CLASS XII d&f-BLOCK ELEMENTS

BASIC CONCEPTS/IMPORTANT FORMULA/EQUATIONS

The elements which have partially filled d-sub orbit or the elements in which the last
electron enters in (n-1) d-orbitals are called transition elements.
The d-block elements are called transition elements also because they exhibit transitional
behaviour between highly reactive ionic-compound-forming s-block elements (electropositive
elements) on one side, and mainly the covalent-compound-forming p-block elements (electronegative
elements) on the other side.

Electronic Configuration of Transition Elements

From the point of view of electronic configuration, the elements which have partially filled dorbitals in their neutral atoms or in their common ions are called transition elements. Thus, the outer
electronic configuration of the transition elements is (n 1)d110 ns12, where n is the outermost shell,
and (n 1) stands for the penultimate shell.
Ques:-Why are Zinc, Cadmium and Mercury not considered as the Transition Elements?
Ans: - In zinc cadmium and mercury the last electron enters in s-orbital not in the (n-1) d-orbital, so
these elements are not called transition elements. Their electronic configurations are (n 1) d10 ns2.
Since, in these metals d-orbitals are completely filled, hence these do not exhibit the general
characteristic properties of the transition elements. Therefore, these metals are not considered as
transition elements.

General Trends in the Chemistry of First Row Transition Elements ( 3d-series)

1. Electronic Configuration
All d-block elements exhibit 3d110 4s12 electronic configuration. Some characteristic features of
the electronic configurations of the transition elements are, Atoms of all transition elements consist of
an inner core of electrons having noble gas configuration. For example,

Sc : [Ar] 3d1 4s2

Y : [Kr] 4d1 5s2

La : [Xe] 5d1 6s2

The half-filled and completely-filled d-orbitals gain extra-stability. So, such con-figurations are
favoured wherever possible. For example

2. Atomic Radii
The atomic radii of 3d-series of elements are compared with those of the neighbouring s- and pblock elements.
164
147
135
129
137
126
125
125
128
137 in pm
The atomic radii of transition elements show the following characteristics.
Ques.:-The atomic radii and atomic volumes of d-block elements in any series decrease with increase
in the atomic number. The decrease however, is not regular. The atomic radii tend to reach minimum
near at the middle of the series, and increase slightly towards the end of the series, why?
Ans: - When we go in any transition series from left to right, the nuclear charge increases gradually by
one unit at each element. The added electrons enter the same penultimate shell, (inner d-shell). These

added electrons shield the outermost electrons from the attraction of the nuclear charge. The increased
nuclear charge tries to reduce the atomic radii, while the added electron tries to increase the atomic
radii. At the beginning of the series, due to smaller number of electrons in the d-orbitals, the effect of
increased nuclear charge predominates, and the atomic radii decrease. In the middle of the series, the
atomic radii tend to have a minimum value as observed Later in the series, when the number of delectrons increases, the increased shielding effect and the increased repulsion between the electrons tend
to increase the atomic radii.
Ques.:-The atomic radii increase while going down in each group. However, in the third transition
series (5d series) from hafnium (Hf) and onwards, the elements have atomic radii nearly equal to
those of the second transition series elements, why?
Ans: - The atomic radii increase while going down the group. This is due to the introduction of an
additional shell at each new element down the group. A nearly equal radius of second (4-d series) and
third transition series (5d series) elements is due to a special effect called lanthanide contraction. In
the 5d- series of transitions elements, after lanthanum (La), the added 14 electrons go to the inner most
4f orbitals (antepenultimate orbitals). The 4f electrons have poor shielding effect. But due to addition of
14 extra protons in the nucleus the outermost electrons experience greater nuclear attraction. So size of
elements of 5-d series becomes smaller then 4-d series.

3. Ionic Radii
For ions having identical charges, the ionic radii decrease slowly with the increase in the atomic
number across a given series of the transition elements.

EXPLANATION. The gradual decrease in the values of ionic radius across the series of
transition elements is due to the increase in the effective nuclear charge.

