pCHAPTER : 8

d- AND f- BLOCK ELEMENTS

d - BLOCK ELEMENTS:
Elements in which the last electron or the differentiating electron enters in
penultimate shell of d-sub shell are known as d-block elements.
The d-block elements are often called transition metals because they are placed in
between highly electropositive s-block elements and the least electropositive p-block
elements as there is a regular decrease in metallic property from left to right in d-block
elements.
TRANSITION ELEMENTS:
Transition metals are those elements which have incompletely filled (partially filled)
d-subshells either in their ground state or in any one of their oxidation states. Zinc,
Cadmium and mercury are not transition elements as per the definition because
they do not have partially filled d-subshell either in their ground state or in their
common oxidation state (i.e., Zn+2, Cd+2, Hg+2). However,being the last members of
three transition series, they may be treated as transition elements since they are
quite similar to other transition elements in some of their properties.
POSITION IN THE PERIODIC TABLE:
The d-block or transition elements occupy positions in between s and p-block in group
3-12 in the periodic table. d-block elements consist of four transition series.
➢ 3d–series: First transition series belonging to 4th period consisting of elements
from Z = 21 (Scandium) to Z = 30 (Zinc)
➢ 4d–series: Second transition series belonging to 5th period consisting of
elements from Z = 39 (Yttrium) to Z = 48 (Cadmium)
➢ 5d–series: Third transition series belonging to 6th period consisting of elements
from Z = 57 (Lanthanum), Z = 72 (Hafnium) to Z = 80 (Mercury) [excluding the
elements Z = 58 (Cerium) to Z = 71 (Lutetium)].
➢ 6d–series: Fourth transition series belonging to 7th period. It is an incomplete
series consisting of elements from Z = 89 (Actinium), Z = 104 (Rutherfordium)
etc.
ELECTRONIC CONFIGURATION OF d-BLOCK ELEMENTS:
The general electronic configuration of d-block elements is
[Noble gas](n-1) d1-10 ns1-2 where (n-1) is the penultimate shell and n is the
outermost shell.
The general electronic configuration of the 3d series is [Ar] 3d1-10 4s1-2.

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The following table gives the electronic configuration of elements of 3d series.
Element Symbol Z Configuration Box diagram No. of
unpaired e–
Scandium Sc 21 [Ar]3d14s2 1
Titanium Ti 22 [Ar]3d24s2 2
Vanadium V 23 [Ar]3d34s2 3
Chromium Cr 24 [Ar]3d54s1 6
Manganese Mn 25 [Ar]3d54s2 5
Iron Fe 26 [Ar]3d64s2 4
Cobalt Co 27 [Ar]3d74s2 3
Nickel Ni 28 [Ar]3d84s2 2
Copper Cu 29 [Ar]3d104s1 1
Zinc Zn 30 [Ar]3d104s2 0

EXCEPTIONAL CONFIGURATION OF CHROMIUM AND COPPER:

• The exceptional electronic configuration of Cr and Cu is due to extra stability of
half-filled and completely filled electronic configuration (d5 and d10) of them
respectively.
• The energy difference between 3d and 4s orbitals is not large enough to
prevent the electron entering the 3d orbital. Thus, to acquire extra stability, one
of the 4s electron goes to nearby 3d-orbital so that 3d-orbital becomes half-
filled in case of chromium and completely filled in case of copper.
• Therefore, the electronic configuration of Cr is [Ar] 3d5 4s1 instead of
[Ar] 3d4 4s2 and for Cu is [Ar] 3d10 4s1 instead of [Ar] 3d9 4s2.

Since, d – orbitals are partially filled in most cases, these elements exhibit certain
characteristic properties such as: exhibiting variable oxidation states, formation of
coloured ions, formation of complexes, catalytic properties and paramagnetic
properties. These properties are based on the number of unpaired electrons present
in the d subshell.

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GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS:
1. Nearly all the transition elements have typical metallic properties such as,
malleability, ductility, high tensile strength, high thermal and electrical conductivity
and metallic lustre.
2. Mercury is a liquid at room temperature, other transition e l e m e n t s a r e typical
metallic solids.
3. Transition metals have high melting and boiling points.
4. They have high density as compared to the metals of group 1 and 2.
5. They are electropositive in nature.
6. Ionisation enthalpy of d-block elements are higher than those of s-block
elements but are lower than those of p-block elements.
Physical properties:
1. Metallic character:
Transition metals display typical metallic properties. Metallic properties of transition
metals are due to their low ionisation enthalpy. Because of this, their ns electrons and
(n-1) d unpaired electrons would take part in the formation of metallic bonds. Further
greater the number of unpaired electrons in the (n – 1)d subshell stronger the
metallic bond.

2. Melting and Boiling point:

• The transition metals (except for
Zn, Cd and Hg) are very hard and
have low volatility.
• Their melting and boiling points
are high.
• The graph depicts the melting
points of the 3d, 4d and 5d
transition metals.
• The high melting points of these
metals are due to the involvement of greater number of electrons from (n-1)d
in addition to the ns electrons in the formation of metallic bond.
• In any row the melting point of these metals rise to a maximum at d5 except
for anomalous values of Mn and Tc and fall regularly as the atomic number
increases.

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 Hence, elements with d5 configuration having maximum unpaired electrons
have the highest melting points. For example: Cr in 3d series, Mo in 4d series
and W in 5d series have maximum melting points.
• Zn, Cd and Hg have abnormally lower melting points due to completely filled
(n–1)d10 ns2 configuration resulting in the formation of weak metallic bonds.

