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Transition Metal Chemistry

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

Cr [Ar] 3d54s1 95Am [Rn]5f77s2


Location in the periodic table
3d series (1st transition series) in period 4
21Sc to 30Zn

4d series (2nd transition series) in period 5


39Y to 48Cd

5d series (3rd transition series) in period 6


57La, 72Hf to 80Hg

6d series (4th transition series) in period 7


89Ac, 104Rf to 118Uuo

Only the chemistry of 3d, 4d,and 5d elements is of


importance.
Electronic Configurations
1st series [Ar]3d1-10 4s2
2nd series [Kr]4d1-10 5s2
3rd series [Xe]4f145d1-10 6s2

The electronic structures of the 2nd and 3rd rows do


not always follow the pattern of the first row. For
example, in group 6, Cr and Mo have d5s1 outer
configuration but W has the expected d4s2
structure. The structures of group 10 elements are:
Ni [Ar]3d8 4s2
Pd [Kr]4d10 5s0
Pt [Xe]4f145d9 6s1
Common Characteristic properties
1. They are all metals characterized by
good electrical and thermal conductivities.
high tensile strength,
high densities
high melting and boiling points.
Explanation
These may be attributed to the ability of the d
orbital electrons to delocalise within the metal
lattice in metallic bond formation.
Common Characteristic properties
2. They show variable oxidation states in their
compounds. These vary in steps of 1 rather 2
as seen in some main group elements. E.g.
Cr2+, Cr3+, Cr4+, Cr5+
Explanation
They are able to use the d and s electrons for
bonding without a high energetic penalty.
Their d orbitals have capacity to participate in
covalent bonding in higher oxidation states
covalent contribution is possible in this block
Common Characteristic properties
2. They have unparalleled propensity for
forming coordination compounds with Lewis
bases.
Explanation
they form small highly charged ions that
attract and hold ligands.
they possess vacant low-energy orbitals that
can accept the lone pairs of electrons donated
by the ligands.
Other properties
Majority form coloured compounds e.g. KMnO4
is deep purple, K2Cr2O7 is orange, [Ni(NH3)6]2+ is
blue while [Ni(H2O)6]2+ is green etc.
They or their compounds are often good
industrial or even biological catalysts; e.g. Ni is
margarine making, V2O5 in Contact process etc.
They form compounds which are often
paramagnetic. E.g. Fe, Co, Ni compounds etc.
Variable Oxidation the first series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d14s2 3d24s2 3d34s2 3d44s2 3d54s2 3d64s2 3d74s2 3d84s2 3d94s2 3d104s2
3d54s1 3d104s1
1 1
2 2 2 2 2 2 2 2 2 2
3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4
5 5 5 5 5
6 6 6
7
The metals can use the penultimate (n-1)d and valence ns
electrons for bonding without a high energetic penalty.
Group oxidation state is possible for the first five elements
due to high 3rd I.E
Variable Oxidation
Similar but not identical trends in oxidation
states occur in the second and third transition
series elements. The main difference is as
follows:
In group 8 (iron group) the second and third row
elements show a maximum oxidation state of +8
instead of +6 for Fe.
Examples
Ru will form RuO4 which is not possible for any other
element in the series and Os will form OsO4
Stability of the various oxidation states
The stability of +2 oxidation state increases as
we proceed from Sc to Zn in the series i.e. the
reducing power of M2+ ion reduces from left
to right.
Example: The V2+ (vanadous) and Cr2+
(chromous) salts are powerful reducing agents
while the M2+ salts of the other metals to the
right of the series are not. On the contrary, Mn2+
ions are not reducing because of the presence of
half filled d5 orbital.
Stability of the various oxidation states
The stability of +3 oxidation state decreases
on proceeding from Sc to Cu in the series.
Thus, the oxidizing power of the +3 state
increases along the series.
Example: Sc3+ is stable, Ti3+ (3d14s0) is reducing,
since it is readily oxidised to Ti4+ (3d04s0) with a
more spherical electronic configuration. Mn3+
(3d44s0) is oxidising since it is reduced to Mn2+
(3d54s0). On the other hand Fe3+ (3d54s0) is
stable due to the presence of the half-filled 3d
subshell.
Stability of the various oxidation states
The stability of a given lower oxidation state
of different transition metals of a given
group decreases as we descend the
subgroup.
Example: Cr2+ is more stable than Mo2+ and
W2+. Thus compounds containing elements of
2nd and 3rd series in which the metal is in low
oxidation state (+2 or +3) are not common or
do not form
See oxides and halides.
Features of stable compounds or oxidation states
They exist at room temperature
They are not oxidized by the air
They are not hydrolyzed by water or water vapour
They do not disproportionate or decompose at
normal temperatures.
Stable oxidation states can be seen in the various
isolable oxides, fluorides, chlorides, bromides and
iodides of the elements.
Oxides of First Series Elements
The highest oxidation state available to an element is generally
usually found among its compounds with oxygen and fluorine
which are the most electronegative elements.

