Intext Question

10
8.1 Silver atom has completely filled d orbitals (4d ) in its ground state.
How can you say that it is a transition element?

We will discuss the properties of elements of first transition series

only in the following sections.
8 . 3 General 8.3.1 Physical Properties
Properties of Nearly all the transition elements display typical metallic properties
the Transition such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre. With the exceptions of Zn,
Elements Cd, Hg and Mn, they have one or more typical metallic structures at
(d-Block) normal temperatures.

Lattice Structures of Transition Metals

Sc Ti V Cr Mn Fe Co Ni Cu Zn

hcp hcp bcc bcc X bcc ccp ccp ccp X

(bcc) (bcc) (bcc, ccp) (hcp) (hcp) (hcp)
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(bcc) (bcc) (hcp)
La Hf Ta W Re Os Ir Pt Au Hg
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(ccp,bcc) (bcc)
4 (bcc = body centred cubic; hcp = hexagonal close packed;
ccp = cubic close packed; X = a typical metal structure).
W
The transition metals (with the exception
Re
Ta of Zn, Cd and Hg) are very hard and have low
volatility. Their melting and boiling points are
3
Mo Os high. Fig. 8.1 depicts the melting points of
Nb Ru transition metals belonging to 3d, 4d and 5d
Ir
series. The high melting points of these metals
Hf Tc
are attributed to the involvement of greater
M.p./10 K
3

Cr Rh number of electrons from (n-1)d in addition to

Zr V Pt
2 the ns electrons in the interatomic metallic
Ti Fe bonding. In any row the melting points of these
Co Pd 5
Ni metals rise to a maximum at d except for
Mn anomalous values of Mn and Tc and fall
Cu regularly as the atomic number increases.
Au
1 Ag They have high enthalpies of atomisation which
Atomic number
are shown in Fig. 8.2. The maxima at about
Fig. 8.1: Trends in melting points of
the middle of each series indicate that one
transition elements unpaired electron per d orbital is particularly

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 favourable for strong interatomic interaction. In general, greater the
number of valence electrons, stronger is the resultant bonding. Since
the enthalpy of atomisation is an important factor in determining the
standard electrode potential of a metal, metals with very high enthalpy
of atomisation (i.e., very high boiling point) tend to be noble in their
reactions (see later for electrode potentials).
Another generalisation that may be drawn from Fig. 8.2 is that the
metals of the second and third series have greater enthalpies of
atomisation than the corresponding elements of the first series; this is an
important factor in accounting for the occurrence of much more frequent
metal – metal bonding in compounds of the heavy transition metals.
–1
D H /kJ mol
V

Fig. 8.2
Trends in enthalpies
of atomisation of
transition elements

8.3.2 Variation in In general, ions of the same charge in a given series show progressive
Atomic and decrease in radius with increasing atomic number. This is because the
Ionic Sizes new electron enters a d orbital each time the nuclear charge increases
of by unity. It may be recalled that the shielding effect of a d electron is
Transition not that effective, hence the net electrostatic attraction between the
Metals nuclear charge and the outermost electron increases and the ionic
radius decreases. The same trend is observed in the atomic radii of a
given series. However, the variation within a series is quite small. An
interesting point emerges when atomic sizes of one series are compared
with those of the corresponding elements in the other series. The curves
in Fig. 8.3 show 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

219 The d- and f- Block Elements

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 increase in atomic size with increasing atomic number. The net result
of the lanthanoid contraction is that the 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 much more than that expected on
the basis of usual family relationship.
19 The factor responsible for the lanthanoid
18 contraction is somewhat similar to that observed
in an ordinary transition series and is attributed
17

Radius/nm
to similar cause, i.e., the imperfect shielding of
16 one electron by another in the same set of orbitals.
However, the shielding of one 4f electron by
15
another is less than that of one d electron by
14 another, and as the nuclear charge increases
13 along the series, there is fairly regular decrease
n
in the size of the entire 4f orbitals.
12
Sc Ti V Cr Mn Fe Co Ni Cu Zn The decrease in metallic radius coupled with
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd increase in atomic mass results in a general
La Hf Ta W Re Os Ir Pt Au Hg increase in the density of these elements. Thus,
from titanium (Z = 22) to copper (Z = 29) the
Fig. 8.3: Trends in atomic radii of significant increase in the density may be noted
transition elements (Table 8.2).

