Silver atom has completely filled d orbitals (4d 10) in its ground state.

How can you

say that it is a transition element?
Ans: The outer electronic configuration of Ag (Z=47) is 4d105s1. It shows+1 and + 2
O.S. (in AgO and AgF2). And in + 2 O.S., the electronic configuration is d9 i.e, d-
subshell is incompletely filled. Hence, it is a transition element.

8.2. In the series Sc(Z = 21) to (Z = 30), the enthalpy of atomisation of zinc is the
lowest i.e., 126 kJ mol-1. Why?
Ans: The enthalpy of atomisation is directly linked with the stability of the crystal
lattice and also the strength of the metallic bond. In case of zinc
(3d104s2 configuration), no electrons from the 3d-orbitals are involved in the formation
of metallic bonds since all the orbitals are filled. However, in all other elements
belonging to 3d series one or more d-electrons are involved in the metallic bonds.
This means that the metallic bonds are quite weak in zinc and it has therefore,
lowest enthalpy of atomisation in the 3d series.

8.3. Which of the 3d series of the transition metals exhibits the largest number of
oxidation states and why?
Ans: Manganese (Z = 25) shows maximum number of O.S. This is because its outer
EC is 3d54s2. As 3d and 4s are close in energy, it has maximum number of e-1 s to
loose or share. Hence, it shows O.S. from +2 to +7 which is the maximum number.

8.4.

Ans.

8.5. How would you account for the irregular variation of ionisation enthalpies (first
and second) in the first series of the transition elements?
Ans:  There is a irregularity in the IE’s of 3d-series due to alternation of energies of 4s
and 3d orbitals when an e-1 is removed. Thus, there is a reorganisation energy
accompanying ionization. This results into release of exchange energy which
increases as the number of e-1 s increases in the dn configuration. Cr has low 1st IE
because loss of 1 e- gives stable EC (3d6). Zn has very high IE because e~ has to be
removed from 4s orbital of the stable configuration (3d10 4s2) After the loss of one e–,
removal of 2nd e–, becomes difficult. Hence, 2nd IE’s are higher and in general,
increase from left to right. However, Cr and Cu show much higher values because
2nd e– has to be removed from stable configuration of Cr+ (3d5) and Cu+ (3d10)

8.6. Why is the highest oxidation state of a metal exhibited by its fluoride and oxide
only? (C.B.S.E. Delhi 2010)
Ans: Both fluorine and oxygen have very high electronegativity values. They can
oxidise the metals to the highest oxidation state. As a result, the highest oxidation
states are shown by the fluorides and oxides of the metals; transition metals in
particular.

8.7.Which is a stronger reducing agent Cr2+ or Fe2+ and why?

Ans: Cr2+ is a stronger reducing agent than Fe2+. This is because E°(Cr3+/Cr2+) is
negative (- 0.41V) whereas E°(Fe3+/Fe2+) is positive (+ 0.77 V). Thus, Cr2+ is easily
oxidised to Fe3+ but Fe2+ cannot be easily oxidised to Fe3+.

8.8.Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).

Ans:

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

Ans: Cu+ (aq) is not stable, while Cu2+ (aq) is stable. This is becuase ΔhydH of Cu2+(aq)
is much higher than that of Cu+(aq) and hence it compensates for the 2nd IE of Cu.
Thus, many Cu(I) compounds are unstable in aqueous solution and undergo
disproportionation as follows :
2 Cu+ —–> Cu2+ + Cu

8.10. Actinoid contraction is greater from element to element than lanthanoid

contraction. Why? (C.B.S.E. Sample Paper 2011, Jharkhand Board 2010)
Ans: The decrease or contraction in atomic radii, as well as ionic radii in actinoid
elements (actinoid contraction), is more as compared to lanthanoid contraction
because 5/ electrons have more poor shielding effect as compared to 4f electrons.
Therefore, the effect of increased nuclear charge leading to contraction in size is
more in case of actinoid elements.