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 - - - -

Notice that only the first four elements La to Os form


oxides in group oxidation states. Low oxidation states
are not stable for these elements except La and Re.
High atomization enthalpy may be the reason for the
instability of Low oxidation states.
Fluorides of first and second series elements
Oxidn Sc Ti V Cr Mn Fe Co Ni Cu Zn
state

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 - - - - -

The low oxidation state fluorides are not stable whereas


high oxidation state fluorides for these elements are
stable.
Deductions from the Tables

The first five elements to the left of each


transition series can attain the maximum
possible oxidation state (or group oxidations
state) while at the right of the series oxidation
state +2 becomes dominant.
This may be attributed to the increase in the third
and higher ionization energies with increasing
atomic number across the series and the
increasingly core-like nature of the d orbitals.
Deductions from the Tables
In the first series the maximum oxidation state
attained with oxygen is +7 in Mn2O7 while
with fluorine the maximum is +6 with CrF6. On
the other hand, in the 2nd and 3rd series the
maximum oxidation state attained with
oxygen is +8 in RuO4 and OsO4, respectively
while with fluorine the maximum oxidation
state attained is +7 in ReF7.
Contributions of covalency
The contribution to bonding from covalency is important in
explaining the stability of high oxidation states because
ionic bonding alone could not provide the energy needed to
form the high oxidation state ions.
Reasoning
As the oxidation state increases, the cost in increased total
ionization enthalpy cannot be met from a purely ionic bonding
model and covalent interactions must contribute.
Example:
In OsO4, although the formal oxidation state of Os is +8, it is
not reasonable to assume that the molecule contains Os8+,
just as we would not normally describe CO2 as containing C4+.
Contributions from Covalency
As the cationic charge increases and the ionic radius
decreases, the cation becomes more and more polarizing
and hence more and more able to distort the electron
cloud around the counter ion such that the appropriate
bonding model becomes less ionic and more covalent.