Table 8.2: Electronic Configurations and some other Properties of

the First Series of Transition Elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Atomic number 21 22 23 24 25 26 27 28 29 30
Electronic configuration
1 2 2 2 3 2 5 1 5 2 6 2 7 2 8 2 10 1 10 2
M 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s
+ 1 1 2 1 3 1 5 5 1 6 1 7 1 8 1 10 10 1
M 3d 4s 3d 4s 3d 4s 3d 3d 4s 3d 4s 3d 4s 3d 4s 3d 3d 4s
2+ 1 2 3 4 5 6 7 8 9 10
M 3d 3d 3d 3d 3d 3d 3d 3d 3d 3d
3+ 1 2 3 4 5 6 7
M [Ar] 3d 3d 3d 3d 3d 3d 3d – –
V –1
Enthalpy of atomisation, ∆aH /kJ mol
326 473 515 397 281 416 425 430 339 126
V –1
∆ iH /kJ mol
Ionisation enthalpy/∆
V
∆ iH I 631 656 650 653 717 762 758 736 745 906
V
∆ iH II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
V
∆ iH III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3837
Metallic/ionic M 164 147 135 129 137 126 125 125 128 137
2+
radii/pm M – – 79 82 82 77 74 70 73 75
3+
M 73 67 64 62 65 65 61 60 – –
Standard
2+
electrode M /M – –1.63 –1.18 –0.90 –1.18 –0.44 –0.28 –0.25 +0.34 -0.76
V
potential E /V M 3+/M2+ – –0.37 –0.26 –0.41 +1.57 +0.77 +1.97 – – –
–3
Density/g cm 3.43 4.1 6.07 7.19 7.21 7.8 8.7 8.9 8.9 7.1

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 Why do the transition elements exhibit higher enthalpies of Example 8.2
atomisation?
Because of large number of unpaired electrons in their atoms they Solution
have stronger interatomic interaction and hence stronger bonding
between atoms resulting in higher enthalpies of atomisation.

Intext Question
8.2 In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation
–1
of zinc is the lowest, i.e., 126 kJ mol . Why?

8.3.3 Ionisation There is an increase in ionisation enthalpy along each series of the
Enthalpies transition elements from left to right due to an increase in nuclear
charge which accompanies the filling of the inner d orbitals. Table
8.2 gives the values of the first three ionisation enthalpies of the first
series of transition elements. These values show that the successive
enthalpies of these elements do not increase as steeply as in the case
of non-transition elements. The variation in ionisation enthalpy along
a series of transition elements is much less in comparison to the variation
along a period of non-transition elements. The first ionisation enthalpy,
in general, increases, but the magnitude of the increase in the second
and third ionisation enthalpies for the successive elements, is much
higher along a series.
The irregular trend in the first ionisation enthalpy of the metals of
3d series, though of little chemical significance, can be accounted for
by considering that the removal of one electron alters the relative energies
of 4s and 3d orbitals. You have learnt that when d-block elements form
ions, ns electrons are lost before (n – 1) d electrons. As we move along
the period in 3d series, we see that nuclear charge increases from
scandium to zinc but electrons are added to the orbital of inner subshell,
i.e., 3d orbitals. These 3d electrons shield the 4s electrons from the
increasing nuclear charge somewhat more effectively than the outer
shell electrons can shield one another. Therefore, the atomic radii
decrease less rapidly. Thus, ionization energies increase only slightly
n
along the 3d series. The doubly or more highly charged ions have d
configurations with no 4s electrons. A general trend of increasing values
of second ionisation enthalpy is expected as the effective nuclear charge
increases because one d electron does not shield another electron from
the influence of nuclear charge because d-orbitals differ in direction.
However, the trend of steady increase in second and third ionisation
enthalpy breaks for the formation of Mn2+ and Fe3+ respectively. In both
the cases, ions have d5 configuration. Similar breaks occur at
corresponding elements in the later transition series.
The interpretation of variation in ionisation enthalpy for an electronic
configuration dn is as follows:
The three terms responsible for the value of ionisation enthalpy are
attraction of each electron towards nucleus, repulsion between the
221 The d- and f- Block Elements

