TRANSITION METALS: d AND f

BLOCK
CONTENTS
1. Introduction
2. Physical properties and occurrence
3. Chemical properties

INTRODUCTION
The elements of d- and f- blocks of periodic table are commonly known
as transition and inner transition elements respectively. The three
series:
i) Sc to Zn,
ii) Y to Cd and
iii) La to Hg (excluding the elements Ce to Lu)
mainly constitute the three transition series, while the lanthanoids and
actinoids form the inner transition elements. The presence of partly
filled d or f orbitals in these elements sets the study of these elements
and their compounds apart from that of the main group elements.
However, the usual valence theory as applicable to the main group
elements also holds for the transition elements. The transition
elements include precious metals such as silver, gold and platinum and
industrially important metals like iron, copper and titanium.
The two terms d-block metal and transition metal are often used
interchangeably; however, they do not mean the same thing. The name
transition metal originally derived from the fact that their chemical
properties were transitional between those of the s and p blocks. Now,
however, the IUPAC definition of a transition element is that it is an
element that has an incomplete d subshell in either the neutral atom or
its ions. Thus the Group 12 elements (Zn, Cd, Hg) are members of the d
block but are not transition elements. In the following discussion, it will
be convenient to refer to each row of the d block as a series, with the
3d series the first row of the block (Period 4), the 4d series the second
row (Period 5), and so on. It will prove important to note the intrusion
of the f block, the inner transition elements, the lanthanoids, into the
5d series. Elements towards the left of the d block are often referred to
as early and those towards the right are referred to as late.

PHYSICAL PROPERTIES AND OCCURRENCE

Key point: Chemically soft members of the block occur as sulfide
minerals and are partially oxidized to obtain the metal; the more
electropositive hard metals occur as oxides and are extracted by
reduction.

The elements on the left of the 3d series occur in nature primarily as

metal oxides or as metal cations in combination with oxoanions.
1. Of these elements, titanium ores are the most difficult to reduce,
and the element is widely produced by heating TiO2 with chlorine
and carbon to produce TiCl4, which is then reduced by molten
magnesium at about 1000C in an inert-gas atmosphere.
2. The oxides of Cr, Mn, and Fe are reduced with carbon, a much
cheaper reagent.
 3. To the right of Fe in the 3d series, Co, Ni, Cu, and Zn occur mainly
as sulfides and arsenides, which is consistent with the increasingly
soft Lewis acid character of their dipositive ions. Sulfide ores are
usually roasted in air either to the metal directly (for example, Ni)
or to an oxide that is subsequently reduced (for exam- ple, Zn).
4. Copper is used in large quantities for electrical conductors;
electrolysis is used to refine crude copper to achieve the high
purity needed for high electrical conductivity.
5. The difficulty of reducing the early 4d and 5d metals Mo and W is
apparent. It reflects the tendency of these elements to have
stable high oxidation states, as discussed later.
6. The platinum metals (Ru and Os, Rh and Ir, and Pd and Pt), which
are found at the lower right of the d block, occur as sulfide and
arsenide ores, usually in association with larger quantities of Cu,
Ni, and Co. They are collected from the sludge that forms during
the electrolytic refinement of copper and nickel.
7. Gold (and to some extent silver) is found in its elemental form.