4. Ionisation Energies
The ionisation energies (now called ionisation enthalpies, IH) of the elements of first transition
series are given below:

The following generalizations can be obtained from the ionisation energy values given above.
Ques.:-The ionisation energies of these elements are high, and in most cases lie between those of sand p-block elements. This indicates that the transition elements are less electropositive than s-block
elements.
Ans: - Transition metals have smaller atomic radii and higher nuclear charge as compared to the alkali
metals. Both these factors tend to increase the ionisation energy, as observed. The ionisation energy in
any transition series increases with atomic number; the increase however is not smooth and as sharp as
seen in the case of s- and p-block elements.
EXPLANATION. The ionisation energy increases due to the increase in the nuclear charge with
atomic number at the beginning of the series. Gradually, the shielding effect of the added electrons also
increases. This shielding effect tends to decrease the attraction due to the nuclear charge.
These two opposing factors lead to a rather gradual increase in the ionisation energies in any
transition series.

Ques.:-The first ionisation energies of 5d-series of elements are much higher than those of the 3dand 4d-series elements, why?.
Ans: - In the 5d- series of transitions elements, after lanthanum (La), the added 14 electrons go to the
inner most 4f orbitals (antepenultimate orbitals). The 4f electrons have poor shielding effect. But due to
addition of 14 extra protons in the nucleus the outermost electrons experience greater nuclear attraction.
So size of elements of 5-d series becomes smaller then 4-d series. This leads to higher ionisation
energies for the 5d-series of transition elements.

5. Metallic Character
All transition elements are metals. These are hard, and good conductor of heat and electricity.
All these metals are malleable, ductile and form alloys with other metals. These elements occur in three
types, e.g., face-centered cubic (fcc), hexagonal closepacked (hcp) and body-centred cubic (bcc),
structures.
EXPLANATION. The ionisation energies of the transition elements are not very high. The
outermost shell in their atoms have many vacant/partially filled orbitals. These characteristics make
these elements metallic in character.
The hardness of these metals, suggests the presence of covalent bonding in these metals. The
presence of unfilled d-orbitals favours covalent bonding. Metallic bonding in these metals is indicated
by the conducting nature of these metals. Therefore, it appears that there exists covalent and metallic
bonding in transition elements. The strength of inter atomic interactions becomes stronger as the
number of unpaired electrons increases. Cr, Mo and W have maximum number of unpaired electrons so
these metals are very hard.
Ques.:- Why is the energy of atomization is very high for d- block elements?

6. Melting and Boiling Points

The melting and boiling points of transition
elements except Cd and Hg are very high as compared
to the s-block and p-block elements. The melting and
boiling points first increase, pass through maxima and
then steadily decrease across any transition series. The
maximum occurs around middle of the series.
EXPLANATION. Atoms of the transition
elements are closely packed and held together by strong
metallic bonds which have appreciable covalent
character. This leads to high melting and boiling points
of the transition elements.
The strength of the metallic bonds depends upon
the number of unpaired electrons in the outermost shell
of the atom. Thus, greater is the number of unpaired
electrons stronger is the metallic bonding. In any
transition element series, the number of unpaired
electrons first increases from 1 to 5 and then decreases back to zero. The maximum five unpaired
electrons occur at Cr (3d series). As a result, the melting and boiling points first increase and then
decrease showing maxima around the middle of the series.
The low melting points of Zn, Cd, and Hg may be due to the absence of unpaired d-electrons
in their atoms.

7. Oxidation States
Most of the transition elements exhibit several oxidation states, i.e., they show variable valency
in their compounds. Some common oxidation states of the first transition series elements are given
below .
Ques.:- Why do d-block elements show variable oxidation states?