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 electrons and the exchange energy. Exchange energy is responsible for
the stabilisation of energy state. Exchange energy is approximately
proportional to the total number of possible pairs of parallel spins in
the degenerate orbitals. When several electrons occupy a set of
degenerate orbitals, the lowest energy state corresponds to the maximum
possible extent of single occupation of orbital and parallel spins (Hunds
rule). The loss of exchange energy increases the stability. As the stability
increases, the ionisation becomes more difficult. There is no loss of
exchange energy at d6 configuration. Mn+ has 3d54s1 configuration and
configuration of Cr+ is d5, therefore, ionisation enthalpy of Mn+ is lower
than Cr+. In the same way, Fe2+ has d6 configuration and Mn2+ has 3d5
configuration. Hence, ionisation enthalpy of Fe2+ is lower than the Mn2+.
In other words, we can say that the third ionisation enthalpy of Fe is
lower than that of Mn.
The lowest common oxidation state of these metals is +2. To
2+
form the M ions from the gaseous atoms, the sum of the first and
second ionisation enthalpy is required in addition to the enthalpy of
atomisation. The dominant term is the second ionisation enthalpy
+
which shows unusually high values for Cr and Cu where M ions
5 10
have the d and d configurations respectively. The value for Zn is
correspondingly low as the ionisation causes the removal of 1s
10
electron which results in the formation of stable d configuration.
The trend in the third ionisation enthalpies is not complicated by
the 4s orbital factor and shows the greater difficulty of removing an
5 2+ 10 2+
electron from the d (Mn ) and d (Zn ) ions. In general, the third
ionisation enthalpies are quite high. Also the high values for third
ionisation enthalpies of copper, nickel and zinc indicate why it is
difficult to obtain oxidation state greater than two for these elements.
Although ionisation enthalpies give some guidance concerning the
relative stabilities of oxidation states, this problem is very complex and
not amenable to ready generalisation.

8.3.4 Oxidation One of the notable features of a transition elements is the great variety
States of oxidation states these may show in their compounds. Table 8.3 lists
the common oxidation states of the first row transition elements.
Table 8.3: Oxidation States of the first row Transition Metals
(the most common ones are in bold types)
Sc Ti V Cr Mn Fe Co Ni Cu Zn

+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

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 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
II III
that their oxidation states differ from each other by unity, e.g., V , V ,
IV V
V , V . This is in contrast with the variability of oxidation states of non
transition elements where oxidation states normally differ by a unit
of two.
An interesting feature in the variability of oxidation states of the d–
block elements is noticed among the groups (groups 4 through 10).
Although in the p–block the lower oxidation states are favoured by the
heavier members (due to inert pair effect), the opposite is true in the
groups of d-block. For example, in group 6, Mo(VI) and W(VI) are
found to be more stable than Cr(VI). Thus Cr(VI) in the form of dichromate
in acidic medium is a strong oxidising agent, whereas MoO3 and WO3
are not.
Low oxidation states are found when a complex compound has
ligands capable of π-acceptor character in addition to the σ-bonding.
For example, in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and
iron is zero.

Name a transition element which does not exhibit variable Example 8.3
oxidation states.
Scandium (Z = 21) does not exhibit variable oxidation states. Solution

Intext Question
8.3 Which of the 3d series of the transition metals exhibits the
largest number of oxidation states and why?

