Chemistry
Lecture 9 By: Syed Ali Shan
Transition Elements
Outline:
General characteristics
Transition Elements
The elements which have partially filled d or f orbitals either in atomic state or any of their
possible oxidation state
They called transition because their properties are transition between s-block and p-block
Inner transition elements f-block
1st inner transition series [Cerium (Ce) to Lutetium (Lu)] called lanthanides
2nd inner transition series [Thorium (Th) to Lawrencium (Lr)] called actinides
Outer transition elements d-block
1st outer transition series 3d [Scandium (Sc) to Zinc (Zn)]
2nd outer transition series 4d [Yttrium (Y) to Cadmium (Cd)]
3rd outer transition series 5d [Lanthanum (La) to Mercury (Hg)]
4th outer transition series 6d [Actinium (Ac) to onwards] not complete
Non-typical IIB (Zn,Cd, Hg) and IIIB (Sc, Y, La)
Typical All others
Valence shell configuration of d-block elements (n-1)d1-10 s1-2
IB (Cu, Ag, Au) Coinage metals
3d-series electrons are firstly filled in them compared to other transition series
General Features
They all metallic in nature
Some of the transition elements play important role in industry i.e. Ti, Cr, Fe, Cu, Mo, W, Zr, Nb,
Ta, Th etc
Hard and strong metals with high M.P and B.P
Good conductors of heat and electricity
They form alloys
With few exception, show variable oxidation state
Their ions and compounds are coloured in solid and solution state
Elements and their compounds are used as catalysts
They form complexes (coordination compounds)
Tough, malleable and ductile
Electronic Structures of 3d
3d- Electronic es-1 s- Electrons in d-orbital No. of Oxidation
elements configuration orbital d-subshell has total 5 orbital Unpaired es-1 states
in s & d
21Sc 18[Ar], 4s2, 3d1 ⇃↾ ↾ s=0 d=1 2, 3
2 2
22Ti 18[Ar], 4s , 3d ⇃↾ ↾ ↾ s=0 d=2 2, 3, 4
2 3
23V 18[Ar], 4s , 3d ⇃↾ ↾ ↾ ↾ s=0 d=3 2 to 5
1 5
24Cr 18[Ar], 4s , 3d ↾ ↾ ↾ ↾ ↾ ↾ s=1 d=5 2 to 6
2 5
25Mn 18[Ar], 4s , 3d ⇃↾ ↾ ↾ ↾ ↾ ↾ s=0 d=5 1 to 7
2 6
26Fe 18[Ar], 4s , 3d ⇃↾ ⇃↾ ↾ ↾ ↾ ↾ s=0 d=4 1 to 6
2 7
27Co 18[Ar], 4s , 3d ⇃↾ ⇃↾ ⇃↾ ↾ ↾ ↾ s=0 d=3 2 to 5
2 8
28Ni 18[Ar], 4s , 3d ⇃↾ ⇃↾ ⇃↾ ⇃↾ ↾ ↾ s=0 d=2 2 to 4
1 10
29Cu 18[Ar], 4s , 3d ↾ ⇃↾ ⇃↾ ⇃↾ ⇃↾ ⇃↾ s=1 d=0 1 to 3
2 10
30Zn 18[Ar], 4s , 3d ⇃↾ ⇃↾ ⇃↾ ⇃↾ ⇃↾ ⇃↾ s=0 d=0 2
Transition elements usually show highest O.S in fluorides and oxides i.e. KMnO4 (Mn = +7) , CrF6
(Cr = +6)
Oxides in low O.S are basic
Oxides in high O.S are acidic
Binding Energy
Electrons of s-orbital and half filled d-orbitals take part in binding
Binding energy ∝ No. of unpaired electrons in d-orbitals
Increases across the period due to increase in binding electrons upto V-B and VI-B
Maximum binding energy is of V and minimum is of Zn
W (tungsten) has highest in 5d series and lowest is of Hg
M.P/B.P
Directly related to binding forces (binding electrons)
Increases up to ‘V’ and then decreases onwards till ‘Zn’ (minimum)
Highest M.P is of V and lowest is of Zn
Mn shows abnormality in M.P due to stable configuration (half filled d-subshell) [change in
structure]
W (tungsten) has highest in 5d series and lowest is of Hg
Covalent Radius and Ionic Radius
Covalent radii decreases rapidly at the start, then becomes almost constant finally begin to