Ans.:- The outermost electronic configuration of the transition elements is (n 1) d110 ns2. The
energy of (n 1) d and ns- orbitals are nearly same, so along with the ns-electrons (n 1) d-electrons
also involved in oxidation state so these elements shows variable oxidation states. Also it arises due to
partially filled d-orbital.
Therefore, the number of oxidation states shown by these elements depends upon the number of
d-electrons it has. For example, Sc having a configuration 3d1 4s2 may show an oxidation state of + 2
(only s-electrons are lost) and + 3 (when d-electron is also lost). The highest oxidation state which an
element of this group might show is given by the total number of ns- and (n 1) d-electrons.
The relative stability of the different oxidation states depends upon the factors such as,
electronic configuration, nature of bonding, stereochemistry, lattice energies and solvation energies.
Ques:-Why highest oxidation states are shown by oxide and fluorides?
The highest oxidation states are found in fluorides and oxides because fluorine and oxygen are
the most electronegative elements.
The highest oxidation state shown by any transition metal is eight. The oxidation state of
eight is shown by Ru and Os.
An examination of the common oxidation states reveals the following conclusions:
The variable oxidation states shown by the transition elements are due to the participation
(a)
of outer ns- and inner (n 1) d-electrons in bonding.
Except scandium, the most common oxidation state shown by the elements of first
(b)
transition series is + 2. This oxidation state arises from the loss of two 4s electrons. This
means that after scandium, d-orbitals become more stable than the s-orbital.
The greatest number of oxidation states is observed near middle of the series. Eg:- Mn
(c)
show +2 to +7 O.S. The highest oxidation states are observed in fluorides and oxides. The
highest oxidation state shown by any transition element (by Ru and Os) is +8.
The transition elements in the + 2 and + 3 oxidation states mostly form ionic bonds. In
(d)
compounds of the higher oxidation states (compounds formed with fluorine or oxygen),
the bonds are essentially covalent. For example, in permanganate ion MnO4, all bonds
formed between manganese and oxygen are covalent.
Within a group, the maximum oxidation state increases with atomic number. For example,
(e)
Iron shows the common oxidation state of + 2 and + 3, but ruthenium and osmium in the
same group form compounds in the + 4, + 6 and + 8 oxidation states.
Transition metals also form compounds in low oxidation states such as + 1 and 0. For
(f)
example, nickel in nickel tetracarbonyl, Ni(CO)4 has zero oxidation state. Fe(CO)5
The bonding in the compounds of transition metals in low oxidation states is not always very simple.

8. Electrode Potentials (E)

Standard electrode potentials of half-cells involving 3d-series of transition elements are negative
except Cu.The negative values of E for the first series of transition elements (except for Cu2+/Cu)
indicate that:
These metals should liberate hydrogen from dilute acids, ,

M
2M

+
+

2H+
6H+

M2+ +
2M3+ +

H2(g)
3H2(g)

i.e., the reactions are favourable in the forward direction. In actual practice however, most of these
metals react with dilute acids very slowly. Some of these metals get coated with a thin protective layer
of oxide. Such an oxide layer prevents the metal to react further.
These metals should act as good reducing agents. There is no regular trend in the E values. This
is due to irregular variation in the ionisation and sublimation energies across the series. Relative
stabilities of transition metal ions in different oxidation states in aqueous medium can be predicted from
the electrode potential data. To illustrate this, let us consider the following:

M(s)

M(g)

H1

Enthalpy of sublimation, subH

M(g)

M+(g) + e

H2

Ionisation energy, IE

M+(g)

M+(aq)

H3

Enthalpy of hydration, hydH

H1 + H2 + H3 = subH + IE + hydH

Adding these equations one gets,

M(s)

M+ (aq) + e H

The H represents the enthalpy change required to bring the solid metal M to the monovalent
ion in aqueous medium, M+(aq).
The reaction, M(s) M+(aq) + e, will be favourable only if H is negative. More negative is
the value of H, more favourable will be the formation of that cation from the metal. Thus, the
oxidation state for which H value is more negative will be more stable in the solution.
Electrode potential for a Mn+/M half-cell is a measure of the tendency for the reaction,

Mn+(aq) + n e

M(s)

Thus, this reduction reaction will take place if the electrode potential for Mn+/M half-cell is
positive. The reverse reaction,

M(s)

Mn+(aq) + n e

involving the formation of Mn+(aq) will occur if the electrode potential is negative, i.e., the tendency for
the formation of Mn+(aq) from the metal M will be more if the corresponding E value is more negative.
In other words, the oxidation state for which E value is more negative (or less positive) will be
more stable in the solution.
When an element exists in more than one oxidation states, the standard electrode potential ( E) values can be
used in predicting the relative stabilities of different oxidation states in aqueous solutions. The following rule is
found useful.
The oxidation state of a cation for which H(= subH + IE + hydH) or E is more negative (or less
positive) will be more stable.

Trends in the M+2 / M+ Standard Electrode Potentials

The observed values of Eo of the solid metal atoms M to M +2 ions in solution and their
standard electrode potentials compared in Fig.
The unique behaviour of Cu, having a positive Eo, accounts for its inability to liberate H2 from
acids. Only oxidising acids (nitric and hot
concentrated sulphuric) react with Cu, the acids
being reduced. The high energy to transform
Cu(s) to Cu+2(aq) is not balanced by its
hydration enthalpy. The general trend towards
less negative Eo values across the series is
related to the general increase in the sum of the
first and second ionisation enthalpies. It is
interesting to note that the value of Eo for Mn,
Ni and Zn are more negative than expected from
the trend.
The stability of the half-filled d sub-shell in
Mn+2 and the complete filled d10 configuration in
Zn+2 are related to their E values, where Eo for
Ni is related to the highest negative
Ques:-Why is Cr+2 reducing and Mn+3 oxidizing when both have d4 configuration?
Ques:-Which is a stronger reducing agent Cr+2 or Fe +2 and why?

