3d block metals

Scandium oxide is very similar to aluminium oxide The most important oxide of titanium is TiO2 which is acidic. Vanadium has four principal oxidation states. VO and V2O3 are both ionic and basic and dissolve in acids to give the lilac [V(H2O)6]2+ ion and the blue-green [V(H2O)6]3+ ion. Both of these ions are readily oxidised to V(IV) or V(V). VO2 is ionic and amphoteric. It dissolves in acids to give the blue VO2+ ion (probably [VO(H2O)5]2+) and in concentrated alkali to give the brown VO44- ion. V2O5 has a borderline ionic/covalent structure. It reversibly loses oxygen on heating, and this may be why it is such an efficient catalyst in the Contact Process for the conversion of sulphur dioxide to sulphur trioxide. It is amphoteric. V2O5(s) + 2H+(aq) 2VO2+(aq) + H2O(l) yellow solution V2O5(s) + 6OH-(aq) 2VO43-(aq) + 3H2O(l) colourless solution The two main oxides of chromium are the green Cr2O3 which is ionic, and the red CrO3 which is covalent. The former is amphoteric as the green-grey precipitate of Cr(OH)3 dissolves in acids to give the purple [Cr(OH)6]3+ ion, and in alkali to give a green solution which may possibly contain the Cr(OH)4- ion. With ammonia solution, the greengrey precipitate dissolves to give a pink-purple [Cr(NH3)6]3+ complex ion. [Cr(H2O)6]3+(aq) + 3OH-(aq) Cr(OH)3(s) + 6H2O(l) This is a deprotonation or acid-base reaction. Cr(OH)3(s) + 6NH3(aq) [Cr(NH3)6]3+(aq) + 3OH-(aq) This is a ligand exchange reaction. Chromium trioxide is acidic and dissolves in water to give the fairly strong acid, H2CrO4 with pKa 0.74. On heating it loses oxygen to give Cr2O3. When treated with alkali the solution contains the yellow CrO42-(aq) ion. This reacts with strong acids to give an orange solution containing the dichromate (VI) ion: CrO3(s) 2CrO4 (aq) yellow
2-

+ H2O(l) +2H (aq)

+

H2CrO4(aq) Cr2O72-(aq) orange + H2O(l)

Manganese(II) compounds contain the very pale pink d5 ion which is resistant to oxidation. If alkali is added to a solution containing the Mn2+(aq) ion, the off white precipitate of

Mn(OH)2 is readily oxidised by air to brown hydrated Mn2O3 and then possibly to 2MnO2.H2O. Reduction of the purple MnO4- ion in alkaline solution (for example by alkenes) yields brown hydrated MnO2. Iron(II) oxide FeO is difficult to prepare as it rapidly oxidises in air to give Fe2O3, which contains the d5 ion. Both of these oxides are basic. Freshly precipitated Fe(OH)2 is green but it rapidly darkens on exposure to air and finally forms brown Fe(OH)3. Pink cobalt compounds contain the [Co(H2O)6]2+ ion. On the addition of NaOH a precipitate of Co(OH)2 is formed which starts off blue but turns pink on warming. The blue form may have four, rather than six, OH- groups round each cobalt ion in the solid state. With ammonia Co(OH)2 dissolves giving a complex which undergoes air oxidation to give the brown [Co(NH3)6]3+(aq) ion. Solutions of nickel(II) containing the green [Ni(H2O)6]2+(aq) ion give, with NaOH, a pale green precipitate of Ni(OH)2 which dissolves in ammonia to give the purple [Ni(NH3)6]2+(aq) ion. When copper(I) oxide Cu2O(s) is treated with aqueous sulphuric acid, the Cu+(aq) ion initially formed disproportionates to a brown precipitate of Cu(s) and the blue Cu2+(aq) ion, The hydrated [Cu(H2O)6]2+(aq) ion has four water molecules more firmly bound than the other two, and it is these water molecules which are substituted when pale blue Cu(OH)2(s) dissolves in aqueous ammonia to give the deep blue [Cu(NH3)4(H2O)2]2+(aq) ion. Zinc oxide goes yellow on heating and returns to white again on cooling. This is result of movement of ions within the crystal lattice which is reversible. It is amphoteric, giving the [Zn(H2O)4]2+(aq) ion with acids and the Zn(OH)3-(aq) and Zn(OH)42-(aq) ions when treated with NaOH. It also reacts with ammonia (contrast Al(OH)3(s), which does not) to give the [Zn(NH3)4]2+(aq) ion.