8.

d and f Block elements

1

The d –block elements are called transition elements.

*The transition elements are those elements which have incompletely

filled(partly filled) d-orbital in their ground state or in any one of their
oxidation states.
*This definition covers coinage metals, Cu, Ag and Au as transition metals
because in their commonly occurring oxidation states, they have partially
filled d-subshells. Although all three elements have completely filled d-
orbital in their Ground States.

Cu has 4s13d10 Cu2+ has 3d9

Ag has 5s14d10 Ag2+ has 4d9
Au has 6s15d10 Au3+ has 5d8
There are mainly three series of the transition metals,
First transition 3d series (Sc to Zn), Z=21 to 3d orbitals are
series
Z=30 gradually filled
Second 4d series (Y to Cd) and Z=21 to 4d orbitals are
transition
Z=30 gradually filled
series
Third 5d series Z=57 to 5d orbitals are
transition
(La to Hg, omitting Ce to Z=72 gradually filled
series
Lu).
Fourth 6d series which begins Z=89 and is
transition incomplete
series
with Actinium(Ac) is still
incomplete.
 2
The fourth 6d series which begins with Ac is still incomplete.

The elements of this block have general characteristic properties intermediate

between the elements of s-block and p-block.

Electronic configuration:
The general electronic configuration of transition elements is (n-1)d1-10ns1-2

However, Very little energy difference between (n-1)d and ns orbitals. Half and
completely filled sets of orbitals are relatively more stable.
For example, Cr, which has 3d 5 4s 1 instead of 3d 44s 2; the energy gap between
the two sets (3d and 4s) of orbitals is small enough to prevent electron entering
the 3d orbitals.
Similarly in case of Cu, the configuration is 3d 104s 1 and not 3d 94s 2.

Outer Electronic Configurations of the Transition Elements (ground state)

The electronic configurations of Zn, Cd and Hg are represented by the

general formula (n-1)d 10ns 2. The orbitals in these elements are completely filled in
the ground state as well as in their common oxidation states. Therefore, they are
not regarded as transition elements.
General Characteristics of transition metals:
Because of similar outer electronic configuration, the transition metals show
similarity in physical and chemical properties.
General properties of transition metals:
a. Their atomic radii are in-between those of s and p-block elements.
b. They have high melting point, boiling points, high enthalpies of
vapourisation, high enthalpies of atomization and high enthalpies of hydration of
their ions.
c.Their first ionization energies are higher than those of s-block elements
and less than those of p-block elements.
d.They are electropositive in nature.
e. They show variable oxidation states.
f. Transition metals and their compounds show catalytic properties.
g. Most of the transition elements form coloured compounds.
h. Their compounds are generally paramagnetic in nature.
i. They have a great tendency to form complexes.
 j. They form interstitial compounds with element like H,C,B and N. 3

k. They form alloys.

They however, differ in some properties due to the difference in number of
electrons in d-orbitals.
Exceptional behaviour fo Zn, Cd and Hg : Due to completely filled d10
configuration Zn, Cd and Hg show exceptional behaviour.
i) It has much higher atomic radius and ionization enthalpies.
ii)Its compounds are white while those of other members are coloured.
iii)It does not show variable oxidation states unlike other members.
iv)Its compounds(containing Zn2+ ions) are diamagnetic ( due to absence of
unpaired electrons) while those of the other members are paramagnetic.
v)It forms lesser number of complexes than other members.

1.Metallic character:
Transition elements are malleable and ductile metals having metallic lusture.
They are good conductors of heat and electricity. Except mercury( a liquid)
all are solid.
The variation in the metallic properties is linked with the variation in the
crystal lattices of these elements.
In general, “the greater number of unpaired d-electrons, greater is the
number of bonds and therefore, greater is strength of these metallic bonds”.

Number of unpaired 1 2 3 6 5 4 3 2 1 0
electrons

Cr24 3d54s1 ↑ ↑ ↑ ↑ ↑ ↑

Ni 28 3d84s2 ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

All the transition elements display typical metallic properties such as high
tensile strength, ductility malleability, high thermal and electrical conductivity and
metallic lustre. With the exceptions of Zn,Cd, Hg and Mn, they have one or more
typical metallic structures at normal temperatures.

Zn,Cd and Hg are not very hard metals due to the absence of unpaired electrons.
The transition metals and their compounds also exhibit catalytic property and 4
paramagnetic behaviour.

In any row the melting points of these metals rise to a maximum at d 5

except for anomalous values of Mn and Tc and fall regularly as the atomic number
increases.
2.Atomic volume and density:
All these metals have low atomic volume and high density.
(Density = Mass/Volume).
Within a period, the density vary inversely with the atomic radii. As we
move in a period, the densities increase ( as the Atomic radii decrease hence
volume decreases).
However, densities increase upon descending a group.
Osmium has the highest density among these elements.
 3.Melting and boiling points: 5

Trends in melting points of transition elements

Melting points and boiling points are directly related to the strength of
metallic bonds which in turn depends on the number of unpaired electrons.
Transition series, in general, they have very strong metallic bonds due to the
involvement of both ns and (n-1)d electrons.
Along each transition series, they tend to increase with the increase in the
atomic numbers (or) number of unpaired electrons.
Midway, they become maximum in the elements having d5 configuration. (ie.,
Maximum number of unpaired electrons). Then they show downward trends.

