Presentation 8

Properties of actinides
 Actinides
• 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.
• 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.
• In the outermost and penultimate shell of these elements, the number of
electrons remains almost the same. That is why the actinide elements
resemble one another very closely.
• The actinides lying beyond uranium, i.e., the elements with Z = 93 to 103
are called transuranium elements
 Electronic Configuration
• The electronic configuration of actinium (Z = 89)
which is followed by fourteen actinides is
[Rn]5f06d17s2, the last electron entering the 6d-
subshell.
• In the next element, Th, the first member of the
actinide series, the additional electron must enter 5f-
subshell and the filling of 5f-subshell must continue
progressively till the last element, Lr.
• Thus, 6d-subshell in all the elements must remain
singly filled thereby giving the expected valence shell
configuration of 5f1-146d17s2 for these elements.
• 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.
• Element Atomic No. (Z) Electronic Configuration of outer orbital

Actinium(Ac) 89 6d17s2
Thorium (Th) 90 5f16d17s2
Protactinium (Pa) 91 5f26d17s2
Uranium (U) 92 5f36d17s2
Neptunium (Np) 93 5f46d17s2
Plutonium (Pu) 94 5f67s2
Americium (Am) 95 5f77s2
Curium (Cm) 96 5f76d17s2
Berkelium (Bk) 97 5f97s2
Californium (Cf) 98 5f107s2
Einsteinium (Es) 99 5f117s2
Fermium (Fm) 100 5f127s2
Mendelevium (Md) 101 5f137s2
Nobelium (No) 102 5f147s2
Lawrencium (Lr) 103 5f146d17s2
• Comparison of the electronic configuration of Ln and An shows both a
substantial overall similarities.
• The energy separation between the 5f and 6d orbitals even smaller in
actinides than between 4f and 5d orbitals in lanthanides.
• Spectroscopic, chemical and other data tell that 5f level becomes
progressively lower in energy compared to 6d level with increasing
atomic number.
• The spatial extension of 5f orbitals relative to 6s and 6p orbitals is thus
greater than 4f orbitals relative to 5s and 5p orbitals.
• The difference is lower binding energies and less effective shielding of
the 5f electrons than those of 4f orbitals.
• The actinides have deeply seated incomplete 5f orbitals compared to 4f
orbitals.
• 4f and 5f orbitals differ in their radial distribution functions. The radial
distribution of 4f orbitals shows a small shell of electron density below
the main 5p orbital.
• Therefore 5f orbitals are more penetrating than 4f
orbitals.
• In lanthanides, there is no interaction between 4f and the
surrounding ligands.
• The 5f orbitals which are more penetrating than 4f
orbitals are little more diffused at the periphery of the
atom and these orbitals are disturbed by the ligands.
• The energy difference between different levels and
sublevels decreases with increasing atomic number. Thus,
in the actinides the energies of 5f,6d,7s and 7p orbitals are
equal.
• Therefore the bonding in the compounds of actinides can
involve any or all of these orbitals.
• Unlike lanthanides, actinides can form complexes not
only with anions such as X-, SO42- but also with pi
bonding ligands such as alkyl phosphines, thioethers and
Cp by the use of 5f orbitals.
 Oxidation states
• Like Ln, An exhibit +3 common oxidation state.
• Actinides show a greater multiplicity of oxidation state since in the
first half of actinides series, the energy required for the conversion
(5f 6d) is less than that of 4f 5d.
• Lower actinides show more higher O.S. such as +4, +5, +6 and +7.
• In second half of the series, the energy required for the conversion
5f 6d is more than that required for the conversion 4f 5d, the
higher actinides show lower O.S.
• The second half of the series appears to parallel with Ln.
• The lower O.S. tend to be ionic and higher ones are covalent.M2+,
M3+ and M4+ ions are all known.
• Hydrolysis of these ions occurs quite readily but can be suppressed
by using acid solution such as perchloric acid.
• Hydrolysis of compounds in the higher O.S. gives +V MO2+ ions
and +VII MO22+ ions.
• The most stable oxidation states for the first four elements are Th(+IV), Pa(+V),
U(+VI).
• Though Np(+VII) exists, the most stable state is (+V).
• Pu shows all the O.S. from +III to +VII, but the most stable is Pu(IV).

