Professional Documents
Culture Documents
Element Ti V Cr Mn Fe Co Ni Cu
Proton no. 22 23 24 25 26 27 28 29
Electronic [Al] [Al] [Al] [Al] [Al] [Al] [Al] [Al]
configuration 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1
iii. Higher oxidation state (+6) are not formed after manganese
→ 3d e- are being paired up & have less tendency to be used in bonding.
vi. The higher oxidation states ( ≥ 4) do not exist in the form of free
aqueous ions
- examples: Ti2+, V2+, [ Fe(H2O)6]2+ …
vii. This is because their high charge density would polarise the water
molecules that are coordinated to them resulting in the formation of
oxo-anions.
-Example: [V(H2O)6]4+ + H2O → [V(H2O)5(OH)]3+ + H3O+
Relative stability of the +2 & +3 oxidation state
i. All transition metals, except vanadium & copper, dissolve in dilute
HCl to form M2+ / M3+ ions.
ii. Determine the stability of M2+/M3+ ions by comparing Eө of M2+/M &
M3+/M ions with Eө = 0.00V (for acidic solution) & Eө = +1.23V (in O2).
iii. Positivity of Eө value & stability of ions (there is extra stability in the
half-filled 3d orbitals).
iv. Consider the standard electrode potentials ( Eө ) for the following system:
System Eө / V
Cr + e- ↔ Cr2+
3+
-0.41
Ti3+ + e- ↔ Ti2+ -0.37
V3+ + e- ↔ V2+ -0.24
Fe3+ + e- ↔ Fe2+ +0.77
Mn3+ + e- ↔ Mn2+ +1.51
Co3+ + e- ↔ Co2+ +1.81
2.00
1.50
E= +1.23V
1.00
Eq /V
0.50
0.00
Ti V Cr Mn Fe Co
-0.50
-1.00
Elements
→ For ions whose Eө (m3+ / m2+) values are higher than +1.23V, the +2
oxidation state will be more stable in the presence on O 2.
→ For ions whole Eө (m3+ / m2+) values are lower than +1.23V, the +3
oxidation state will be more stable in the presence of O 2.
2. Coloured Ions
Ions Colour
Sc3+ *Colourless
Ti3+ Purple
V3+ Green
Cr , CrO42-, Cr2O72-
3+
Green, yellow, orange
Mn2+, MnO42- Pinkish, purple
Fe2+, Fe3+ Green, brown
Co2+ Pink
Ni2+ Green
Cu2+ Blue
Zn2+ * Colourless
I. Overlapping of the d-orbital in central metal with ligand causes the 3d subshell of the metal to
have different energy level.
II. Example: [Cu(H2O)6]2+
4
∆E
III. On transcending to a higher energy level (d-d transition), the electrons absorb a light photon of
a particular wavelength (same energy as in between d-orbitals).
IV. The ions filter out this particular wavelength and appears coloured.
V. Different ions exhibit different colours:
Different energy levels → different wavelengths absorbed → different colours exhibited
Example: [Cr(H2O)6]3+ → red light absorbed → appears green
VI. Colours can change when:
Sc3+ [Ar]
3. Complex Ions
(a) Transition metal complexes consist of a transition metal atom or ion surrounded by ligands.
: Example (i) water, H2O (ii) Cyanide, CN- (iii) Ammonia, NH3
- can form ions with a small size and a high charge density
- have empty orbitals to accommodate the lone pairs of electrons from a ligand
- 2 donor atoms
- 6 donor atoms
- Example: EDTA
- bidentate ligands & hexadentate ligands are included in poly dentate ligands
- the number of coordinate bonds formed between the ligands & the central metal ion
- diamminesilver(I), [Ag(NH3)2]+
[H3N → Ag ← NH3]+
(ii) complexes with coordination number of 4 are either tetrahedral or square planar.
Examples:
Co
C C
l l
C
l
(iii) complexes with the coordinate number of 6 are octahedral. Example:
- tetraamminedichlorochromium(III), [Cr(NH3)4Cl2]+
C
H3N NH3
C
r
H3N NH3
C
(e) Almost all transition metal ions form complexes with water molecules when dissolved. Example:
[Fe(H2O)6]2+ (light green)
Types of complexes:
- anionic complexes
- cationic complexes
- neutral complexes
cation anion
Nomenclature rules :
cation
3. Anionic ligands end in letter “o”. (Example: chloro- (Cl-), cyano- (CN-), oxo- (O-))
* H2O (aqua)
* CO (carbonyl)
* NH3 (ammine)
4. Number of each ligand is specified by the Greek prefix, for example: di, tri, tetra.
8. For neutral and cationic complexes, normal name of the metal is used.
9. In anionic complexes, the suffix –ate is added to the name of the metal.
Examples:
Metal Name Metal Name
Aluminium Aluminate Chromium Chromate
Cobalt Cobaltate Vanadium Vanadate
Manganese Manganate Iron Ferrate
Nickel Nickelate Copper Cuprate
Zinc Zincate Silver Argentate
Examples:
Types of Formula Name
complexes
Neutral K2[CoCl4] Potassium tetrachlorocobaltate(II)
K3Fe(CN)6
NH4[Cr(NH3)2(SCN)4]
[Pt(NH3)6]Cl4
[Co(H2NCH2CH2NH2)3]2(SO4)3
(NH4)2[Ni(C2O4)2(H2O)2]
Cationic [Ag(NH3)2]+ Diamminesilver(I) ion
[PtCl2(NH3)4]2+
[Ni(H2NCH2CH2NH2)3]2+
[Cr(NH3)5Cl]2+
[V(H2O)4O2]+
Anionic [CuCl4]2- Tetrachlorocuprate(II) ion
[Fe(C2O4)3]3-
[Fe(CN)6]4-
[Cr(C2O4)3]3-
[Ni(EDTA)]2-
4. Catalyst
Homogeneous Catalysis
The intermediate species, Fe2+ ions, then reduces S2O82- ions to SO42- while Fe3+ is regenerated
S2O82- + 2Fe2+ → 2SO42- + 2Fe3+
Heterogeneous Catalysis
(ii) The H-H and C=C bonds are weakened to form bonds with
the metal surface.
optical isomerism
structural isomerism
Geometrical Isomerism
(a) Square planar complexes with formula of Ma 2b2 (a & b are monodentate
ligands).
o Fac-isomer : the three identical groups ( a or b ) are in the same face of the octahedron.
o Mer-isomer : the three identical groups ( a or b ) are not found in the same face of the octahedron.
Optical Isomerism
i. Optical isomerism occurs in octahedral complexes which do not have a plane of symmetry.
ii. Optical isomer occurs in pairs . One is the mirror image of the other and they are not
superimposable.
iii. Optical isomers are also called enantiomers . They are optically active.
iv. Enantiomers dextro(+): rotate plane polarised light in the clockwise direction.
Example : [Ni(EDTA)]2-
Structural Isomerism
Occurs in complexes having the same molecular formula but are different with respect to the
types of ligands that are bonded to the central ion.
Example : CrCl3.6H20
Only the Cl- ions that are not bonded to the central metal ion can be subjected to reaction/
precipitation. [ Example : in isomer III , 3 Cl- ions can react ]
Isomer Formula Structure of complex ions
I [Cr(H2O)4Cl2]+.Cl-.2H2O
II [Cr(H2O)5Cl]2+.2Cl.H2O
III [Cr(H2O)6]3+.3Cl-