Number of unpaired 1 2 3 6 5 4 3 2 1 0
electrons

Cr, Mo and W have maximum number of unpaired electrons and, therefore

these are very hard metals and have maximum melting point(See the graph). The
elements Zn, Cd and Hg do not have any unpaired electrons, therefore, these are
not very hard. But they have one or more typical metallic structures at normal
temperature.
It rises to the maximum and then decreases in a period.
It increases in a group.
Mn and Tc have abnormally low melting points. Hg melts at -38°C.
The dip in the melting point at Mn in the first transition series and at Tc in
the second transition series and somewhat in Re in the third transition series can
be explained on the basis that they have exactly half-filled d-orbitals. As a result,
in each case, the electronic configuration is stable ie., electrons are held tightly by6
the nucleus so that the delocalization (ie., Metallic bond) is less and the metallic
bond is much weaker than that preceding element.
Tungston(W) has the maximum MP and Re has second higher melting point.
Partially filled especially half filled d orbitals form additional covalent bonding due
to d overlapping of adjacent atoms resulting in high MP and BP, hard and brittle
nature.
Enthalpy of Atomisation (or) Enthalpy of Sublimation:
Enthalpy change involved in breaking the metallic lattice of the crystalline
metal into atoms. (or) Heat required to break the metal lattice to get free atoms.

The high values of enthalpies of atomisation may be attributed to the

strong metallic bonds that are present.

The metals of second (4d series) and third (5d series) have greater
enthalpies of atomisation of their corresponding elements of first transition
series. This is due to more metal-metal bonding in their compounds.
4.Atomic radii:
i) Atomic radii of transition elements in a period smaller than s-block
elements and larger than p block elements.

ii) In general, (3d, 4d or 5d) series atomic radii decreases with increase in
atomic number but this decrease in atomic radii becomes small after midway. For
example, for the elements of first transition series, the atomic radii decrease
gradually from scandium to chromium but from chromium to copper, it remains
practically constant.
Explanation:
In the beginning, with increase in atomic number, the nuclear charge
goes on increasing. However, we know that the electrons enter the
penultimate(last but one) shell and the added d-electrons screen the outermost s-
electrons. The shielding effect of d-electrons is small (ie., poor shielding) so that 7
the net electrostatic attraction between the nuclear charge and the outermost
electron increases. Consequently, the atomic radius decreases. As the number of
d-electrons increases, the screening effect increases. This neutralizes the effect
of increased nuclear charge due to increase in atomic number and consequently,
atomic radius remains almost constant after chromium.
iii)At the end of the period, there is a slight increase in the atomic radii i.e.,
Zn, Cd and Hg there is increase in atomic radii. This is due to electron-electron
repulsions between added electrons in the same orbitals are greater than the
attractive forces due to the increased nuclear charge. This results in the
expansion of the electron cloud and thus atomic radius increases.

iv)Atomic radii increases down the group

The 5d transition elements atomic radii are greater than the 4d transition
elements, as the number of shell increases, their atomic radii are larger.
But 5d transition elements and 6d transition elements have nearly the same
radii due to the lanthanoid contraction.
{The steady decrease in atomic and ionic sizes of lanthanide elements [ie., f-
block elements] with increasing atomic number is called lanthanoid contraction}.
5.Ionic Radii:
i)The trend followed by the ionic radii is the same as that followed by atomic
radii.
ii)Ionic radii of transition metals are different in different oxidation states.

Ionic size of M3+ cations < Ionic size of Mn2+ cations

{We know that Cations are smaller than the parent atom and Anions are
greater than the parent atom}
In general, in ionic radii decrease with increase in oxidation state.
Thus, the ionic size of M3+ cations are smaller than those of Mn2+ cations. This is
because the ionic radius decreases with increase in effective nuclear charge.
However, ionic radii of cations in the same oxidation state decrease with the
increase in atomic number.
It decreases from left to right. Ionic radii decreases with increase in
oxidation state. For the same oxidation state the ionic radii generally decrease
with increase in nuclear charge.
 6.Ionization energy(or) Enthalpy(∆iH): 8

The first ionization enthalpy of d-block elements are higher than those of s-
block elements but lesser than p-block elements. Thus, these are less
electropositive than the elements belonging to p-block present in the same period.
The ionization enthalpies increase as we move across each series(due to decrease
in size), not quiet regularly. In the series IE increases with decrease in size.
{ Because of the irregular variation of atomic size, Transition metals show
very little and irregular variation in their ionization energies.}
Irregular trend in the first ionization enthalpy of the first transition
series elements is due to the fact that the removal of one electron alters the
relative energies of 4s and 3d orbitals. Therefore, there is a reorganization
energy accompanying ionisation with some gains in exchange energy as the number
of electrons increases in the dn configuration and also from the transference of s-
electrons into d-orbitals.

