Actinides

[B] Actinides (5f- Block elements)

Definition: The elements in which the extra electron enters 5f- orbitals of (n-2)th main shall are
known as 5f-block elements, actinides or actinones. Thus, according to the definition of
actinides only thirteen elements from Th90 (5f0 6d2 7s2) to No102 (5f14 6d0 7s2) should be the
members of actinide series. However, all the fifteen elements from Ac89 (5f0 6d1 7s2) to Lw103
(5f14 6d1 7s2) are considered as the members of actinide series, since all these fifteen elements
have same physical and chemical properties. In fact actinium is prototype of actinides as
lanthanum is the prototype of lanthanides.
General electronic configuration of actinides is 2,8,18, 32, 5s2, p6 d10 f0-14, 6s2 p6 d0-2, 7s2

 Electronic configuration of actinides:

Nos. Name At. No. and symbol Electronic configuration
1 Actinium Ac89 [Rn] 5f0 6d1 7s2
2 Thorium Th90 [Rn] 5f0 6d2 7s2
3 Protactinium Pa91 [Rn] 5f2 6d1 7s2
4 Uranium U92 [Rn] 5f3 6d1 7s2
5 Neptunium Np93 [Rn] 5f4 6d1 7s2
6 Plutonium Pu94 [Rn] 5f6 6d0 7s2
7 Americium Am95 [Rn] 5f7 6d0 7s2
8 Curium Cm96 [Rn] 5f7 6d1 7s2
9 Berkelium Bk97 [Rn] 5f9 6d0 7s2
10 Californium Cf98 [Rn] 5f10 6d0 7s2
11 Einstenium Es99 [Rn] 5f11 6d0 7s2
12 Fermium Fm100 [Rn] 5f12 6d0 7s2
13 Mendelevium Md101 [Rn] 5f13 6d0 7s2
14 Nobelium No102 [Rn] 5f14 6d0 7s2
15 Lawrencium Lw103 [Rn] 5f14 6d1 7s2

 Oxidation states of actinide elements:

Composition of the oxidation states of lanthanides with those of actinides indicates that +3
oxidation state is most common for both the series of elements. The oxidation state of actinide
element is given below:

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
+2
+3 - - +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7

This oxidation state becomes increasingly more stable as the atomic number increases in the
actinide series. The increasing stability of +3 oxidation state is illustrated by the increasing
difficulty of oxidation above +3 oxidation state. Actinides show a greater multiplicity of
oxidation states. Since in the first half of the actinide series (i.e. lower actinides) the energy
required for the conversion 5f→6d is less than that required for the conversion 4f→5d, the
lower actinides should show higher oxidation state such as +4, +5, +6 and +7. Correspondingly,
since in the second half of the actinide series (i.e. higher actinides), the energy required for the
conversion 5f→6d is more than that required for the conversion 4f→5d, and the higher
actinides should show more lower oxidation states such as +2.
The tripositive oxidation state occurs widely in each series. The two groups of elements are
not entirely comparable in this respect. The +3 state characteristic of lanthanides does not
appear in aqueous solution of Th and Pa and this oxidation state become the predominantly
stable oxidation state in aqueous solution of the actinides only when we reach Am.
For Th & Pa the +4 & +5 oxidation states are important respectively. From Uranium onward
there is very closely related groups U, Np, Pu & Am in which the stability of higher oxidation
sate takes place.
The different oxidation states are explained as under:
+2 oxidation state: Only Am (Americium) is known to form a stable +2 state. This state is stable
in CaF2 only and has been studied by optical and electron spin resonance spectra.
+3 oxidation state: +3 state is a general oxidation state for most of the actinides. For Th and Pa
+4 and +5 state respectively are important. An+4ions resemble Ln+4 ions in their properties. A
large number of isomorphous salts are given by the elements of both the series. Trichlorides
and trifluorides of Ac, U, Np, Pu and Am are isomorphous. On hydrolysis all the halides give
oxyhalides Ac, Pu, and heavier elements give the oxides of An2O3 type. Nitrate, perchlorates
and sulphates are soluble while hydroxides, fluorides and carbonates are insoluble.
+4 oxidation state: This is the principle oxidation state for Th and is a stable oxidation state up
to Am. Am+4 and Cm+4 exist only as complexes in concentrated fluorides solution of low acidity.
General chemistry of An+4ions is similar to that of Ln+4 ions. The hydrated fluorides and
phosphates of both An+4 and Ln+4 ions are insoluble ThO2, PaO2, UO2, NpO2, AmO2, CmO2 and
BkO2 have fluorite structure. The tetrachlorides and tetrabromides of Th, Pa,U and Np are only
known, while tetraiodides of Th, U and Np can be prepared by heating AnX4 with Sb2O3. An+4
ions from complexes mostly with anionic ligands like HSO4-, No3-, Cl- etc.
+5 oxidation state: This state is very important for Pa. Pa+5 resemble very much Na+5 and Ta+5.
U, Np, Pu and Am also exist in +5 oxidation states, but these are less characterized. The only
known pentahalides are those of Pa+5 and U+5. Fluoro anions of Pa, U, Np and Pu of the types
AnF6- , AnF7-2 and AnF8-3 are known to exist in the solid state; AnO2+ is the most important ion
which contains An+5 cation. It has linear structure both in solid and solution.
+6 oxidation state:U, Np, Pu and Am show +6 oxidation state in divalent dioxo cation AnO2+2.
This cation is linear both in solid and solution. The simple molecular halide, UO2F2 has the linear
O-U-O group with flourine bridges .The O-U bond distance is 1.75 o 2.00 Å. The overall structure
is flattened octahedron .Although AnO2+2cation is linear in shape, it forms complexes with
exceptional geometries, e.g. four, five and six co-ordinated complexes are given by this cation.
+7oxidation state: +7 oxidation state is shown only by Np and Pu. Electrolysis or ozone
oxidation of Np+5 or Np+6 in NaOH gives a green solution of NpO5-3 which is slowly reduced to
Np +6 at 250C.