3. Enthalpies of atomization:
• It is the heat energy required to break the metal lattice to get free atoms.
• Transition metals have high enthalpies of
atomization which are shown in the
graph.
• It is the maximum in the middle of each
series due to d5 configuration. Greater
the number of unpaired electrons,
stronger the metallic bond.
• In general, the m.pt and atomization
enthalpies increase in the following
order of 3d – series < 4d – series < 5d – series.

4. Variation of atomic and ionic size (radius):

• By definition, the distance between the centre of the nucleus and the outermost
shell of electrons in an isolated and gaseous atom of an element is the atomic
radius.
• The distance between the centre of the nucleus and the point up to which the
nucleus extends its influence of attractive force in an ion is called ionic radius.

The following tables give the atomic radii of the elements of the 3d series.

Element (3d series) Sc Ti V Cr Mn Fe Co Ni Cu Zn

Atomic radius in pm 144 132 122 117 117 117 116 115 117 125
It is observed that the atomic radius in 3d series decreases up to Cr with d5
configuration, then almost remains constant up to Cu and then increases drastically
for Zn with 3d10 4s2 configuration.

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Explanation:

Let us consider the variation of atomic radii of

3d series.

• The variation of atomic radii across the

period depends on two factors.
i. effective nuclear charge (i.e, the number of protons in the nucleus)
ii. Shielding effect.

Note:
The shielding effect of electrons caused for an electron by the electrons of the same
shell and inner shells is in the order s > p > d > f since the size of these orbitals is
in the order s < p < d < f (smaller the size, more the shielding effect).
In 3d series, the subshells 1s, 2s, 2p, 3s, 3p and 4s are already filled, the shielding
effect caused by these electrons remain constant from Sc to Zn.
Hence, any variation in the atomic radius must be attributed to the variation of
nuclear charge and shielding effect of 3d electrons alone.

• Across the period, nuclear charge increases. Shielding effect caused for electrons
of 3d by other electrons of 3d is poor. Hence, the atomic radius decreases from Sc
to Cr.
• From Cr to Cu, the 3d subshell has more electrons and therefore the . shielding
effect is more. But the increase in the shielding effect and increase in the nuclear
charge compensates each other and hence, the atomic radius remains almost
constant till Cu.

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 • From Cu to Zn there is a sudden increase in atomic radius because 3d subshell is
completely filled and there is inter electronic repulsion which expands the
electron cloud causing an increase in atomic radius.

• Down the group in each transition series, the atomic radius increases from 3d to
4d but almost remains constant from 4d to 5d after the first element in the series
due to lanthanoid contraction which is due to the ineffective shielding of 4f
electrons.

5. Ionisation enthalpies of transition metals:

The following table gives the first, second and third ionisation enthalpies of 3d series
elements.

Element (3d Sc Ti V Cr Mn Fe Co Ni Cu Zn
series)
IE1 in kJ 631 656 650 652 717 762 758 736 745 905
mol–1
IE2 in kJ 1245 1320 1376 1635 1513 1564 1648 1757 1962 1736
mol–1
IE3 in kJ 2451 2721 2874 2995 3258 2964 3238 3401 3561 3839
mol–1

• The first ionisation enthalpies of d–block elements are greater than those of s–block
and lesser than those of p–block elements. This is due to increase in effective
nuclear charge.
• The ionisation enthalpy of 3d series increases as we move across each series from
left to right. but the difference in values between the successive members is very
less.
• The first ionisation enthalpies of Zn, Cd and Hg are very high due to completely
filled (n–1)d10 ns2 configurations.
• The second IE of Cr is greater than Mn
• 2nd IE of Cu is greater than that of Zn.
It is because, after the removal of the first electron from Cr and Cu atoms, they
develop a stable d5 and d10 configuration respectively.

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• The third IE of Mn is very high due to the stable 3d5 electronic configuration after
the removal of second electron from the atom of Mn.

• Third IE of Fe is small due to the attainment of stable 3d5 electronic configuration

after losing the third electron in Fe. Thus, 3rd I.E of Mn is higher than Fe.

6. Oxidation states of Transition elements:

The following table gives the oxidation states of the elements of 3d series:

Element Box diagram configuration Oxidation states (oxidation states in

parenthesis are unstable)
Sc +3

electronic configuration are highly stable.

ionic compounds and in higher oxidation

2. In the lower oxidation state they form
Ti +2, +3, +4

state they form covalent compounds

1. Metal ions having d0, d5 and d10
V +2, +3, +4, +5
Cr +2, +3, +4, (+5), +6
Mn +2, +3, +4, (+5), +6, +7
Fe +2, +3, (+4), (+5), (+6)

which are acidic.

Co +2, +3, (+4), (+5)
Ni +2, (+3), (+4)
Cu +1, +2
Note:

Zn +2

• Since, in transition elements, electrons present in (n–1)d and ns subshells do not

differ much in their energies, both set of electrons take part in bond formation.
Therefore, these elements exhibit variable oxidation state.
• In 3d series, Sc and Zn do not exhibit variable oxidation state. Sc shows +3 and
Zinc shows +2 oxidation states.
• For a given transition element, the oxidation states differ from each other by unity
as in case of V(II), V(III), V(IV) and V(V) unlike the case of non–transition elements
like p – block where they differ by 2 units as in case of Pb(II) and Pb(IV).
• The most common oxidation state of the 3d series is +2 except for Sc.