Zn has the highest IE, due to fully filled orbitals {Symmetrical and Stable
configuration} though the size is larger.
IE3 > IE2 > IE1 due to positive charge on them.
IE2 of V < Cr > Mn and Ni < Cu > Zn and IE3 of Mn is much higher than that of
Fe due to their electronic configuration. ( Mn has half filled d orbitals i.e., 3d54s2).

IE1 of 5d series is much higher than those of 4d and 3d to weak shielding of 4f

electrons.
Predicting thermodynamic stabilities of compounds on the basis of ionization
enthalpy:
“Smaller the ionisation enthalpy of a metal, greater will be the thermodynamic
stability of its compound”
For example, first four ionization enthalpies of Ni and Pt, the two metals
belonging group 10 are listed.
(∆iH1 + ∆iH2) (∆iH3 + ∆iH4) Total
ie., Ni(II) & Pt(II) ie., Ni(IV) & Pt(IV)
Nickel (Ni) 2.49 x 103 KJ mol-1 8.8 x 103 KJ mol-1 11.29 x 103 KJ mol-1
Platinum (Pt) 2.66 x 103 KJ mol-1 6.70 x 103 KJ mol-1 9.36 x 103 KJ mol-1
 9

From the values listed, it is clear that the ionization enthalpy for the formation of
Ni2+ ion is less than for Pt2+ ion. This means that Ni(II) compounds are
thermodynamically more stable than Pt(II) compounds. However, the value for the
formation of Pt4+ ion is less than for Ni4+ ion which means that Pt(IV) compounds
are thermodynamically more stable than Ni(IV) compounds. This is further
confirmed by the fact that K2PtCl6 with Pt(IV) is a well established compound while
the corresponding K2NiCl6 is not known.
8.Oxidation States:
i)All transition elements except first and last number of the series exhibit
variable oxidation states. This is due to the participation of inner(n-1)d electrons
in addition to outer ns-electrons because , the energies of the ns and (n-1)d-
orbitals are almost equal. For example, in 3d series, cr(3d54s1) and Cu (3d10 4s1)
are +1 while for others, it is +2 (3d1-104s2).
ii)Except Scandium, the common oxidation of the first transition series is +2
which arises due to the loss of two 4s-electrons. [This means that after Scandium
3d-orbitals become more stable and therefore, are lower in energy than the 4s-
orbitals. As a result, electrons are first removed from 4s-orbitals].
iii)The elements which show the greatest number of oxidation states occur
in or near the middle of the series. For example, first transition series, manganese
exhibits all the oxidation states from +2 to +7.
The small number of oxidation states at the extreme left hand side end(Sc,Ti)
is to lose or share. On the other hand, at the extreme right hand side end (Cu,Zn),
it is due to large number of d-electrons so that only a fewer orbitals are available
in which the electron can share with others for higher valence.
For the first five elements, the minimum oxidation state is equal to the number
of electrons in the s-orbitals and the other oxidation states are given by the sum
of outer s- and some or all d-electrons. The highest oxidation state is equal to the
sum of the outer s and d electrons upto manganese.(e.g., TiIVO2, VVO2 +, CrV1O42–,
MnVIIO4–) .

For the remaining five elements, the minimum oxidation state is given by the
electrons in s-orbital while the maximum oxidation state is not related to their
electronic configuration .e.g., Fe(II) and (III), Co(II) andIII, Ni(II), Cu(II) and
(III), Zn(II).

The highest oxidation state shown by any transition metal is +8. For example,
Ruthenium and Osmium show highest oxidation states of +8 in some of their
compounds.
The variability of oxidation states, a characteristic of transition elements, arises 10
out of incomplete filling of d orbitals in such a way that their oxidation states
differ from each other by unity, e.g., VII and VIII, VIV, VV. This is in contrast with
the variability of oxidation states of non transition elements where oxidation
states normally differ by a unit of two.

An interesting feature in the variability of oxidation states of the d–block

elements is noticed among the groups (groups 4 through 10). Although in the p–
block the lower oxidation states are favoured by the heavier members (due to
inert pair effect), the opposite is true in the groups of d-block. 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.
5. Transition metals also form compounds in low oxidation states such as +1 and
zero or negative in their compounds. For example, in Ni(CO)4 and Fe(CO)5, the
oxidation state of nickel and iron is zero. [Low oxidation states are found when a
complex compound has ligands capable of π-acceptor character in addition to the
σ-bonding.]

The maximum oxidation state shown by first series increases from Sc to Mn and
then decrease. The common oxidation state of first series is +3(except Sc). The
highest oxidation state of transition elements is 8 (Os and Ru).

+3 +2, +2,+ +2, +2, +2, +2, +2, +1, +2

+3, 3,+4, +3, +3, +3, +3, +3, +2
+4 +5 (+4), +4, (+4), (+4) +4
(+5) (+5), (+5),
+6 +6, (+6).
+7
**Oxidation state within the brackets are unstable.