Various oxidation states of the actinides are listed below:

Element Oxidation states
Ac +3
Th +2, +3, +4
Pa +3, +4, +5
U +3, +4, +5, + 6
Np +3, +4, +5, +6, +7
Pu +3, +4, +5, +6, +7
Am +2, +3, +4, +5, +6,
Cm +3, +4
Bk +3, +4
Cf +3, +4
Es +2, +3
Fm +2, +3
Md +2, +3
No +2
Lr +3
 Atomic and Ionic radii- Actinide contraction
• The atomic size/ ionic radii of tri positive actinides ions decrease
steadily from Th to Lr due to increasing nuclear charge and
electrons entering the inner (n-2) f orbital. Imperfect screening of
the increasing nuclear charge by the additional 5f electrons results
in a contraction of the outer or valence orbital. This gradual
decrease in the size with an increasing atomic number is
called actinide contraction like lanthanide contraction.
• The jumps in the contraction between consecutive elements in
the An is greater than in the Ln.
• The greater contraction is due to the lesser shielding of 5f
electrons which are therefore pulled more strongly by the
nucleus.
• The actinide contraction leads to a decrease in the basicity of
the elements with increasing atomic number.
 Color and absorption spectra
• Actinides ions are generally colored. The color of the ions depends upon
the number of f-electrons.
• The pairs of ions which have the same number of f-electrons have roughly
comparable colors.
• 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 electronic spectra of actinide compounds arise from the following three
types of electronic transitions:
• (a) f-f transitions: These are Laporte (orbitally) forbidden but the selection
rule in relaxed partially by the action of crystal field in distorting the
symmetry of the metal ion. Because the actinides show greater field, hence
the bands are more intense. These bands are narrow and more complex, are
observed in the visible and UV regions and produce the colours in aqueous
solutions of simple actinide salts
• (b) 5f-6d transitions: These are Laporte and spin allowed transitions and
give rise to much more intense bands which are broader. They occur at
lower energies and are normally confined to the UV region hence do not
affect the colours of the ions.
• (c) Metal to ligand charge transfer: These transitions are also fully
allowed and produce broad, intense absorptions usually found in UV
region, sometimes trailing in the visible region. They produce the intense
colours which are characteristic of the actinide complexes.
• The spectra of actinide ions are sensitive to the crystal field effects
and may change from one compound to another.
• It is not possible to deduce the stereochemistry of actinide
compounds due to complexity of the spectra. Most of the actinide
cations and salts are coloured mainly due to f-f transitions. Those
with f0, f7 and f14 configurations are colorless. The colors of some of
the compounds in different oxidation states are given below:
• NpBr3 : green; NpI3 : brown; NpCl4 : red-brown;
• NpF6 : brown PuF3 : purple; PuBr3 : green;
• PuF4 : brown; PuF6 : red brown AmF3 : pink;
• AmI3 : yellow;
 Magnetic Properties
• The actinide elements like lanthanides show paramagnetism in the
elemental and ionic states.
• Tetravalent thorium (Th4+) and hexavalent uranium (U6+) ions are
diamagnetic due to the absence of unpaired electrons.
• Spin-orbit coupling is strong (2000-4000cm-1) in the actinides
• 5f and 6d-subshells are sufficiently close in energy for the lighter
actinides to make 6d levels accessible. As a result, each actinide
compound has to be considered individually. This must allow the mixing
of J levels obtained from Russel-Saunders coupling and population of
thermally available excited levels.
• The magnetic properties of actinides are smaller than the theoretical
values. This is due to the fact that 5f electrons of actinides are more
exposed to crystal field and therefore, are less effectively shielded which
results in quenching of the orbital contributions.
• An equation used for the calculation of molar susceptibility XM is
given by,
• XM = (Ng2 2J(J+1)/3kT ) + Nα
• Where N = Avogadro’s number, g= lande splitting factor Which is
given by:
𝑆 𝑠+1 +𝐽 𝐽+1 −𝐿(𝐿+1)
• g=1+
2𝐽(𝐽+1)
• β = Bohr magneton = eh/2mc= 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
 Comparison of Actinide and Lanthanide elements:

Lanthanides Actinides
Binding energies of 4f are higher Binding energies of 5f are lower
4f electrons have comparatively greater 5f electrons have poor shielding effect
shielding effect
They have low tendency to form complex. They have greater tendency to form complex
They form complex with ligand having with π-accepter ligand and anions.
oxygen or oxygen plus nitrogen like glycine,
oxalate etc.
Their colour absorptive spectra are less Their colour absorptive spectra are more
intense than actinides intense than lanthanides
They have lower ionic radii than actinides They have greater ionic radii than lanthanides

They have more magnetic moment than the They have less magnetic moment than the
actinides lanthanides.
Except prometheium they are non-radioactive All of them are radioactive
They do not form oxocations They form oxocations
Maximum oxidation state exhibited by Ln is Due to lower binding energies they show
+4 higher oxidation states such as +4, +5 ,+6 and
+7
• Similarities

• The elements of both series exhibit +3 oxidation state which is

prominent and predominant state.
• Just like Ln contraction, we have An contraction
• In both the series, f orbitals are being progressively filled.
• Absorption spectra of the elements of both the series sharp line
like bands appear due to f-f transitions.