NCERT EXERCISES
8.1. Write down the electronic configuration of (i) Cr 3+ (ii) Pm3+ (iii) Cu+ (iv) Ce4+(v)
Co2+ (vi) Lu2+(vii) Mn2+ (viii) Th4+.
Sol: (i) Cr3+ = [Ar]183d3
(ii)Pm3+ = [Xe]54 4f4
(iii)Cu+ = [Ar]18 3d10
(iv)Ce4+ = [Xe]54
(v)Co2+ = [Ar]18 3d7
(vi)Lu2+ = [Xe]54 4f14 5d1
(vii) Mn2+ = [Ar]18 3d5 (viii)Th4+= [Rn]86

8.2. Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their+3
state?
Sol: Electronic configuration of Mn2+ is 3d5. This is a half-filled configuration and
hence stable. Therefore, third ionization enthalpy is’very high, i. e., third electron
cannot be lost easily. Electronic configuration of Fe2+ is 3d6. It can lose one electron
easily to achieve a stable configuration 3d5.

8.3. Explain briefly how+2 state becomes more and more stable in the first half of
the first row transition elements with increasing atomic number?
Sol: Here after losing 2 electrons from j-orbitals, the 3d-orbital gets gradually
occupied with increase in atomic number. Since the number of unpaired electrons in
3d orbital increases, the stability of the cations (M2+) increases from Sc2+ to Mn2+.

8.4. To what extent do the electronic configurations decide the stability of oxidation
states in the first series of the transition elements? Illustrate your answer with
examples.
Sol: In the first series of transition elements, the oxidation states which lead to
exactly half-filled or completely filled d-orbitals are more stable. For example, Mn (Z =
25) has electronic configuration [Ar] 3d5 4 s2. It shows oxidation states + 2 to + 7 but
Mn (II) is most stable because of half-filled configuration [Ar] 3d 5. Similarly Sc3+ is
more stable then Sc+ and Fe3+ is more stable than Fe2+ due to half filled it f-orbitals.

8.5. What may be the stable oxidation state of the transition element with the
following delectron configurations in the ground state of their atoms: 3d 3,3d5,
3d8 and 3d4?
Sol: (a) 3d3 4s1 = + 5.
(b) 3d5 4s2 = + 2, + 7,3d5 4s1 =+6.
(c)3d84s2 = + 2.
(d)3d44s2 = 3d5 4s1 = + 6(and + 3).

8.6. Name the oxometal anions of the first series of the transition metals in which
the metal exhibits the oxidation state equal to its group number.
Sol: Cr2072- and Cr042- (Group number = Oxidation state of Cr = 6).
Mn04–  (Group number = Oxidation state of Mn = 7).
8.7. What is lanthanoid contraction? What are the consequences of lanthanoid
contraction?
Sol: Lanthanoid Contraction : In the lanthanoids , the electrons are getting filled in
the 4f-subshell. On moving from left to right, the nuclear charge increases and this
increase is expected to be compensated by the increase in the magnitude of
shielding effect by the 4 f- electrons However,
the f-electrons have very poor shielding effect. Consequently, the atomic and ionic
radii decrease from left to right and this is knwon as lanthanoid contraction.
Consequences of lanthanoid Contraction
(a)Separation Lanthanoids: All the lanthanoids have quite similar properties and due
to this reason they are difficult to separate.
(b)Variation in basic strength of hydroxides: Due to lanthanoid contraction, size of
M3+ ions decreases and thus there is a corresponding increase in the covalent
character in M—OH bond. Thus basic character of oxides and hydroxides decreases
from La(OH)3 to Lu(OH)3.
(c)Similarity in the atomic sizes of the elements of second and third transition series
present in the same group. The difference in the value of atomic radii of Y and La is
quite, large as compared to the difference in the value of Zr and Hf. This is because
of the lanthanoid contraction.
(d)Variation in standard reduciton potential: Due to lanthanoid contraction there is a
small but steady increase in the standard reduction potential (E°) for the reduction
process.
M3+ (aq) + 3e– —–> 4 M(aq)
(e)Variation in physical properties like melting point, boiling point, hardness etc.

