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Lanthanides
Lanthanides Definition
Properties of Lanthanides
Characteristics of
Lanthanides
Uses of Lanthanides

Chemistry Inorganic Chemistry Main Group Elements Lanthanides

Related Concepts
Actinides and Lanthanides
Lanthanide Chemistry
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Lanthanides

The arrangement of all elements is based on the electronic configuration of the

elements and the "long form" of the Periodic table or the Modern Periodic table is

Group 1 (ia) Element - Hydrogen

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designed keeping this factor in mind.

Accordingly the elements in which the f-block is getting filled are kept at the bottom
portion of the periodic table and are called f-block elements or Lanthanides in the 6th
period and an incomplete 7th period called Actinides.

Periodic Table Element Groups

Reactivity of Group 1 Elements

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The lanthanides are a series of fifteen metal elements that are next to each other near
the bottom of the periodic table. The name of the series comes from lanthanum, the
element that marks the beginning of the series. All members of the series have similar
chemical properties. In nature, they are found together in the same minerals and it is
difficult to separate them into individual elements.
Atomic Number Name

Symbol

57

lanthanum

La

58

cerium

Ce

59

praseodymium Pr

60

neodymium

Nd

61

promethium

Pm

62

samarium

Sm

63

europium

Eu

64

gadolinium

Gd

65

terbium

Tb

66

dysprosium

Dy

67

holmium

Ho

68

erbium

Er

69

thulium

Tm

70

ytterbium

Yb

71

lutetium

Lu

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Lanthanides Definition

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Lanthanides can be defined as those elements in which the 4f-block gets

filled gradually from 4f1(Cerium) to 4f14(Lutetium) where the filling up of
electrons take place at n-2 orbit (second orbit below the outermost orbit).

Lanthanides have the uncharacteristic feature of having almost similar properties.

They were initially known as rare earth metals but now they are mostly termed as inner
transition elements. An alternative term for lanthanide is "rare earth". The word earth,
once used by chemists for compounds, is now called oxides. A compound is formed
when atoms of different elements bond together during a chemical reaction. Rare earth
was the term used for the oxides of lanthanide elements to distinguish them from
better known earths.

Properties of Lanthanides

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The properties of Lanthanides can be classified as general (Physical) and Chemical

Properties.

Solubility
Most of the salts of lanthanides are soluble in water as they show water of
crystallization. This can be attributed to the availability of empty spaces in d and f
orbitals. Most of the salts of lanthanides resemble the salts of group 2 elements like
Ca, Ba in their solubilities. Flourides, oxalates and carbonates are almost insoluble
while chlorides and nitrates are soluble.
However, unlike the sulphates of Ca and Ba which are insoluble, the lanthanide
sulphates are soluble in water. With ammonium of I group metals like Na and K
lanthanides form double salts which can be crystallized well. For example, Na2SO4
Ln2(SO4)3.8H2O. This property helps in the separation of lanthanides from one another
due to the varying solubility of these double salts.

Colored Compounds
Like the transition elements (d block elements) the f-block lanthanides in their +3
oxidation state also produce colors in crystalline as well as in solution forms. The
depth of the color increases with the increase in the number of unpaired electrons in
the f orbital. The compounds in which the lanthanides are in some other oxidation state
and iso electronic with their counterparts will not form colored compounds.

Magnetic Properties
Lanthanum ion(La3+) and Cerium ion (Ce4+) have no 4f electrons while Lutetium (Lu3+)
has 14 electrons in the f shell which means there are no unpaired electrons in them.
Hence they are diamagnetic. All the other lanthanides will have unpaired electrons
which are responsible for their paramagnetic quality. The paramagnetism increases
with increase in the number of unpaired electrons.

Oxidation States
Most stable oxidation state among the lanthanides is the +3 state. Certain compounds
in +2 and +4 states are also formed but they are less stable. This is because the sum
value of the first three ionization energies is lower while the second and fourth
ionization energies are higher.
Lower oxidation states occur in compounds with bromides and iodides while higher

oxidation state in fluorides and oxides. The oxidation states +2 and +4 are possible
only if this leads to either a noble gas configuration, fully filled orbital state or half filled
orbital state.
The following table gives the idea of the similarities of the lanthanides in relation to the
ionization energies, electrode potentials and ionic radii. The gradual reduction in the
atomic and ionic radius with increase in atomic number is a special characteristic of
the lanthanides.

