d and f block Elements ((n-1)d1–10 ns1–2 ) ( Thing to Remember )

3d-Series 21 22 23 24 25 26 27 28 29 30
Sc Ti V Cr Mn Fe Co Ni Cu Zn
[Ar]18 3d1 3d2 3d3 3d5 3d5 3d6 3d7 3d8 3d10 3d10
3d-seeries 4s2 4s2 4s2 4s1 4s2 4s2 4s2 4s2 4s1 4s2
4d-Series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5d-Lathanoids series La Hf Ta W Re Os Ir Pt Au Hg
6d-Actinoids Series Ac Rf Db Sg Bh Hs Mt Ds Rg Uub

In general, the electronic configuration of outer orbitals of these elements is (n-1)d 1–10 ns 1–2.
In general, the electronic configuration for Zn, Cd , Hg and Cn(Copernicium) is (n-1)d 10 ns 2
Transition elements:
• They have incomplete d- subshell in its ground state or in its more stable common oxidation states.
• They have + 2 common oxidation state.
• Zinc, cadmium and mercury of group 12 have full d10 configuration in their ground state as well as in their +2 common oxidation states and
hence, are not regarded as transition metals.
• Cu , Ag and Au they also possess completely filled d- orbitals but they are considered as transition metals bcos these metals in their common
oxidation states have incompletely filled d- orbitals e.g. Cu2+ has 3d9 and Au3+ has 5d8 configuration.

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• Physical Properties :
o Metallic Nature:
Main point: Higher the number of unpaired electrons higher the metallic bonding so higher the metallic character.
Nearly all the transition elements display typical metallic properties such as high tensile strength, ductility, malleability, high thermal and electrical
conductivity, and metallic luster. With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic structures at normal temperatures.

• Melting and Boiling point :

➢ The high melting points of these metals due to the involvement of greater number of electrons from
(n-1)d in addition to the electrons in the interatomic metallic bonding.
➢ Melting point of Mn and Tc are abnormally low due to stable electronic configuration . As the
3d-electrons are more tightly held by the nucleus the electrons are not available for bonding
resulting weaker metallic bonding in Mn.
Then why in case of tungsten(W) melting point is highest?
Answer: 4d and 5d transition elements (2nd and 3rd series) are Larger in size than the
corresponding 3d elements. Hence the valence electrons are less tightly held and form M-M
bond more frequently.

• Transition element posses high enthalpies of atomisation:

➢ Enthalpy of atomization means the energy required to get free atoms from any element .
➢ Transition element possess large number of unpaired electrons in their atoms so they have stronger
interatomic –atomic interaction and hence stronger bonding between atoms resulting in higher
enthalpies of atomization .
❖ The enthalpy of atomisation of zinc is the lowest, i.e., 126 kJ mol–1 : due to its fully filled d-subshell.
Question: Why in heavy transition metals there is more frequent metal – metal bonding in compounds
as compaired to first and second row transition metals.
Answer: 4d and 5d transition elements (2nd and 3rd series) are Larger in size than the corresponding 3d
elements. Hence the valence electrons are less tightly held and form M-M bond more frequently.

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 Density: As we move along a transition series from left to right the atomic radii decrease due to increase in nuclear charge. Hence , the atomic volume
decreases . At the same time , atomic mass increases . Hence the density increases.
• *Among the transition elements ,Iridium and osmium has the highest density whereas scandium has the lowest density.

Atomic size and ionic size in Series /period :

❖ High nuclear charge responsible for decrease in size ,
❖ Poor shielding effect also responsible for decrease in size .
➢ In beginning size decreases because nuclear charge increses and shilding is poor.
➢ in the middle the size of the metals are nearly same because of counter balance of nuclear
charge and increases shielding effect .
➢ But the size of the last element is quite bigger because of completely filled d subshell there is
greater electron – electron repulsion .

• Atomic Size down the group:

The radii of the third (5d) series are virtually the same as those of the corresponding members
of the second (4d) series:
Answer: The curves in Fig. 8.3 show an increase from the 3d series to 4d series of the elements, but
the radii of 5d series are nearly same the same as members of the 4d series because in 5d series the 4f
orbitals are their which are responsible for poor shielding and poor shielding is responsible for
decrease in size as a result there is a regular decrease in atomic radii called Lanthanoid contraction.

*The shielding of one 4f electron is very poor than that of one d electron, and as the nuclear charge
increases along the series, there is fairly regular decrease in the size of the entire 4f n orbitals.