The compounds of transition elements in lower states +2 and +3 are mostly

ionic and of higher oxidation states are covalent, e.g., ZnCl 2 and CdCl2 are ionic
Cr2O72- and MnO4- are covalent in nature, higher oxidation state of transition
elements are shown in oxides and oxoacids( e.g., MnO4-). Transition metals with
fluorine and oxygen exhibit higher oxidation state due to higher electronegative
nature of fluorine and oxygen exhibit higher oxidation state due to higher
electronegative nature of fluorine and oxygen. Transition metals also exhibit +1
and 0 oxidation states.
Cu2Cl2, AgCl, Hg2Cl2 Oxidation State of metal is +1
Ni(CO)4, Fe(CO)5 Oxidation State of metal is 0
 11

When the metal exhibit more than one oxidation state their relative stabilities can
be known from their standard electrode potential, e.g.,
Cu2+(aq) + 2e- ---------→ Cu(s) E°red = 0.34 volt
+ -
Cu (aq) + e ---------→ Cu(s) E°red = 0.52 volt
Lower standard reduction potential indicates Cu2+ is more stable than Cu+ in
aqueous medium. In other words, more negative Standard reduction potential of a
particular ion, greater will be its stability.

9.Standard electrode potential: Electrode potential is the electrode potential

developed on a metal electrode when it is equilibrium with a solution of its ions,
taking electrons from the electrode. There is irregular variation in electrode
potential due to irregular variation in ionization enthalpy, sublimation energy and
energy of hydration. The E° value decreases from left to right across the series.
Mn, Ni and Zn have higher values than expected because of their half-filled or
completely filled 3d-orbitals in case of Mn2+ and Zn2+ and the higher negative
enthalpy of hydration Ni2+.
______
Process involved: M (s) → Mn+ (aq)
+
ne-

Process completed in three steps:

M (s) ---∆H(reaction)→ Mn+ (aq)

Overall
---∆H(sublimation)→

---∆H(hydration)→
Step 1

Step 3
(aqueous)

M (g) ---∆H(ionisation)→ Mn+ (g)

Step 2

All the above process except Enthalpy of hydration are endothermic

reaction. Enthalpy of hydration is exothermic reation.

We have already seen the irregular trends in the values of ionization enthalpies.
Same is the case with the sublimation enthalpies as well. This means that
enthalpies of the reaction do not show a regular trend. Consequently, there is no
regular gradation in the standard reduction potentials of these metals.
10.Reduction Properties: 12

The electrode (oxidation) potentials of the first transition series metals (except
Cu) are quite high. Hence, they are expected to be oxidized easily to their ions.
M -----------------→ M2+ + 2e-
Hence, they should be good reducing agents but they are not because of their high
heat of vapourisation, high ionization potentials and low heat of hydration. Since
the oxidation potentials of Cu (-0.34 V) is negative, it has a low tendency to change
to Cu2+ ions and does not displace H+ ions from acid solutions. { Remember: The
reduction potential of Cu (+0.34 V)}.
12.Magnetic properties:
Substances containing unpaired electrons are said to be paramagnetic. A
diamagnetic substance is one in which all the electrons are paired. Except d 0 (Sc+3,
Ti+4) or d10(Cu+, Zn+2) configurations, all other simple ions of transition elements
contain unpaired electrons in their (n-1)d subshell and are, therefore,
paramagnetic. The magnetic moments( ) of the elements of first transition series
can be calculated with the unpaired electrons(n) by the spin only formula.

Spin only formula:

B.M. (Bohr Magneton)
13.Complex formation:
The tendency to form complex ions is due to
a) the high charge on the transition metal ion
b) the availability of d-orbitals for accommodating electrons donated by the
ligand atoms.
14.Catalytic Property:
Most of the transition metals and their compounds possess catalytic
properties, the catalytic activity of transition metal ions is attributed to the
following two reasons:
a)Variable oxidation states due to which they can form a variety of unstable
intermediate products.
b)Large surface area so that the reactants are adsorbed on the surface and
come closer to each other facilitating the reaction process.
15.Colour:
Most of the transition metal ions in solution as well as in solid states are
coloured. This is due to the partial absorption of visible light. The absorbed light
promotes the electron from one orbital to another orbital of the same d subshell.
The colour observed corresponds to the complementary colour of the light
absorbed. Since the electronic transition occurs within the d-orbitals of the
transition metal ions, they are called d-d transitions. It is because of these d-d
transitions occurring in a transition metal ion by absorption of visible light that 13
they appear coloured.

Colours of some of the

first row transition metal
ions in aqueous solutions.
From left to right:

V4+,V3+, Mn2+, Fe3+, Co2+,

Ni2+ and Cu2+ .

Colours of Some of the First Row (aquated) Transition Metal Ions

(In aqueous solutions where water molecules are the ligands)

Consider, for example, the complex [Ti(H2O)6]3+, which is violet in colour.