223 The d- and f- Block Elements

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8.3.5 Trends in the Table 8.4 contains the thermochemical parameters related to the
2+ 2+
M /M transformation of the solid metal atoms to M ions in solution and their
V
Standard standard electrode potentials. The observed values of E and those
Electrode calculated using the data of Table 8.4 are compared in Fig. 8.4.
V
Potentials The unique behaviour of Cu, having a positive E , accounts for its
inability to liberate H2 from acids. Only oxidising acids (nitric and hot
concentrated sulphuric) react with Cu, the acids being reduced. The
high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration
V
enthalpy. The general trend towards less negative E values across the

Fig. 8.4: Observed and calculated values for the standard

electrode potentials
(M2+ →M°) of the elements Ti to Zn

series is related to the general increase in the sum of the first and second
V
ionisation enthalpies. It is interesting to note that the value of E for Mn,
Ni and Zn are more negative than expected from the trend.

Example 8.4
Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Cr is reducing as its configuration changes from d to d , the latter Solution
2+ 4 3

having a half-filled t2g level (see Unit 9) . On the other hand, the change
3+ 2+ 5
from Mn to Mn results in the half-filled (d ) configuration which has
extra stability.

Intext Question
V 2+
8.4 The E (M /M) value for copper is positive (+0.34V). What is possible
V V
reason for this? (Hint: consider its high ∆aH and low ∆hydH )

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 Table 8.4: Thermochemical data (kJ mol-1) for the first row Transition
Elements and the Standard Electrode Potentials for the
Reduction of MII to M.
V V V V V
Element (M) ∆a H (M) ∆ iH 1 ∆ 1H 2 ∆ hydH (M2+) E /V
Ti 469 656 1309 -1866 -1.63
V 515 650 1414 -1895 -1.18
Cr 398 653 1592 -1925 -0.90
Mn 279 717 1509 -1862 -1.18
Fe 418 762 1561 -1998 -0.44
Co 427 758 1644 -2079 -0.28
Ni 431 736 1752 -2121 -0.25
Cu 339 745 1958 -2121 0.34
Zn 130 906 1734 -2059 -0.76
2+
The stability of the half-filled d sub-shell in Mn and the completely
10 2+ V
filled d configuration in Zn are related to their E values, whereas
V V
E for Ni is related to the highest negative ∆hydH .
V 3+ 2+
8.3.6 Trends in An examination of the E (M /M ) values (Table 8.2) shows the varying
3+
the M3+/M2+ trends. The low value for Sc reflects the stability of Sc which has a
Standard noble gas configuration. The highest value for Zn is due to the removal
10 2+
Electrode of an electron from the stable d configuration of Zn . The
2+ 5
Potentials comparatively high value for Mn shows that Mn (d ) is particularly
stable, whereas comparatively low value for Fe shows the extra stability
3+ 5
of Fe (d ). The comparatively low value for V is related to the stability
2+
of V (half-filled t2g level, Unit 9).

8.3.7 Trends in Table 8.5 shows the stable halides of the 3d series of transition metals.
Stability of The highest oxidation numbers are achieved in TiX4 (tetrahalides), VF5
Higher and CrF6. The +7 state for Mn is not represented in simple halides but
Oxidation MnO3F is known, and beyond Mn no metal has a trihalide except FeX3
States and CoF3. The ability of fluorine to stabilise the highest oxidation state is
due to either higher lattice energy as in the case of CoF3, or higher bond
enthalpy terms for the higher covalent compounds, e.g., VF5 and CrF6.
+5
Although V is represented only by VF5, the other halides, however,
undergo hydrolysis to give oxohalides, VOX3. Another feature of fluorides
is their instability in the low oxidation states e.g., VX2 (X = CI, Br or I)
Table 8.5: Formulas of Halides of 3d Metals
Oxidation
Number
+ 6 CrF6
+ 5 VF5 CrF5
+ 4 TiX4 VXI4 CrX4 MnF4
+ 3 TiX3 VX3 CrX3 MnF3 FeXI3 CoF3
III II
+ 2 TiX2 VX2 CrX2 MnX2 FeX2 CoX2 NiX2 CuX2 ZnX2
III
+ 1 CuX