*Zr 155 pm, Hf 156 pm have similar size due to lanthanoid contraction so they have similar physical
and chemical properties

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• Coloured ions:
➢ Most of the compounds or ions of transition elements are coloured due to presence of unpaired electron in d-subshell because they have
incomplete (n-1)d-subshell.
➢ Unpaired electron absorb energy from visible light so there is excitation of electron from the d-orbitals of lower energy to the d-orbitals of
higher energy(Excitation between t2g and eg) .This is called d-d transition .(responsible for colour )
Eg ; [Si(H2O)6]3+ is colourless due to absence of unpaired electron whereas [Ti(H2O)6]3+ is coloured due to presence of unpaired electron .
❖ Question: In given compounds [Ni(H2O]2+ and [Ni(NH3)6]2+ both have Ni2+ but they have different colour. Why?
Ans: Because in both compound ligands are different and these ligands absord light of different wavelength.

Irregular variation of ionization enthalpies :

Ionisation enthalpy depends upon following factors:

➢ Attractive forces between nucleus and electrons
➢ Repulsive force between inner electron and valence electron
➢ Exchange of energy ( higher the exchange of energy higher will be the stability) and at d6 no exchange of energy so its not stable so
easy to remove electrons.
The irregular ionisation enthalpy of the metals can be accounted by considering that the removal of one electron alters the relative energies of
4s and 3d orbitals that why irregular ionisation enthalpy depends upon the sum of IE1 + IE2.
A general trend of increasing values of second ionisation enthalpy is expected as the effective nuclear charge increases because one d-electron
does not shield another electron from the influence of nuclear charge because d-orbitals differ in direction. However, the trend of steady
increase in second and third ionisation enthalpy breaks for the formation of Mn2+ and Fe3+ respectively. In both the cases, ions have
d 5 configuration. Similar breaks occur at corresponding elements in the later transition series(in 4d and 5d series).

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 Irregular variation of first ionization enthalpies (first and second) is mainly due to varying degree of stability of different
3d- configurations. do ,d5 and d10 configurations have extra stability and hence in such cases the values of ionization enthalpies are usually
high.
Exchange energy:
• The loss of exchange energy increases the stability. As the stability increases, the ionisation becomes more difficult. There is no loss of
exchange energy at d6 configuration.
Q: Why there is no loss of exchange energy at d6 configuration.
Ans: In the d6 configuration out of six four electrons are unpaired so they can not exchange their position until any of the strong field ligands
approaches, that is why there is no loss of exchange energy.
• Fe2+ has d6 configuration and Mn2+ has 3d5 configuration. Hence, ionisation enthalpy of Fe2+ is lower than the Mn2+.
• Mn+ has 3d54s1 configuration and configuration of Cr+ is d5, therefore, ionisation enthalpy of Mn+ is lower than Cr+
Complex formation:
a) due to the comparatively smaller sizes of the metal ions
b) their high ionic charges
c) availability of d orbitals for bond formation.

• Alloy formation :
▪ Due to similar radii or atomic size , these can replace one another in metallic bond.
▪ The alloys so formed are hard and have often high melting points.
▪ 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).
• Interstitial compound :
▪ Interstitial compounds are those which are formed when small atoms like H, C or N are trapped inside the crystal lattices of metals.
▪ They are usually non stoichiometric and are neither typically ionic nor covalent, for example, TiC , Mn4N ,etc .
The principal physical and chemical characteristics of these compounds are as follows:
➢ They have high melting points, higher than those of pure metals.
➢ They are very hard, some borides approach diamond in hardness.
➢ They retain metallic conductivity.
➢ They are chemically inert

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• Variable oxidation states :
3-Series 21 22 23 24 25 26 27 28 29 30

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Oxidation +3 +2 +2 +2 +2 +2 +2 +2 +1 +2
states +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 ,+6 +5, +6 ,+7