This is an octahedral complex where the single electron (Ti3+ is a 3d1 system) in the
metal d orbital is in the t2g level in the ground state of the complex. The next
higher state available for the electron is the empty eg level. If light corresponding
to the energy of yellow-green region is absorbed by the complex, it would excite
the electron from t2g level to the eg level (t2g 1eg0 → t2g0eg1). Consequently, the
complex appears violet in colour.

Transition of an electron in [Ti(H2O)6]3+

 14
It is important to note that in the absence of ligand, crystal field splitting
does not occur and hence the substance is colourless. For example, removal of
water from [Ti(H2O)6]Cl3 on heating renders it colourless. Similarly, anhydrous
CuSO4 is white, but CuSO4.5H2O is blue in colour.

16. Interstitial compounds:

Transition metals are those in which small atoms occupy the intertial
sites in the crystal lattice. Interstitial compounds are well known for transition
metals because small-sized atoms of H, B, C, N, etc., can easily occupy positions in
the voids present in the crystal lattices of transition metals.

17. Non-Stoichiometry compounds:

Transition metals form non-stoichiometric compounds having indefinite
compositions and unique structures, e.g., FeO0.84 to FeO0.98 etc.
18.Reactivity:
Though the transition elements are sufficiently electropositive, yet they
are not very reactive because of
a)their high heats of sublimation and b)their high ionization energies.
19.Oxides:
Transition metals form oxides of the general composition MO, M2O3, MO2
(or) M2O4, M2O5, M2O6(or) MO3. Oxides in the lower oxidation states are generally
basic in nature and those in the higher oxidation states are amphoteric or acidic in
nature. For example,
+2 +3 +8/3 +4 +7
MnO Mn2O3 Mn3O4 MnO2 Mn2O7
Basic Amphoteric Amphoteric Amphoteric Acidic
 15

Potassium dichromate K2Cr2O7:

Potassium dichromate is a very important chemical used in leather industry and
as an oxidant for preparation of many azo compounds.
Preparation of Potassium dichromate K2Cr2O7 :
Potassium dichromate is prepared from chromite ore (FeCr2O4 )as follows:
Step 1: Conversion of Chromite ore to sodium Chromate :
Chromite ore (FeCr2O4 ) is fused with sodium hydroxide in the presence of air.
Fuse
4FeCr2O4 + 8Na2CO3 + 7O2 ---------→ 8 Na2CrO4 + 2Fe2O3↓ + 8CO2↑
Chromite Ore free air Sodium Chromite Solid Gas
(yellow solution)
Step II: Conversion of Sodium chromate to Sodium dichromate :
The yellow solution of Sodium chromate (Na2Cr2O4) is filtered and acidified with
H2SO4 to give a solution of Sodium dichromate (Na2Cr2O7).

2Na2CrO4 + 2H+---------→ Na2Cr2O7 + 2Na+ + H2O

On cooling, sodium sulphate seperates out as Na2SO4.10H2O and the solution

contains sodium dichromate in it. From this solution orange Na2Cr2O7. 10H2O can
be crystallized.
Step III: Conversion of Sodium dichromate into potassium dichromate :
Potassium dichromate prepared by treating sodium dichromate with potassium
chloride.
Na2Cr2O7 + 2 KCl ---------→ K2Cr2O7 ↓ + 2 NaCl
Sodium dichromate Potassium dichromate
Solution form Orange Crystal form
( Sodium dichromate is more soluble than potassium dichromate.)

Effect of PH :
The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution.

H+
------→
←------
OH-

Tetrahedral Two tetrahedral sharing one corner with Cr–O–Cr

bond angle of 126°
The oxidation state of chromium in chromate and dichromate is the same. i.e., (+6 State)
 16

The above reaction is

2 CrO4 2– + 2H+ ------→ Cr2O7 2– + H2O
Cr2O7 2– + 2 OH- ------→ 2 CrO4 2– + H2O
Oxidising Properties of K2Cr2O7 :

1)Acidified potassium dichromate will oxidize iodides to iodine.

Molecular form of the equation:

K2Cr2O7 + 4H2SO4 ---------→ K2SO4 + Cr2(SO4)3 +4H2O + 3[O]
2KI + H2SO4 +[O] ---------→ K2SO4 + I2 + H2O] X3
K2Cr2O7 +7H2SO4 + 6KI ---------→ 3K2SO4 + Cr2(SO4)3 + 7 H2O +3I2
Ionic equation:
Cr2O72- + 6I- + 14H+ ---------→ 2Cr3+ + 7 H2O + 3I2
(or)
Ionic equation:
Cr2O72- + 14H+ + 6e- ---------→ 2Cr3+ + 7H2O E° = 1.33V
2 I- ---------→ I2 + 2e-] X3 E° = 0.54V
Cr2O72- + 6I- + 14H+ ---------→ 2Cr 3+
+ 3I2 + 7 H2O

2)Acidified potassium dichromate will oxidize tin(II) to tin(IV).