Key: X = F → I; XI = F → Br; XII = F, CI; XIII = CI → I

225 The d- and f- Block Elements

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 II
and the same applies to CuX. On the other hand, all Cu halides are
2+ –
known except the iodide. In this case, Cu oxidises I to I2:
2Cu2 + + 4I− → Cu2I2 ( s ) + I2
However, many copper (I) compounds are unstable in aqueous
solution and undergo disproportionation.
+ 2+
2Cu → Cu + Cu
2+ +
The stability of Cu (aq) rather than Cu (aq) is due to the much
V 2+ +
more negative ∆hydH of Cu (aq) than Cu , which more than
compensates for the second ionisation enthalpy of Cu.
The ability of oxygen to stabilise the highest oxidation state is
demonstrated in the oxides. The highest oxidation number in the oxides
(Table 8.6) coincides with the group number and is attained in Sc2O3
to Mn2O7. Beyond Group 7, no higher oxides of Fe above Fe2O3, are
2–
known, although ferrates (VI)(FeO4) , are formed in alkaline media but
they readily decompose to Fe2O3 and O2. Besides the oxides, oxocations
v + IV 2+ IV 2+
stabilise V as VO2 , V as VO and Ti as TiO . The ability of oxygen
to stabilise these high oxidation states exceeds that of fluorine. Thus
the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
The ability of oxygen to form multiple bonds to metals explains its
superiority. In the covalent oxide Mn2O7, each Mn is tetrahedrally
n-
surrounded by O’s including a Mn–O–Mn bridge. The tetrahedral [MO4]
V Vl V Vl VII
ions are known for V , Cr , Mn , Mn and Mn .

Table 8.6: Oxides of 3d Metals

Oxidation Groups
Number 3 4 5 6 7 8 9 10 11 12
+ 7 Mn2O7
+ 6 CrO3
+ 5 V2O5
+ 4 TiO2 V2O4 CrO2 MnO2
+ 3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3
* * *
Mn3O4 Fe3O4 Co3O4
+ 2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO
+ 1 Cu2O
* mixed oxides

How would you account for the increasing oxidising power in the Example 8.5
+ 2– –
series VO2 < Cr2O7 < MnO4 ?
This is due to the increasing stability of the lower species to which they Solution
are reduced.

Intext Question
8.5 How would you account for the irregular variation of ionisation
enthalpies (first and second) in the first series of the transition elements?

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8.3.8 Chemical Transition metals vary widely in their chemical reactivity. Many of
Reactivity them are sufficiently electropositive to dissolve in mineral acids, although
V
and E a few are ‘noble’—that is, they are unaffected by single acids.
Values The metals of the first series with the exception of copper are relatively
more reactive and are oxidised by 1M H+, though the actual rate at
+
which these metals react with oxidising agents like hydrogen ion (H ) is
sometimes slow. For example, titanium and vanadium, in practice, are
V
passive to dilute non oxidising acids at room temperature. The E values
2+
for M /M (Table 8.2) indicate a decreasing tendency to form divalent
V
cations across the series. This general trend towards less negative E
values is related to the increase in the sum of the first and second
V
ionisation enthalpies. It is interesting to note that the E values for Mn,
Ni and Zn are more negative than expected from the general trend.
5 2+
Whereas the stabilities of half-filled d subshell (d ) in Mn and completely
10 e o
filled d subshell (d ) in zinc are related to their E values; for nickel, E
value is related to the highest negative enthalpy of hydration.
V 3+ 2+
An examination of the E values for the redox couple M /M (Table
3+ 3+
8.2) shows that Mn and Co ions are the strongest oxidising agents
2+ 2+ 2+
in aqueous solutions. The ions Ti , V and Cr are strong reducing
agents and will liberate hydrogen from a dilute acid, e.g.,
2+ + 3+
2 Cr (aq) + 2 H (aq) → 2 Cr (aq) + H2(g)

Example 8.6 For the first row transition metals the Eo values are:
o
E V Cr Mn Fe Co Ni Cu
2+
(M /M) –1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34
Explain the irregularity in the above values.
Solution The EV (M2+/M) values are not regular which can be explained from
the irregular variation of ionisation enthalpies ( ∆i H1 + ∆ i H 2 ) and also
the sublimation enthalpies which are relatively much less for
manganese and vanadium.