Where contribution from covalency is limited or absent


as in the case of the lanthanides, high oxidation states
are not possible. In the lanthanide Ln3+ ions the 5d
orbitals are empty and electrons in the core-like 4f
orbitals are unable to enter into covalent bonding to
any significant extent.
Ionic/covalent character of compounds of transition metal
Covalent character increases with increase in
oxidation state of the metal.
Example
VCl2 is ionic, VCl3 is less ionic while VCl4 and VCl5 are
covalent.
Explanation
As the oxidation state of the metal increases, the
charge density on the metals also increases,
polarising power also increases and hence increased
polarisation of the anion charge cloud by the metal
ion. Covalent character increases as a consequence
(see Fajans rules).
Basic/acidic character of transition metal compounds
The compounds of a given transition metal
become more and more acidic as the
oxidation state of the metal increases.
V VO V2O3 VO2 V2O5
Oxides
Oxid state +2 +3 +4 +5
of V
Nature Basic Basic Amphoteric Acidic
Cr oxides CrO Cr2O3 CrO2 CrO3
Oxid state +2 +3 +4 +6
Nature of Basic Amphoteric Amphoteric Acidic
the oxide
Mn oxides MnO Mn3O4 Mn2O3 MnO2 MnO3 Mn2O7
Oxid state +2 +8/3 +3 +4 +6 +7
Nature Basic Amphoteric Amphoteric Amphoteric Weakly Strongly
acidic acidic
Catalytic Properties of transition elements
They are able to form numerous oxidation states,
and as such, are able to form unstable
intermediate compounds during a reaction
providing an alternative route with a lower overall
activation energy.
Example
V2O5 is used as a catalyst in the oxidation of SO2 to SO3
in the contact process
V2O5 V2O4 + O
SO2 + O SO3
2V2O4 + O2 V2O5
Catalytic Properties of transition elements
In other cases the metal may provide a suitable
reaction surface that coordinates the reactants
allowing them to react.
Finely divide Ni used in various hydrogenation
processes. For example, hydrogenation of alkenes
to alkanes in the Sabatier process:
Ni /410oC CH3 CH3
CH2 CH2 + H2

This finds use in the hardening of oils saturation


Examples of Catalysts
Catalyst Application
TiCl3 Ziegler-Natta catalyst in production of polyethene
V2O5 Converts SO2 to SO3 in the contact process
MnO2 Catalyst to decompose KClO3 to give O2
Fe In the Haber-Bosch process for making NH3
FeCl3 Production of CCl4 from CS2 and Cl2
FeSO4 and H2O2 Fentons reagent for oxidizing alcohols to aldehyde
PdCl2 Wacker process for converting C2H4 to CH2CHO
Pd Hydrogenation reactions e.g. phenol to
cyclohexanone
Pt In car exhaust fumes converters
Cu Direct process for manufacture of (CH3)2SiCl2 used
to make silicones
Metal Enzyme/metalloprotein Biological function
Mo Xanthine oxidase Metabolism of purines
Nitrate reductase Utilization of nitrates
Mn2+ Arginase Urea formation
Phosphotransferases Adding or removing PO43-
Fe2+ or Fe3+ Aldehyde oxidase Oxidation of aldehydes
Catalase Decomposes H2O2
Decomposes H2O2
Cytochromes Electron transfer
Ferredoxin Photosynthesis
(Haemoglobin) O2 transport in higher animals
Succinic dehydrogenase Aerobic oxidation of carbohydrates
Fe and Mo Nitrogenase Fixation or dinitrogen
Co Glutamic mutase Metabolism of amino acids
Ribonucleotide reductase Biosynthensis
Biological roles of some metals
Cu+ or Cu2+ Amine oxidase Oxidation of amines
Ascorbic oxidase Oxidation of ascorbic acid
Cytochrome oxidase Principal terminal oxidase
Galactose oxidase Oxidation of galactose
Lysine oxidase Elasticity of aortic wall
Dopamine Producing noradrenaline to generate nerve
hydroxylase impulses in the brain
Tyrosinase Skin pigmentation
Ceruloplasmin Utilization of Fe
(Haemocyanin) O2 transport in invertaebrates
Plastocyanine Photosynthesis
Zn2+ Alcohol Metabolism of alcohol
dehydrogenase
Alkaline phosphatase Releasing PO43-
Carbonic anhydrase Regulation of PH and CO2 formation
Carboxypeptidase Digestion of proteins
Colour in Transition metal compounds
Colour of Clear Violet Blue/blue Green yellow Orange Red red-
solution green purple
Absorbed Ultra yellow Orange/ Purple Violet Blue Blue/ green
colour violet red green
(nm) <400 400 500 530 580 610 680 700
absorbed
Origin of Colour

(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

Some values are positive while other are negative.


