Transition Elements

Transition Element
 Found in d block between group 2 and 13 but not all is classified as transition
elements.
 A transition element is s d-block element that forms one or more stable ions
with an incomplete d subshell.
 All are metals and able to form more than one cation i.e., positive ions.

Electronic Configurations
 4s subshell is normally filled except for
Cr and Cu
Ions
 Able to form more than one ions due to different oxidation number
which lead to different colours of transition elements. Eg : Cu2+ and
Cu+.
 Different oxidation states can be seen in the names of the
compounds.
 Across the period, harder to remove an electron as the nuclear
charge increases.
Question pg 368
Physical Properties of the Transition
Elements
 High melting point, high density, hard and rigid, good conductors of
electricity and heat.
 The first ionization energy across the period does not increase that
much.

s-block metal d-block metal

• Melting point is lower
• Density is lower
• Atomic radius is larger
• Ionic radius is larger
• First ionization energy is lower
• Electrical conductivity is higher
• Melting point is higher
• Density is higher
• Atomic radius is smaller
• Ionic radius is smaller
• First ionization energy is higher
• Electrical conductivity is lower
 Redox Reactions
Oxidation Reduction
• OIL- Oxidation Is Losing Electron • RIG – Reduction Is Gaining Electron
• Oxidation number increase • Oxidation number reduce
• Act as reducing agent • Act as an oxidizing agent
• Less positive Eө value • More positive Eө value

Example
Fe3+ e-  Fe2+ Eө = +0.77V
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O Eө = +1.52V
(i) Label the oxidation and reduction half equation and write the full equation
(ii) Find the total Eө of the reaction above and state whether the reaction is in forward or backward reaction.
Redox Reactions cont..
 Large positive Eө value indicates that the reaction proceed in forward
direction.
 Titration can be used to find the accurate value of a specific cation
present in the solution.
 MnO4- and Cr2O72- can be used as an oxidizing agent in titration.
Question pg 371
 Ligands and Complex Formation
 Fe2+ ion is surrounded by 6 H2O molecules.
 Water molecules  ligands
 Resulting ion i.e., [Fe(H2O)6]2+ complex ion
 Complex with 6 ligands  octahedral
 Complex with 4 ligands  square planar / tetrahedral
 All ligands can donate an electron pair to central transition metal
ion.
 Co-ordination number  number of co-ordinate (dative) bonds
to the central metal ion.
 Bidentate ligand  two co-ordinate bonds from each
ion/molecules to the transition metal.
 Monodentate  one co-ordinate bond from each ion/molecules
to the transition metal e.g : water and ammonia.
Question pg 373
 Stereoisomerism in Transition Metal
Complexes
 Geometric isomerism  complexes with the same
molecular formula but different geometrical
arrangements of their atoms. Eg : cis- and trans-
platin.
 Stereoisomerism  shown by octahedral (six co-
ordinate) complexes associated with bidentate
ligands. Eg : Ni as transition metal and 1,2-
diaminoethane (NH2CH2CH2NH2) as the bidentate
ligand. The isomers are mirror images of each other
and cannot be superimposed.
Question pg 374
 Substitution of Ligands
 Ligands can be exchanged.
[Cu(H2O)6]2+(aq) + 2OH–(aq) ↔ Cu(OH)2(H2O)4(s) + 2H2O(l)
blue solution pale blue precipitate
 Cu(OH)2(H2O)4(s) + 4NH3(aq) ↔ [Cu(H2O)2(NH3)4]2+ (aq) + 2H2O(l) + 2OH–(aq)
deep blue solution