Actinide Contraction: The shielding of one f-electron by another from the effect of nuclear
charge is quite weak on account of the shape of the f- orbital, hence with increasing atomic
number, the effective nuclear charge experienced by each 5f-electron increases. This causes
shrinkage in the radius of atoms or ions as one proceed from Ac to Lw. This accumulation of
successive shrinkage is called actinide contraction.
 Comparison of Actinide and Lanthanide elements:

Lanthanides Actinides
1. In lanthanide the newly added electron 1. In actinide the newly added electron enters
enters in 4f- orbitals. in 5f- orbitals.
2. The name lanthanide is given because the 2. The name actinide is given because the first
first element is lanthanum and all the other element is actinium and all the other elements
elements have similar property to that of have similar property to that of actinium
lanthanum element. element.
3. They have less binding energy, hence less 3. They have more binding energy, hence
shielding effect in 4f- orbital. more shielding effect in 5f- orbital.
4. They have low tendency to form complex. 4. They have greater tendency to form
They form complex with ligand having oxygen complex with π-accepter ligand and anions.
or oxygen plus nitrogen like glycine, oxalate
etc.
5. Their colour absorptive spectra are less 5. Their colour absorptive spectra are more
intense than actinides. intense than lanthanides.
6. They have lower ionic radii than actinides. 6. They have greater ionic radii than
lanthanides.
7. They have more magnetic moment than the 7. They have less magnetic moment than the
actinides. lanthanides.

 Position of Actinides in the Periodic table:

The position of actinides can be explained in two ways:
(i) Prior to the discovery of the trans-uranium elements:
Before 1940, the existence of the lanthanide series helped that another series of elements
resulting from the addition of the electrons to an (n-2) f- shell (i.e. 5f - shell) should occurs
somewhere in the heavy elements region. Prior to the discovery of trans-uranium elements, the
naturally occurring heaviest known elements namely Th90, Pa91, and U92 where placed below
Hf72, Ta73, W74 in IV B, V B and VI B groups of the periodic table because these elements showed
+4, +5 and +6 oxidation states and resembled Hf, Ta and W respectively in many of their
properties. The undiscovered trans-uranium elements with atomic numbers 93 to100 were thus
expected to occupy the position in the periodic table below Re75, Os76, Ir77, Pt78, Au79, Hg80, Tl81
and Pb82 respectively as shown below:

(ii) Following the discovery of the trans-uranium elements:

The discovery of the element neptunium (Np93) came in 1940 and this discovery was
followed shortly by the discovery of plutonium (Pu94) in 1941. The tracer chemical experiment
 with Np93 and Pu94 showed that the chemical properties of these of Re75 and Os76. On this basis
in 1944, the position of U92, Np93 and Pu94 was shown in the periodic table as shown below:

It was thought that the undiscovered elements with atomic numbers 95 and 96 should be
very much like U92, Np93 and Pu94 in their chemical properties. This assumption, however, proved
to be wrong, since the experiments directed towards the discovery of elements with atomic
numbers 95 and 96 on the pattern of discovery of Np93 and Pu94 failed. Later on in the same year
(1944) Seaborg thought that all the known elements heavier than Ac89 were wrongly placed in
the periodic table as shown in above figure.
He advanced the idea that the elements having atomic numbers greater than that of
Ac89 might constitute a second series of inner transition elements similar to the lanthanides
series. There elements are called actinide elements. The new position of the actinides was
further confirmed by the fact that all the predicted elements up to 130 were discovered by
1961. As shown in figure below:

 Separation of Actinide elements:

(1) Solvent extraction method:
This method depends on the extractability of the various oxidation state
of actinide elements. This technique finds extensive application in the recovery of U and Pu
from used – up nuclear fuels. This process is based on the distribution of a metal between the
aqueous solution and an organic solvent. Thus with methyl isobutyl ketone (hexone) Np+4, Np+5,
Pu+6 and U+6 are extracted while Pu+3 is not extracted. Diethyl ether and tri-n-butyl phosphate
(TBP) are other solvent which are used as extractants. Because of the high velocity and density,
TBP is used as 20% solution in kerosene. The method is preferentially applied to nitrate system,
because other ions like sulphate, perchlorate, fluoride etc are strongly complexing and tend to
retain the method in aqueous solution. Hexane and diethyl ether require a high concentration
of No3- ions in the aqueous phase and it is achieved by adding Al(No3)3 which has a high salt –
out action. TBP is resistant to nitric acid oxidation and acts by itself as a salt agent. Solvent
extraction of Pu and U by hexone and TBP is shown below:
(i) Separation of Pu and U from fission products (FP’s) by solvent extraction with hexone (Redox
process).

(ii) Separation of Pu and U from fission products (FP’s) by solvent extraction with tributyl
phosphate TBP (Purex process):

(2) Ion – exchange technique:

This is the best technique to separate the actinide ions. This method involves the
following two steps:
(i) Lanthanide – actinide separation:
The actinide as a group are separated from lanthanides by cation – exchange resin. Strong
HCl is used as the eluting agent. The actinide ions from chloride complexes more easily and
hence are eluted first.
 Separation of actinides from Lanthanides is now done on an anion – exchange resin with
10ml LiCl as eluent at elevaled temperature up to 900c with the exceptions of Gd, Ho and of Cm,
Es the elution sequences proceed in the order of increasing atomic number. Thus La is absorbed
least strongly.
(ii) Separation of individual actinide elements:
The actinide ions can be separated from each other by removing from the cation
exchange resin by elution with ammonium citrate, lactate, α-hydrogen isobutyrate and ethylene
diamine tetracetate. If the activity is plotted against the number of drops of eluent , elution
curves will be obtained as shown below:

Lw (at. no. z = 103) is predicted to leave the column first to be followed by No (z= 102) and so on
down the scale of atomic numbers. Elution position for Md (z= 101) Fm (z= 100) and down to
Am (z=95) are shown in the typical elution carves elution carves for lanthanides are also shown
in figure as under.

3+ 3+
Figure: Elution curves showing the elution positions of Ln and An ions eluted from Dowex-50 ion-
exchange resin with ammonia alpha-hydroxy-isobutyrate. The dotted elution curve indicates the
predicted position of the then undiscovered elements with atomic number 102.
It may be noted that a very striking similarity occurs in the spacing of the corresponding
elements in the two series (e.g. Am and Eu, Cm and Gd, Bk and Tb etc.). It is similarity that made
possible for scientists to predict the elution positions of the elements from Bk97 to Md101 before
their discovery and which also makes possible today to predict the elution position of elements
with no (z= 102) and Lw(z = 103).
There is a distinct breakdown between Gd and Tb (Lanthanide series) and between
Cm and Bk (actinide series), which can be attributed to the small change in ionic radians made
 by the half-filling of 4f and 5f shells respectively. The elution order is not always regular as
shown in above figure.
 Color and Absorption spectra of actinide ions:
Colors and the wavelengths of the more prominent light absorption bands of actinide ions
like An+3, An+4, AnO2+ and AnO2+2 are given in table as under.
Table: Color and Wave lengths (in Å) of more prominent light absorption bands of actinide ions.
Elements An3+ ions An4+ ions AnO2+ ions AnO22+ ions
–
Ac Colorless (5fo) – –
Colorless (5fo)
Th – – –
Colorless (5f1)
Pa – (2240,2550,2700) Colorless –