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• In this series, the minimum oxidation state shown by an element is equal to the
number of electrons in 4s orbital. The maximum oxidation state is equal to the sum
of electrons in 4s and the unpaired electrons in 3d orbitals.
• The elements with the highest number of oxidation states and with highest
oxidation state occur in or near the middle of the series. For example, Manganese
exhibits all the oxidation states from +2 to +7.

• The lesser number of oxidation states and with the least oxidation state appear at
the extreme ends.
• The only oxidation state of zinc is +2 (no d electrons are involved) due to
completely filled d subshell which makes it stable.
• In p–block elements, the lower oxidation states are favoured by the heavier
members (due to inert pair effect), while in the d – block higher oxidation states
are more stable for heavier transition metals.

• For example, in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI).
Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising agent,
whereas MoO3 and WO3 are not.
• Osmium exhibits the maximum oxidation state (+8) among transition metals.

• In Metal carbonyls, the oxidation state of 3d elements will be zero. For example,
in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero.

• Many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.
The stability of Cu2+(aq) is more than Cu+(aq) due to more negative ∆hydHO of Cu2+(aq)
than Cu+. The high hydration enthalpy compensates for the second ionisation
enthalpy of Cu.
2Cu+ → Cu2+ + Cu

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 (Additional information: Stability of a given oxidation state of an element can
be better understood by the values of the standard reduction potentials
(electrode potential) of these elements. This might be the M2+|M or M3+|M2+.
This occurs in in four steps. They are sublimation of the metal, ionisation, and
hydration and formation. Hence, the electrode potential for the transformation of
M(s) to Mn+(aq) is the measure of the sum of the enthalpies of the above said
processes in accordance with Hess’s law of constant heat summation.

Where, ∆Hf = enthalpy formation of Mn+(aq) from M(s).

∆Hs = Enthalpy of sublimation.
∆HIE = Enthalpy of ionisation.
∆Hhyd = Enthalpy of hydration of Mn+(g) ions))
.

7. Trends in M+2|M standard electrode potentials:

• Most of the elements show negative standard reduction potentials for conversion
of solid metal to the hydrated M2+ ions. This is due to high electropositive nature
and low ionisation enthalpy of the metals. Their hydration enthalpy also is negative
and hence their reduction potentials are negative.
• These values become less negative across the series with increase in atomic number
indicating the higher tendency to undergo reduction. This is due to increase in the
IE1 and IE2 values across the period.
• Only Cu in the series, possess positive standard reduction potential value for
E MO 2+ | M . This accounts for its inability to liberate hydrogen from non–oxidising
acids like HCl, etc.
• Mn, Ni and Zn show more negative values than their previous neighbours in the
series. This is due to the stability of half–filled d5 configuration in Mn2+ and
completely filled d10 configuration in Zn2+ and in Ni, due to high negative value of
hydration enthalpy.

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Trends in M3+|M2+ standard electrode potentials:

• E MO 3+
| M 2+
for Sc is more negative or very low which means the tendency of Sc3+ to
become Sc2+ is very low. This is due to the attainment of stable octet configuration
of argon (noble gas) in Sc3+.
• E MO |M for Zn is more positive or very high. This is due to the removal of an
3+ 2+

electron from a stable d10 configuration of Zn2+.

• E MO |M for Mn is more positive or very high. This is due to the removal of an
3+ 2+

electron from a stable half–filled d5 configuration of Mn2+

• E MO |M for Fe is low. As Fe3+ has a stable half–filled d5 configuration.
3+ 2+

• Similarly, in V, formation of V2+ has low EO values due to half–filled t2g orbitals.

8. Trends in stability of higher oxidation states in Transition elements:

Table of halides of transition metals with different oxidation states:

Oxidation state Compounds

+6 CrF6
+5 VF5, CrF5
+4 TiF4, TiCl4, TiBr4, TiI4, VF4, VCl4, VBr4, CrF4, CrCl4, CrBr4, CrI4, MnF4
+3 TiF3, TiCl3, TiBr3, TiI3, VF3, VCl3, VBr3, VI3, CrF3, CrCl3, CrBr3, CrI3, FeF3,
FeCl3, FeBr3, CoF3
+2 TiI2, VF2, VCl2, VBr2, VI2, CrF2, CrCl2, CrBr2, CrI2, MnF2, MnCl2, MnBr2,
MnI2, FeF2, FeCl2, FeBr2, FeI2, CoF2, CoCl2, CoBr2, CoI2, NiF2, NiCl2,
NiBr2, NiI2, CuF2, CuCl2, ZnF2, ZnCl2, ZnBr2, ZnI2,
+1 CuI

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Table of Oxides of transition metals with different oxidation states:

Oxidation state Compounds

+7 Mn2O7
+6 CrO3
+5 V2O5
+4 TiO2, V2O4, CrO2, MnO2
+3 Sc2O3, Ti2O3, V2O3, Cr2O3, Mn2O3, Fe2O3,
[Mn3O4, Fe3O4, Co3O4 (mixed oxides)]
+2 TiO, VO, (CrO), MnO, FeO, CoO, NiO, CuO, ZnO
+1 Cu2O
• The highest oxidation numbers are achieved in TiX4 (tetrahalides), VF5 and CrF6.
• The +7 state for Mn is not known in simple halides but MnO3F is known.
• Besides the oxides, oxo cations stabilise V5+ as VO2+, V+6 as VO2+ and Ti+4 as TiO2+.
• The ability of oxygen to stabilise these high oxidation states exceeds that of
fluorine. Thus, the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
The ability of oxygen to form multiple bonds to metals explains its superiority.
• Oxides of metals with lower oxidation states are basic.
Oxides of metals with moderate oxidation states are amphoteric.
Oxides of metals with higher oxidation states are acidic.