➢ In transition elements energy of ( n-1)d and ns is nearly same so both of them can take part in chemical bonding . ns electrons are responsible
for +2 common state and (n-1)d responsible for +3 to +8 oxidation state .
➢ Variability in oxidation states of transition metals different from that of the non-transition metals because:
▪ In transition elements, the oxidation state can vary from +1 to the highest oxidation state by removing all its valence electrons. Also, in
transition elements, the oxidation states differ by1 (Fe2+ and Fe3+; Cu+ and Cu2+).
▪ In non-transition elements, the oxidation states differ by 2, for ex, +2 and +4 or +3 and +5, etc.
In the p–block: the lower oxidation states are stable down the group, this is due to inert pair effect that is unavailability of s-electron to involve
in bonding,
In d block: the opposite is true means down the group higher oxidation state is more stable in the groups of d-block due to easier availability of
both d and s electrons for ionization
For example, in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI) because the stability of high oxidation states increases
down the group due to easier availability of both d and s electrons for ionization so after loss of 6 valence electron, they become more stable.
The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice energy as in the case of CoF3, or higher bond
enthalpy terms for the higher covalent compounds, e.g., VF5 and CrF6.
Due to less lattice enthalpy in low oxidation states Fluorides are less stable that’s why in low oxidation state chloride , bromide and iodide
compounds are more stable. e.g., VX2 (X =CI, Br or I).

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 • Magnetic properties:
➢ The magnetic moment is determined by the number of unpaired electrons
and is calculated by using the ‘spin-only’ formula, i.e.,  = n(n+2) where
n is the number of unpaired electrons and μ is the magnetic moment in units
of Bohr magneton (BM).
➢ With atomic number 25, the divalent ion in aqueous solution will have d5
configuration (five unpaired electrons).
The magnetic moment, μ is  = 5(5+2) = 5.92B.M.

Standars electrode potential:

it is the sum of
• Enthalpy of Ionisation
• Enthalpy of Sublimation
• Enthalpy of Atomisation
• Enthalpy of Hydration

The Eo value for Mn, Ni, and Zn are more negative than expected from the trend: Negative EΘ values for Mn2+ and Zn2+ are related to
stabilities of half-filled and fully filled configuration, respectively. But for Ni2+, EΘ value is related to the highest negative enthalpy of hydration.
Copper having positive Eo value, does not liberate hydrogen from hydrochloric acids. It react only with oxidizing acids such as HNO3 and
conc. H2SO4. (Cu will not react with HCl at room temperature).
Chromium, despite its high negative reduction potential value is an unreactive metal as it does not liberate hydrogen due to a thin coating of
Cr2O3 on its surface but ion of Cr (Cr2+) can liberate H2.
2+ 2+ 2+
The ions Ti , V and Cr are strong reducing agents and will liberate hydrogen from a dilute acid.

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 The Eo (M2+/M) value for copper is positive (0.34V) :
▪ Eo (M2+/M) for any metal depends on the sum of enthalpies of atomization , ionization energies and hydration energies . Copper has high
enthalpy of atomization and low hydration energy . Hence, Eo (Cu2+/Cu) is positive.
The stability of Cu2+ (aq) rather than Cu+(aq) is due to the much more negative ΔhydHo of Cu2+ (aq) than Cu+, which more than compensates
for the second ionisation enthalpy of Cu.
All Cu(II) halides are known except the iodide: Because in this case, Cu2+ oxidises I– to I2 : 2Cu2+ 4I- → Cu2I2 + I2
• Cr2+ reducing and Mn3+ oxidising when both have d4 configuration : Cr2+ is reducing as its configuration changes from d4 to d3, the latter
having a half-filled t2g level. On the other hand, the change from Mn3+ to Mn2+(common oxidation state ) results in the half-filled (d5)
configuration which has extra stability.
• Highest oxidation state of a metal exhibited in its oxide or fluoride only and which is more stable oxides or fluorides: because of small
size and high electronegativity of oxygen and fluorine, the metal can be oxidized to highest oxidation state . Oxides are more stable due to
presence of multiple bonds in molecules.
• Cr2+ is stronger reducing agent than Fe2+ because: The highest oxidation state of Chromium is +6 so chromium must lose 3/4 more electron
to change from Cr2+ / Cr3+ to Cr6+ whereas Fe needs to lose only one electron to attain +3 oxidation state.
• The Oxides in which metal exhibits the oxidation state equal to its group number: MnO4- and Cr2O72-
• Cobalt (ll) is stable in aqueous solution but in presence of ligands it is easily oxidized .
Co =[Ar]18 3d7 4s2 Co2+ = 3d74s0 ; Co3+ = 3d64s0
Because it undergoes change in oxidation state from +2 to +3 and is easily oxidised. This is because CO3+ has more tendency to form
coordination complexes than Co2+.

