur naturally in significant quantities. All the remaining actinides, i.e.
trans uranium elements are unstable and are made artificially. The elements above Fm (Z = 100)
exist as short lived species, some of them existing only for a few seconds.
 Amounts of Pa and Ac occurring naturally are too small. Therefore, they are artificially produced
by nuclear reactions along with the remaining actinoids.
 The naturally occurring isotopes of U and Th (238U, 99.275%, t1/2 = 4.46 x 109 year; 235U, 0.720%,
t1/2 =7.04 x 108 year; 234U, 0.005%, t1/2 = 2.45 x 105 year; 232Th, 100%, t1/2 =1.4 x 1010 year) are all
radioactive and their decay chains give rise to isotopes of actinium and protactinium:

42
 Uranium and thorium are isolated from natural sources. Thorium is extracted from monazite
as ThO2 , and the most important source of uranium is pitchblende (U3O8).
 The uranium ore is heated with H2SO4 in the presence of an oxidizing agent to give the sulfate
salt of the uranyl cation, UO22+
UO2 + 2 Fe3+ → UO22+ + 2Fe2+
UO3 + 2H+ → UO22+ + H2O
 The uranium is precipitated as the oxo-peroxo complex UO2(O2).2H2O.
 Thermal decomposition gives yellow UO3 which can be converted to UF4.

 Reduction of UF4 with Mg yields U metal.

 239Np and 239Pu have been produced synthetically by the bombardment of particular heavy
nuclides with particles such as neutrons as shown below

43
 Lengthy irradiation of 239Pu in a nuclear pile leads to the successive formation of small
quantities of 240Pu, 241Pu, 242Pu and 243Pu. The last is a β- -emitter (t1/2 = 5h) and decays to
243Am (t 244Cm
1/2 = 7400 year) which gives

 Both 243Am and 244Cm are available on a 100 g scale, and multiple neutron capture followed by β--
decay yields milligram amounts of 249Bk, 252Cf, 253Es and 254Es, plus microgram amounts of 257Fm. The
isotopes of elements above Fm are short-lived and only tracer quantities are accessible.
 All of transuranium elements have been produced synthetically by the bombardment of particular heavy
nuclides with particles such as neutrons and 126Cn+ or 188On+ ions

 The target materials in the above equations are actinoid elements which have relatively long half-lives
( 249 248
97𝐵𝑘, t1/2 = 300 days; 96𝐶𝑚, t1/2 = 3.5 x 10 year).
5

 Studying the product nuclides is extremely difficult because of their short half-lives ( 260
103𝐿𝑟, t1/2= 3
min; 261
103𝑅𝑓, t1/2 = 65 s).
44
Physical and Chemical Properties
 The actinoids metals are all silvery in appearance with a variety of structure.
 Their melting points are moderating high but are considerable low as compared to those of
transition elements.
 All the actinides are very reactive and show the phenomenon of radioactivity. The dominant
feature of the actinoids is their nuclear instability as they have tendency to undergo spontaneous
fission and decay becomes more pronounced with the heavier elements. The radioactivity of Th
and U is probably responsible for much of the earth’s internal heat.
 The actinoids metals are highly electropositive and are reactive, reactivity increase with increase
in atomic number.
 They tarnish rapidly in air (pyrophoric when finely divided), forming an oxide coating which is
protective in case of Th but less for the other elements.
 The metals react with most non-metals especially on heating, but resist alkali attack and are less
reactive towards acids than might be expected. Concentrated HC1 react rapidly but concentrated
HNO3 makes Th, U and Pu passive.
 With boiling water or steam, H2 is obtained and metal is converted into oxide.
 Metals react rapidly with H2 forming hydrides which are decomposed by H2O.
45
UO2 UH3
U U
Δ

 The actinide elements have much higher tendency to form complexes than
lanthanoids. A characteristic feature of the compounds and complexes of actinides,
like the lanthanides, is the occurrence of high coordination numbers up to 12 as in
[Th(NO3)6]2-. 46
 The instability of the actinoids with respect to radioactive decay has already been mentioned,
and Table 2.5 lists data for the longest-lived isotope of each element.
 All the actinoids are highly toxic, the ingestion of long-lived α-emitters such as 231Pa being
extremely hazardous. Extremely small doses are lethal.
 Table 2.5 Half-lives and decay modes of the longest-lived isotopes of actinium and the
actinoids.

47
 Actinium occurs in traces in U minerals, but can be made on a milligram scale by neutron
reaction. It is a soft metal which glows in the dark. It is readily oxidized to Ac2O3 in moist air,
and liberates H2 from H2O. It is lanthanum-like in its chemistry, which is difficult to study
because of the intense radiation of the decay products.
 Thorium is widely distributed, but the chief mineral is monazite sand, a complex phosphate
that also contains lanthanides. It is relatively stable in air, but is attacked slowly by H2O and
rapidly by steam or dilute HCl. On heating, Th reacts with H2 to give ThH2, halogens to give
ThX4, and N2 and C to give nitrides and carbides; it forms alloys with a range of metals (e.g.
Th2Zn, CuTh2).
 Protactinium can be isolated from residues after the extraction of uranium from pitchblende.
It is ductile and malleable, is not corroded by air, but reacts with O2, H2 and halogens when
heated, and with concentrated HF, HCl and H2SO4.