9. Magnetic properties:
• Based on the behaviour of a substance in the presence of magnetic field,
substances are classified into,
• i. Diamagnetic substances: These are the substances which are repelled by the
applied magnetic field. Diamagnetic nature is due to the absence of unpaired
electrons. Example: Cu+ and Zn2+ ions are diamagnetic as they do not contain
unpaired electrons.
• ii. Paramagnetic substances: These are the substances which are attracted by
the applied magnetic field. Paramagnetic nature is due to the presence of
unpaired electrons. Example: Mn2+ and Fe3+ ions are paramagnetic as they
contain unpaired electrons.
• Many of the transition metal ions are paramagnetic in nature which is due to
the presence of unpaired electrons.

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 Calculation of magnetic moment:
The magnetic moment of transition metal elements depends only on the spin
angular momentum and is calculated using the formula  = n( n + 2) BM .
Where ‘n’ is the number of unpaired electrons and μ is the magnetic moment in
units of Bohr magneton (BM).

1 BM = 9.27 X 10-24 Am-2

Magnetic moments of ions of 3d series

Ion Electronic Number of unpaired Magnetic moment in BM

configuration electrons calculated observed

Sc3+ 3d0 0 0 0
Ti3+ 3d1 1 1.73 1.75
Ti2+ 3d2 2 2.82 2.76
V2+ 3d3 3 3.87 3.86
Cr2+ 3d4 4 4.90 4.80
Mn2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3 – 5.5
Co2+ 3d7 3 3.87 4.4 – 5.2
Ni2+ 3d8 2 2.82 2.9 – 3.4
Cu2+ 3d9 1 1.73 1.8 – 2.2
Zn2+ 3d10 0 0 0
NOTE: The magnetic behaviour of dn and d10-n transition atoms or ions will be similar.
For example: d1 and d9, d2 and d8, d3 and d7, d4 and d6 will have similar magnetic
moment.

Compounds with d0 and d10 electronic configurations are diamagnetic.

10. Formation of coloured ions:

Both ionic and covalent transition metal compounds are coloured in solid state as
well as in their aqueous solutions.

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 The colour of compounds of a transition metal is due to,

• The presence of unpaired electrons.

• d-d transition.
The splitting of degenerate d-orbitals (orbitals having same energy) into two sets,
one of which has lower energy and the other has higher energy occurs under the
influence of ligands.

When anions or neutral species( called ligands) approach the metal, the d – orbitals
which are degenerate will split into two sets one consisting of dxy, dyz and dxz orbitals
of one energy level and the other d x 2 − y 2 and d z of one energy level. Thus the electron
2

can jump from lower energy d-orbital to higher energy d-orbitals. The energy required
to excite the electron to higher energy within the same d-sub shell corresponds to
energy of certain colours of visible light.

Therefore, when white light falls on a transition metal compound, radiation of certain
wavelength corresponding to certain colour is absorbed and the electron gets excited
from lower energy set of orbitals to higher energy set of orbitals. The unabsorbed
radiations with certain wavelength are transmitted. The colour of the compound is
complementary to the colour of radiation absorbed.

For example: Cu2+ salts absorb red light and appear blue. This transition of electrons
between d orbitals of different energy levels is called d – d transition.

11. Complex formation: The compounds in which a metal atom or cation is bonded
to a set of anions or neutral molecules with lone pairs (called ligands) by coordinate
covalent bonds such that all the ions do not ionise in solutions are named as complex
compounds or coordinate compounds. Transition metals form a wide variety of
complex compounds. Examples: K4[Fe(CN)6], [Cu(NH3)4]SO4, etc. The reasons for
transition metals possessing the tendency to form complex compounds are

i. Small atomic size

ii. Large effective nuclear charge
iii Large polarising power. ( Polarising power is Charge/size)
iv. Availability of vacant d – orbitals such that they can accept lone pairs of electrons
donated by the ligands.

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12. Catalytic property:
Transition metals and their compounds have wide application as catalysts both in
laboratories and in industries for various reactions. This property of transition metals
is attributed to:

i. Ability to exhibit multiple oxidation states.

ii. Formation of intermediate compounds:

For example, iron(III) catalyses the reaction between iodide and persulphate ions.

2 I– + S2O82– → I2 + 2 SO42–

An explanation of this catalytic action can be given as:

2 Fe3+ + 2 I– → 2 Fe2+ + I2

2 Fe2+ + S2O82– → 2 Fe3+ + 2SO42–

iii. Provide a large surface area for the adsorption of reactants.

13. Formation of interstitial compounds:

Interstitial compounds are those which are formed when
small atoms like H, B, C or N are trapped inside the
interstitial lattice space of the metals. They are usually
non stoichiometric and are neither ionic nor covalent, for
example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc. The
characteristics of these compounds are as follows:

(i) Their melting points are higher than those of pure metals.
(ii) They are very hard, some borides approach the hardness of diamond
(iii) They retain metallic conductivity.
(iv) They are chemically inert.