9. Formation of Coloured Ions: -

Most of the compounds of the transition elements are

coloured in the solid state and/or in the solution phase. The compounds of transition metals are coloured
due to the presence of unpaired electrons in their d-orbitals. This occurs as follows.

EXPLANATION. In an isolated atom or ion of a

transition element, all the five d-orbitals are of the same
energy (they are said to be degenerate). Under the
influence of the combining anion(s), or electron-rich
molecules, the five d-orbitals split into two (or some time
more than two) groups of different energies i.e. t2g and
eg-orbitals. The difference between the two energy levels
depends upon the nature of the combining ions. Generally
this difference corresponds to the energy of the visible
region, ( = 380 760 nm).
Typical splitting for octahedral and tetrahedral
geometries are shown in Fig. 9.4.
Relationship between the colour of the absorbed radiation and that of the transmitted light is given in
Table 9.4.

Colour of the
absorbed light
transmitted light
IR
Red
Orange
Yellow
Yellow-green
Green

White
Blue-green
Blue
Indigo
Violet
Purple

Colour of the
absorbed light
transmitted light
green
Blue
Indigo
Violet
UV

Red
Orange
Yellow
Yellow-green
White

10. Magnetic Properties: - Most of the transition elements and their compounds show
paramagnetism. The paramagnetism first increases in any transition element series, and then decreases.
The maximum paramagnetism is seen around the middle of the series. The paramagnetism is described
in Bohr Magneton (BM) units. The paramagnetic moments of some common ions of first transition
series are given below in Table 9.5 on the next page.
EXPLANATION: A substance which is attracted by magnetic field is called paramagnetic
substance. The substances which are repelled by magnetic field are called diamagnetic substances.
Paramagnetism is due to the presence of unpaired electrons in atoms, ions or molecules.
The magnetic moment of any transition element or its compound/ion is given by (assuming no
contribution from the orbital magnetic moment),

where, S is the total spin (n s) : n is the number of unpaired electrons and s is equal to 1/2
(representing the spin of an unpaired electron).

11. Formation of Complex Ions

Transition metals and their ions show strong tendency for complex formation. The cations of
transition elements (d-block elements) form complex ions with certain molecules containing one or
more lone-pairs of electrons, viz., CO, NO, NH3 etc., or with anions such as, F , Cl, CN etc. A few
typical complex ions are,

[Fe(CN)6]4, [Cu(NH3)4]2+, [Y(H2O)6]2+, [Ni(CO)4], [Co(NH3)6]3+, [FeF6]3

EXPLANATION. This complex formation tendency is due to,
(a) Small size of the transition metal cations.
(b) High positive charge density
(c) The availability of vacant inner d-orbitals of suitable energy to accept lone pair of electrons.

12. Formation of Interstitial Compounds

Transition elements form a few interstitial compounds with elements having small atomic radii,
such as hydrogen, boron, carbon and nitrogen. The small atoms of these elements get entrapped in
between the void spaces (called interstices) of the metal lattice. Some characteristics of the interstitial
compounds are,
(a) These are non-stoichiometric compounds and cannot be given definite formulae.
(b) These compounds show essentially the same chemical properties as the parent metals, but differ
in physical properties such as density and hardness.
Steel and cast iron are hard due to the formation of interstitial compound with carbon. Some nonstoichiometric compounds are, VSe 0.98 (Vanadium selenide), Fe0.94O, and titanium hydride TiH1.7.

Some properties
1. Interstitial compounds are hard and dense. This is because; the smaller atoms of lighter
elements occupy the interstices in the lattice, leading to a more closely packed structure.
2. Mp are higher and
3. They are chemically inert. Due to greater electronic interactions, the strength of the metallic
bonds also increases.

13. Catalytic Properties

Most of the transition metals and their compounds particularly oxides have good catalytic
properties. Platinum, iron, vanadium pentoxide, nickel, etc., are important catalysts. Platinum is a
general catalyst. Nickel powder is a good catalyst for hydrogenation of unsaturated organic compounds
such as, hydrogenation of oils. Some typical industrial catalysts are:
(a) Vanadium pentoxide (V2O5) is used in the Contact process for the manufacture of sulphuric acid,
(b) Finely divided iron is used in the Habers process for the synthesis of ammonia.
EXPLANATION. Most transition elements act as good catalyst because of,
(a) The presence of vacant d-orbitals.
(b) The tendency to exhibit variable oxidation states.
(c) The tendency to form reaction intermediates with reactants. The presence of defects in their
crystal lattices.