A large negative value of E implies that the
reduced form of the couple is a good reducing
agent.
Example
V2+ +2e- V Eo = -1.19 V,
Thus, V is a good reducing agent i.e. the
backward reaction is more favourable.
(Compare, Cu2+ +2e- Cu Eo = +0.34V)

A large positive value of Eo implies that the


oxidized form of the couple is a good oxidizing
agent.
Example: Co3+ + e- Co2+ Eo = +1.84
It shows that the Co3+ is a good oxidizing agent.
Applications
The oxidized form of a couple will oxidize the
reduced form of a second couple if the Eo value of
the first couple is more positive than that of the
second couple.
Example: consider the two half-reactions:
H2O2(aq) + 2H+(aq) + 2e- 2H2O(l) Eo = +1.76 V

3+
Fe (aq) + e - Fe2+(aq) Eo = +0.77 V

Hydrogen peroxide will oxidize iron(II) to iron (III):


H2O2(aq) + 2H+(aq) + 2Fe2+ 2Fe3+(aq) + 2H2O(l)

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

Follow the trends of the atomic radii both


across the periods and down the groups.
Decrease with increasing oxidation state. E.g.
Ti2+> Ti3+> Ti4+ etc. Thus, the metal ions
become more and more polarizing with
increase in oxidation state.
c) Metallic character and related properties

Many of the metals are sufficiently electropositive to react


with mineral acids, liberating H2.
A few however, have low standard electrode potentials (less
negative) and remain unreactive or noble. This noble
character is most pronounced for the platinum group of
metals (Ru, Rh, Pd, Os, Ir and Pt).
Noble character is favoured by high enthalpies of
sublimation, high ionization energies and low enthalpies of
solvation. The smaller atoms have high ionization energies
but these are offset by the high solvation enthalpies of the
corresponding smaller ions.
Trends in Metallic Character

Decreases across a period


increases on descending the group.
Example:
The basic character of the pentoxides of the
elements of group 5 (V2O5, Nb2O5, and Ta2O5)
increases in the order V2O5 < Nb2O5 < Ta2O5; i.e.
increases down the group with increasing ionic size
of the cation.
(i) Electrical and thermal conductivity
These elements are good conductors due to availability of
mobile electrons involved in metallic bonding. Cu, Ag and Au
have exceptionally high thermal and electrical conductivities.
(ii) Hardness
Transition elements are generally hard (cannot be cut with a
knife) and are brittle.
The hardness can be attributed to strong metallic bonds between
the atoms. For example, since Cr, Mo and W have the maximum
number of unpaired electrons, they are very hard. Zn, Cd and Hg
have no unpaired electrons and hence are not very hard.

(iii) Crystal structure


Transition elements adopt simple hexagonal close-packed
(hcp), cubic close-packed (ccp), and body centred cubic (bcc),
lattices which are characteristic of metals.
(iv) Alloy formation
Generally many transition metals have almost the
same size and hence atoms of one metal can be
replaced with atoms of another metal. This
replacement leads to the formation of alloys.
Example: when manganese is dissolved in molten
iron and the solution the manganese iron alloy is
formed. Alloys are hard, have high melting points
and are mostly more resistant to corrosion. Such
properties are sought after in certain industrial or
engineering applications.
(d) Atomic volumes and Densities

The atomic volumes of transition elements are


generally lower than those of the elements of the
s-block.
We know that density and atomic volumes are inversely
proportional to each other. Thus, transition metals have high
densities (> 5 gcm-3 except Sc 3.0 gcm-3 and Y and Ti 4.5 gcm-3).
The densities increase across the periods (See Table 10).
(d) Atomic volumes and Densities
The densities increase as well down the Groups.
The densities of third transition series elements
are almost double those of the 2nd series
elements.
This is because the atomic weights of the elements of
the 3rd series are also almost double those of the 2nd
transition series. Because of the lanthanide
contraction the atomic volumes of 3rd transition series
become very small. Consequently the packing of the
atoms in their metallic crystals become so much
compact that their densities become very high.