14. Alloy formation: Alloys are homogeneous solid solutions in which the atoms
of one metal are distributed randomly among the atoms of the other.

• Alloys are formed by atoms with metallic radii that are within about 15
percent of each other. Because of similar radii and other characteristics of
transition metals, alloys are readily formed by these metals.

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The alloys so formed are,

• hard
• have high melting points.
• resistant to corrosion.

The best known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and
manganese are used for the production of a variety of steels and stainless steel. Alloys
of transition metals with non–transition metals such as brass (copper-zinc) and
bronze (copper-tin), are also of considerable industrial importance.

Some important compounds of transition metals:

Potassium dichromate – Manufacture, properties and uses:

Potassium dichromate is a very important chemical for the leather industry and an
oxidant for the preparation of many compounds, like dyes, etc. used in qualitative and
quantitative analysis.

Manufacture of K2Cr2O7 from chromite ore (FeCr2O4).

This is done in three steps as follows:

• Step 1: Chromite ore is roasted in the presence of sodium carbonate to obtain
sodium chromate and ferric oxide. Sodium chromate (yellow solution) is soluble
in water and is separated from insoluble ferric oxide by filtration.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 2 Fe2O3 + 8 Na2CrO4 + 8 CO2
• Step 2: Sodium chromate solution is acidified with sulphuric acid to obtain
sodium dichromate and sodium sulphate. Less soluble sodium sulphate gets
separated and filtered to obtain sodium dichromate solution.
2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
• Step 3: Sodium dichromate solution is reacted with potassium chloride to
obtain potassium dichromate and sodium chloride. The solution is boiled and
concentrated, less soluble potassium dichromate is separated. This is
recrystallised to obtain pure potassium dichromate.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl

Properties: it is orange red crystals. It is moderately soluble in cold water but freely
soluble in hot water.

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 • Chemical properties:
1. Action of alkali: When potassium dichromate is reacted with alkali, it gives
potassium chromate. In the alkali medium, it exists as chromate. In the acid
medium, it exists as dichromate. At pH 4, they exist at equilibrium.
K2Cr2O7 + 2 KOH 2 K2CrO4 + H2O
2.OXIDISING CHARACTER:
Potassium dichromate acts as powerful oxidising agent in acidic medium. In
the presence of dilute sulphuric acid, K2Cr2O7 liberates nascent oxygen and
therefore acts as an oxidising agent.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

Oxidising properties: In the acid medium K2Cr2O7 gets reduced to Cr3+ ions.

Cr2O72− + 14 H + + 6 e − ⎯⎯
→ 2 Cr 3+ + 7 H 2O

In acid medium,it oxidises I-, Sn2+, H2S and Fe2+ to I2, Sn4+, S and Fe3+ respectively.

Cr2O72− + 14 H + + 6 I − ⎯⎯
→ 2 Cr 3+ + 3 I 2 + 7 H 2O

Cr2O72− + 14 H + + 3 Sn 2+ ⎯⎯
→ 2 Cr 3+ + 3 Sn 4+ + 7 H 2O

Cr2O72− + 8 H + + 3 H 2 S ⎯⎯
→ 2 Cr 3+ + 3 S + 7 H 2O

Cr2O72− + 14 H + + 6 Fe 2+ ⎯⎯
→ 2 Cr 3+ + 6 Fe 3+ + 7 H 2O

Structure of Chromate and dichromate ions:

The structure of chromate ion and dichromate ion are shown below. Chromate ion is
tetrahedral and dichromate ion consists of two tetrahedra with a bridged O atom.

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POTASSIUM PERMANGANATE: (KMnO4) PREPARATION:
Potassium permanganate is prepared from pyrolusite ore (MnO 2). It involves the
following steps.

Method 1:

• Pyrolusite ore is fused with potassium hydroxide in presence of air or

oxidising agent such as KNO3, a green mass of potassium manganate
(K2MnO4) is obtained.

2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O

• Manganate ion disproportionates in a neutral or acidic solution to give

permanganate.,
3MnO4 2- + 4H+ 2MnO4 - + MnO2 + 2H2O

Method 2: Step 1 of method 2 is same as method 1. The potassium manganate so

formed is electrolysed between iron electrodes. Manganate ions are oxidised to
permanganate at the anode and hydrogen gas is liberated at the cathode.

At anode : MnO42− ⎯⎯
→ MnO4− + e −
At cathode :2 H + + 2 e − ⎯⎯
→ H2

Properties: Potassium permanganate is a dark purple (almost black) crystals with a

greenish lustre which becomes dull in air due to superficial oxidation. It is moderately
soluble in water at room temperature and is more soluble in hot water.

Chemical properties:

Action of heat: When heated it decomposes at 513 K to form potassium manganate

and oxygen.

2 KMnO4 ⎯⎯

→ K 2 MnO4 + MnO2 + O2
Oxidising nature: Potassium permanganate acts as an oxidising agent in acid, alkaline
and neutral medium.

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i. In acidic medium, it oxidises I– to I2, Fe2+(green) to Fe3+(yellow), H2S to S, C2O42–
(oxalate) to CO2 and H2O, SO32– (sulphite) to SO42– (sulphate) and NO2– (nitrite) to
NO3– (nitrate).