increase at the end of the series
This is possibly due to increase in shielding effect of 3d-orbitals
Ionic radii are much less regular
See graph from book to see the change only
Paramagnetism
A substance weakly attracted by magnetic field
Paramagnetism: Due to presence of unpaired electrons
Paramagnetism ∝ No. of unpaired electrons
Mn+2 and Fe+3 has maximum unpaired electrons (5 each), have maximum Paramagnetism
A substance having no unpaired electron and is weakly repelled by magnetic field is diamagnetic
The substances which can be magnetized or strongly attracted by magnetic field are
ferromagnetic i.e. Fe, Co, Ni
Magnetic moment (𝜇) = √n(n + 2) (n represents number of unpaired electrons)
Measured in Bohr magneton (BM) and predicts nature and oxidation state of metal compounds
Oxidation state
Apparent charge on an atom
+2 is common O.S (when only electrons of s-orbital are involved)
Electrons of both ‘s’ and ‘d’ (unpaired) participate while giving the highest O.S
Color of Transition Metal Complexes
If all the incident radiation is absorbed, then the substance looks black
If all the incident radiation is reflected then the substance looks white
If only a very small proportion of the incident white light is absorbed and if all the radiations in
the visible region of spectrum are transmitted equally then the substance will appear colorless
For color:
Presence of unpaired electrons (incomplete d-subshell)[Main factor]
Nature of ligand (cause splitting of d-orbitals)
Ligand splits the d-orbitals into two energy levels
2 of higher and 3 of lower energy
Electrons residing in lower energy level absorb part of visible light and jumps to higher energy
level (called d-d transition)
Every ion absorbs different wavelength while transmits other (gives color)
[Ti(H2O)6]+3 absorbs yellow light and transmits blue + red = violet
Complementary color scheme: (VBGYOR)
Red ⟺ Green
Blue ⟺ Orange
Yellow ⟺ Violet
Interstitial Compounds
Small non metals i.e. H, B, C, N fill the interstices of transition elements
Impart useful features to metal
These are non-stoichiometric compounds
No bond formed
Also termed as interstitial alloys
Alloy Formation
Homogeneous mixture of two or more than metals forming substitutional alloy
Owing to similar size, some transition metal atoms are able to replace one another
Properties
Stoichiometric compounds
Alloys are comparatively cheap
Strong and flexible but hard alloys can be prepared
Don’t corrode (long life)
High M.P, better conductors but non-conductor alloys can also be prepared
Examples Steel (iron atoms are substituted by Cr, Mn and Ni)
Uses as a Catalyst
Transition elements and their compounds are catalyst due to;
Presence of partially or vacant d-orbitals
Defects in crystal lattices
Exhibit variable O.S
Form reaction intermediates which decompose
Form interstitial compounds which can adsorb an activator to reacting species
Some Examples:
Fe in Haber process of ammonia synthesis
Ni, Pt, Pd in Hydrogenation
MnO2 for decomposition of H2O2
Cu in preparation of benzene form acetylene and oxidation of alkanes (synthesis of fatty acids)
FeX3 in halogenation of aromatic compounds
ZnCl2 in preparation of alkyl halides from alcohols
ZnO + Cr2O3 in prep. of methanol from water gas