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• Catalytic properties:
➢ The transition metals act as a good catalyst because they possess
• Incomplete d- subshell so they can provide surface for the reactant to react with each other by this they can decrease the activation
energy .
• Variable oxidation state so the transition metal ions can change their oxidation states, so they become more effective as
catalysts. This activity is ascribed to form complexes.
Lanthanides [Xe]4f1-145d0-16s2 Actinides [Rn] 5f 1–14 6d0–1 7s2.
1. Except promethium all the remaining lanthanides are All actinides are radioactive
nonradioactive.
2. Besides +3 oxidation state, lanthanides in some cases Besides +3 oxidation state, actinides shows a variety of oxidation
show +2 and +4 oxidation states. states like +2, +4, +5,+6 and +7 also .
3. Lanthanides do not form oxo-ions. Actinides form oxo-ions such as UO+, UO2+ etc.These ions are
stable in acid and aqueous solutions .
4. Oxides and hydroxides of lanthanides are less basic. Oxides and hydroxides of actinides are more basic.
5. Lanthanides have less tendency to form complex Actinides have more tendency to form complex compounds on
compounds on account of low charge density. account of high charge density.
6. Most of the tripositive ions are colourless. Most of the tripositive and tetrapositive ions are coloured.

• Lanthanide Contraction:
Nuclear charge increases at each step, while there is no comparable increase in the mutual shielding effect of 4f-electrons so the atomic and
ionic radii go on decreasing from La57 to Lu71 .
• Consequence of Lanthanide contraction :
o Similarity in atomic radii of second row and third row transition elements : because the increase in size on moving down the group
from second to third transition elements is cancelled by the decrease in size due to lanthanide contraction.
o Basic strength of oxides and hydroxides: Due to lanthanide contraction the decrease in size of lanthanides ions, from La3+ to Lu3+ so
covalent character increases and basic strength decreases. Thus La(OH)3 is the most basic while Lu(OH)3 is the least basic.
o Seperation of Lanthanides: Due to the similar size (Because of lanthanide contraction) of the lanthanides, it is difficult to separate
them. But slight variation in their properties is utilized to separate.
• Actinoid contraction is greater than lanthanoid contraction because: In actinoids 5f orbitals have a poorer shielding effect than 4f orbitals
(in lanthanoids). Thus, the effective nuclear charge experienced by electrons in valence shells in case of actinoids is much more that that
experienced by lanthanoids.

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 • Q: Why there is greater range of oxidation states among the actinoids than that in lanthanoids?
• Ans: Actinides exhibits larger oxidation states than lanthanides, because of very small energy gap between 5f, 6d and 7s sub shells. Thus, the
outermost electrons get easily excited to the higher energy levels, giving variable oxidation states.

• Misch metals :
o A well known alloy is mischmetall which 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.
• Why Cerium(III) can be easily oxidized to Ce(IV) :
o Ce3+ has the configuration 4f1 5d0 6s0 . It can easily lose an electron to acquire more stable configuration ( 4f0 5d0 6s0) , So Ce3+ can be
easily oxidized to Ce4+. Ce3+ → Ce4+ + e-
• Sm2+ , Eu2+ and Yb2+ good reducing agents : The most stable oxidation state of Lanthanides is +3 . Hence , ions in +2 state tend to change to
+3 oxidation state by loss of electron and act as reducing agents.
• +3 oxidation state of gadolinium ( Z = 64) and lutetium (Z = 91) especially stable: because gadolinium in +3 state has half filled
4f-subshell (4f7 ) and lutetium in +3 state has completely filled 4f-subshell which are very stable configurations.
• Zr and Hf exhibit similar properties: Due to Lanthanide contraction , the atomic radii of both Zr and Hf are same . Hence, their properties
are similar
• Arrange according to their increasing oxidising power which is directly proportinal to oxidation no. : VO2+ < Cr2O72– < MnO4–
• MnF4 is less stable as compared to Mn2O7 :
o The reason for this is the ability of oxygen to form multiple bonds with the metal atoms .
o in higher oxidation state the fluorides of metals are less stable so they are easily hydrolysed with water .

Q) In moist air, copper corrodes to produce a green layer on the surface. Explain.
Ans) 2Cu + O2 + H2O + CO2 → CuCO3.Cu(OH)2 …Basic copper carbonate
Green layer

Q) Why are iron containers used in transportation of mercury?

Ans) Mercury does not form amalgam with iron hence Iron is used in the transportation of mercury .