MnO4− + 8 H + + 5 Fe 2+ ⎯⎯
→ Mn 2+ + 5 Fe 3+ + 4 H 2O
2 MnO4− + 16 H + + 10 I − ⎯⎯
→ 2 Mn 2+ + 5 I 2 + 8 H 2O
2 MnO4− + 16 H + + 5 C 2O42− ⎯⎯
→ 2 Mn 2+ + 10 CO2 + 8 H 2O
→ 2 H + + S 2−
H 2 S ⎯⎯
2 MnO4− + 16 H + + 5 S 2− ⎯⎯
→ 2 Mn 2+ + 5 S + 8 H 2O
2 MnO4− + 6 H + + 5 SO32− ⎯⎯
→ 2 Mn 2+ + 5 SO42− + 3 H 2O
2 MnO4− + 6 H + + 5 NO2− ⎯⎯
→ 2 Mn2+ + 5 NO3− + 3 H 2O

ii. In faintly alkaline (or acidic) or neutral medium: it oxidises Mn2+ to MnO2, I– (iodide)
to IO3– (iodate) and S2O32– (thiosulphate) to SO42– (sulphate).

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NOTE: Permanganate titrations in presence of hydrochloric acid are unsatisfactory
as hydrochloric acid gets oxidised to chlorine

Uses of potassium permanganate:

Potassium permanganate is used in inorganic and organic qualitative and quantitative

analysis. It is used as oxidant in organic preparations.

Structure of manganate and permanganate ions:

f – block elements inner transition elements

Elements in which the differentiating electrons enter the ante penultimate f–subshell
are called f block elements.

They are also known as inner transition elements as the last electron in them enters
into (n–2)f orbitals, i.e. inner to the penultimate energy level and they form a
transition series within the transition series (d–block elements).

Their general electronic configuration is [Noble gas](n–2)f1–14(n–1)d0–1 ns2.

Classification of f – block elements: Depending upon whether the last electron enters
a 4f orbital or 5f orbital, the f–block elements have been divided into two series as
follows.:

i. The lanthanide series/lanthanoid series/lanthanons/4f series: The 14 elements

from Ce (Z = 58) to Lu (Z = 71) are called lanthanoids. This is because, they appear
immediately after lanthanum (Z = 57) in the periodic table. In these elements the last

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electron enters the 4f–orbitals. They are the least abundant elements in the earth’s
crust. Hence, called rare earths. Together these elements are represented by the
common symbol ‘Ln’.

ii. The Actinide series/Actinoid series/Actinons/5f series: The 14 elements from

Thorium Th (Z = 90) to Lr (Z = 103) are called Actinoids. They are also called by other
names as mentioned above. This is because, they appear immediately after Actinium
(Z = 89) in the periodic table. In these elements the last electron enters the 5f–orbitals.
All elements in this series are radioactive and the elements after uranium are
obtained from uranium by artificial radioactive transmutation. Hence, called trans
uranium elements.

• Though lanthanum a d – block element, it is included in the lanthanoid series

because, it is closely resembling lanthanoids.
• Similarly, actinium is also included in the actinoid series.
• Further the study of lanthanoids is comparatively easier because, they show only
one stable oxidation state.
• On the other hand, the chemistry of actinoids is much more complex because they
show wide range of oxidation states and most of them are radioactive and have
short half–life period of few days to few minutes.

Lanthanoids:
Electronic configuration:

• All the lanthanoid elements have the electronic configuration with 6s 2 common.
The electronic configuration of all the tri positive ions (the most stable oxidation
state of all the lanthanoids) are of the form 4fn (n = 1 to 14 with increasing atomic
number).
• The energies of 5d and 4f orbitals are nearly equal. Except cerium, gadolinium and
lutetium, the single electron present in 5d orbital comes to 4f orbital. Thus, the
elements cerium, gadolinium and lutetium have 5d1 configuration whereas the rest
of the elements have 5d0 configuration.
• Europium and gadolinium have half-filled f -orbitals (4f7) whereas ytterbium and
lutetium have completely filled f – orbitals (4f14) which gives extra stability to their
configuration.
NOTE: The general electronic configuration for lanthanoids is [Xe] 4f 1–145d0–16s2

Oxidation states:

• The typical oxidation state of lanthanoids is +3

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• The oxidation state of +2 and +4 are also exhibited by some of the elements which
by losing 2 or 4 electrons acquire a stable configuration of f0, f7 or f14. For example:
Eu2+ is [Xe] 4f7, Yb2+ is [Xe] 4f14, Ce+4 is [Xe]4f0 and Tb4+ is [Xe]4f7.
• The formation of Ce4+ ion is favoured by its noble gas configuration [Xe] 4f0.
• Lanthanoids in higher oxidation state are good oxidising agents (oxidants) and
those in lower oxidation states are good reducing agents (reductants).
• Each case tends to revert to the more stable oxidation state of +3 by loss or gain of
an electron. Hence, Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents
and aqueous solutions of Ce4+and Tb4+ are good oxidising agents.
• The EO values for Ce4+|Ce3+ is +1.74V which suggests that it can oxidise water.
however, the reaction rate is very slow and hence Ce(IV) is used as a good analytical
reagent.

The following table gives the electronic configuration of the lanthanides and their
oxidation state.