Example 8.7 Why is the EV value for the Mn3+/Mn2+ couple much more positive
3+ 2+ 3+ 2+
than that for Cr /Cr or Fe /Fe ? Explain.
Solution Much larger third ionisation energy of Mn (where the required change
5 4
is d to d ) is mainly responsible for this. This also explains why the
+3 state of Mn is of little importance.

Intext Questions
8.6 Why is the highest oxidation state of a metal exhibited in its oxide or
fluoride only?
2+ 2+
8.7 Which is a stronger reducing agent Cr or Fe and why ?

8.3.9 Magnetic When a magnetic field is applied to substances, mainly two types of
Properties magnetic behaviour are observed: diamagnetism and paramagnetism
(Unit 1). Diamagnetic substances are repelled by the applied field while
the paramagnetic substances are attracted. Substances which are

227 The d- and f- Block Elements

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 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.
Paramagnetism arises from the presence of unpaired electrons, each
such electron having 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.,
µ= n (n + 2)
where n is the number of unpaired electrons and µ is the magnetic
moment in units of Bohr magneton (BM). A single unpaired electron
has a magnetic moment of 1.73 Bohr magnetons (BM).
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. The magnetic moments calculated from the ‘spin-only’
formula and those derived experimentally for some ions of the first row
transition elements are given in Table 8.7. The experimental data are
mainly for hydrated ions in solution or in the solid state.

Table 8.7: Calculated and Observed Magnetic Moments (BM)

Ion Configuration Unpaired Magnetic moment

electron(s) Calculated Observed

Sc3+ 3d0 0 0 0
3+ 1
Ti 3d 1 1.73 1.75
Tl2+ 3d2 2 2.84 2.76
2+ 3
V 3d 3 3.87 3.86
2+ 4
Cr 3d 4 4.90 4.80
Mn2+ 3d5 5 5.92 5.96
2+ 6
Fe 3d 4 4.90 5.3 – 5.5
Co2+ 3d7 3 3.87 4.4 – 5.2
Ni2+ 3d8 2 2.84 2.9 – 3, 4
2+ 9
Cu 3d 1 1.73 1.8 – 2.2
Zn2+ 3d10 0 0

Calculate the magnetic moment of a divalent ion in aqueous solution Example 8.8
if its atomic number is 25.
With atomic number 25, the divalent ion in aqueous solution will have Solution
5
d configuration (five unpaired electrons). The magnetic moment, µ is
µ = 5 ( 5 + 2 ) = 5.92 BM

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 Intext Question
2+
8.8 Calculate the ‘spin only’ magnetic moment of M (aq) ion (Z = 27).

8.3.10 Formation When an electron from a lower energy d orbital is excited to a higher
of Coloured energy d orbital, the energy of excitation corresponds to the frequency
Ions of light absorbed (Unit 9). 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.
In aqueous solutions
where water molecules are
the ligands, the colours
of the ions observed are
listed in Table 8.8. A few
coloured solutions of Fig. 8.5: Colours of some of the first row
d–block elements are transition metal ions in aqueous solutions. From
illustrated in Fig. 8.5. left to right: V4+,V3+,Mn2+,Fe3+,Co2+,Ni2+and Cu2+ .

Table 8.8: Colours of Some of the First Row (aquated)

Transition Metal Ions

Configuration Example Colour

0 3+
3d Sc colourless
3d0 Ti4+ colourless
3d1 Ti3+ purple
3d1 V4+ blue
2 3+
3d V green
3 2+
3d V violet
3 3+
3d Cr violet
4 3+
3d Mn violet
4 2+
3d Cr blue
5 2+
3d Mn pink
5 3+
3d Fe yellow
6 2+
3d Fe green
6 7 3+ 2+
3d 3d Co Co bluepink
3d8 Ni2+ green
3d9 Cu2+ blue
3d10 Zn2+ colourless

8.3.11 Formation Complex compounds are those in which the metal ions bind a number
of Complex of anions or neutral molecules giving complex species with
3– 4–
Compounds characteristic properties. A few examples are: [Fe(CN)6] , [Fe(CN)6] ,
2+ 2–
[Cu(NH3)4] and [PtCl4] . (The chemistry of complex compounds is

229 The d- and f- Block Elements

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 dealt with in detail in Unit 9). 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.