8.8. What are the characteristics of the transition . elements and why are they
called transition elements? Which of the d-block elements may not be regarded as
the transition elements?
Sol: General characteristics of transition elements.
(i)Electronic configuration – (n -1) d1-10 ns1-2
(ii)Metallic character – With the exceptions of Zn, Cd and Hg, they have typical
metallic structures.
(iii)Atomic and ionic size-ions of same charge in a given series show progressive
decrease in radius with increasing atomic number.
(iv)Oxidation state-Variable; ranging from+2 to +7.
(v)Paramagnetism – The ions with unpaired electrons are paramagnetic.
(vi)Ionisation enthalpy – Increases with increase in charge.
Formation of coloured ions – Due to presence of unpaired electrons.
(viii) Formation of complex compounds – Due to small size and high charge density
of metal ions.
(ix)They possess catalj^c properties – Due to
their ability to adopt multiple oxidation states. .
(x)Formation of interstitial compounds.
(xi)Alloy formation.
They are called transition elements due to their incompletely filled d-orbitals in
ground state or in any stable oxidation state and they are placed between s and p-
block elements. Zn, Cd and Hg have fully filled d- orbitals in their ground state hence
may not be regarded as the transition elements.

8.9. In what way are the electronic configuration of the transition elements different
from non-transition elements?
Sol: Electronic configuration of transition elements : (n – 1)d1-10 ns1-2. Electronic
configuration of non-transition elements : ns1-2 or ns2np1-6. From comparison, it is quite
evident that the transition elements have incomplete d-orbitals (s- orbitals in some
cases) while the non-transition elements have no d-orbitals present in the valence
shells of their atoms. This is responsible for the difference in the characteristics of
the elements belonging to these classess of elements.

8.10. What are the different oxidation states exhibited by the lanthanoids?
Sol: Lanthanides exhibits + 2, + 3 and + 4 oxidation states. The most common
oxidation state of lanthanoids is +3.

8.11. Explain giving reasons:

(i)Transition metals and many of their compounds show paramagnetic behaviour.
(ii)The enthalpies of atomisation of the transition metals are high.
(iii)The transition metals generally form coloured compounds.
(iv)Transition metals and their many compounds act as good catalyst
Sol: (i) Magnetic properties: Transition elements and many of their compounds are
paramagnetic, i.e., they are weakly attracted by a magnetic field. This is due to the
presence of unpaired electrons in atoms, ions or molecules. The paramagnetic
character increases as the number of . unpaired electrons increases. The
paramagnetic character is measured in terms of magnetic moment and is given by
μ=n(n+2)−−−−−−−√ where n – number of unpaired electrons.
(ii) Because of large number of unpaired electrons in d-orbitals of their atoms they
have stronger interatomic intefactions and hence stronger metallic bonding between
atoms resulting in higher enthalpies of atomisation.
(iii) Formation of coloured compounds (both in solid state as well as in aqueous
solution) is another very common characteristics of transition metals. This is due to
absorption of some radiation from visible light to cause d-d transition of electrons in
transition metal atom. The d-orbitals do not have same energy and under the
influence of ligands, the d-orbitals split into two sets of orbitals having different
energies; transition of electrons can take place from one set of d-orbitals to another
set within the same sub-shell. Such transitions are called d-d transitions. The energy
difference for these d-d transitions fall in the visible region. When white light is
incident on compounds of transition metals, they absorb a particular frequency and
remaining colours are emitted imparting a characteristic colour to the complex.
Zn2+ and Ti4+ salts are white because they do not absorb any radiation in visible
region.
(iv)Catalytic properties: Many of transition metals and their compounds act as
catalyst in variety of reactions, e.g., finely divided iron in manufacture of NH 3 by
Haber’s process, V2O5 or Pt in manufacture of H2S04 by Contact process, etc.). The
catalytic activity is due to following two reasons.
(a)The ability of transition metal ion to pass ” easily from one oxidation state to
another
and thus providing a new path to reaction with lower activation energy.
(b)The surface of transition metal acts as very good adsorbent and thus provides
increased concentration of reactants on their surface causing the reaction to occur.
8.12. What are interstitial compounds? Why are such compounds well known for
transition metals?
Sol: Transition metals form large number of interstitial compounds. They are able to
entrap small atoms of elements like H, G, N, B, etc., in their crystal lattice and even
can make weak bonds with them.
Due to formation of interstitial compounds, their malleability and ductility decreases
and tensile . strength increases. Steel and cast iron are hard in comparison to
wrought iron due to the presence of trapped carbon atoms in interstitial spaces.