Ionic equation:
Cr2O72- + 14H+ + 6e- ---------→ 2Cr3+ + 7H2O E° = 1.33V
Sn2+ ---------→ Sn4+ + 2e-] X 3 E° = -0.14V
Cr2O72- + 3Sn2+ +14H+ ---------→ 2Cr3+ +3Sn4+ + 7 H2O

3)Acidified potassium dichromate will oxidize iron(II) salts to iron(III).

Ionic equation:
Cr2O72- + 14H+ + 6e- ---------→ 2Cr3+ + 7H2O E° = 1.33V17
2 Fe2+ ---------→ 2 Fe3+ + 2e-] X3 E° = -0.44V
2- 2+ + 3+ 3+
Cr2O7 + 6Fe + 14H ---------→ 2Cr + 6Fe + 7 H2O
4)Acidified potassium dichromate will oxidize sulphides to sulphur.

Ionic equation:
Cr2O72- + 14H+ + 6e- ---------→ 2Cr3+ + 7H2O E° = 1.33V
H2S ---------→ S + 2H+ + 2e-] X 3
Cr2O72- + 3H2S + 8H+ ---------→ 2Cr3+ + 3S + 7 H2O
Uses:

Sodium and potassium dichromates both are strong oxidising agents.

Sodium dichromate has a greater solubility in water and is used as an oxidising

agent in organic chemistry.

Potassium dichromate is used as a primary standard in volumetric analysis. (ie., to

prepare Standard solution Potassium dichromate is used )

Potassium dichromate is used in chromyl chloride test.

Extra point: A test for drunken drivers

Acidified solution of potassium dichromate provides a test to find out whether
a driver is drunken or not. The orange colour solution is taken in a beaker or tube
and the driver is asked to breath into the solution. If the colour of solution
changes to green, this means that the driver is in drunken state. If the colour
remains unchanged, this means that the driver has not consumed any alcohol.
Actually, ethyl alcohol (C2H5OH) is oxidized to acetic acid (CH3COOH). But
potassium dichromate is also reduced to chromium sulphate (light green in colour)
during the reaction. Thus, a change of colour of the dichromate solution from
orange to light green indicates that the driver has consumed alcohol. No change in
colour of the solution shows that the driver has not consumed alcohol.

Potassium permanganate KMnO4

Preparation of Potassium permanganate (on small scale):
Potassium permanganate is prepared by fusion of MnO2 (Pyrolusite) with an alkali metal
hydroxide and an oxidising agent like KNO3.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
Pyrolusite Potassium manganate
This produces the dark green K2MnO4 which disproportionates in a neutral or acidic solution
to give permanganate.
 3MnO42– + 4H+ 2MnO4– + MnO2 + 2H2O 18
Potassium manganate(or) permanganate ion
Manganate ion
Preparation of Potassium permanganate (Commercial (or) on large scale):
KMnO4 is prepared by fusion of MnO2 (Pyrolusite) with oxidizing agent like KNO3
(or) alkali metal hydroxide(KOH) in the presence of O2.

Fused with KNO3

MnO2 MnO42–
Pyrolusite Manganate ion (Green)
Electrolytic oxidation in alkaline solution (or) Electrolysis
MnO42– MnO4–
Manganate ion (Green) Permanganate ion (Purple)

Preparation of Potassium permanganate (Laboratory method):

Manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

2Mn2+ + 5S2O8 2– + 8H2O ---------→ 2MnO4– + 10SO42– + 16H+

Manganese (II) salt Peroxodisulphate Permanganate ion (Purple)

Potassium permanganate forms dark purple (almost black) crystals which are
isostructural with those of KClO4

When heated it decomposes at 513 K.

2KMnO4 ---------→ K2MnO4 + MnO2 + O2
Weak temperature dependent paramagnetism :

The manganate and permanganate ions are tetrahedral.

The green manganate is paramagnetic with one unpaired electron but the
permanganate is diamagnetic.

The -bonding takes place by overlap of p orbitals of oxygen with d orbitals of

manganese. (According to molecular orbital theory)
Oxidising properties of KMnO4 in Acidic medium: 19

1.Acidified permanganate solution oxidises oxalates to carbon dioxide at 333 K(or)60°C :

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O ] X2 E°=+1.52 V
- -
C2O4 ---------→ 2CO2 + 2e ] X5
- - + 2+
2MnO4 + 5 C2O4 +16H ---------→ 2Mn + 10CO2 + 8 H2O
2.Acidified permanganate solution oxidises iron(II) to iron(III):

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O E°=+1.52 V
Fe2+ (Green) ---------→ Fe3+( Yellow) + e-] X 5
MnO4- + 5Fe2+ + 8H+ ---------→ Mn2+ + 5Fe3+ + 4 H2O
3.Acidified permanganate solution oxidises nitrites to nitrates:

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O ] X2 E°=+1.52 V
NO2- + H2O ---------→ - +
NO3 +2H + 2e ]-
X5
2MnO4- + 5 NO2- + 6H+ ---------→ 2+ -
2Mn + 5 NO3 + 3 H2O

4.Acidified permanganate solution oxidises iodides to free iodine:

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O] X2 E°=+1.52 V
2I- ---------→ I2 + -
2e ] X5
2MnO4- + 10 I- + 16H+ ---------→ 2+
2Mn + 5I2 + 8H2O

