Formation of Colored Ions

• When an electron from a lower energy d-orbital is excited

to a higher energy d-orbital, the energy of excitation
corresponds to the frequency of light absorbed.
• This frequency generally lies in the visible region. The
colour observed corresponds to the complementary colour
of the light absorbed.
• These color properties are mainly due to either d-d
transition or charge transfer spectra.
• Complex ions with d⁰ and d¹⁰ electron are colorless due to
no d-d transition. Exceptions KMnO₄ shows purple color
and K₂Cr₂O₇ shows orange color due to charge transfer
spectra
Configuration Example Color
Formation of Complex compounds
• The transition metals form a large number of complex
compounds. This is due to the comparatively smaller
sizes of the metal ions, their high ionic charges,
variable oxidation states and the availability of d
orbitals for bond formation.

Size ↓, Charge ↑, tendency to attract e⁻ ↑

• During complex formation, each ligand donates

electron pair to vacant orbitals of metal ion and form
ligand to metal type complex.
 • Coordination number of central atom tells
about the shape and geometry of complex.

CN 4

Square planner (dsp³) Tetrahedral (SP³)

Strong field ligand, Weak ligand, high spin,
low spin, spin pair spin free, no pairing
Pairing energy < transition energy Pairing energy > Transition energy
[Ni(CN)₄]⁻², [Pt(NH₃)]⁺² [NiCl₄]⁻², [Ni(NH₃)₄]⁺²
 CN 6

Inner orbital (d²sp³) Outer orbita (SP³d²)

Strong field ligand, Weak ligand, high spin,
low spin, spin pair spin free, no pairing
Pairing energy < transition energy Pairing energy > Transition energy
[Fe(CN)₆]⁻⁴, [Co(NH₃)]⁺³ [CoF₆]⁻³, [Cr(H₂O)₆]
Q. Explain hybridization, shape, magnetic
moment and magnetic character of the given
complex. Is it high spin or low spin?
• [Fe(CN)₆]⁻⁴
 Catalytical properties
• The transition metals and their compounds act as a catalyst in
various reaction.
• This activity is ascribed to their ability to adopt multiple oxidation
states and to form complexes.
• some of the examples are
– Vanadium(V) oxide (V₂O₅) - in Contact Process (Sulfuric acid
formation)
– finely divided iron - in Haber’s Process (Ammonia formation)
– nickel - in Catalytic Hydrogenation of oils
– Platinum – in manufacture of sulfuric acid
• Catalysts at a solid surface involve the formation of bonds between
reactant molecules and atoms of the surface of the catalyst .This
has the effect of increasing the concentration of the reactants at
the catalyst surface and also weakening of the bonds in the reacting
molecules (the activation energy is lowering).
• Catalytical properties depends on the following
factors
– Presence of vacant d-orbitals
– Large surface area
– Variable oxidation state
– Ability to form complex compounds
• Catalyst combines with reactant and forms a low
energy intermediate which is highly unstable, it
decomposes to form product.
 In contact process og sulfuric acid
manufacture, variable OS of V₂O₅
V₂O₅
Step 1: 2SO₂ + O₂ SO₃
Step 2: V₂O₅ + SO₂ V₂O₄ + SO₃
Step 3: 2V₂O₄ + O₂ 2V₂O₅