8.13. How is the variability in oxidation states of transition metals different from
that of the non-transition metals? Illustrate with examples.
Sol: The transition metals show a number of variable oxidation states due to the
participation of (n – 1) d electrons in addition to ns electrons in the bond formation.
They therefore, exhibit a large number of variable oxidation states. On the other
hand, the non-transition metals generally belonging to s-block do not show variable
oxidation states because by the loss of valence s-electrons, they acquire the
configuration of the nearest noble gas elements.

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 MoO 3 and
WO3 are not.

8.14. Describe the preparation of potassium dichromate from iron chromite ore.
What is the effect of increasing pH on a solution of potassium dichromate?
Sol: Potassium dichromate is prepared from chromate, which in turn is obtained by
the fusion of chromite ore (FeCr2O3) with sodium or potassium carbonate in free
excess of air. The reaction with sodium carbonate occurs as follows:

The yellow solution of sodium chromate is filtered and acidified with sulphuric acid
to give a solution from which orange sodium dichromate, Na2Cr,07.2H20 can be
crystallised.

Sodium dichromate is more soluble than potassium dichromate. The latter is

therefore, prepared by treating the solution of sodium dichromate with potassium
chloride.

Orange crystals of potassium dichromate crystallise out. The chromates and

dichromates depending upon pH of the solution. If pH of potassium dichromate is
increased it is converted to yellow potassium chromate.

8.15. Describe the oxidising action of potassium dichromate and write the ionic
equations for its reaction with:
(i)iodide
(ii)iron (II) solution and
(iii)H2S
Sol: K2Gr207is a powerful oxidising agent. In dilute sulphuric acid medium the
oxidation state of Cr changes from+6 to + 3. The oxidising action can be represented
as follows:

8.16. Describe the preparation of potassium permanganate. How does the acidified
permanganate solution react with (i) iron (II) ions (ii) S0 2 and (iii) oxalic acid? Write
the ionic, equations for the reactions.
Sol: Potassium permanganate (KMn04) is prepared by the fusion of a mixture of
pyrolusite (Mn02),potassiufn hydroxide and oxygen, first green coloured potassium
manganate is formed. 2MnO2 + 4KOH + 02 —> 2K2Mn04+2H20 The potassium
manganate is extracted by water, which then undergoes disproportionation in neutral
or acidic solution to give potassium permanganate.

8.17. For M2+/M and M3+/M2+ systems the E° values

for some metals are as follows:
Cr2+/Cr   –> -0.9 V
Mn2+/Mn  –> -1.2V
Fe2+/Fe     –> -0.4 V
Cr3+/Cr2+  –> -0.4 V
Mn3+/Mn2+   –>+ 1.5V
Fe3+/Fe2+   –>+ 0.8V
(ii)the ease with which iron can be oxidised as compared to a similar process for
either chromium or manganese metal.
Sol: (i) Cr3+/Cr2+ has negative reduction potential. Hence, Cr3+ cannot be reduced to
Cr2+. Mn3+/Mn2+ has a large positive reduction potential. Hence, Mn3+ can be easily
reduced to Mn2+. Fe3+/Fe2+ has small positive reduction potential. Hence, Fe3+ is more
stable than Mn3+ but less stable than Cr3+.
(ii)From the E° values, the order of oxidation of the metal to the divalent cation is :
Mn > Cr > Fe.
8.18. Predict which of the following will be coloured in aqueous solution?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+, Co2+.
Sol: Only those ions will be coloured which have incomplete d-orbitals. The ions with
either empty or filled d-orbitals are colourless. Keeping this in view, the coloured ions
among the given list are :
Ti3+(3d1), V3+(3d2), Mn2+(3d5), Fe3+(3d5), Co2+ (3d7)
Sc3+ (3d°) and Cu+ (3d10) ions are colourless.

8.19. Compare the stability of +2 oxidation state for the elements of the first
transition series.
Sol: In general, the stability of +2 oxidation state in first transition series decreases
from left to right due to increase in the sum of first and second ionisation energies.
However Mn2+ is more stable due to half filled d-orbitals (3d5) and Zn2+ is more stable
due to completely filled d-orbitals (3d10).