5.Acidified permanganate solution oxidises Hydrogen sulphide (H2S) to sulphur (S) being
precipitated:

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O ] X2 E°=+1.52 V
+ -
H2S ---------→ 10H + S + 2e ] X5
2MnO4- + 5 H2S + 6H+ ---------→ 2+
2Mn + 5S + 8H2O

6.Acidified permanganate solution oxidises Sulphurous acid or sulphite(SO32- ion)

to a sulphate or sulphuric acid(SO42- ion):

Ionic equation:
MnO4- + 8H+ + 5e- ---------→ Mn2+ + 4H2O ] X2 E°=+1.52 V
SO32- + H2O ---------→ 2- +
SO4 + 2H + 2e ]-
X5
2MnO4- + 5SO32- + 6H+ ---------→ 2+ 2-
2Mn + 5 SO4 + 3H2O
Oxidising properties of KMnO4 in neutral or faintly(weakly) alkaline solutions: 20

1. Weakly alkaline solutions permanganate solution oxidises iodides (I-)to IO3- (I5+):

Ionic equation:
MnO4- + 2H2O + 3 e- ---------→ MnO2 + 4OH- ] X 2 E° = +1.23 V
I- + 6 OH- ---------→ -
IO3 + 3 H2O + 6 e -

2MnO4- + I- + H2O ---------→ 2MnO2 + IO3 - + 2OH-

(or) The above equation may be written as

Molecular equation:
2KMnO4 + H2O -------→ 2MnO2 + 2KOH + 3[O] E° = +1.23 V
KI + 3[O] -------→ KIO3
2KMnO4 + KI + H2O -------→ 2MnO2 + KIO3 + 2KOH
In fact, during the course of the reaction, the alkali[OH-] produced renders
the medium alkaline even when start with neutral solutions.

2.Weakly alkaline solutions permanganate solution oxidises iodides (S2O32-)to (SO42-) :

Ionic equation:
2KMnO4 + H2O -------→ 2MnO2 + 2KOH + 3[O] E° = +1.23 V
Na2S2O3 + [O] -------→ Na2SO4 + S ]X3
-
2KMnO4 +3Na2S2O3+H2O ------→ 2MnO2 + 3 Na2SO4+ 2KOH +3S
3. Weakly alkaline solutions permanganate solution oxidises (Mn2+)to MnO2 :

Ionic equation:
2KMnO4 + H2O -------→ 2MnO2 + 2KOH + 3[O] E° = +1.23 V
MnSO4 + H2O + [O] -------→ MnO2 + H2SO4 ] x3
2KOH + H2SO4 -------→ K2SO4 + 2H2O
2KMnO4 + 3 MnSO4+ 2H2O ------→ 5MnO2 + K2SO4 + 2H2SO4
In KMnO4 titration, dil. H2SO4 is used for acidification and not HCl because HCl
gets oxidized to Cl2 and H2O.

Uses:

It is used as oxidizing agent in organic chemistry.

It is used as disinfectant.

INNER TRANSITION ELEMENTS(f-BLOCK ELEMENTS)

 The inner transition elements consists of lanthanoids and actinoids. They 21
are characterised by filling of the „f‟ orbitals.
Lanthanoids:
The series involving the filling of 4f orbitals following lanthanum La (Z=57) is called
the lanthanoid series. They are 14 elements in this series, starting with Cerium
Ce(Z=58) to Lutetium Lu (Z=71).
The lanthanoids
are highly dense metals.
have high melting points.
form alloys easily with other metals.
are soft, malleable and ductile with low tensile strength.
i) Oxidation State:
The most characteristic oxidation on the state of lanthanoid elements is +3.
Some of the elements also exhibit +2 and +4 oxidation states.
ii)Colour:
Some of the trivalent ions of lanthanoids are coloured. This is due to the
absorption in visible region of the spectrum, resulting in f-f transitions because
the have partly filled orbitals.
iii)Magnetic properties:
Among lanthanoids, La+3 and Lu+3, which have 4f0 pr 4f14 electronic
configurations are diamagnetic and all the other trivalent lanthanoid ions are
paramagnetic because of the presence of unpaired electrons.
The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+
and Lu3+) are all paramagnetic. The paramagnetism rises to maximum in neodymium.

iv)Reactivity:
All lanthanoids are highly electropositive metals and have an almost similar
chemical reactivity. In their chemical behaviour, in general, the earlier members of
the series are quite reactive similar to calcium but, with increasing atomic number,
they behave more like aluminium.
v)Lanthanoid Contratction:
In lanthanoids, with increasing atomic number, the atomic and ionic radii
decreases from one elelement to the other, but the decrease is very small. It is
because, for every additional proton in the nucleus, the correspoinding electron
goes into a 4f subshell, which is too diffused to screen the nucleus as effectively
as the more localized inner shell. Hence, the attraction of the nucleus for the
outermost electrons increases steadily with the atomic number.