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 Potassium dichromate: K2Cr2O7

Potassium dichromate is a very important chemical used in leather industry and as an oxidant for preparation of many azo compounds.
Q) Give the preparation of Potassium dichromate?
Ans) Ore: FeCr2O4 (Ferrochrome, chrome iron, chromite)
i) 4 FeCr2O4 + 8 Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
ii) The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from which orange sodium dichromate,
Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
iii) Sodium dichromate is more soluble than potassium dichromate therefore, prepared by treating sodium dichromate with potassium chloride.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

Q) Explain the effect of pH on the colour of dichromate ore?

⎯⎯ ⎯
→
-
OH
Ans) Cr2O72− + H2O ⎯⎯ ⎯ CrO42− + H +
H+
On adding base (pH >7) the reaction proceeds in the forward direction producing yellow chromate solution. On the other hand, when an acid is added
the concentration of H+ ions is increased, and the reaction proceeds in the backward direction producing an orange red dichromate solution.

• Oxidizing properties of Potassium dichromate:

• K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 2H2O + 3[O]
common reaction: Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
Acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III). The half-reactions
are noted below:
Half reactions: All these oxidised by potassium dichromate:
(i) Iodide to iodine: 2I– → I2 + 2e–
(ii) Iron(II) to Iron(III): Fe2+ → Fe3+ + e–
(iii) Tin(II) to Tin(IV): Sn2+ → Sn4+ + 2e–
(iv) Sulphide to Sulphur: H2S → 2H+ + S + 2e–

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 Answer Answer
1 Cr2O72-+ 14H + 6e → 2Cr3+ + 7H2O
+ -
2 Cr2O72-+ 14H + 6e → 2Cr + 7H2O
+ - 3+

6I– → 3I2 + 6 e– 3Sn2+ → 3Sn4+ + 6e–

Cr2O72- + 14H+ + 6I- → 2Cr3++ 3I2 +7H2O Cr2O72- + 14H+ + 3Sn2+ → 2Cr3+ + 3Sn4+ + 7H2O

3 Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O 4 Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
3 H2S → 6H+ + 3S + 6e– 6Fe2+ → 6Fe3+ + 6e–
Cr2O72- + 8H+ + 3H2S → 2Cr3+ + 3S + 7H2O Cr2O72- + 14H+ + 6 Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O

Q) Give the preparation of potassium permanganate?

Ans) (i) 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
(ii) 3MnO42– + 4H+ → 2MnO4─ + MnO2 + 2H2O
Commercially, it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation of manganate (Vl).

Fused with KOH, oxidised with air or KNO Electrolytic oxidation in alkaline solution
MnO ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ 3→ MnO 2− ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → MnO4−
2 4

Manganate ion Permanganate ion

Laboratory preparation: , a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

Mn2+ 4H2O → MnO4– + 8H+ + 5e─ ] x 2

S2O82– + 2e─ → 2 SO42– ] x 5
2Mn2+ + 5S2O82– + 8H2O → 2MnO4– + 10SO42– + 16H+

Q) Explain the nature of potassium permanganate?

Ans) KMnO4 forms dark purple (almost black) crystals which are isostructural with those of KClO4.
The salt is not very soluble in water (6.4 g/100 g of water at 293 K), but when heated it decomposes at 513 K.
2KMnO4 K2MnO4 + MnO2 + O2
The manganate and permanganate ions are tetrahedral; the green manganate is paramagnetic with one unpaired electron, but the permanganate is
diamagnetic.
The π-bonding takes place by overlap of p orbitals of oxygen with d orbitals of manganese.

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 • Oxidizing properties of KMnO4
common reaction : MnO4- + 8H+ + 5e- → 2Mn2+ + 4H2O
a) Iodide to iodine: 2I– → I2 + 2e–
b) Iron(II) to Iron(III): Fe2+ → Fe3+ + e–
c) Oxalate ion to CO2: C2O42- → 2CO2 + 2e-
d) Sulphite to sulphate: SO32- + H2O → SO42- + 2H+ + 2e-
e) Nitrite to nitrate: NO2─ + H2O → NO3─ + 2H+ + 2e-
f) Sulphide to Sulphur: H2S → 2H+ + S + 2e–

1. [ MnO4- + 8H+ + 5e- → Mn2+ + 4H2O ] x 2 2 MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
[ 2I– → I2 + 2e– ] x 5 5 Fe2+ → 5Fe3+ + 5e–
2MnO4- + 16H+ + 10I- → 2Mn2+ + 5I2 + 8H2O MnO4- + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O

