UNIT I TRANSITION ELEMENTS

Transition elements
In these elements, either in their atomic state or in any of their common oxidation state, the last electron enters the d-orbital of the penultimate (inner to ultimate) shell, i.e., the last electron goes to (n-1)d orbital.

Why are d-block elements called Transition elements?

The d-block elements are called transition elements because they exhibit transitional behavior between highly reactive ionic compound forming s-block elements (electropositive elements) on one side and mainly covalent compound forming p-block elements (electronegative elements) on the other side.

Position of d-block elements in the periodic table:d-block elements are located in between s-(ionic compound forming elements) and p-(covalent compound forming elements) block elements. Thus these elements are located in the middle of the periodic table and occur in fourth (n=4) and subsequent periods of the periodic table. It is because of their inclusion in between s- and p-block elements that the properties of d-block elements are intermediate between those of s- and p-block elements. Thus the elements of the groups III-B, IV-B, V-B VI-B, VII-B, VIII, I-B and II-B belong to this block. The outermost shell of these elements varies from (nd)d1 .ns2 to (n-d)d10.ns2 .

General characteristic of the d-block elements:1) Metallic properties:All the d-block elements exhibit typical metallic properties. Such as high melting and boiling points, high tensile strength, ductility, malleability, high thermal and electrical conductivity and metallic lustre.

2) Atomic and ionic radii:The covalent radii of the elements decrease from left to right across a row in the transition series, until near the end when the size increase slightly.

s-block elements

p- block elements

d-block elements (Transition elements) IA II A III B IV B V B VI B VII B VIII IB II B III A IV A V A VI A VII A Zero

Highly reactive Metals and form Ionic compounds

Show intermediate properties between s- and p-block elements

Form covalent compounds

POSITION OF d BLOCK ELEMENTS IN THE PERIODIC TABLE

3) Ionization energies:Ionization energy increases along a series from left to right due to decrease in atomic size.

4) Variable oxidation states:A characteristic property of the d-block elements is their ability to exhibit variable oxidation states. The common oxidation states of some of these elements are as follows. Se(+2, +3); Ti(+2, +3, +4); V(+2, +3, +4, +5); Cr(+1, +2, +3, +4, +5, +6); Mn(+2, +3, +4, +5, +6, +7)

5) Complex formation:The d-block elements have a tendency to form coordination compounds (complex compounds) due to their small size, higher nuclear charge and presence of low energy vacant orbitals to accept lone pair of electrons donated by ligands.

6) Magnetic properties:Transition metals and many of their compounds show paramagnetic behavior where there are unpaired electrons. Magnetic moment, = n(n+2) B.M where n = number of unpaired electrons. Magnetic moment increases as the number of unpaired electrons increases.

7) Colour:The transition metal ions are usually coloured both in solid state and in aqueous solutions. No.of unpaired electrons 0 1 2 3 4 5 Corresponding ions and colours in aqueous solutions Se3+ (colourless), Cu+ (colourless), Zn2+ (colourless) Ti3+ (purple), V4+ (blue) V3+ (green), Ni2+ (green) Cr3+ (violet), Co2+ (pink) Cr2+ (blue), Mn3+ (violet), Fe2+ (green) Mn2+ (pink), Fe (yellow)

8) Formation of non-stoichiometric compounds:Transition elements exhibit the property of forming compounds of indefinite structures and proportions which are called non-stoichiometric compounds. The non-stoichiometric compounds are

generally written with a bar over the formula e.g., FeO indicates that Fe and O are not present as 1:1 ratio.

9) Catalytic activity:Various transition elements and their compounds are used as catalysts.

10) Formation of interstitial compounds:The transition elements form a number of interstitial compounds, in which they take up atoms of small size (e.g., H, C, N) in the vacant species in their lattices and form bonds with them.

The Chemistry of Transition Metals

1. Form coloured compounds and ions in solution:Transition metals tend to form more coloured compounds more than other elements either in solid form or dissolved in a solvent like water. Examples of the colours of some transition metal salts in aqueous solution are shown below. These coloured ions/compounds often have quite a complex structure and indeed called complexes. Sc - scandium salts, such as the chloride, ScCl3, are colourless Ti - titanium(III) chloride, TiCl3, is purple V - vanadium(III) chloride, VCl3, is green Cr - chromium(III) sulphate, Cr2(SO4)3, is dark green (chromate(VI) salts are yellow, dichromate(VI) salts are orange)

2. Action of heat:Many of the transition metal carbonates are unstable on heating and readily undergo thermal decomposition.

Metal carbonate
e.g.,

Metal oxide

+ Carbon dioxide

CuCO3(s) Copper(II) carbonate

CuO(s) + Copper(II) oxide

CO2(g) Carbon dioxide

ZnCO3(s) Zinc carbonate

ZnO(s) Zinc oxide

CO2(g) Carbon dioxide

3. Action of NaOH:Many transition metal ions (e.g. in soluble salt solutions) give hydroxide precipitates when mixed with aqueous sodium hydroxide solution.

Transition metal salt solution + Sodium hydroxide

Solid hydroxide precipitate + Sodium salt

Ionically the precipitation reaction is:

Metal ion + Hydroxide ion M2+(aq) + 2OH-(aq)

Hydroxide precipitate M(OH)2(s)

FeSO4(aq)

2NaOH(aq) Sodium hydroxide

Fe(OH)2(s)

Na2SO4(aq) Sodium sulphate

Iron(II) sulphate

Iron(II) hydroxide

FeCl2(aq) + Iron(III) chloride

2NaOH(aq)

Fe(OH)2(s) + Iron (II) hydroxide

2NaCl(aq) Sodium chloride

4. Catalytic properties:Many transition metals are used directly as catalysts in industrial chemical processes and in the anti-pollution catalytic converters in car exhausts. For example iron is used in the Haber process for the synthesis of ammonia:

N2(g) + Nitrogen

3H2(g) Hydrogen

2NH3(g) Ammonia

Platinum and rhodium (in other transition series below Sc-Zn) are used in the catalytic converters in car exhausts to reduce the emission of carbon monoxide and nitrogen monoxide, which are converted to the non-polluting gases nitrogen and carbon dioxide. Some compounds of transition metals are also used as catalysts.

For example manganese dioxide (or manganese(IV) oxide), MnO2, a black powder, readily decomposes an aqueous solution of hydrogen peroxide.

2H2O2(aq) Hydrogen peroxide

2H2O(l) Water

O2(g) Oxygen