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SCH 400
Dr. Evans C. Ogwagwa
Objectives of the course
To describe the chemistry of the transition
elements
To explain the principles that underlie the
chemistry of the transition elements
To highlight the catalytic and other industrial
uses of the transition elements
To highlight the biological roles of the transition
metals
The Periodic Table Blocks
Definitions
A transition element is one whose atom has
an incomplete d sub-shell, or one which can
give rise to cations with an incomplete d sub-
shell.
Examples:
Sc [Ar]3d14s2 Sc3+ [Ar]
(n-1) d orbitals are
Ti [Ar] 3d24s2 Ti2+ [Ar]3d2 progressively filled up
Cr [Ar] 3d54s1 Cr3+ [Ar]3d4 with electrons
Cu2+ [Ar]3d9
Cu [Ar] 3d104s1
Zn2+ [Ar]3d10
Zn [Ar] 3d104s2
Exceptions
Cu, Ag and Au qualify to be transition elements
because
They form compounds in more than one oxidation state
In their common oxidation state, their cations have partially
filled or incomplete d subshell.
Zn, Cd and Hg are by definition not transition
elements because:
their d subshells are full both in elemental and ionic state
in most cases they form compounds in only one oxidation
state.
Alternate Definition
A transition element is one whose atom has a
partially filled d or f sub-shell or which can
give rise to cations with a partially filled d or f
sub-shell. This includes the f-block elements
(also known as the inner transition elements.
Examples
Sc [Ar]3d14s2 58Ce [Xe]4f15d16s2
Ti [Ar] 3d24s2 63Eu [Xe]4f76s2
Oxid Sc Ti V Cr Mn Fe Co Ni Cu Zn
state
1 - - - - - - - - Cu2O
2 - TiO VO - MnO FeO CoO NiO CuO ZnO
3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3 Co3O4 - - -
4 - TiO2 VO2 CrO2 MnO2 - - NiO2 - -
5 - - V2O5 - - - - - -
6 - - - CrO3 - - - - - -
7 - - - - Mn2O7 - - - - -
Oxides of second series Elements
Oxidn Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
state
1 - - - - - - - - Ag2O -
2 - - NbO - - - PdO AgO CdO
3 Y2O3 - - - - - Rh2O3 Pd2O3 - -
4 - ZrO2 NbO2 MoO2 TcO2 RuO2 RhO2 PdO2 - -
5 - - Nb2O5 Mo2O5 - - - - -
6 - - - MoO3 TcO3 - - - - -
7 - - - - Tc2O7 - - - - -
8 - - - - - RuO4 - - - -
Oxides of Third series elements
Oxidn La Hf Ta W Re Os Ir Pt Au Hg
state
2 - - - - ReO - - - - HgO
3 La2O3 - - - Re2O3 - Ir2O3 Pt2O3 Au2O3 -
4 - HfO2 TaO2 WO2 ReO2 OsO2 IrO2 PtO2 - -
5 - - Ta2O5 Re2O5 - -
6 - - WO3 ReO3 OsO3 IrO3 PtO3 - -
7 - - - - Re2O7 - - - - -
8 - - - - - OsO4 - - - -
1 - - - - - - - - - -
2 - - VF2 CrF2 MnF2 FeF2 CoF2 NiF2 CuF2 ZnF2
3 ScF3 TiF3 VF3 CrF3 MnF3 FeF3 CoF3 - - -
4 - TiF4 VF4 CrF4 MnF4 - - - - -
5 - - VF5 CrF5 - - - - - -
6 - - - CrF6 - - - - - -
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
1 - - - - - - - - AgF -
2 - - - - - - - PdF2 AgF2 CdF2
3 YF3 ZrF3 NbF3 MoF3 - RuF3 RhF3 - - -
4 - ZrF4 NbF4 MoF4 - RuF4 RhF4 PdF4 - -
5 - - NbF5 MoF5 - RuF5 RhF5 - - -
6 - - MoF6 TcF6 RuF6 RhF6 - - -
Fluorides of the Third transition series elements
Oxidn La Hf Ta W Re Os Ir Pt Au Hg
state
1 - - - - - - - - - Hg2F2
2 - - - - - - - - - HgF2
3 LaF3 - - - - - IrF3 - AuF3 -
4 - HfF4 - - ReF4 OsF4 PtF4 - -
5 - - TaF5 - ReF5 OsF5 IrF5 PtF5 AuF5 -
6 - - - WF6 ReF6 OsF6 IrF6 PtF6 - -
7 - - - - ReF7 - - - - -
(i) Polarization
E.g. AgCl, is also colourless but on the other
hand AgBr is pale yellow and AgI is yellow. The
colour arises because Ag+ polarizes the halide
ions making ligand-to-metal charge transfer
easy and of low energy (in the visible range).