Complex Formation
All the lanthanides form complexes with complexing agents like EDTA. Lutetium forms
a stronger complex than Cerium because it's the smallest in the series. Although,
oxalates are insoluble, oxalate addition with complexing agent results in the formation
of a soluble complex.

Chemical Properties of Lanthanides

1. The +3 lanthanide compounds are much more reactive than Aluminium
compounds but slightly more reactive than Magnesium compounds (refer to the
electrode potentials). They react slowly with cold water but rapidly with hot
water.
2. Hydroxides are precipitated by ammonia as gelatinous precipitates. They are
less basic than Ca(OH)2 but more basic than Al(OH)3.
3. Above 300-400c lanthanides react with hydrogen to form solid hydrides. These
hydrides have a non stoichiometric formula with 2H- ions while the metal is in +3
state. Yb forms approximately YbH2.5 hydride.
4. Lanthanides tarnish readily in air, forming oxides. On heating with oxygen also
they form the oxide M2O3. Ce is an exception and forms CeO2.
5. Anhydrous halides are made by heating metal and halogen or alternatively, by
heating oxide with the appropriate ammonium halide.
6. Hydrated lanthanum chloride on heating dissociates into Lanthanum oxychloride
with fumes of water and HCl.
7. On arc melting metal with carbon in inert atmosphere, metal carbide is formed
which has one electron in the conduction band with formula LnC2 and Ln4(C2)3.
These carbides with water produce acetylene and hence are called acetylides.
8. At high temperatures lanthanides react with n.P, As, Sb. Like AlN, these
nitrides also give ammonia on getting wet with water.
9. Lanthanides also form a wide variety of oxo salts with nitrates, sulphates
phosphates.

Characteristics of Lanthanides

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The most significant characteristic of Lanthanides is the contraction of the atomic size
with increase in atomic number called lanthanide contraction. While moving along
the lanthanides series from Ce(58) to Lu71, a regular decrease in the size of the
atom/ion and increase in atomic number is observed. This decrease in size is called
the lanthanide contraction. The decrease in size, though continuous, is not regular.
Lanthanide contraction takes place due to imperfect shielding of one 4f- electron which
increases by one more in the same sub-shell.
The covalent and ionic radii are periodic properties. In the periodic table the radii
increases in a group from top to bottom since there is an orbit added in a group for
every step downwards. The covalent and ionic radii decrease in a period going from
left to right because every added electron and proton increases the effective nuclear
charge.
The shielding effect of electrons decreases in the order s>p>d>f. In case of d block
transition elements, the decrease is not very significant. In case of lanthanides the
additive effect over 14 lanthanides from Ce to Lu is about 0.2 which is quite
significant. This is called lanthanide contraction which is a characteristic of
lanthanides.
The electron filling in a lanthanide is at n-2 level and hence the combining capacity of
the metal is decided by the n-1 d orbital electrons. The most common valency of 3 for
the lanthanide compounds is another characteristic of Lanthanide. The lanthanides are
soft and silvery white metals. They are very reactive. Heavier metals are less reactive
than the lighter metals.

Uses of Lanthanides

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1. Monazite sand is a source of lighter lanthanides in their trivalent phosphate

form. The application of Lanthanide elements as biological tracers is used to

trace the effectiveness and target route of drugs in humans and animals. As
their peaks are narrow and very characteristic, they can be easily followed in
the system by spectroscopy.
2. Many lanthanides show fluoresce in Ultra violet radiation, which is used to
study the defects in metals etc.
3. Lanthanides are strong reducing agents and are also used as catalysts.
4. Lanthanides are used in lamps, lasers and in projector lighting.
5. Cigarette lighter flints are made out of a special alloy of lighter lanthanides and
are known as Misch metal. They are also used in X-ray, and focus lights. Due
to its magnetic qualities, the lanthanides are used to make magnets.
6. Thus, Lanthanides find extensive use in various industrial and research
applications.

P-block Elements

Noble Gas

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Electron shells

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