 Only few compounds, some of Pa4+ but mostly Pa5+, are known. For example, the chloride is
Pa2Cl10, the oxide is Pa2O5, and the fluoroanions [PaF6]-, [PaF7]2-, and [PaF8]3- are formed.
48
 Uranium corrodes in air; it is attacked by water and dilute acids but not alkali. The
scheme given below gives selected reactions. With O2, UO2 is produced, but on
heating, U3O8 forms.

 Uranium normally has a black oxidized film. When enriched in 235U, the metal can
initiate a nuclear explosion above a certain critical mass, and this is true also for
plutonium.
 The most common and known element is Uranium, which is used as nuclear fuel when
it’s converted into plutonium, through a nuclear reaction.

49
 U reacts with H2 even at room temperature but the reaction is faster at 250 oC as
compared to room temperature:
2U + 3H2 → 2UH3
 This hydride is often more suitable for the preparation of uranium compounds than is
the massive metal. Some typical reactions are:
 2UH3 + 4H2O → 2UO2 + 7H2

 2UH3 + 4Cl2 → 2UCl4 + 3H2

 2UH3 + H2S → 2US2 + 4H2

 2UH3 + 8HF → 2UF4 + 7H2

 UH3 + 3HCl → UCl3 + 3H2

50
 Neptunium is a reactive metal which quickly tarnishes in air. It reacts with dilute
acids liberating H2, but is not attacked by alkali.
 Despite the fact that the critical mass of plutonium is <0.5 kg and it is extremely
toxic, its uses as a nuclear fuel and explosive make it a much-studied element. It reacts
with O2, steam and acids, but is inert towards alkali. On heating, Pu combines with
many non-metals to give, for example, PuH2, PuH3, PuCl3, PuO2 and Pu3C2.
 Americium is a very intense α- and γ-emitter. It tarnishes slowly in dry air, reacts with
steam and acids, and on heating forms binary compounds with a range of non-metals.
 Curium corrodes rapidly in air; only minute quantities can be handled (<20 mg in
controlled conditions).
 Berkelium and californium behave similarly to Cm, being attacked by air and acids,
but not by alkali. Curium and the later elements are handled only in specialized
research laboratories.

51
Some important points to be noted are as follows:
 The chemical properties of the actinoids show less uniformity across the series than those of the
lanthanoids. However, the radioactivity associated with most of the actinoids has hindered their
study. Because the later actinoids are available in such tiny amounts, little is known about their
reactions. The early actinoids, particularly uranium and plutonium, are of great importance in the
generation of power through nuclear fission and their chemical properties have been investigated
thoroughly.
 Uranium is the heaviest naturally occurring element.
 After uranium, 12 more elements have been artificially synthesized (having atomic number more
than 92).
 All actinoids are radioactive (having different half-lives).
 Due to their high radioactivity, studies of their properties become difficult. Many of the physical
and chemical properties of the actinoids are unknown because only minuscule quantities have ever
been isolated; in addition to being radioactive, many actinoids are known to be poisonous and all
are treated as hazardous in the laboratory.
 The 5f orbitals extend in space beyond 6s and 6p orbitals and participate in bonding. The f-f
transitions are broader and more intense than for the lanthanoids because the 5f orbitals interact
more strongly with the ligands. 52
 Ionization energy of the early actinoids are smaller than those of early lanthanoids. When
electrons are being filled into 5f-orbitals they will penetrate less into the inner core of the electrons
and thus these occupied 5f-electrons will be more effectively shielded from the nuclear charge
than are the 4f-electrons of the corresponding lanthanoids.
 Actinides have the ability to form stable complexes with ligands, such as chloride, sulfate,
carbonate and acetate.
 The emission of radioactivity, toxicity, pyrophoricity, and nuclear criticality are properties that
make actinides hazardous to handle.

53
Uses of actinoids
 Their current primary use is in nuclear reactors and nuclear weapon (239Pu and 235U).
 Thorium (232Th) is used as fuel rods in nuclear reactors and Thorium (227Th) used in the treatment of
cancer.
 Uranium salts are used to impart green colour to glass and are used in medicines.
 Detecting smoke with 241Am: Commercial smoke detectors may function using a photoelectric detector or an
ionization chamber. An ionization detector consists of two plates across which a voltage (supplied by a battery) is applied
(see diagram). One plate has a hole in it, and under the hole lies a small quantity (typically 2 x 10-4 g) of 241Am, an α-
particle emitter with t1/2 = 432 yr. As the α-particles enter the chamber, they ionize atmospheric gas molecules, resulting in
X+ ions which are attracted to the negatively charged plate, and electrons which migrate to the positively charged plate. A
current flows which is calibrated to correspond to a smoke-free zone. When smoke enters the chamber, the current changes
as ions interact with the smoke particles. The sensor is equipped with an alarm which is triggered when a change in current
is detected.

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