Characteristics of Inner Transition Elements

INTRODUCTION
Elements in the Periodic Table can be classified in three major ways, namely,
1. The s-block comprises the first two groups (alkali metals and alkaline earth
metals) as well as hydrogen and helium.
2. The p-block comprises the last six groups, which are groups 13 to 18 in
IUPAC group numbering (3A to 8A in American group numbering) and
contains, among other elements, all of the metalloids.
3. The d-block comprises groups 3 to 12 and contains all of the transition. The
f-block, often offset below the rest of the periodic table, has no group numbers
and comprises lanthanides and actinides. The block classification is shown in
the figure below,
In view of its unique electronic configuration, the lanthanides and actinides are
separated from the rest of the periodic Table and are placed as separate rows at the
bottom of the Table (see Fig. 1).

1
 F Block Elements

• F block elements are divided into two series, namely lanthanoids and actinoids.
This block of elements are often referred to as inner transition metals because
they provide a transition in the 6th and 7th row of the periodic table which
separates the s block and the d block elements (because they form a transition
series within the transition elements.).
• The general electron configuration for elements in the f block is ( n - 2 )f 1-
14
ns 2 . The seven orbitals of the f sublevel accommodate 14 electrons, so
the f block is 14 elements in length.

Classification of F-Block elements?

1. The first series of elements are called lanthanides. The lanthanides are the 14
elements from cerium (atomic number 58) to lutetium (atomic number 71).
The 4 f sublevel is in the process of being filled for the lanthanides. These
elements are non-radioactive (except for promethium, which is radioactive).
2. The second series of elements are called actinides. The actinides are the 14
elements from thorium (atomic number 90) to lawrencium (atomic number
103). The 5 f sublevel is in the process of being filled. The actinides are all
radioactive elements and only the first four have been found naturally on
Earth. All of the others have only been artificially made in the laboratory. The
lanthanides and actinides together are sometimes called the inner transition
elements.

2
 Position in the Periodic Table
• F block elements are placed separately at the bottom of the periodic table.
They are a subset of 6th and 7th periods.
General Characteristics of f-block elements
Properties of F block Elements
• Have electrons added to the ‘f’ sub-orbitals of (n-2) level
• Are placed between (n-1)d and ns block elements in the periodic table.
• Properties are similar to d-block elements.
The lanthanide series
THE CHEMISTRY OF LANTHANIDES (INTRODUCTION)

• Lanthanides (also called lanthanoids) are called first inner transition series or third
transition and come immediately after lanthanum. They are classified as f block
elements along with the actinides. They are commonly called the rare earths. They
are characterized by the filling up of the 4f energy levels which are not usually
involved in bonding. These highly electropositive elements have a common
oxidation state of +3 and generally resemble each other in their chemical and
physical properties. The have a generic symbol “Ln”. DISCOVERY AND
OCCURRENCE (see Table 1) In 1794.
• The Lanthanide series include fifteen elements i.e. lanthanum (57 La) to lutetium
(71 Lu). Lanthanum and Lutetium have no partly filled 4f- subshell but have
electrons in 5d-subshell. Thus, these elements should not be included in this series.
However, all these elements closely resemble lanthanum and hence are considered
together.

3
Classification of Lanthanide (rare-earth minerals)
The rare-earth minerals fall into two distinct classes:

(1) Cerium Group Minerals. These are also called cerite-earth minerals or simply
cerium earths and are rich in cerite-earths. This group of minerals contains largely
elements of atomic numbers from 57 to 63 (i.e. La57-Eu63), the light lanthanide
elements.

(2) Yttrium Group Minerals. These are also called yttrium-earth minerals or
simply yttrium earths and are rich in gadolinite earths. This group contains largely
yttrium and lanthanides of atomic numbers from 64 to 71 (Gd64-Lu71), the heavier
lanthanides

4
General properties of Lanthanides
1. Electronic configuration
We know that at Ba56 6s-orbital is completely filled (Ba56-[Xe]6s2) and at La 57
5d-orbital is singly occupied (La57-[Xe] 5d1 6s2). But after La57 further filling of
5d-orbitals is discontinued. As the nuclear charge increases by one unit from La57
to Ce58, 4f-orbitals which were higher in energy up to La57, fall slightly below the
5d level. 4f-orbitals, therefore, begin to fill and are completely filled up to Lu71
before the filling of 5d-orbitals is resumed. Gd and Lu have 5dl arrangement because
the f shell are already half filled and full, which gives increased stability. The
lanthanides are characterized by the uniform (+III) oxidation state shown by all the
metals. They typically form compounds which are ionic and trivalent. The electronic
structures of the ions are Ce3+ f1, Pr3+ f2, Nd3+ f3, ... Lu3+ f14. The 4f electrons in the
antepenultimate shell are very effectively, shielded from their chemical environment
outside the atom by the 5s and 5p electrons. Consequently, the 4f electrons do not
take part in bonding. Whether the f orbitals are filled or empty has little effect on the
normal chemical properties. However, it does affect their spectra and their magnetic
properties.

5
 2. Oxidation states
• The common oxidation state exhibited by all the lanthanides is +3 (Ln3+) in aqueous
solutions and in their solid compounds. Some elements exhibit +2 and +4 states as
uncommon oxidation states.
• The Ln2+ and Ln4+ ions that do occur are always less stable than Ln3+. The higher
oxidation states occur in the fluorides and oxides, and the lower oxidation states
occur in the halides.
Oxidation numbers (+II) and (+IV) occur, particularly when they lead to:
1. a noble gas configuration, e.g.Ce4+(f°)
2. a half-filled f shell, e.g. Eu2+ and Tb4+ (f7)
3. a completely filled f level, e.g.Yb2+(f14).
• In addition (+II) and (+IV) states exist for elements that are close to these
states. Thus Sm2+and Tm2+ occur with f6 and f13 arrangements and Pr4+ and
Nd4+ have f1 and f2 arrangements. The (+III) state is always the most common
and the most stable. The only (+IV) and (+11) states which have any aqueous
chemistry are Ce4+, Sm2+, Eu2+and Yb2+.

6
7