Nearly all the transition elements display typical metallic properties

such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity, and metallic lustre. Except mercury which is a
liquid at room temperature, other transition elements have typical
metallic structures. Their melting and boiling points are high. Table 1
depicts the melting points of the 3d, 4d, and 5d transition metals. The
high melting points are attributed to strong interatomic bonding, which
involves the participation of both ns and (n-1) d electrons. In any row,
the melting points of these metals rise to a maximum at d6 except for
anomalous values of Mn and Tc and fall regularly as the atomic number
increases. With the exception of zinc, cadmium and mercury, the
transition elements are much harder and less volatile. They exhibit high
enthalpies of atomization; the maxima at about the middle of each
series indicate that one unpaired electron per d orbital is particularly
favourable for strong interatomic interaction. In general, greater the
number of valence electrons, stronger is the resultant bonding. Since
the enthalpy of atomization is an important factor in determining the
standard electrode potential of a metal, those with highest enthalpy of
atomization tend to be noble metals. Another interesting generalization
that may be drawn is that the metals of the second (4d) and third (5d)
series have greater enthalpies of atomization than the corresponding
elements of the first series; this is an important factor for their having
much more frequent metalmetal bonding in their compounds. The
decrease in metallic radius coupled with increase in atomic mass results
in a general increase in the density of these elements. Thus, from
titanium to copper there is increase in density.

Table 1
Element Sc Ti V

Atomic number 21 22 23

Electronic config M 3d14s2 3d24s2 3d34s2

M+ 3d14s1 3d24s1 3d34s1

M2+ 3d1 3d2 3d3

M3+ [Ar] 3d1 3d2
Enthalpy of atomization/kJ mol1 326 473 575
Ionization enthalpy/ kJ mol1 I 631 656 650
 II 1235 1309 1414
III 2393 2657 2833
r/pm M 164 147 135
M2+ 79
M3+ 73 67 64
E0/V M2+/M 1.18
M3+/M2+ -0.26
Density/g cm-3 3.43 4.1 6.07

Element Cr Mn Fe Co
Atomic number 24 25 26 27
Electronic config M 3d54s1 3d54s2 3d64s2 3d74s2
M+ 3d5 3d54s1 3d64s1 3d74s1
M2+ 3d4 3d5 3d6 3d7
M3+ 3d3 3d4 3d5 3d6
Enthalpy of atomization/kJ mol1 397 281 416 425
Ionization enthalpy/ kJ mol1 I 653 717 762 758
II 1592 1509 1561 1644
III 2990 3260 2962 3243
r/pm M 129 137 126 125
 M2+ 82 82 77 74
M3+ 62 65 65 61
E0/V M2+/M 0.90 1.18 0.44 0.28
M3+/M2+ -0.41 +1.57 +0.77 +1.97
Density/g cm-3 7.19 7.21 7.8 8.7

Element Ni Cu Zn
Atomic number 28 29 30
Electronic config M 3d84s2 3d104s1 3d104s2
M+ 3d84s1 3d10 3d104s1
M2+ 3d8 3d9 3d10
M3+ 3d7 3d8 3d9
Enthalpy of atomization/kJ mol1 430 339 126
Ionization enthalpy/ kJ mol1 I 736 745 906
II 1752 1958 1734
III 3402 3556 3829
r/pm M 125 128 137
M2+ 70 73 75
M3+ 60
E0/V M2+/M 0.25 +0.34 -0.76
M3+/M2+
Density/g cm-3 8.9 8.9 7.1

Atomic size:
In general, ions of the same charge in a given series show progressive
decrease in radius with increasing atomic number. This is because the
extra electron enters a d orbital each time the nuclear charge increases
by unity. The shielding effect of a d electron is small, the net
electrostatic attraction between the nuclear charge and the outermost
electron increases and the ionic radius decreases. The atomic radius
also decreases in the same way. The variation within a series is quite
small. An interesting point emerges when sizes of elements in one
series are compared with the sizes of the corresponding elements in
other series. The data shows an increase from the first (3d) to the
second (4d) series of the elements but the radii of the third (5d) series
are virtually the same as those of the corresponding members of the
second series. This phenomenon is associated with the intervention of
the 4f orbitals, which must be filled before the 5d series of elements
begin. The filling of 4f before 5d orbital results in a regular decrease in
atomic radii called lanthanoid contraction which essentially
compensates for the expected increase in atomic size with increasing
atomic number. The net result of the lanthanoid contraction is that the
corresponding elements of second and the third d series exhibit similar
radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar physical and
chemical properties.

