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The Elements Of The First transition series

The Elements Of The First transition series. The Metals. Ti 1668, hard, corrosion resistant V 1890, hard, corrosion resistant Cr 1875, brittle, corrosion resistant Mn 1244, white, brittle, reactive Co 1493, Hard, bluish color Ni 1453, quite, corrosion resistant

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The Elements Of The First transition series

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  1. The Elements Of The First transition series

  2. The Metals • Ti 1668, hard, corrosion resistant • V 1890, hard, corrosion resistant • Cr 1875, brittle, corrosion resistant • Mn 1244, white, brittle, reactive • Co 1493, Hard, bluish color • Ni 1453, quite, corrosion resistant • Cu 1083, soft and ductile, reddish color

  3. The lower oxidation • The oxidation states less than II • π–Acid ligands: CO, NO, CN–, bipy • π–ligands: alkenes, acetylenes, aromatic

  4. The lower oxidation • The II oxidation state • Binary compounds: Ionic, oxides being basic Ti, V and Fe often forming nonstoichiometric oxides • The Aqua ions: Ti2+, unknown V2+, Cr2+, Fe2+ are oxidized by air

  5. The lower oxidation • The II oxidation state • Complex: noncomplexing anions Hydrated salts: FeSO4·7H2O, Fe(H2O)62+ Complexing anions Hydrated salts: MCl2·2H2O (M = Mn, Fe, Co, Ni, and Cu) contain trans- [MCl4(H2O)2] unit, a linear polymeric edge-shared chain

  6. The lower oxidation • The II oxidation state • Complex NH3, en, EDTA4–, CN–, SCN–, X–, acac, etc Normal octahedral: most Distorted octahedral: Cr2+, Cu2+ Jahn-Teller effect

  7. The III oxidation state • All elements form at least some compounds in this state: • Cu(III) occur only in a few complexes or solid state • Mn3+, Co3+ are readily reduced by water • Ti3+, V3+ are oxidized by air • High acidities are required preventing hydrolysis to form hydrous oxides

  8. The III oxidation state 4. There are many anionic, cationic or neutral complexes Cr3+, Co3+ are inert substitutionally 5. The halides act as Lewis acids and for adducts Such FeCl4–

  9. The IV and higher oxidation state • Important for Ti: TiO2 and TiCl4 • Important for V, usually in the form of oxovanadium(IV) or vanadyl ion VO2+ • A stable compound for Mn is MnO2 • Higher oxidation states are known for V, Cr, Mn, Fe in fluorides, fluorocomplexes or oxo anions, powerful oxidizing reagents

  10. Scandium (Sc) • Electron configurations • 4s23d14s13d13d1[Ar] • Appearance • Soft, silvery-white metal, which becomes slightly tinged with yellow or pink upon exposure to the air. • Source • In the mineral Thortvetite Sc2O3; found in Scandinavia. • Chemistry • Similar to aluminum. • Favors coordination numbers of 6. • Main oxidations states: +2 (d1) & +3(d0) • Uses • isotope tracing in crude oil analysis • the iodide added to mercury vapor lamps and produces a highly efficient light source resembling sunlight, which is important for indoor or night-time color TV transmission.

  11. Reaction of scandium with air and water • Scandium metal tarnishes in air and burns readily to form scandium (III) oxide, Sc2O3. • 4Sc + 3O2 2Sc2O3 • When finely divided, or heated, scandium metal dissolves in water to form solutions containing the aquated Sc(III) ion together with hydrogen gas, H2. • 2Sc(s) + 6H2O(aq)  2Sc3+(aq) + 6OH-(aq) + 3H2(g)

  12. Reaction of scandium with the halogens • Scandium is very reactive towards the halogens fluorine, F2, chlorine, Cl2 bromine, Br2, and iodine, I2, and burns to form the trihalides scandium(III) fluoride, ScF3 , scandium(III) chloride, ScCl3, scandium(III) bromide, ScBr3, and scandium(III) iodide, ScI3 respectively. • 2Sc(s) + 3X2(g)  2ScX3(s) • Reaction of scandium with acids • Scandium metal dissolves readily in dilute hydrochloric acid to form solutions containing the aquated Sc(III) ion together with hydrogen gas, H2. • 2Sc(s) + 6HCl(aq)  2Sc3+(aq) + 6Cl-(aq) + 3H2(g)

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