3 [ MnO4- + 8H+ + 5e- → Mn2+ + 4H2O ] x 2 4 [ MnO4- + 8H+ + 5e- → Mn2+ + 4H2O ] x 2
[ C2O42- → 2CO2 + 2e- ] x 5 [ SO32- + H2O → SO42- + 2H+ + 2e- ] x 5
2MnO4- +16H+ + 5C2O42- →2Mn2++10CO2 +8H2O 2MnO4- + 6H+ + 5 SO32- → 2Mn2+ + 5SO42- + 3H2O

[ MnO4─ + 8H+ + 5e- → Mn2+ + 4H2O ] x 2

[ NO2─ + H2O → NO3─ + 2H+ + 2e- ] x 5
2MnO4- + 5NO2- + 6H+ → Mn2+ + NO3- + H2O ( nitrite to nitrate )

• Oxidising properties in basic medium: MnO4─ + 2H2O + 3e─ → MnO2 + 4OH─

o Iodide to iodate : MnO4─ + H2O + I─ → MnO2 + IO3─ + 2OH─
o Thiosulphate to sulphate: 8MnO4─ + H2O + 3S2O32─ → 8MnO2 + 6SO42─ + 2OH─
• Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide catalyses the oxidation:
2MnO4 – + 3Mn2+ + 2H2O ——> 5MnO2 + 4H+
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Q) Why Permanganate titrations in presence of hydrochloric acid are unsatisfactory.
Ans) Permanganate titrations in presence of hydrochloric acid are unsatisfactory since hydrochloric acid is oxidised to chlorine.

8.6 Name the oxo metal anions of the first series of the transition metals in which the metal exhibits the oxidation state equal to its
group number.
Ans: MnO4- and Cr2O72-

Q) Explain the chemistry of oxide of Transition elements?

Ans) In the case of Mn, Mn2O7 is a covalent green oil. Even CrO3 and V2O5 have low melting points. In these higher oxides, the acidic
character is predominant.
The well characterized CrO is basic but Cr2O3 is amphoteric.

Q) What do you mean by Chromyl Chloride test?

OR
When an orange coloured crystalline compound ‘A’ was heated with common salt and concentrated sulphuric acid, an orange red
coloured gas ‘B’ was evolved. The gas ‘B’ on passing through NaOH solution gave a yellow solution ‘C’.
Ans)This is a test of chloride ion . When a mixture of a metal chloride ion and potassium dichromate is heated with conc. H2SO4 , orange red
vapours of chromyl chloride are evolved

K2Cr2O7 + 6H2SO4 + 4NaCI → 2KHSO4 + 4NaHSO4 + 2CrO2CI2 + 3H2O

When CrO2Cℓ2 vapours are passed through NaOH solution ,yellow coloured solution is obtained
4NaOH + CrO2CI2 → Na2CrO4 + 2NaCI + 2H2O
[Chlorides of Ag ,Hg ,Pb and Sn do not gives this test ]

Q. How would you account for the increasing oxidising power in the series: VO2+< Cr2O72– < MnO4–?
Answer) This is due to the increasing stability of the lower species to which they are reduced.

Q) Why is it not advisable to dissolve KMnO4 in conc. H2SO4?

Ans: On addition of conc. H2SO4 to KMnO4, it may explode due to formation of Mn2O7
2KMnO4 + H2SO4 → K2SO4 + Mn2O7 + H2O
( explosive)
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 THE INNER TRANSITION ELEMENTS ( f-BLOCK)
The f-block consists of the two series, lanthanoids (the fourteen elements following lanthanum) and actinoids (the fourteen elements following
actinium). Because lanthanum closely resembles the lanthanoids, it is usually included in any discussion of the lanthanoids for which the general
symbol Ln is often used. Similarly, a discussion of the actinoids includes actinium besides the fourteen elements constituting the series.
The lanthanoids resemble one another more closely than do the members of ordinary transition elements in any series. They have only one
stable oxidation state and their chemistry provides an excellent opportunity to examine the effect of small changes in size and nuclear charge
along a series of otherwise similar elements.
The chemistry of the actinoids is, on the other hand, much more complicated. The complication arises partly owing to the occurrence of a
wide range of oxidation states in these elements and partly because their radioactivity creates special problems in their study; the two series will
be considered separately here.