[Cu(H2O)6]2+(aq) + 4Cl–(aq) ↔ [CuCl4]2– (aq) + 6H2O(l)

blue solution yellow solution
 [Cu(H2O)6]2+(aq) + 6NH3(aq) ↔ [Co(NH3)6]2+ (aq) + 6H2O(l)
 [Cu(H2O)6]2+(aq) + 4Cl–(aq) ↔ [CoCl4]2– (aq) + 6H2O(l)
(Aqueous cobalt(II) ions usually form tetrahedral complexes with monodentate anionic ligands
such as Cl–, SCN– and OH–)
Question pg 375
Stability Constants
 Different ligands form complexes with different stabilities.
 Eg : conc. NH3 is added to CuSO4 solution. NH3 ligand displace H2O.
Cu(H2O)6]2+(aq) + NH3(aq) ↔ [Cu(NH3)(H2O)5]2+ (aq) + H2O(l)
[Cu(NH3)(H2O)5]2+ (aq) + NH3(aq) ↔ [Cu(NH3)2(H2O)4]2+ (aq) + H2O(l)
 As [NH3] increases, this process continues until four of the water
molecules are replaced by ammonia to form a deep blue solution.
 Overall process:
Cu(H2O)6]2+(aq) + 4NH3(aq) ↔ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O(l)
 Position of equilibrium lies in the direction of the more stable complex
 Stability Constants cont..
 Stability constant, Kstab : stability of the complex is expressed in terms of the
equilibrium constant for ligand displacement.
 Kstab  Equilibrium constant for the formation of the complex ion in a solvent from its
constituent ions or molecules.
 Stability constants can be used to compare the stability of any two ligands.
 The higher the value of the stability constant, the more stable the complex.
 Eg : [Cu(H2O)6]2+ + 4Cl–(aq) ↔ [CuCl4]2– (aq) + 6H2O(l)
 Kstab =
 water does not appear in the equilibrium expression because it is in such a large excess
that its concentration is regarded as being constant.
 The units for the stability constant are worked out in the same way as for the units of
Kc.
Stability Constants cont..
 Bidentate ions have higher stability than monodentate ions.
 We can use the values of the stability constants to predict the effect
of adding different ligands to complex ions.
 Eg : the addition of excess NH3 to the complex [CuCl4]2– (aq) should
result in the formation of a dark blue solution of the ammonia
complex because the stability constant of the ammonia complex is
higher than that of the chloride complex. The position of equilibrium
is shifted to the right in the direction of the more stable complex.
Question pg 376
 The Colour of Complexes
 White light is made up of all the colours of the visible spectrum. When a
solution containing a transition metal ion in a complex appears coloured, part
of the visible spectrum is absorbed by the solution.
 d-orbitals in transition metal atom/ions degenerate i.e., all at the same
energy level.
 In the presence of ligands, TM ion is not isolated. The co-ordinate bonding
from ligands causes the five d-orbitals to split into two sets of non-
degenerate orbitals at slightly different energy levels.
 The Colour of Complexes cont..

 In ion complexes, metal is located at the center surrounded by ligands.

 Eg : 6 ligands. Octahedral shape. Lone pairs donated by ligands into the TM repel
electrons in two dx2-y2 and dz2 orbitals. These d-orbitals line up with the co-
ordinate bonds and closer to the bonding electrons in the octahedral arrangement
resulting increased repulsion between the electrons. Thus, the orbitals are split
with these 2 orbitals slightly higher energy level than other d-orbitlas.
 The Colour of Complexes cont..
Eg : Cu2+ has electronic configuration of [Ar]3d9

 The difference in the energy between the non-degenerate d-orbitals is labelled

ΔE i.e., the part of the visible spectrum of light.
 When light shines on the solution containing the Cu(H2O)62+ complex, an electron
absorbs this amount of energy. It uses this energy to jump into the higher of the
two non-degenerate energy levels. In copper complexes, the rest of the visible
spectrum that passes through the solution makes it appear blue in colour.
 ΔE changes results in a slightly different amount of energy being absorbed by
electrons jumping up to the higher orbitals. Therefore a different colour is
absorbed from visible light, so a different colour is seen.
The Colour of Complexes cont..