Properties of Lanthanide and Actinides

Electron Configuration
Oxidation States
Magnetic Properties
Atomic radii and ionic radii
Colour
Application
 The inner transition elements (f-block) in the periodic table

Why are the Lanthanide and Actinide

Series Separated from the Periodic Table?

Lanthanide and actinide are separated

from the main body of the periodic table
because of how electrons get filled up.
They belong to the category of f-block
elements in which the f orbital is
progressively filled as electrons are added
to the atoms. The properties of these
elements differ from d-block and s-block.

Lanthanides and Actinide Series are Lanthanides

both referred to as Rare Earth Metals Actinides
The inner transition elements (f-block) in the periodic table

Lanthanides
Actinides
f orbital
 The inner transition elements (f-block) in the periodic table

• The lanthanides are the 14 elements

from cerium (atomic number 58) to
lutetium (atomic number 71). In these
elements the differentiating electron
enters 4f orbitals.
• The word comes from the Greek
“lanthanein” meaning “to be
hidden.” The name probably arose
because these elements all hide behind
one another in the periodic table.

Lanthanides
 The inner transition elements (f-block) in the periodic table
• Only promethium (Pm) [Link]
does not occur naturally in the earths crust, while the
others are relatively abundant in rocks and soils.
• The Bayan Obo mine located in the Inner Mongolia
region of China is the world’s biggest rare earth element
(REE) mine both by recoverable reserves and
production.
• It accounts for more than 40% of the total known REE
reserves in the world and nearly half of the global rare
earth production.

Lanthanides

[Link]
 Properties of lanthanides

• The metals have a silvery shine when freshly cut.

However, they can tarnish quickly in air, especially Ce, La
and Eu.
• The remainder of the lanthanides are not as reactive,
and some (Gd, Lu) retain their silvery metallic
appearance for a long time. When contaminated with
nonmetals, such as oxygen or nitrogen, the lanthanides
become brittle. They will also corrode more easily if
contaminated with other metals, such as calcium.
• Lanthanides are soft malleable and ductile in nature.
• The lanthanides form alloys with many other metals,
and these alloys exhibit a wide range of physical
properties.

A brief intro to the lanthanides - Chemical elements: properties and reactions

[Link]
 Properties of lanthanides

Chemical Behaviour:
The first few members of the series are quite reactive like calcium. However with increasing atomic number,
their behaviour becomes similar to that of aluminum.
• The lanthanides form compounds with many nonmetals, such as hydrogen, fluorine, phosphorous, carbon,
sulfur and chlorine and heating may be required to induce these reactions.
Lanthanide + carbon = carbides
Lanthanide + halogen = halides

•Lanthanides react with dilute acids to liberate hydrogen gas.

•The lanthanides react slowly with cold water (more rapidly with hot water) to form hydrogen gas
•Lanthanides form oxides and hydroxides of the type N2O3 and M(OH)3 which are basic alkaline earth metal
oxides and hydroxides.
•Complex formation: The lanthanides do not show much tendency to form complexes due to low charge
density because of their size. However, the tendency to form complex and their stability increases with
increasing atomic number.
 Electron configuration of lanthanides
• The general electron configuration of lanthanides is [Xe] (n-2)f1-14 (n-1)d0-1 ns2.
• Electronic configuration of outermost shells are (n-2)f1-14 (n-1)d0-1 ns2.
• After Lanthanum, the energy of the 4f subshell falls below that of the 5d subshell. This means that the
electron start to fill the 4f subshell before the 5d subshell.
• Lanthanide elements anomalies are indicated in red box
 Oxidation state of lanthanides
Electronic configuration of outermost shells

• Common oxidation
state is +3 (Ln3+) more
stable.
• Loses of two 6s
electrons and one 5d
or 4f electron.
• Some either show +2
or +4 oxidation state.
• Electronic
configuration of
outermost shells are
(n-2)f1-14 (n-1)d0-1 ns2
indicated in red box
 Magnetic properties of lanthanides
• All lanthanide ions ada paramagnetics EXCEPT La3+ and Ce4+ (4f0) and Yb2+ and
Lu3+ (4f14) are diamagnetic.
• Lanthanides have very high magnetic susceptibilities due to their large
numbers of unpaired f-electrons.
• Magnetic properties some of their ions, which makes them useful as contrast
agents in Magnetic Resonance Imaging (MRI) applications.

Image of the brain

obtained with MRI
 Atomic radii and ionic radii of lanthanides
• The size of the atomic and ionic radii is determined by
both the nuclear charge and by the number of electrons
that are in the electronic shells.
• Within those shells, the degree of occupancy will also
affect the size. In the Lanthanides, there is a gradual
decrease in atomic size from La to Lu with increasing
atomic number. This decrease is known as
the Lanthanide Contraction.
 Atomic radii and ionic radii of lanthanides
Lanthanide Contraction:
• electron entered into the 4f orbital one at each step.
• the shielding or screening effect of f orbital is very much
less than ‘s’ , ‘p’ even than that of d orbital . This is due
to the shape of f orbital.
• Hence the effective nuclear charge increases by one at
each step.
• Consequently , the inward pull experienced by the 4f
electrons increases.
• As a result , the size of the entire 4f n shell reduces .
 Colour and light absorbance of lanthanides

• The colour of the lanthanides emerge from f to f

transitions (transition of the electrons from the lower
energy f-orbitals to the higher energy f-orbital).
• f→f transitions are much weaker and narrower than those
from d→d transitions. This makes the colours of
lanthanides complexes far fainter than those of transition
metal complexes.
 Colour and light absorbance of lanthanides

