Chapter 13 Transition Elements

Transition Elements and Their Ions

▪ Transition element is strictly defined as an element that forms at least a stable ion with incomplete or partially filled d orbitals.
▪ Sc and Zn are d-block elements but not transition elements as they did not form simple ions with partially filled d orbitals
▪ General properties of transition elements
o High melting points
o Possess variable oxidation states
(Energy difference between 3d and 4s orbitals are small)
o Form coloured ion/compound (d-d transition)
o Form complex ions (empty orbitals and high charge density)
- High charge density and high polarising power which able to attract ligand to itself
- Presence of empty orbitals to accept lone pairs from the ligand to form dative bond
o Act as catalyst
o Often paramagnetic
(with unpair electron and attracted by a magnetic field)

Atomic Radii

▪ Atomic radii of d-block elements show little variation across period

o Slight increase in effective nuclear charge
o Electron is added to the inner 3d subshell
o The added electrons shield the outer electrons from the nucleus and minimize /cancel the increase in nuclear charge

Densities

▪ Transition element have higher density than s-block elements

o Relative small atomic radii of the atoms
o Close-packed structure in the crystal lattice
▪ Gradual increase in density from Sc to Cu
o Small decreases in metallic radii
o Increase in atomic mass
o Electron is added to the inner 3d subshell
o The added electrons shield the outer electrons from the nucleus and minimize/cancel the increase in nuclear charge

Ionic Radii
▪ Ionic radius for a positive ions is always smaller than the atomic radius
▪ Ionic radius is affected by oxidation state
▪ Ionic radii decreases with increasing of the oxidation state

Melting and Boiling Points

▪ High boiling and melting points
o Strong metallic bond in the solid lattice structure

▪ Potassium in the same period has lower melting point (64℃) and boiling point (774℃) as compared to the transition elements because
only one valence electron in the 4s orbital is involved in the metallic bond formation.
▪ Mn and Zn has lower melting point and boiling point
o Extra stability of the half-filled and fully-filled d subshell
o d electrons are less available
o Only 4s electrons are available for the metallic bond formation
 Ionisation Energy
▪ Ionisation energy rise steeply across the period as electrons become more difficult to remove from the increasing nuclear charge
▪ 1st IE and 2nd IE increase relatively little

▪ 1st ionisation energy

o First electron is removed from the outer 4s orbital which shielded from the nucleus
o It cancels the increase in effective nuclear charge

▪ 2nd ionisation energy

o 2nd ionisation energy of Cr and Cu is higher
o Second electron is removed from an inner 3d orbital that has more stable electronic configuration

▪ 3rd ionisation energy

o 3rd ionisation energy of Fe is lower
o Removal of third electron will results in a half-filled 3d subshell (Fe3+ more stable ion)

Electrical Conductivity
▪ High electrical conductivity
▪ Have more delocalised valence electrons from 4s and 3d orbitals involve in metallic bond formation

Oxo Ions of Transition Elements

Oxidation state Ti V Cr Mn Fe Co Ni Cu
1 Cu+
2 Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+
Simple ions Light pink Pink Green Blue
3 Ti3+ V3+ Cr3+ Fe3+ CO 3+
Violet Green Green Brown
4 TiO2+ VO2+
5 VO2+
VO3-
6 CrO42-
Complex ions Yellow MnO42- FeO42-
Cr2O72- Green
Orange
7 MnO4-
Purple
▪ Transition metal have covalent characteristics and are good oxidising agents
Species Oxidation state Properties
MnO +2
Basic
Mn2O3 +3
MnO2 +4 Amphoteric
Mn2O7 +7 acidic
▪ Most of the transition metals are inert toward acids or react slowly with oxygen (protective layer of oxide)

Ligands
Anionic/
Type Description Ligand Name
neutral
Monodentate ▪ One donor atom Anionic :F- fluoro
▪ Form one dative bond with central :Cl- chloro
metal ion
:Br- bromo
-
:OH hydroxo
:CN- cyano
:NO2- nitro
:SCN- thiocyanato
Neutral :NH3 ammine
H2O: aqua
:NO nitrosyl
:CO carbonyl
Bidentate ▪ Two donor atoms Anionic C2O42- / ox oxalate/ethanedioato
▪ Form two dative bonds with central Neutral H2N̈CH2CH2N̈H2 / en ethylenediamine
metal ion
Hexadentate ▪ Six donor atoms Anionic EDTA4- ethylenediaminetetraacetato
▪ Form six dative bonds with central
metal ion
▪ Form ring structure (chelation)
▪ In anionic complexes, the suffix -ate is added to the name of metal as in vanadate, chromate, manganate, ferrate, cobaltate, nickelate,
cuprate and platinate.
▪ Stability of a complex is determined by the stability constant, Kstability
M(aq) + nL(aq) ⇌ MLn(aq)
metal ion ligand complex ion

[𝑀𝐿𝑛 ]
𝐾𝑠𝑡𝑎𝑏𝑖𝑙𝑖𝑡𝑦 =
[𝑀][𝐿]𝑛

▪ The larger the stability constant, the more stable the complex ions
▪ Relative strength of ligand
o EDTA4- > NH3 > H2O
o H2NCH2CH2NH2 > H2O
o F- > SCN- > H2O

Factors affecting the Stability of a Complex

▪ Type of ligand – chelating effect (chelation refers to the binding of polydentate ligands to the central metal ion)
o Chelating agent form more stable complexes than non-chelating agent such as water
o Chelating agent is attached to the metal ion by several bonds

▪ Oxidation state of the central metal ion

o Central metal ion with higher oxidation state will form a more stable complex ion
o The higher the charge density of the central metal ion, the stronger the bonds formed between the central metal ions and the
ligands

Formation of Coloured Ions and Compounds

▪ Have incomplete or partially filled d subshell of the transition metal ions
▪ d-d electronic transition occurs
▪ correspond to the visible region of the electromagnetic spectrum and cause it form coloured ion
Element Complex Oxidation State Colour
Titanium [Ti(H2O)6]3+ +3 Violet
Vanadium [V(H2O)6]2+ +2 Violet
[V(H2O)6]3+ +3 Green
Chromium [Cr(H2O)6]2+ +2 Blue
[Cr(H2O)6]3+ +3 Green, Violet
[Cr(OH)6]3- +3 Bright green
[Cr(H2O)5Cl]2+ +3 Light green
[Cr(H2O)4Cl2]+ +3 Dark green
Cr2O72- +6 Orange
CrO42- +6 Yellow
Manganese [Mn(H2O)6]2+ +2 Light pink
MnO42- +6 Green
MnO4- +7 Purple
Iron [Fe(H2O)6]2+ +2 Pale green
[Fe(CN)6]4- +2 Yellow
[Fe(H2O)6]3+ +3 Yellow
[Fe(CN)6]3- +3 Yellow
[Fe(H2O)5SCN]2+ +3 Blood red
Cobalt [Co(H2O)6]2+ +2 Pink
[Co(NH3)6]2+ +2 Yellow
[CoCl4]2- +2 Blue
[Co(H2O)6]3+ +3 Brown
Nickel [Ni(H2O)6]2+ +2 Light green
[Ni(NH3)6]2+ +2 Light blue
Copper [Cu(H2O)6]2+ +2 Blue
[Cu(NH3)4]2+ +2 Dark blue
[CuCl4]2- +2 Yellow
[Cu(EDTA)]2- +2 Light blue

Catalytic Activity
▪ Catalyst (provide alternative route by lower the activation energy)
▪ Transition elements can use as catalyst
o Exhibit variable oxidation state (homogeneous)
o Availability of empty orbitals (heterogeneous)