14. Alloy Formation

Transition metals form alloys among themselves. The alloys of transition metals are hard and
high melting as compared to the host metal. Various steels are the alloys of iron with metals such as
chromium, vanadium, molybdenum, tungsten, manganese etc.
EXPLANATION. The atomic radii of the transition elements in any series are not much
different from each other. As a result, they can very easily replace each other in the lattice and form
solid solutions over an appreciable composition range. Such solid solutions are called alloys.

15. Chemical Reactivity

The d-block elements (transition elements) have lesser tendency to react, i.e., these are less
reactive as compared to s-block elements.
EXPLANATION. Low reactivity of transition elements is due to,
(i)
their high ionisation energies,
(ii)
low heats of hydration of their ions,
(iii)
Their high heats of sublimation.

General Chemical Properties of First Row Transition Metal Compounds

The transition metals form a number of binary compounds with non-metals, e.g., carbon,
nitrogen, phosphorus, oxygen, sulphur and halogens. The chemical reactivity of transition elements may
be seen through the study of their oxides, sulphides and halides.
Oxides of First Row Transition Elements
Transition metals of first row (3d-series) generally react with oxygen at higher temperatures.
Because of the tendency to exhibit variable oxidation states, these metals form a number of oxides of
different varieties.

Some general characteristics of the oxides of 3d-transition series are given below.
(i) Formulae. The general formulae of the oxides of first row transition metals (3d-series) are,
MO, M2O3, M3O4, MO2, M2O5 and MO3.
(ii) Acidic, basic or amphoteric character. The character of an oxide depends upon the
oxidation state of the metal in it. For example,
The oxides of metals in low oxidation states are basic. For example, TiO, VO, MnO, Cu2O
etc., are basic in nature.
The oxides of metals in high oxidation states are acidic. For example, V2O5, CrO3, Mn2O7 are
acidic.
The oxides of metals in the intermediate oxidation states, are generally amphoteric.
For example, CuO, Cr2O3, MnO2 etc., are amphoteric.
Important oxides of the first transition series elements are given in Table 9.6.

SOME IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

Potassium Permanganate, (KMnO4)
Potassium permanganate is a salt of an unstable acid HMnO4 (permanganic acid). The Mn is in +
7 state in this compound.
Preparation. Potassium permanganate is obtained from pyrolusite as follows.
(i)
Conversion of pyrolusite to potassium manganate. When manganese dioxide is fused
with potassium hydroxide in the presence of air or an oxidising agent such as potassium
nitrate or chlorate, potassium manganate is formed, possibly via potassium manganite.

(ii)

Oxidation of potassium manganate to potassium permanganate. The potassium

manganate so obtained is oxidised to potassium permanganate by either of the following
methods.
(a) By chemical method: The fused dark-green mass is extracted with a small quantity of water.
The filtrate is warmed and treated with a current of ozone, chlorine or carbon dioxide. Potassium
manganate gets oxidised to potassium permanganate and the hydrated manganese dioxide precipitates
out. The reactions taking place are,
When CO2 is passed:

When chlorine or ozone is passed:

The purple solution so obtained is concentrated and dark purple, needle-like crystals having
metallic lustre are obtained.
(b) Electrolytic method: Presently, potassium manganate (K2MnO4) is oxidised electrolytically.
The electrode reactions are,

The purple solution containing KMnO4 is evaporated under controlled conditions to get
crystalline sample of potassium permanganate.
Physical properties.
(i)
KMnO4 crystallizes as dark purple crystals with greenish luster (m.p. 523 K).
(ii)
It is soluble in water to an extent of 6.5 g per 100 g at room temperature. The
aqueous solution of KMnO4 has a purple colour.
Chemical properties. Some important chemical reactions of KMnO4 are given below:
(i)
Action of heat. KMnO4 is stable at room temperature, but decomposes to give oxygen at
higher temperature

(ii)

Oxidising action. KMnO4 is a powerful oxidising agent in neutral, acidic and alkaline media.
The nature of reaction is different in each medium. The oxidising character of KMnO 4 (to be
more specific, of MnO4) is indicated by high positive reduction potentials for the following
reactions.