• The lanthanides have an ability security inks

to emit fluorescent light.
• Fluorescence is the emission of
light by atoms or molecules
after having absorbed energy
(usually from electromagnetic
radiation or light).
• When lanthanides are
illuminated with visible light,
their electrons absorb the
energy contained within the
incoming photons of light, and
most of this energy is, in turn,
• The most remarkable properties are bright and color pure
emitted in the form of light
luminescence, and thus explains their application including
within the visible and near-
phosphors for lighting and displays, security inks and tags, lasers,
infrared range of the
optical fibers, night vision, photocatalysis, bioprobes, nanoscopy, and
electromagnetic spectrum.
light-activated drug delivery.
Applications of lanthanides
 The inner transition elements (f-block) in the periodic table

• The actinides are the 14 elements from

thorium (atomic number 90) to
lawrencium (atomic number 103).
• The 5f sublevel is in the process of being
filled.
• The most common and known element is
uranium, which is used as nuclear fuel
when its converted into plutonium,
through a nuclear reaction.
• Thorium and uranium occur naturally in
substantial quantities. The other
actinides are purely synthetic elements.
Actinides
 Properties of actinides

• Actinides are typical metals. All of them are soft.

• Actinides have a silvery color (but tarnish in air), and have relatively high density and plasticity.
• Some of them can be cut with a knife. The hardness of thorium is similar to that of soft steel, so heated
pure thorium can be rolled in sheets and pulled into wire. Thorium is nearly half as dense as uranium and
plutonium but is harder than both of them.
• Actinide series have the same properties as the d-block. Members of the actinide series can lose multiple
electrons to form a variety of different ions.
• All actinides are radioactive, and thus the study of their chemistry in the laboratory is difficult.
• Chemical behavior:
- actinides react with boiling water to give a mixture of oxide and hydride.
- actinides combine with most of the nonmetals at moderate temperature.
- all these metals are attacked by HCl but the effect of HNO3 is very small due to the formation of a
protective oxide layer on their surface.
- Actinides have higher tendency to form complexes than lanthanides, due to higher charges and
smaller size of cations of actinides. This results in higher charge density and high effective nuclear
charge. This facilitates the acceptance of lone pairs of electrons from ligands.
 Electron configuration and oxidation states of actinides

• The general electron configuration of actinides is (n–2)f¹⁻¹⁴ (n–1)d⁰⁻¹ ns².

• They have an oxidation state of +3. However, this is not always the most stable oxidation state.
• The most stable oxidation states for Th is +4, Pa is +5, U is +6 and Np is +5.
• Pu shows all oxidation states from +3 to +7 but the most stable is Pu +4.
• Am and the remaining actinides is the most stable oxidation state.
 Atomic radii and ionic radii of actinides
• The actinides show actinide contraction (very
much like lanthanide contraction) due to the
poor shielding effect of the 5f-electrons.
• As a result, the radii of the atoms or ions of
these metals decrease regularly across the
series.
• The contraction is greater from element to
element in this series due to poorer shielding
by 5f electrons.
• This is because 5f orbitals extend in space
beyond 6s and 6p orbitals while 4f orbitals
are buried deep inside the atom.

Magnetic properties of actinides

• Like lanthanides, the actinide elements are strongly paramagnetic.
• The variation in magnetic susceptibilities of actinides with the increasing number of unpaired electrons is
similar to that of lanthanides but the values are HIGHER for the actinides than for the lanthanides.
 Colour of actinides
• These metals are silvery white.
• However, actinide cations are generally
coloured due to the presence of unpaired
electrons.
• The colour of the cation depends upon the
number of 5f-electrons.
• The cations containing no 5f-electron or
having seven 5f-electrons (i.e., exactly half-
filled f-subshell) are colourless.
• The cations containing 2 to 6 electrons in
the 5f–subshell are coloured both in the
crystalline state as well as in an aqueous
solution.
• The colour arises due to f-f transition within
the 5f–subshell, e.g., Ac3+ (5f0) = colourless,
U3+ (5f3) = Red, Pu3+ (5f5) = Violet
• The electronic transitions of actinides are
about ten times more intense than those of
lanthanides due to difference in 4f and 5f
Different colors of Pu and Np at different Oxidation States electrons.
 Applications of actinides

• Radioactive nuclides are used in cancer therapy, analytical chemistry, and in basic research in the study of
chemical structures and mechanisms.

• The explosive power of uranium and plutonium are well exploited in making atom bombs. In fact, the
uranium enriched atom bomb that exploded over Japan was the first uranium bomb released.

• Nuclear reactions of uranium-235 and plutonium-239 are currently utilized in atomic energy powerplants to
generate electric power. Thorium is economically useful for the reason that fissionable uranium-233 can be
produced from thorium-232.

• Plutonium-238 is used in implants in the human body to power the heart pacemaker, which is does not
need to be replaced for at least 10 years.

• Curium-244 and plutonium-238 emit heat at 2.9 watts and 0.57 watts per gram, respectively. Therefore,
curium and plutonium are used as power sources on the Moon to provide electrical energy for transmitting
messages to Earth.
 The inner transition elements (f-block) in the periodic table

Differences between Lanthanides and Actinides

Lanthanides
Actinides
 The inner transition elements (f-block) in the periodic table

Similarities between Lanthanides and Actinides

Lanthanides
Actinides