8.3.12 Catalytic The transition metals and their compounds are known for their catalytic
Properties activity. This activity is ascribed to their ability to adopt multiple
oxidation states and to form complexes. Vanadium(V) oxide (in Contact
Process), finely divided iron (in Haber’s Process), and nickel (in 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 lowering).
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– 2–
2 I + S2O8 → I2 + 2 SO4
An explanation of this catalytic action can be given as:
3+ – 2+
2 Fe + 2 I → 2 Fe + I2
2+ 2– 3+ 2–
2 Fe + S2O8 → 2 Fe + 2SO4

8.3.13 Formation Interstitial compounds are those which are formed when small atoms
of like H, C or N are trapped inside the crystal lattices of metals. They are
Interstitial usually non stoichiometric and are neither typically ionic nor covalent,
Compounds for example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc. The formulas
quoted do not, of course, correspond to any normal oxidation state of
the metal. 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.

8.3.14 Alloy An alloy is a blend of metals prepared by mixing the components.

Formation 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 a 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.

Chemistry 230

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 Example 8.9 What is meant by ‘disproportionation’ of an oxidation state? Give an
example.
Solution When a particular oxidation state becomes less stable relative to other
oxidation states, one lower, one higher, it is said to undergo disproportionation.
For example, manganese (VI) becomes unstable relative to manganese(VII) and
manganese (IV) in acidic solution.
VI 2– + VII – IV
3 Mn O4 + 4 H → 2 Mn O 4 + Mn O2 + 2H2O

Intext Question
+
8.9 Explain why Cu ion is not stable in aqueous solutions?

8 . 4 Some 8.4.1 Oxides and Oxoanions of Metals

Important These oxides are generally formed by the reaction of metals with
Compounds of oxygen at high temperatures. All the metals except scandium form
MO oxides which are ionic. The highest oxidation number in the
Transition oxides, coincides with the group number and is attained in Sc2O3 to
Elements Mn2O7. Beyond group 7, no higher oxides of iron above Fe2O3 are
V + IV
known. Besides the oxides, the oxocations stabilise V as VO2 , V as
2+ IV 2+
VO and Ti as TiO .
As the oxidation number of a metal increases, ionic character
decreases. In the case of Mn, Mn2O7 is a covalent green oil. Even CrO3
and V2O5 have low melting points. In these higher oxides, the acidic
character is predominant.
Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7.
3–
V2O5 is, however, amphoteric though mainly acidic and it gives VO4 as
+
well as VO2 salts. In vanadium there is gradual change from the basic
V2O3 to less basic V2O4 and to amphoteric V2O5. V2O4 dissolves in acids
2+
to give VO salts. Similarly, V2O5 reacts with alkalies as well as acids
to give VO34− and VO+4 respectively. The well characterised CrO is basic
but Cr2O3 is amphoteric.
Potassium dichromate K2Cr2O7
Potassium dichromate is a very important chemical used in leather
industry and as an oxidant for preparation of many azo compounds.
Dichromates are generally prepared from chromate, which in turn are
obtained by the fusion of chromite ore (FeCr2O4) with sodium or
potassium carbonate in free access of air. The reaction with sodium
carbonate occurs as follows:
4 FeCr2O4 + 8 Na2CO3 + 7 O2 →8 Na2CrO4 + 2 Fe2O3 + 8 CO2
The yellow solution of sodium chromate is filtered and acidified
with sulphuric acid to give a solution from which orange sodium
dichromate, Na2Cr2O7. 2H2O can be crystallised.
+ +
2Na2CrO4 + 2 H → Na2Cr2O7 + 2 Na + H2O

231 The d- and f- Block Elements

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