TiCl4 + Al(C2H5)3 better quality of polythene
V2O5/Pt in contact process
Mo is also sometimes used as a promoter
Formation of Complexes
Due to small size of metal cation
Due to high charge of metal cation
Due to availability of vacant d-orbital
Central Metal Atom:
Atom to which ligands are attached
Fe is central metal atom in K4[Fe(CN)6]
Ligands:
Species attached to central metal atom and donating electron pair to metal
CN is ligand in K4[Fe(CN)6] and are 6 in strength
Neutral Ligands: NH3 (amine), H2O (aqua), CO (carbonyl), N2H4 (hydrazine), H2N-CH2-CH2-NH2
(ethylene diammine (en))
Negative Ligands: CN-1 (cyano), Cl-1 (chloro), F-1 (fluoro), NO2-1 (nitro), OH-1 (hydroxo), CO3-2
(carbonato), CH3COO-1 (acetato), -1OOC-COO-1 (oxalato) [ending name with ‘O’]
Positive Ligands: NH2NH3+ (Hydrazinium), NO+ (Nitrosonium)
Monodentate Ligands: Only donating one electron pair to metal i.e. NH 3, H2O, CN-1, Cl-1, NO2-1,
OH-1 etc
Bidentate Ligands: Donate two electron pairs to metal i.e. N2H4, CO3-2, -1OOC-COO-1,
H2N-CH2-CH2-NH2
Tridentate Ligands: H2N-CH2-CH2-NH-CH2-CH2-NH2 (diethylene triammine)
Hexadentate Ligands: EDTA (Ethylenediaminetetraacetate ion)
Coordination Sphere: Square brackets containing both metal atom and ligands.
Charge on Coordination Sphere: Charge present on metal ion + total charge on the ligands i.e. in
K4[Fe(CN)6], charge on coordination sphere = -4
Coordination Number: Total no. of electron pairs donated by ligands to metal atom i.e. in K4[Fe(CN)6],
coordination number = 6
Most common coordination number in the complex compounds is 6 (most common geometry is
octahedral)
Chelate:
All the donor atoms of polydentate ligand get
coordinated with metal ion, a complex is formed
consisting of one or more rings called chelate
Two 5-membered rings
Coordination no. = 4
Nomenclature:
Name of cation followed by anion
Name of Coordination sphere (can be cation or anion):
Name of ligand + name of metal
Different ligands are named alphabetically regardless of their nature
If same ligand, use prefixes di, tri, tetra etc
Metal name ends with “ate”(suffix) if charge on coordination sphere is negative
otherwise remains same
Name of metal is followed by its O.S written in Roman numerals
For example K4[Fe(CN)6] Potassium hexacyano ferrate (II)
In writing the formula, [metal + negative ligands (alphabetically) + neutral ligands
(alphabetically)]
Geometry and Isomerism of Complex ions with Coordination Number 4 and 6
Geometry:
Common geometry is octahedral
Factors affecting geometry:
No. of electron pairs donated by ligands
Hybridization state of metal
Nature of ligand
No. of e- pairs Hybridization Geometry
2 sp Linear
3 sp2 Triangular
4 sp3 Tetrahedral
dsp2 Square planner
5 dsp3/sp3d Trigonal bipyramidal
6 d2sp3/sp3d2 Octahedral
Square planner: [Cu(NH3)4]+2, [Pt(NH3)4]+2, [AuCl4]-1, [Ni(NH3)4]+2, [Ni(CN)4]-2, [PdCl4]-2, [Cu(en)2]+2,
[Ni(dmg)2]0 {dmg stands for dimethylglyoximate ion (-ONC(CH3)C(CH3)NOH) a bidentate ligand
Tetrahedral: [MnCl4]-2, [CuCl4]-2, [ZnCl4]-2, [Cu(CN)4]-2, [Hg(CN)4]-2, [Ni(CO)4]0, [FeCl4]-, [ZnBr4]-2,
[CuX4]-2(X = Cl-, Br-, CNS-), [Zn(CN)4]-2, [Zn(NH3)4]-2
Oxyanions such as VO4-3, CrO4-2, FeO4-2, MnO4- also give tetrahedral.