Z Name Symbol Electronic configuration outside [Xe] core Oxidation

Ln Ln2+ Ln3+ Ln4+ states

57 Lanthanum La 5d1 6s2 5d1 4f0 – +3

58 Cerium Ce 4f1 5d1 6s2 4f2 4f1 4f0 +3, +4
59 Praseodymium Pr 4f3 5d0 6s2 4f3 4f2 4f1 +3, +4
60 Neodymium Nd 4f4 5d0 6s2 4f4 4f3 4f2 +2, +3, +4
61 Promethium Pm 4f5 5d0 6s2 4f5 4f4 – +3
62 Samarium Sm 4f6 5d0 6s2 4f6 4f5 – +2, +3
63 Europium Eu 4f7 5d0 6s2 4f7 4f6 – +2, +3
64 Gadolinium Gd 4f7 5d1 6s2 4f75d1 4f7 – +3
65 Terbium Tb 4f9 5d0 6s2 4f9 4f8 4f7 +3, +4
66 Dysprosium Dy 4f10 5d0 6s2 4f10 4f9 4f8 +3, +4
67 Holmium Ho 4f11 5d0 6s2 4f11 4f10 – +3
68 Erbium Er 4f12 5d0 6s2 4f12 4f11 – +3
69 Thulium Tm 4f13 5d0 6s2 4f13 4f12 – +2, +3
70 Ytterbium Yb 4f14 5d0 6s2 4f14 4f13 – +2, +3
71 lutetium Lu 4f14 5d1 6s2 4f145d1 4f14 – +3

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Atomic and ionic radii: [Table contains AR and IR (Ln3+) in pm]

E La Ce Pr Nd Pm Sm Eu Gd T.b Dy Ho Er Tm Yb Lu
AR 187 183 182 181 181 180 199 180 178 177 176 175 174 173 –

IR 106 103 101 99 98 96 95 94 92 91 89 88 87 86 –

ATOMIC AND IONIC RADII: (LANTHANOID CONTRACTION) I

In lanthanide series,

the steady decrease in atomic and ionic radii of lanthanide elements with increasing
atomic number is called lanthanide contraction.

CAUSES FOR LANTHANOID CONTRACTION:

• Poor shielding effect of 4f e- }

In the lanthanoid series, as we move from one element to another, the nuclear
charge increases by one unit and one electron is added. The new electrons are
added to the same inner 4f-orbitals. The shielding effect of 4f electron 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-
subshell.

CONSEQUENCES OF LANTHANIDES/ LANTHANOID CONTRACTION: The important

consequences of lanthanides are,

• Separation of lanthanides is difficult.

• Variation in basic strength of hydroxides.
• Similarity in the atomic sizes of the elements of second (4d-series) and third
(5d-series) transition series present in the same group.

General characteristics of lanthanoids:

• All the lanthanoids are silvery white metals and tarnish rapidly in air. The hardness
increases with increasing atomic number, samarium being steel hard.
• Their MP range between 1000 K and 1200 K except samarium which has a very high
MP of 1623 K.
• All of them have typical metallic structure and are good conductors of heat and
electricity.
• Density and other properties vary smoothly with increasing atomic number except
for Eu and Yb and occasionally for Sm and Tm.
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• Most of the trivalent lanthanoid ions are coloured, both in solid state and in
aqueous solutions, which may be dueto the presence of partially filled f – orbitals
which permit f – f transition.
• The lanthanoid ions other than the f0 type (La3+ and Ce4+) and f14 type (Yb2+ and
Lu3+) are all paramagnetic. This property is due to the presence of unpaired
electrons in the 4f subshell. The paramagnetism rises to maximum in neodymium.
• The first ionisation enthalpies of lanthanoids are around 600 kJ mol –1 and second
about 1200 kJ mol–1 which are comparable with those of calcium.
• Further the loss of third electron is easier, i.e., third ionisation enthalpy is low if it
leads to stable empty, half – filled or completely filled configuration as indicated by
abnormally low third ionisation enthalpies of La, Gd and Lu
• Chemical behaviour:
The first few members of the series are quite reactive, almost like calcium.
However, with increasing atomic number, they behave more like aluminium. Their
general reactions are as follows:
i. They combine with hydrogen on gentle heating.
ii. When heated with carbon, they form carbides
iii. On burning in the presence of halogens, they form halides.
iv. They react with dilute acids to liberate H2 gas.
v. They form oxides and hydroxides of the type M2O3 and M(OH)3 respectively which
are basic like alkaline earth metal oxides and hydroxides.

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USES OF LANTHANIDES:

• Lanthanoids are used in the production of alloy steels to improve the strength
and workability of steel.
• Mischmetal is an alloy consists of a lanthanoid metal (~ 95%) and iron (~ 5%)
and traces of S, C, Ca and Al.
A good deal of mischmetal is used in Mg-based alloy to produce bullets, shell
and lighter flint.
• Mixed oxides of lanthanides are employed as catalysts in petroleum cracking.
• Some Ln oxides are used as phosphorescence materials in television screens.
• Their compounds are used in making magnetic and electronic devices.
• Ceric sulphate is a well–known oxidising agent in volumetric analysis.
• Cerium salts are used in dyeing cotton and as catalyst.

The actinoids:

The actinoids include the 14 elements from Th (Z = 90) to Lr (Z = 103). Most of the
actinoids are radioactive elements and the earlier members have relatively long
half–lives while the latter ones have half–life values ranging from a day to 3 minutes
(Lr = 103).

