Block D and F Elements

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Payal Gupta

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8.39 Lanthanoids show oxidation states of +2, +3, +4 because of the large energy gap between 5d and 4f sub-shells while actinoids show oxidation states of +3 to +7 because of the small energy difference between 5f, 6d, and 7s orbitals.

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Payal Gupta

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8.38 The inner transition elements are those in which the last electron enters the f-subshell. The lanthanoids atomic number 58-71 and actinoids 90-103. The atomic numbers 59, 95 and 102 are inner transition elements

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Payal Gupta

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8.37 An alloy is a homogenous mixture of two or more metals or non-metals. Lanthanoid is used for the production of alloy steels for plates and pipes called as mischmetals. It contains about 95% lanthanoid metal, iron and traces of Al, S, C etc. in traces. It is used in magnesium- based alloy to produce bullets, shells and lighter flint.

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Payal Gupta

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8.36 (i) The chromite ore (FeCr2O4) is fused with sodium hydroxide (NaOH)

4FeCr2O4 +16 NaOH+ 7O2 → 8Na2CrO4 +2Fe2O3 +8H2O

The yellow solution of sodium chromate is then filtered and acidified with sulphuric acid giving its dichromate.

2Na2CrO4 +H2SO4→ Na2Cr2O7 + Na2SO4 +H2O

On cooling, sodium sulphate crystallizes out as Na2SO4.10H2O and is removed.

Na2Cr2O7 +2KCl → K2Cr2O7 + 2NaCl

(ii) The pyrolusite ore(MnO2) is oxidised in the presence of potassium hydroxide by heating.

2MnO2 + 4KOH +O2→ 2K2MnO4 + 2H2O

The green potassium manganate (K2MnO4) is then treated with a current of chlorine or ozone to oxidise potassium manganate to potassi

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8.35  (i) The lower oxide have low oxidation state while the higher oxide has high oxidation state, example MnO is basic and Mn2O7 is

(ii) Oxygen and fluorine have a small size and high electronegativity and can easily oxidize metals, example V2O5.

(iii) Oxoanions of metals have higher oxidation states because of high electronegativity of oxygen and highly oxidizing property example, Cr in CrO7 2- has an oxidation state of +6

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Payal Gupta

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8.34 From the table given below:

Mn3+ : 3d4

unpaired electrons = 4

V3+ : 3d2

unpaired electrons =2

Cr3+ : 3d3

unpaired electrons= 3

Ti3+ : 3d1

unpaired electrons =1

Cr3+ is most stable in aqueous solution because of half filled d-orbital.

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Payal Gupta

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8.33 Copper (29) has electronic configuration 1s22s22p63s23p63d104s1. It can easily lose one electron to give stable configuration as it has completely filled d-orbital.

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Payal Gupta

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8.32 The reactions in which same substance gets oxidized as well as reduced due to unstable oxidation state.

Example:

2MnO42- + 4H+? 2MnO4- + MnO2 + 2H2O

Mn (VI) is oxidised to Mn (VII) and also reduced to Mn (IV).

2CrO4 3- +2H+? CrO4 2- +Cr3+ + 4H2O

Cr (V) is oxidised to Cr (VI) and also reduced to Cr (III).

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8.31 (i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing: The +2 oxidation state becomes more stable on moving across a period i.e. the tendency of metals to give electrons becomes more. Therefore, vanadium(II) oxide and chromium(II) oxide are strong reducing agents.

As if the value of electrode potential is higher i.e. more energy required to withdraw an electron from an isolated atom, more readily it can be reduced and lesser the electrode potential more readily it can be oxidized.

The electrode potential of Cr3+? Cr2+is negative so it acts reducing agent or can undergo oxidation which makes it

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8.30 

 

Lanthanoids

Actinoids

Electronic Configuration

It is represented by [Xe]4fx5dy6s2, where x varies from 0 to 14 and y= 0 or 1

It is represented by [Rn]5fx6dy7s2, where x varies from 0 to 14 and y= 0

or 1.

Oxidation state

Generally shows +3 oxidation state only in some cases it is +2 or +4 but never greater than +4

It has +3 oxidation state but also shows higher oxidation states such as +4, +5, +6, +7.

Atomic and ionic sizes

Ionic radii of M3+ions decrease in size with increase in atomic number this is called as lanthanoid contraction.

There is a gradual decrease in the size of M3+ ions across the series, this is known as actinoid contraction.

Chemical Reactivity

Lanthanoids are less reactive in nature and form oxides, sulphides, nitrides etc. They have a lesser tendency to form complexes.

They are highly reactive in nature when they are in the finely divided state. They have a higher tendency to form complexes and even react with non-metals at moderate temperature.

Actinoid Contraction > Lanthanoid contraction

Lanthanoids show lanthanoid contraction due to which their size is quite small as compared to actinoids although there is actinoid contraction also lanthanoid contraction has more impact on elements as there is one shell less than actinoids, so lanthanoids have less tendency to lose an electron and to undergo any reaction like the formation of oxide etc.

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