Ionisation Enthalpy:
With increasing nuclear charge, which accompanies the filling of the
inner d orbitals, there is an increase in ionization enthalpy along each
series of the transition elements from left to right, but many small
variations occur. Table 1 gives the values for the first three ionization
enthalpies of the first row elements. These values show that although
the first ionization enthalpy, in general, increases, the increase in the
second and third ionization enthalpies for the successive elements are
not of the same magnitude. However, the trend is similar for the
second ionization enthalpies, which for the most part increase
smoothly as the atomic number increases, the exceptions are
chromium and copper for which these values are notably larger than
those of their neighbours. These exceptions are attributed to the extra
stability of half-filled or completely filled set of d orbitals in chromium
and copper. The third ionization enthalpies are quite high and there is a
marked break between the values for Mn2+ and Fe2+. Also, the high
values for copper, nickel and zinc indicate why it is difficult to obtain
oxidation state greater than two for these elements. Although
ionization enthalpies give some guidance concerning the relative
stabilities of oxidation states, this problem is very complex one and not
amenable to ready generalization.

CHEMICAL PROPERTIES

Oxidation Enthalpy:
One of the notable features of a transition element is the great variety
of oxidation states it may show in its compounds. The elements which
give the greatest number of oxidation states occur in or near the
middle of the series. Manganese, for example, exhibits all the oxidation
states from +2 to +7. The lesser number of oxidation states at the
extreme ends stems from either too few electrons to lose or share (Sc,
Ti) or too many d electrons (hence fewer orbitals available in which to
share electrons with others) for higher valence (Cu, Zn). Thus, early in
the series scandium(II) is virtually unknown and titanium(IV) is more
stable than Ti(III) or Ti(II). At the other end, the only oxidation state of
zinc is +2 (no d electrons are involved). The maximum oxidation states
of reasonable stability correspond in value to the sum of the s and d
electrons upto manganese (TiIVO2, VVO2+, CrV1O42, MnVIIO4) followed by
a rather abrupt decrease in stability of higher oxidation states, so that
the typical species to follow are FeII,III, CoII,III, NiII, CuI,II, ZnII. The
variability of oxidation states, a characteristic of transition elements,
arises out of incomplete filling of d orbitals in such a way that their
oxidation states differ from each other by unity, e.g., VII, VIII, VIV, VV.
This should be contrasted with the variability of oxidation states of non-
transition elements where oxidation states normally differ by units of
two.

The range of oxidation states of the d metals accounts for the

interesting electronic properties of many solid compounds, their ability
to participate in catalysis, and their subtle and interesting role in
biochemical processes. In this section we focus on trends in the
stabilities of oxidation states within the d block.
(a) High oxidation states