Consequences of lanthanide contraction

Important consequences of lanthanide contraction are given below. 22
i) Basicity of ions
Due to lanthanide contraction, the size of Ln3+ ions decreases regularly with
increase in atomic number. According to Fajan‟s rule, decrease in size of Ln3+ ions
increase the covalent character and decreases the basic character between Ln3+
and OH- ion in Ln(OH)3. Since the order of size of Ln3+ ions are
La3+ > Ce3+ ............... >Lu3+ .

ii) There is regular decrease in their ionic radii.

iii) Regular decrease in their tendency to act as reducing agent, with increase in
atomic number.
iv) Due to lanthanide contraction, second and third rows of d-block transistion
elements are quite close in properties.
v) Due to lanthanide contraction, these elements occur together in natural
minerals and are difficult to separate.

Uses of Lanthanoids:
The pure metals have no specific use. So they are used as alloys or
compounds. The alloys are called „misch metals‟ which consists of a lanthanoid
metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. Mischmetall is used in
Mg-based alloy to produce bullets, shell and lighter flint.
Steel mixed with La, Ce, Pr, and Nd is used in the manufacture of flame
throwing tanks.
Lanthanoid oxides are used for polishing glass. Neodymium and
praseodymium oxides are used for making coloured glasses for goggles.
Pyrophoric alloys are used for making tracer bullets and shells.
Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.

Some individual Ln oxides are used as phosphors in television screens and

similar fluorescing surfaces.
Actinoids
The elements following Actinium Ac(Z=89), upto Lawrencium(Z=103), are called
actinoids.
The Actinoids
i)are highly dense metals with a high melting point and form alloys with other
metals, specially iron.
ii)are silvery white metals, which are highly reactive.
iii)get tarnished when exposed to alkalis and are less reactive towards aicds.

i) Actinoid Contraction:
 The atomic and ionic size decreases with an increase in atomic number. Electrons23
are added to the 5f shell, as a result the nuclear charge increases causing the
shells to shrink inwards.
ii)Electronic Configuration:
The actinoids involve the filling of 5f subshells. Actinium has the electronic
configuration 6d17s2. From thorium(Z=90) onwards, 5f orbitals get progressively
filled up. Because of equal energy of 5f and 6d subshells, there are some
uncertainities regarding the filling of 5f and 6d sunshells. Most of their
properties are comparable to that of lanthanoids.
iii)Oxidation State:
Generally a +4 oxidation state is preferred in actinoids. A few of the
actinoid elements exist in a +6 oxidation state, e.g., uranium, neptunium and
plutonium.
iv)Colour:
The actinoid ions are coloured.
v)Magnetic properties:
Many of the actinoid ions are paramagnetic.
vi)Reactivity:
They are also hghly electropositive and form salts as well as complexes.
Many of these elements are radioactive.
vii)Uses of actinoids:
Thorium is used in the treatment of cancer and in incandescent gas mantles.
Uranium is used in the glass industry, textile industry, in medicines and as nuclear
fuel.
Plutonuium is used in atomic reactors and in atomic bombs.

Differences between Lanthoids and Actinoids:

Sl.No Lanthanoids Actinoids

1 4f-orbitals is progressively filled. 5f-orbital is progressively filled.

2 Binding energies of 4f Binding energies of 5f electrons are

electrons are higher. lower.
3 +3 oxidation state is most common Due to lower binding energies they
along with +2 and +4. Maximum show higher oxidation states such
oxidation state exhibited by as +4, +5 and +6. Uranium
lanthanides is +4 e.g. Ce4+ exhibits +6 oxidation state in UF6
e.g. Ce4+ and UO2Cl2
4 4f electrons have greater 5f electrons have poor shielding
shielding effect. effect.
5 Most of their ions are Most of their ions are coloured U3+ 24
colourless. (red), U4+ (green) and UO2 2+
(yellow)
6 They are paramagnetic but They are also paramagnetic but
magnetic properties can be their magnetic properties are very
easily explained. difficult to interpret.
7 They do not form complexes They have much greater tendency
easily to form complexes
8 Only promethium (Pm) is radioactive. All are radioactive.

9 They are less reactive than actinoids. They are more reactive.

10 Their compounds are less Their compounds are more basic.

basic.
11 They do not form oxocations. They form oxocations such as UO22+,
UO+, NpO2+, PuO2+.

******************

Extra:

Sl.No Lanthanoids Actinoids

1 4f-orbitals is progressively filled. 5f-orbital is progressively filled.

2 +3 oxidation state is most common They show +2,+3,+4,+5,+6 and +7

along with +2 and +4. Maximum oxidation states.
oxidation state exhibited by
lanthanides is +4 e.g. Ce4+
3 Only promethium (Pm) is radioactive. All are radioactive. 25

4 They are less reactive than actinoids. They are more reactive.

5 Magnetic properties are less Magnetic properties are more

complex. complex.

Prepared by

Shri. R.Sekar, M.Sc, M.Phil., M.Ed.,

PGT Chemistry,
Kendriya Vidyalaya No.2,
KALPAKKAM-603 102