Transition Metals

General Properties
d-block element
form one or more stable ions
partially filled d orbitals

Chemical Properties
Very small difference in energy between 3d & 4s orbitals
Maximum Oxidation Number = no. of (4s e- + unpaired 3d e-)

Anomaly
Scandium and Zinc
-> One known oxidation state

Physical Properties

Across Period 3 Elements Transition Elements
Atomic radii Decreases significantly Relatively constant
1st IE Increases significantly Relatively constant
Reasons - Nuclear charge increases
- Electrons are added to the same
valence shells
- Screening effect remains
approximately constant
- Effective nuclear attraction on the
outer electrons increases
significantly
- Nuclear charge increases
- Electrons are added to the
inner quantum shell
- Screening effect increases
due to the increase in number
of inner shell electrons
- Effective nuclear attraction on
the outer electrons is almost
constant
Density Lower Higher

- Small atomic radii
- Higher atomic mass
- Closed pack substance
Melting and Boiling points Lower Higher (Strong metallic bond)

- Small differences in energies
between the 3d and 4s allow
the 3d and 4s electrons to
contribute to the sea of
delocalised electrons around
cations
- Strength of metallic bond is
proportional to the number of
delocalised electrons
Electrical and Heat
Conductivities
Group I - III: Good Good





Chemical Properties
Variable Oxidation State Close similarity in energies of the 3d & 4s orbitals

Beyond Magnesium
- Increasing difficulty to remove a 3d electron as the nuclear charge increase

Ti (+4) & V (+5) can exist only as covalent compounds
- High charge density: High polarising power
- Distort the e- cloud of neighbouring anion to a large extent
- lead to overlap of e- cloud
- thus a high degree of covalent character
Formation of complexes Complex contains a metal ion/atom linked to ligands (ions/neutral
molecules with at least an available lone pair of e-) through
dative bond.

- High charge density: High polarising power
- Cause cation has a strong tendency towards attracting ligands
- Forming compounds with covalent character
- The lone pair of e- on ligand is donated into the vacant orbitals of the
central transition metal ion to form the dative covalent bond

Co-ordination No (CN). & Shape of Complexes
- +1 Transition element cation (Ag+, Cu+) forms complexes with CN 2
- Co2+, Ni2+ & Cu2+ form complexes with CN 4
- CN 6 is most common. All H2O ligands have CN 6.
Ligand exchange reaction Cu2+ + H2O + NH3
(Cu(H2O)6)2+ (aq) + 4NH3 (aq) (Cu(NH3)3)2+ (aq) + 6H2O (l)
Observations: Pale blue -> Deep blue
Deductions: Ammonia is a stronger ligand than water.

Haemoglobin
- Consists of 4 haem groups attached to a protein
- Each haem group (giant complex molecule) contains hexacoordinated
Fe2+
HbO2 + COHbCO + O2
Colour of complexes Due to uneven absorption of light in the visible region of the electromagnetic
spectrum

Shapes of d-orbital

E- density concentrated: - Along x, y & z axes (energy raised greater extent)
head-on collision: stronger inter-electronic repulsion
- Between x,y & z axes

D-D splitting (visible light energy range)
- When ligands approach transition metal, repulsion occurs
- e- in D orbitals are repelled to different extents by e- pairs of approaching
ligands
- Five d-orbitals spilt
Crystal field of splitting energy
Magnitude: Determine by nature/ strength of approaching ligand

D-D transition
- Particular wavelengths is absorbed
- e- from lower energy d-orbitals are promoted to the higher energy d-orbitals
- As energy is not remitted, transition metal has a characteristic colour

Factors affecting colours
1. No. of d e- present
Different no. of e- in the d orbitals have different interactions with e- from
H2O ligands, giving rise to different splitting energies, hence different
wavelengths of light being absorbed.

2. Nature of Ligands
Different ligands cause different amount of repulsion. Split 3d orbitals into
different energy gaps. Different wavelengths of light being absorbed.
Different colours observed.
Catalytic Activity Heterogeneous (Adsorption, Reaction, Desorption)
- Presence of partially filled d-orbitals
- Act as e- acceptors
- Weak interactions formed between reactant particles and catalyst surface
- Lowering activation energy

Homogeneous
- Interconversion of O.S enables ions of transition elements to provide
chemical reactions with an alternative pathway of lower AE.






Transition Metal Formula O.N Colour



V
(V(H2O)6)2+ +2 Purple
(V(H2O)6)3+ +3 Green
VO 2+ +4 Blue
VO2 + +5 Yellow



Cr
(Cr(H2O)6)3+
+3
Green
(Cr(OH)6)3- Dark Green
CrO4 2-
+6
Yellow
Cr2O7 2- Orange


Mn
(Mn(H2O)6)2+ +2 Pale Pink/ Colourless
MnO2 +4 Brown ppt
MnO4 - +7 Purple




Fe
(Fe(H2O)6)2+ +2 Pale Green
Fe(OH)2 +2 Dirty Green ppt
(Fe(H2O)6)3+

+3
Yellow
Fe(OH)3 Reddish Brown ppt
(Fe(SCN)(H2O)5) 2+ Blood Red




Cu
CuCl, CuI +1 White ppt
(Cu(H2O)6) 2+


+2
Blue
Cu(OH)2 Pale Blue ppt
(Cu(NH3)4)2+ Deep Blue
(CuCl4) 2- Yellow