Key point: The group oxidation state can be achieved by elements

that lie towards the left of the d block but not by elements on the
right. Oxygen is usually more effective than fluorine at bringing
out the highest oxidation states because less crowding is
involved.
The group oxidation state (in which the oxidation number is equal to
the Group number) can be achieved by elements that lie towards the
left of the d block but not by elements on the right. For example, Sc, Y,
and La in Group 3, with configurations nd1(n+1)s2, are found in
aqueous solution only in oxidation state +3, which corresponds to the
loss of all their outermost electrons, and the majority of their
complexes contain the elements in this state. The group oxidation state
is never achieved after Group 8 (Fe, Ru, and Os). This limit on the
maximum oxidation state correlates with the increase in ionization
energy and hence noble character from left to right across each series
in the d block. We see that the group oxidation states of Sc, Ti, and V
fall in the lower part of the diagram. This location indicates that the
element and any species in intermediate oxidation states are readily
oxidized to the group oxidation state. By contrast, species in the group
oxidation state for Cr and Mn (+6 and +7, respectively) lie in the upper
part of the diagram. This location indicates that they are very
susceptible to reduction. The Frost diagram shows that the group
oxidation state is not achieved in Groups 8-12 of the 3d series (Fe, Co,
Ni, Cu, and Zn), and also shows the oxidation states that are most
stable under acid conditions; namely Ti3+, V3+, Cr3+, Mn2+, Fe2+, Co2+, and
Ni2+. The binary compounds of the 3d-series elements with the
halogens and with oxygen also illustrate the trend in stabilities of the
group oxidation states. The earliest metals can achieve their group
oxidation states in compounds with chlorine (for example, ScCl3 and
TiCl4), but the more strongly oxidizing halogen fluorine is necessary to
achieve the group oxidation state of V (Group 5) and Cr (Group 6),
which form VF5 and CrF6, respectively. Beyond Group 6 in the 3d series,
even fluorine cannot produce the group oxidation state, and MnF7 and
FeF8 have not been prepared. Oxygen brings out the group oxidation
state for many elements more readily than does fluorine because fewer
O atoms than F atoms are needed to achieve the same oxidation
number, thus decreasing steric crowding. For example, the group
oxidation state of +7 for Mn is achieved in manganate(VII) salts, such as
potassium permanganate, KMnO4. As can be inferred from the Frost
diagram, chromate(VI) CrO42-, manganate(VII) MnO4-, and ferrate(VI)
FeO42- are strong oxidizing agents and become stronger from CrO42- to
FeO42-. This trend is another illustration of the decreasing stability of
the maximum attainable oxidation state for Groups 6, 7, and 8. Yet
another example of the greater difficulty of oxidizing an element to the
right of Cr to its group oxidation state is that the air oxidation of MnO2
in molten potassium hydroxide does not take Mn to its group oxidation
state but instead yields the deep green compound potassium
manganate(VI), K2MnO4. The disproportionation of MnO42- in acidic
aqueous solution yields manganese(IV) oxide (MnO2) and the deep
purple manganate(VII) ion MnO4-: 3MnO4 2-(aq) + 4H+(aq) 2MnO4-(aq)
+ MnO2(s) + 2H2O(l)
(b) Intermediate oxidation states in the 3d series

Key point: Oxidation state +3 is common to the left of the 3d

series and +2 is common for metals from the middle to the right
of the block.
Most unipositive d-metal ions (M+) disproportionate (to M and M+2)
because the bonds in the solid metal are so strong and, for the 3d
metals, the +2 oxidation state is generally the lowest one it is necessary
to consider in aqueous solution. Exceptions are mainly confined to
metal-metal bonded and organometallic compounds, such as the metal
carbonyls Ni(CO)4 and Mo(CO)6 discussed in Chapter 22, in which the
metal is in oxidation state 0. The second and third ionization energies of
the 3d metals show the expected increase across the period, in line
with increasing nuclear charge. The anomalous values for manganese
and iron are a result of the very stable d5 configurations of the Mn2+
and Fe3+ ions. The dipositive aqua ions, M2+(aq) (specifically, the
octahedral complexes [M(OH2)6]2+), play an important role in the
chemistry of the 3d-series metals. Many of these ions are coloured as a
result of d-d transitions in the visible region of the spectrum. For
example, Cr2+(aq) is blue, Fe2+(aq) is green, Co+2(aq) is pink, Ni2+(aq) is
green, and Cu+2(aq) is blue. The +3 oxidation state is common at the left
of the period, and is the only oxidation state normally encountered for
scandium. Careful inspection of the Frost diagrams gives the balance of
stability between the +3 and +2 oxidation states. Titanium, vanadium,
and chromium all form a wide range of compounds in oxidation state
+3, and under normal conditions the +3 oxidation state is more stable
than the +2 state. Manganese(II) is especially stable due to its half-filled
d shell, and relatively few Mn(III) compounds are known. Beyond
manganese, many Fe(III) complexes are known, but are often oxidizing.
In acid solution, Co3+(aq) is powerfully oxidizing and O2 is evolved:
4Co3+(aq) + 2H2O(l) 4Co+2(aq) + 4H+(aq) + O2
Ecell0=0.58 V
Species such as Co(III) are stabilized as oxido compounds (for instance,
CoO(OH)), which are formed under basic conditions, or when
complexed by good donor ligands such as amines. Aqua ions of Ni3+ and
Cu3+ have not been prepared. In contrast, M(II) becomes increasingly
common from left to right across the series. For example, among the
early members of the 3d series, Sc2+(aq) (Group 3) is unknown and
Ti2+(aq) (Group 4) is formed only upon bombarding solutions of Ti3+
with electrons in the technique known as pulse radiolysis. For Groups 5
and 6, V2+(aq) and Cr2+(aq) are thermodynamically unstable with
respect to oxidation by H+ ions:
2V2+(aq) + 2H+(aq) 2V3+(aq) + H2(g)
Ecell0=0.26 V
Despite this instability, the slowness of the evolution of H2 makes
it possible to work with aqueous solutions of these dipositive ions in
the absence of air, and as a result they are useful reducing agents.
Beyond Cr (for Mn2+, Fe2+, Co2+, Ni2+, and Cu2+), M(II) is stable with
respect to reaction with water, and only Fe2+ is oxidized by air. Water is
incompatible with many metal ions because it can serve as an oxidizing
agent. A wider range of M2+ ions is therefore known in solids than in
aqueous solution. For example, TiCl2 can be prepared by the reduction
of TiCl4 with hexamethyldisilane,
 (CH3)3Si-Si(CH3)3(l) + TiCl4(l) TiCl2(s) + 2(CH3)3SiCl(l)
but it is oxidized by both water and air to give TiO2. With the exception
of ScCl2, these dihalides are well described by structures containing
isolated M2+ ions.
(c) Intermediate oxidation states in the 4d and 5d series