There are a large number of oxidation-reduction reactions involved in the chemistry of

manganese compounds. Some typical reactions are
(a) In the presence of excess of reducing agent in acidic solutions permanganate ion gets
reduced to manganous ion, e.g.,
(b) An excess of reducing agent in an alkaline solution reduces permanganate ion only to
manganese dioxide, e.g.,
(c) In faintly acidic and neutral solutions, manganous ion is oxidised to manganese dioxide
by permanganate.
(d) In strongly basic solutions, permanganate oxidises manganese dioxide to manganate ion.
(e) In acidic medium, KMnO4 oxidises,
(i) Ferrous salts to ferric salts

This reaction forms the basis of volumetric estimation of Fe2+ in any solution by KMnO4.
(ii) Oxalic acid to carbon dioxide

(iii) Sulphites to sulphates

(iv) Iodides to iodine in acidic medium

Potassium Dichromate (K2Cr2O7)

Potassium dichromate is one of the most important compound of chromium, and also among
dichromates. In this compound Cr is in the hexavalent (+ 6) state.
Preparation. It can be prepared by any of the following methods:
(i)
From potassium chromate: Potassium dichromate can be obtained by adding a calculated
amount of sulphuric acid to a saturated solution of potassium chromate.

K2Cr2O7 crystals can be obtained by concentrating the solution and crystallisation.

(ii)
Manufacture from chromite ore: K2Cr2O7 is generally manufactured from chromite ore
(FeCr2O4). The process involves the following steps.
(a) Preparation of sodium chromate. Finely powdered chromite ore is mixed with soda ash and
quicklime. The mixture is then roasted in a reverberatory furnace in the presence of air. Yellow
mass due to the formation of sodium chromate is obtained.

(b) Conversion of chromate into dichromate. Sodium chromate solution obtained in step (a) is
treated with concentrated sulphuric acid when it is converted into sodium dichromate.

On concentration, the less soluble sodium sulphate, Na2SO4.10H2O crystallizes out. This is
filtered hot and allowed to cool when sodium dichromate, Na2Cr2O7.2H2O, separates out on standing.

(c) Conversion of sodium dichromate to potassium dichromate. Hot concentrated solution of sodium
dichromate is treated with a calculated amount of potassium chloride, when potassium
dichromate being less soluble crystallizes out on cooling.

Chemical properties.
(i) Action of alkalies. With alkalies, it gives chromates. For example, with KOH,

On acidifying, the colour again changes to orange-red owing to the formation of dichromate.

Actually, in dichromate solution, the Cr2O7 2 ions are in equilibrium with CrO4 2 ions.
(iv) Oxidising nature. In neutral or in acidic solution, potassium dichromate acts as an excellent
oxidising agent, and Cr2O7 2 gets reduced to Cr3+. The standard electrode potential for the reaction,
is + 1.31 V. This indicates that dichromate ion is a fairly strong oxidising agent, especially in
strongly acidic solutions. That is why potassium dichromate is widely used as an oxidising agent, for
quantitative estimation of the reducing agents such as, Fe2+.
It oxidises,
(a) Ferrous salts to ferric salts
Ionic equation:
(b) Sulphites to sulphates and arsenites to arsenates.
Ionic equation:
Similarly, arsenites are oxidised to arsenates.
(c) Hydrogen halides to halogens.
Ionic equation:
(d) Iodides to iodine
Ionic equation:
Thus, when KI is added to an acidified solution of K2Cr2O7 iodine gets liberated.
(e) It oxidises H2S to S.
Ionic equation:
(i)

Formation of insoluble chromates. With soluble salts of lead, barium etc., potassium
dichromate gives insoluble chromates. Lead chromate is an important yellow pigment.

(ii)

Chromyl chloride test. When potassium dichromate is heated with conc. H2SO4 in the
presence of a soluble chloride salt, the orange-red vapour of chromyl chloride (CrO 2Cl2) is
formed.

Chromyl chloride vapour when passed through water give yellow-coloured solution containing
chromic acid.

Structure of Chromate and Dichromate Ions

.

f-block elements
Inner-Transition Elements: Lanthanoides and Actinoids
The elements which in their elemental or ionic form have partly filled f-orbitals are called fblock elements. As the f-orbitals lie inner to the penultimate (second outermost) shell i.e.
antepenultimate orbitals, therefore these elements having partially filled f-orbitals are also known as
inner-transition elements.
There general electronic configuration is
(n-2)f1-14(n-1)d0 or 1ns2
There are two series of inner-transition elements, each having 14 elements. The elements in
which 4f orbitals are progressively filled are called lanthanides. The elements in which 5f orbitals are
progressively filled are termed actinides.
Lanthanides thus belong to the first inner-transition series, while actinides belong to the second
inner-transition series.