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Oxidation • In the lanthanoids, La(II) and Ln(III) compounds are predominant species. However, occasionally +2 and +4 ions in solution
state: or in solid compounds are also obtained. This irregularity (as in I.E.) arises mainly from the extra stability of empty, half-
filled or filled f- subshell.
• Thus, the formation of CeIV is favoured by its noble gas configuration, but it is a strong oxidant reverting to the common +3
state. The Eo value for Ce4+/ Ce3+ is + 1.74 V which suggests that it can oxidise water. However, the reaction rate is very
slow and hence Ce(IV) is a good analytical reagent.
• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is formed by losing the two s electrons and its f 7
configuration accounts for the formation of this ion. However, Eu2+ is a strong reducing agent changing to the common +3
state. Similarly, Yb2+ which has f 14 configuration is a reductant. TbIV has half-filled f-orbitals and is an oxidant. The
behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation states.
General • All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
Characteristics
• The hardness increases with increasing atomic number, samarium being steel hard.
• They have typical metallic structure and are good conductors of heat and electricity.
• Density and other properties change smoothly except for Eu and Yb and occasionally for Sm and Tm.
• 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. Values for Eo for the half-reaction:
Ln3+(aq) + 3e– → Ln(s)
are in the range of –2.2 to –2.4 V except for Eu for which the value is – 2.0 V. This is, of course, a small variation.
➢ The metals combine with hydrogen when gently heated in the gas. The carbides, Ln3C, Ln2C3 and LnC2 are formed when the
metals are heated with carbon. They liberate hydrogen from dilute acids and burn in halogens to form halides. They form
oxides M2O3 and hydroxides M(OH)3. The hydroxides are definite compounds, not just hydrated oxides. They are basic like
alkaline earth metal oxides and hydroxides.
4 Ln(s) + 3 O2(g) 2 Ln2O3(s) (Ln any lanthanoid element)
4 Ln(s) + 6 S(g) 2 La2S3(s)
2 Ln(s) + N2(g) 2 LnN(s)
2 Ln(s) + 3 H2SO4(aq) 2 Ln3+(aq) + 3 SO42−(aq) + 3 H2(g)
2 Ln(s) + 3 X2(g) 2 LnX3(s) ( X= Halogens)
2 Ln(s) + 6 H2O(l) 2 Ln(OH)3(aq) + 3 H2(g)

Ln + 2C LnC2

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 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.
Coloured Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of these ions may be attributed to
the presence of f -electrons. Neither La3+ nor Lu3+ ion shows any colour but the rest do so. However, absorption bands are narrow,
probably because of the excitation within f level. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the
f 14 type (Yb2+ and Lu3+) are all paramagnetic.

Actinoids
The actinoids are radioactive elements and the earlier members have relatively long half-lives, the latter ones have half-life values
ranging from a day to 3 minutes for lawrencium (Z =103). The latter members could be prepared only in nanogram quantities. These
facts render their study more difficult.
Electronic All the actinoids are believed to have the electronic configuration of 7s2 and variable occupancy of the 5f and 6d subshells. The
configuration fourteen electrons are formally added to 5f, though not in
thorium (Z = 90) but from Pa onwards the 5f orbitals are complete at element 103. The irregularities in the electronic configurations
of the actinoids, like those in the lanthanoids are related to the stabilities of the f 0, f 7 and f 14 occupancies of the 5f orbitals. Thus, the
configurations of Am and Cm are [Rn] 5f 77s2 and [Rn] 5f 76d17s2. Although the 5f orbitals resemble the 4f orbitals in their angular
part of the wave-function, they are not as buried as 4f orbitals and hence 5f electrons can participate in bonding to a far greater
extent.
size There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as the actinoid contraction
(like lanthanoid contraction). The contraction is, however, greater from element to element in this series resulting from poor
shielding by 5f electrons.
Oxidation There is a greater range of oxidation states, which is in part attributed to the fact that the 5f, 6d and 7s levels are of comparable
state 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 and +4 ions tend to hydrolyse.
General The actinoid metals are all silvery in appearance but display a variety of structures. The structural variability is obtained due to
properties irregularities in metallic radii which are far greater than in lanthanoids.
Hydrochloric acid attacks all metals but most are slightly affected by nitric acid owing to the formation of protective oxide layers;
alkalies have no action.
The magnetic properties of the actinoids are more complex than those of the lanthanoids.

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