This is also why Ag2CO3 and Ag3PO4 are
coloured yellow and Ag2O and Ag2S are black.
(ii) Incomplete d-subshell
The nature of the metal ion, specifically the
oxidation state of the metal e.g. Fe2+ is pale-
green while Fe3+ is rusty brown
The arrangement of the ligands around the
metal ion (for example geometric isomers can
display different colours).
The nature of the ligands surrounding the metal
ion. The stronger the ligands then the greater
the energy difference between the split high and
low d groups. For example [Ni(NH3)6]2+ is blue
while [Ni(H2O)6]2+ is green, etc.
Standard Reduction Potentials
Ti V Cr Mn Fe Co Ni Cu
M2+ + 2e- = M - -1.19 -0.91 -1.18 -0.44 -0.28 -0.24 +0.34
M3+ + e- = M2+ -0.37 -0.25 -0.41 +1.59 +0.77 +1.84 - -
Colour M2+(aq) - Violet Sky Pale Pale green Pink Green Blue
blue pink green
Colour M3+(aq) Violet Blue Violet Brown v. pale Blue - -
purple
3+
Fe (aq) + e - Fe2+(aq) Eo = +0.77 V
Explanation
The overall Eo value is +1.76 - 0.77 = 0.99 V, which
being positive makes the Gibbs energy change
negative and the reaction thermodynamically
feasible. (Remember Go = -nEoF)
It is however, important to note that although a
reaction is thermodynamically feasible, it might
be slow for kinetic reasons.
Physico-chemical Properties of
Transition Elements
a) Atomic (covalent) radii
Atoms of the transition elements are smaller
than those of Group 1 or 2 in the same period
Reason:
Partly because of the usual contraction in size
across a horizontal period discussed below, and
partly because the orbital electrons are added to
the penultimate d shell instead of the outer shell
of the atom
Atomic Radii Trends
Sc Ti V Cr Mn Fe Co Ni Cu Zn
144 132 122 118 117 117 116 115 117 125
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
162 145 134 130 127 125 125 128 134 148
La ** Hf Ta W Re Os Ir Pt Au Hg
169 144 134 130 128 126 127 130 134 149
Across the series the radii generally decrease.
The observed increase in atomic radii at the end of each
series is attributed to increased electron-electron
repulsion between the electrons being paired in the d
orbitals.
Lanthanide contraction
Down the groups the atomic radii generally increase
due to the increase in the number of electron sub-
shells. The increase is not regular.
Examples:
The elements in the first group show the expected
increase in size Sc Y La.
Groups 4 12 there is an increase in radius of 0.1
0.2 between the first and second member, but hardly
any increase between the second and third elements.
This is attributed to Lanthanide contraction the
general decrease in atomic radii of the f-block
lanthanide elements between the 2nd and 3rd transition
series.
Effects of the Lanthanide contraction
The atomic radii of the lanthanides are smaller
than would normally be expected.
The covalent and ionic radii of the second and
third transition series elements are similar. As
a result they have similar lattice energies,
solvation energies and ionization energies.
Elements of 2nd and 3rd transition series
elements are significantly different from those
of the first transition series.
Effects of the Lanthanide contraction
The radii of the elements following the lanthanides
are smaller than would be expected if there were no
f-transition metals.
There is a general trend of increasing Vickers
hardness, Brinell hardness, density and melting point
from cerium to lutetium (with ytterbium being the
most notable exception). Lutetium is the hardest and
most dense lanthanide and has the highest melting
point.
b) Ionic Radii