Key points: Complexes of M(II) with sigma-donor ligands are

common for the 3d-series metals but complexes of M(II) of the
4d- and 5d-series metals are less common; they generally contain
pi-acceptor ligands.
In contrast to the 3d-series, the 4d- and 5d-series metals only rarely
form simple M2+(aq) ions. A few examples have been characterized,
including [Ru(OH2)6]2+, [Pd(OH2)4]2+, and [Pt(OH2)4]2+. However, the 4d-
and 5d-series metals do form many M(II) complexes with ligands other
than H2O; they include the very stable d6 octahedral complexes, such as
(1), and the much rarer square-pyramidal d6 complexes, such as (2),
which form with bulky ligands. Palladium(II) and platinum(II) form many
square-planar d8 complexes, such as [PtCl4]2-. Much of the
rationalization of this behaviour relates to the bonding of the ligands.
The Ru(II) complex in (1) is obtained by reducing RuCl3.3H2O with zinc in
the presence of ammonia; it is a useful starting material for the
synthesis of a range of ruthenium(II) pentaammine complexes that
have pi-acceptor ligands, such as CO, as the sixth ligand:
[Ru(NH3)5(OH2)]2+(aq) + L(aq) [Ru(NH3)5L]2+(aq) + H2O(l) (L = CO,
N2, N2O)
These Ru and the related Os pentaammine species are strong pi donors,
and consequently the complexes they form with the pi-acceptors CO
and N2 are stable.
Magnetic Properties
When a magnetic field is applied to substances, two types of magnetic
behaviour are observed: diamagnetism and paramagnetism.
Diamagnetic substances are repelled by the applied field while the
paramagnetic substances are attracted. Substances which are attracted
very strongly are said to be ferromagnetic. In fact, ferromagnetism is an
extreme form of paramagnetism. Many of the transition metal ions are
paramagnetic, i.e., attracted by a magnetic field. Paramagnetism arises
from the presence of unpaired electrons. Each such electron has a
magnetic moment associated with its spin angular momentum and
orbital angular momentum. For the compounds of the first series of
transition metals, the contribution of the orbital angular momentum is
effectively quenched and hence is of no significance. For these, the
magnetic moment is determined by the number of unpaired electrons
and is calculated by using the spin-only formula, i.e.,
=((n)(n+2))1/2
Where n is the number of unpaired electrons and is the magnetic
moment in Bohr magneton(B) units. A single 1s electron has a
magnetic moment of 1.73 Bohr magnetons (B). The magnetic moment
increases with the increasing number of unpaired electrons. Thus, the
observed magnetic moment gives a useful indication about the number
of unpaired electrons present in the atom, molecule or ion.