Lanthanoides
The fourteen elements (atomic no. 58 71) after lanthanum are known as lanthanides or
lanthanons. All these elements closely resemble one another in their properties. Because of their limited
availability, these are also known as the rare earth elements.
Names and the outer-electronic configurations of the lanthanides are given in Table 9.10.

General Characteristics of Lanthanides

General physical characteristics of lanthanides are described below:

(1) Electronic configuration. The outer-electronic configurations of lanthanides are given

in Table 11.9. There is however, some uncertainty about the correctness of these configurations. The 5d
and 4f energy levels are very close-by. It is not always possible to decide with certainty whether the
electron has entered 5d or 4f level. Due to the extra-stability of half-filled and completely filled orbitals,
there is a tendency to acquire f7 and f14 configurations wherever possible. The general electronic
configuration of lanthanides may be described as 4f114 5d 01 6s2.
(2) Oxidation states. All Lanthanoides exhibit a common stable oxidation state of +3. in
addition some lanthaniodes shows +2 and +4 oxidation state also. These are shown by those elements
which by doing so attain the stable f0, f7 and f14 configurations. For example:
(i) Ce and Tb exhibit +4 oxidation states.
Cerium (Ce) and terbium (Tb) attain f0 and f7 configuration respectively when they get +4
oxidation state, as shown below:
Ce4+ :
[Xe]4f0
Tb4+ :
[Xe]4f7
(ii) Eu and Yb exhibit +2 oxidation states.
Europium and yetterbium get f7 and f14 configuration in +2 oxidation state, as shown below:
Eu2+ :
[Xe]4f7
Yb2+ :
[Xe]4f14
(iii) La, Gd, and Lu exhibit only +3 oxidation states due to empty, half filled and fulfilled
4f-sub orbit.
The stability of different oxidation state has strong effect on the properties of those elements.
For example, Ce(IV) is favoured because of its noble gas configuration. But it is strong oxidant
changing to common +3 oxidation state.
Similarly, Eu2+ is stable because of its half filled 4f 7 configuration. However, it is a strong
reducing agent changing to Eu3+ (common oxidation state.) Similarly, Yb2+ having the configuration 4f14
is a reductant. Samarium also behaves like europium exhibiting both +2 and +3 oxidation states.
Important note: - Irrespective of noble gas configuration 4f 0 Ce+4 is strong oxidizing agent
and it changes to +3 state. It is because the E o value for Ce+4| Ce+3 is +1.74 V which suggests that it
can oxidise water. But its reaction rate is very slow so Ce+4 is good analytical reagent.

Similarly Eu+2 is stable with half filled 4f7 configuration but Eu+2 is strong reducing agent and
it changes to +3 state. It is because the Eo value for Eu+3 | Eu+2 is negative.
(3) Magnetic properties. La3+ and Lu3+ are diamagnetic, while the trivalent ions of the rest of
the lanthanides are paramagnetic in nature. The paramagnetic moment values of the lanthanide ions are
higher than those expected on the basis of the number of unpaired electrons. This occurs due to an
appreciable contribution from orbital angular momentum.
(4) Reduction potentials and metallic character . The standard electrode (reduction)
potentials of the lanthanide ions become less negative across the series. Thus, their reducing power
decreases in going from Ce to Lu. The highly negative E values indicate these elements to be highly
electropositive metals capable of displacing hydrogen from water.
The M(OH)3 are ionic and basic in character. These hydroxides are stronger than Al(OH) 3 and
weaker than Ca(OH)2. The basic strength decreases in going from La to Lu.
(5) Atomic and ionic size: Lantha-nide contraction . The atomic and ionic sizes
decrease steadily in going from Ce to Lu. This decrease can be explained as follows.
EXPLANATION. In the atoms of lanthanides, the nuclear charge increases with
atomic number, and the added electrons go to the inner 4f orbitals. The shielding effect of 4f electrons
from the increased nuclear charge, is poor. Thus, as the atomic number increases, the effective nuclear
charge experienced by each 4f electron increases. This causes a slight reduction in the entire 4f shell.
The successive contractions accumulate and the total effect for all the lanthanides is called lanthanide
contraction.
The variation of ionic radii of lanthanide ions is shown in Fig. 9.16.
The 4f electrons also shield the valence shell from contracting appreciably. In lanthanides, the
decrease of radius for fourteen elements (Ce to Lu) is 15 pm.
This may be compared with the second period decrease of 81
pm in the radii for 7 elements (Li to F) and with that of the
third period elements (Na to Cl), 86 pm. Consequences of
lanthanide contraction. The lanthanide contraction has a
highly significant effect on the relative properties of the
elements which precede and follow lanthanides in the
periodic table. Some important consequences of lanthanide
contraction are:
(i) The radius of La3+ ion, for example, is 22 pm larger
than that of Y3+ ion which lies immediately above it in
the periodic table. On this basis, if the fourteen
lanthanides had not intervened, the radius of Hf 4+
should have been greater than that of Zr 4+ (which
lies immediately above it) by about 20 pm. But, the
lanthanide contraction of about the same magnitude
almost cancels the expected increase. As a result, Hf
4+
and Zr 4+ have almost equal radii, being 80 and 81
pm respectively.
It is seen that the normal increase in size from Sc Y La disappears after the
lanthanides and the pairs of elements such as, Zr Hf, Nb Ta, Mo W, etc., have almost the
same size. The properties of these elements are also very similar. It is thus a direct consequence
of lanthanide contraction that the elements of the second and third transition series resemble
each other much more closely than do the elements of the first and second transition series.