Electronic configuration:

• All the actinoids have a common 7s2 configuration and variable occupancy of 5f and
6d subshells.
• The 14 electrons are formally added to 5f, though no in thorium (Z = 90) but from
Pa onwards till the 5f orbitals are almost complete at element Lr (Z = 103).
• The irregularities in the electronic configurations of actinoids are related to the
stabilities of f0, f7 and f14 configurations. For example, the configurations of Am and
Cm are [Rn] 5f7 6d0 7s2 and [Rn]5f7 6d1 7s2 respectively.
• Although the 5f orbitals resemble the 4f orbitals in their shapes, they are not as
buried as 4f orbitals and hence, 5f electrons can participate in bonding to a far
greater extent.
NOTE: The general electronic configuration of actinoids is [Rn]5f1–14 6d0–1 7s2

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 Electronic configuration of Actinoids
Z Name Symbol Electronic configuration outside [Rn] Oxidation states
core
M M3+ M4+
89 Actinium Ac 6d1 7s2 5f0 – +3
90 Thorium Th 6d2 7s2 5f1 5f0 (+3), +4
91 Protoactinium Pa 5f2 6d1 7s2 5f2 5f1 +3, +4, +5
92 Uranium U 5f3 6d1 7s2 5f3 5f2 +3, +4, +5, +6
93 Neptunium Np 5f46d1 7s2 5f4 5f3 +3, +4, +5, +6, +7
94 Plutonium Pu 5f6 7s2 5f5 5f4 +3, +4, +5, +6, +7
95 Americium Am 5f7 7s2 5f6 5f5 +3, (+4), +5, +6

96 Curium Cm 57 6d1 7s2 5f7 5f6 +3, (+4)

97 Berkelium Bk 5f9 7s2 5f8 5f7 +3, +4
98 Californium Cf 5f10 7s2 5f9 5f8 +3
99 Einsteinium Es 5f11 7s2 5f10 5f9 +3
100 Fermium Fm 5f12 7s2 5f11 5f10 +3
101 Mendelevium Md 5f13 7s2 5f12 5f11 +3
102 Nobelium No 5f14 7s2 5f13 5f12 +3
103 Lawrencium Lr 5f14 6d1 7s2 5f14 5f13 +3
Oxidation states given in brackets are less stable.

Oxidation states:

• Unlike the lanthanoids, actinoids show a variety of oxidation states. It is because

electrons in 5f, 6d and 7s orbitals can take part in bonding as these levels have
comparable energies.
• The actinoids show, in general, +3 oxidation state.
• The elements in the first half of the series frequently exhibit higher oxidation states.
For example, the maximum oxidation state increases from +4 in Th to +5, +6 and +7
respectively in Pa, U and Np but decreases in succeeding elements.
• The actinoids resemble the lanthanoids in having more compounds in +3 state than
in the +4 state. However, +3, +4 ions tend to hydrolyse.

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 Atomic and ionic radii:

• There is a regular decrease in the radii of atoms or ions with increase in the atomic
number of actinoids as we go across the series which is referred to as the actinoid
contraction (like lanthanoid contraction).
• This is due to poor shielding effect of 5f – electrons.
• The actinoid contraction is greater from element to element in the series than
lanthanoid contraction which is due to poor shielding effect of 5f – electrons in
actinoids than those of 4f – electrons in lanthanoids. This is because 5f orbitals
extend in space beyond 6s and 6p orbitals whereas, 4f orbitals are buried deep
inside the atom.

General characteristics of actinoids:

• The actinoids are metals with silvery appearance.

• The actinoids have lower ionisation enthalpies than lanthanoids. It is because 5f
orbitals are less penetrating than 4f orbitals and hence are more effective shielded
from the nuclear charge. Therefore, the outer electrons are less firmly held and can
be easily removed.
• The actinoid elements are strongly paramagnetic due to the presence of unpaired
electrons. However, their magnetic properties are more complex than those of
lanthanoids.

Properties:

• Actinoids have high melting and boiling points like lanthanoids.

• All actinoids except thorium and americium have high densities.
• The actinoid cations like are generally coloured due to the presence of partially
filled f – orbitals and f–f transition.
• All the known actinoid metals are highly electropositive.
• All the actinoid elements are radioactive.

Chemical reactivity:

They are highly reactive. Especially in the finely divided state.

i. They react with boiling water to give a mixture of oxide and hydride.
ii. They combine with most of the non–metals at moderate temperature.
iii. Hydrochloric acid attacks all metals but most of them are slightly affected by nitric
acid owing to the formation of protective oxide layers.
iv. Alkalis have no action on them.

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Uses of actinoids

i. Thorium is used in atomic reactors and in the treatment of cancer.

ii. Uranium is used as nuclear fuel.

iii. Plutonium is used in making atomic bombs and as nuclear fuel.

Similarity between lanthanoids and actinoids:

1. In both lanthanides and actinides f-orbitals are filled gradually.

2. Both exhibit an oxidation state of +3 predominantly.

3. Both are highly electropositive and have high reactivity.

4. Ionic radius of elements of both the series decreases with increase in atomic number
i.e., like lanthanide contraction, there is actinoid contraction. These contractions are
due to poor shielding effect of 5f electrons in actinides and 4f electrons in .lanthanides
respectively.

5. Lanthanoid and actinoid cations have unpaired electrons and hence are
paramagnetic.

……………………………………….

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 .

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