Formation of Coloured Ions

When an electron from a lower energy d orbital is excited to a higher
energy d orbital, the energy of excitation corresponds to the frequency
of light absorbed. This frequency generally lies in the visible region. The
colour observed corresponds to the complementary colour of the light
absorbed. The frequency of the light absorbed is determined by the
nature of the ligand.
Formation of Complex Compounds
Complex compounds are those in which the metal ions bind a specific
number of anions or neutral molecules giving complex species with
characteristic properties. A few examples are : [Fe(CN)6]3, [Fe(CN)6]4,
[Cu(NH3)4]2+ and [PtCl4]2. The transition metals form a large number of
complex compounds. This is due to the comparatively smaller sizes of
the metal ions, their high ionic charges and the availability of d orbitals
for bond formation.
Catalytic Properties
The transition metals and their compounds are known for their catalytic
activity. This activity is ascribed to their ability to adopt multiple
oxidation states and to form complexes. Vanadium(V) oxide (Contact
Process), finely divided iron (Habers Process), and nickel (Catalytic
Hydrogenation) are some of the examples. Catalysts at a solid surface
involve the formation of bonds between reactant molecules and atoms
of the surface of the catalyst (first row transition metals utilise 3d and
4s electrons for bonding); this has the effect of increasing the
concentration of the reactants at the catalyst surface and also
weakening of the bonds in the reacting molecules (the activation
energy is lowered). Also because the transition metal ions can change
their oxidation states, they become more effective as catalysts.
For example, iron(III) catalyses the reaction between iodide and
persulphate ions, 2 I + S2O82 I2 + 2 SO42
An explanation of this catalytic action can be given as: 2 Fe3+ + 2 I 2
Fe2+ + I2
2 Fe2+ + S2O82
2 Fe3+ + 2 SO42
Formation of Interstitial Compounds
 Interstitial compounds are those which are formed when small atoms
like H, N or C are trapped inside the crystal lattices of metals. They are
usually non-stoichiometric and are neither typically ionic nor covalent.
Many of the transition metals form interstitial compounds particularly
with small non-metal atoms such as hydrogen, boron, carbon and
nitrogen. These small atoms enter into the voids sites between the
packed atoms of the crystalline metal, e.g., TiC, Mn4N, Fe3H, TiH2, etc.
The formulae quoted do not, of course, correspond to any normal
oxidation state of the metal and often nonstoichiometric material is
obtained with such composition as VH0.56 and TiH1.7. Because of the
nature of their composition, these compounds are referred to as
interstitial compounds. The principal physical and chemical
characteristics of these compounds are as follows: (i) They have high
melting points, higher than those of pure metals. (ii) They are very
hard, some borides approach diamond in hardness. (iii) They retain
metallic conductivity. (iv) They are chemically inert.
Alloy Formation
An alloy is a blend of metals prepared by mixing the components.
Alloys may be homogeneous solid solutions in which the atoms of one
metal are distributed randomly among the atoms of the other. Such
alloys are formed by atoms with metallic radii that are within about 15
percent of each other. Because of similar radii and other characteristics
of transition metals, alloys are readily formed by these metals. The
alloys so formed are hard and have often high melting points. The best
known are ferrous alloys; chromium, vanadium, tungsten,
molybdenum, and manganese are used for the production of variety of
steels and stainless steel. Alloys of transition metals with non-transition
metals such as brass (copper-zinc), and bronze (copper-tin) are also of
considerable industrial importance.