(ii)

Due to lanthanide contraction, i.e., decrease of ionic size on moving from La3+ to Lu3+, the
covalent character in bonding increases in the direction La3+ Lu3+. As a result, the basic
character of the lanthanide hydroxides (M(OH)3) decreases with increase in atomic number.
Thus, La(OH)3 is the most basic, while Lu(OH)3 is the least basic. This aspect has been
utilized in the separation of lanthanides from each other.

(6) Formation of complex salts and ions. Lanthanide ions (M3+) have high charge, but
due to their larger size, these cannot polarize the neighbouring anion/molecule. As a result, these
lanthanides do not show a strong tendency towards complex formation.
(7) Colour of the salts and ions in solution . Most of the lanthanide trivalent ions are
coloured in solid as well as in the solution phase. The ions containing x and (14 x) electrons show the
same colour. The colour of the salts or ions is due to the f f transition of electrons.

Actinoides
The fourteen elements (atomic number 90103) after actinium are called actinides. These are also called
second series of inner-transition elements. The general electronic configuration of actinides is 5f 114 6d
01
7s2. Names and the outer-electronic configurations of actinides are given below in Table 9.11.
General Characteristics of Actinides
(1) Oxidation states. The oxidation states commonly exhibited by actinides are given in
Table 9.12. The most stable state is indicated by bold letter. The + 3 state becomes more stable as the
atomic number increases.

(2) Atomic and Ionic radii. The radii for tripositive (M3+) and tetrapositive (M4+) ions
decrease in going from Th to Cm. This steady decrease is similar to that observed in lanthanides and is
called actinide contraction.
Fact: The actinide contraction is larger than lanthanide contraction.
Reason: because in lanthanoids electrons are filled in 4f orbital whose screening effect is more
stronger than 5f orbitals of actinoid elements.
(3) Colour of salts and ions in solution. Most of the salts of actinides having M3+ or M4+
ions are coloured. Ions having 5f , 5f 1 and 5f 7 configurations are colourless, while those containing 5f
2
, 5f 3, 5f 4, 5f 5 and 5f 6 configurations are coloured.

Uses of Lanthanides
Due to their alloy-forming tendencies, actinides and lanthanides form many alloys particularly
with iron. These elements improve the workability of steel. A well known alloy is misch-metal which
consists of a rare earth element (94 95%), iron (up to 5%) and traces of sulphur, carbon, calcium and
aluminium.
The pyrophoric alloys containing rare-earth metals are used in the preparation of ignition
devices, e.g., tracer bullets and shells and flints for lighters. This alloy has normally the composition:
cerium 40.5%, lanthanum + neodymium 44%, iron 4.5%, aluminium 0.5% and the remainder calcium,
silicon and carbon.
(i)
Cerium constitute about 30-50% of the alloys of lanthanides. They are used fro
scavenging oxygen and sulphur.
(ii)
Thorium is used in the manufacture of fine rods of atomic reactor.
(iii)
Thorium salts are also used in treatment of cancer.
(iv)
Uranium and Plutonium are used for production of nuclear energy by the
nuclear fission.