Red (5f3) Green (5f2) Yellow

U –
(5200,8800,9000) (5500, 6500) (4000, 4110,4250)
Blue or Purple (5f4) Yellow-Green (5f3) Pink to Red
Np Green
(5520, 6610, 7875) (5040, 7430, 8250) (4760, 5570)
Blue or Violet (5f5) Tan to orange brown (5f4) Yellow to pink orange
Pu Reddish-Purple
(5600, 6000, 6030) (4700, 6550, 8150) (8330, 9530, 9830)
Pink (5f6) Yellow Run-colored
Am Rose (5f7)
(5027, 8200) (5131, 7151) (6660, 9950)
Colorless (5f7)
Cm – – –
(2368, 2680, 2774)

If may be seen that by comparing the colors of Ln+3 and An+3 ions the pairs of ions which have
the same number of f- electrons (4f and 5f electron) have roughly comparable color. The pairs
viz. (i) Nd+3 (4f3- reddish) and U+3 (5f3- reddish) and (ii) Gd+3 (4f7- colorless) and Cm+3 (5f7 –
colorless) illustrate this point. Ce+3 (4f1) and Pa+4(5f1) ions are colorless.
The absorption spectra of actinide ions, in aqueous solution and in crystals, contain
narrow bands in the visible, near ultraviolet and near infrared regions of the spectrum. The
bands seen in case of actinide ions arise from electronic transitions between energy states
within the 5f- electron sub- sell. It has been found that the absorption bands seen in case of
actinide ions are about ten times sharper than those seen in case of lanthanide ions. The
absorption spectra of lanthanide ions are observed due to electronic transitions between
energy states within the 4f-electron sub-shell.
Light absorption spectra of lanthanides are much more affected by environment.
Charge-transfer phenomena occur more frequently and the bands are more intense in the
actinides because of lower energy involved in transitions. Moreover, the overlap of 5f- orbitals
with the ligand orbitals increases the intensity of absorptions bands.

 Magnetic properties of Actinide elements:

In the 5f-series, Pu+3 and Am+3 ions show analogous behavior as noted for Sm+3 and
Eu+3 ions in 4f-series. The magnetic properties of the actinides ions are considerably more
difficult to explain than those of the lanthanide ions. The values of magnetic moments found
experimentally are usually lower than those calculated using russellsaunders coupling scheme.
This is due perhaps to the inadequacy of the russellsaunders coupling scheme for 5fn ions and
also to more soluble ligand field effects which involve 5f-orbitals to a greater extent than the
4f-orbitals are involved in bonding in the lanthanide complexes.
An equation used for the calculation of molar susceptibility XM is given by,

( )
XM = + Nα

Where N = Avogadro’s number, g= lande splitting factor

Which is given by:

( ) ( ) ( )
g= 1 +
( )

β = Bohr magneton =
= 9.27 x 10-21 erg/gauss
J = Total angular momentums of atom = | L+S|
K = Boltzmann constant, T = absolute temperature and α = small temperature independent
term due to second order Zeeman effect.
Strictly speaking the above equation can be applied only to gaseous ions in which the
multiplet intervals are larger compound to KT and value of J to be used in it is taken from the
ground state symbols of ions.

Figure: Comparison of magnetic susceptibility of Lanthanides and Actinides

A comparison of the plots of molar magnetic susceptibilities of tripositive lanthanide and
actinide ions against the number of 4f or 5f – electrons (as shown in above figure) reveals that
there are remarkable similarities between the two plots. The plot of lanthanide ions has two
humps while that of actinide ions has only one. In both the cases the first hump is at the
identical place. The moments of the lanthanide ions agree closely with theoretical predictions
 but those of the transuranic ions are somewhat lower than expected as shown in figure below.
This is because the 5f-electons of the transuranic ions are less effectively screened from the
crystal field and then are the 4f-electrons of the lanthanide ions.

Figure: Comparison of magnetic moments of Lanthanides and Actinides.

 Complex formation of Actinide elements

The degree of complex formations decreases in the order:

An+4 > AnO2+2 > An+3 > AnO2+

The complexing power of different singly charged and doubly charged anions follows the order:

Singly charged anions: F- > No3- > Cl-

Doubly charged anions: Co3-2 > Ox-2 > So4-2

Actinides also form complexes with a large number of organic substances.