8.20. Compare the chemistry of actinoids with that of the lanthanoids with special
reference to
(i)electronic configuration,
(ii)atomic and ionic sizes and
(iii)oxidation state
(iv)chemical reactivity.
Sol: (i) Electronic configuration: The general electronic configuration of lanthanoids
is [Xe]54 4f1-14 5d0-1  6s2 and that of actinoids is [Rn]86 5f0-14 6d0-1  7s2, lanthanoids . belong
to 4 f series whereas actinoids belong to 5f-series.
(ii) Atomic and ionic sizes: Both lanthanoids and actinoids show decrease in size of
their atoms or ions in + 3 oxidation state as we go from left to right. In lanthanoids,
the decrease is called lanthanoid contraction whereas in actinoids, it is called
actinoid contraction. The contratibn is greater from element to element in actinodes
due to poorer shielding by 5f electrons.
(iii)Oxidation state: Lanthanoids show limited oxidation states (+ 2, + 3, + 4) out of
which + 3 is most common whereas actinoids show +3, +4, +5, +6, +7 oxidation
states.This is because of large energy gap between 4f 5d and 6s orbitals. However,
actinoids show a large number of oxidation states because of small energy ap-
between 5f 6d and Is orbitals.
(iv) Chemical reactivity: The earlier members
of the lanthanoids series are quite reactive similar to calcium but, with increase in
atomic number, they behave more like aluminium. The metals combine with
hydrogen when . gently heated in the gas. Carbides, Ln3C, Ln2C3 and LnC2 are formed
when the metals are heated with carbon. They liberate hydrogen from dilute acid and
burn in halogens to form halides. They form oxides M203 and hydroxides M(OH)3.
Actinoids are highly reactive metals, especially when finely divided. The action of
boiling water on them gives a mixture of oxide and hydride and combination with
most non-metals take place at moderate temperatures. HCl attacks all metals but
most are slightly affected by nitric acid owing to the formation of protective oxide
layers, alkalis have no action. Actinoids are more reactive than lanthanoids due to
bigger atomic size and lower ionisation energy.
8.21. How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly
oxidizing.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing
reagents it is easily oxidised.
(iii) The d1 configuration is very unstable in ions.
Sol: (i) E° value for Cr3+/Cr2+ is negative (-0-41 V) whereas E° values for Mn3+/Mn2+is
positive (+1.57 V). Hence, Cr2+ ion can easily undergo oxidation to give Cr3+ ion and,
therefore, act as strong reducing agent whereas Mn3+ can easily undergo’ reduction
to give Mn2+ and hence act as an oxidizing agent.
(ii) Co (III) has .greater tendency to form coordination complexes than Co (II). Hence,
in the presence of ligands, Co (II) changes to Co (III), i.e., is easily oxidized.
(iii) The ions with dx configuration have the tendency to lose the only electron
present in d-subshell to acquire stable d° configuration. Hence, they are unstable and
undergo oxidation or disproportionation.

8.22. What is meant by disproportionation? Give two examples of

disproportionation reaction in aqueous solution
Sol: Disproportionation reactions are those in which the same substance undergoes
oxidation as well as reduction, i.e., oxidation number of an element increases as well
as decreases to form two different products.

8.23. Which metal in the first transition metal series exhibits +1 oxidation state
most frequently and why?
Sol: Cu with configuration [Ar] 4s13d10 exhibits +1 oxidation state and forms Cu+ ion
because by losing one electron, the cation or positive ion acquires a stable
configuration of d-orbitals (3d10).

8.24. Calculate the number of unpaired electrons in the following gaseous ions :
Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution.
Sol: Mn3+ = 3d1 = 4 unpaired electrons, Cr3+ = 3d3 = 3 electrons,V3+ = 3d2 = 2 electrons,
Ti3+=3d1 = l electron.Out of these, Cr3+ is most stable in aqueous solution because of
half-filled t2g level.

8.25. Give examples and suggest reasons for the following features of the
transition metal chemistry:
(i) The lowest oxide of transition metal is basic the highest is amphoteric/ acidic.
(ii) A transition metal exhibits highest oxidation state ih oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Sol: (i) The lower oxide of transition metal is basic because the metal atom has low
oxidation state whereas higher once are acidic due to high oxidation state. For
example, MnO is basic whereas Mn2O7is acidic. Oxides in lower oxidation state are
ionic hence basic. Oxides in higher oxidation state are covalent hence acidic
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides
because oxygen and fluorine are highly electronegative elements, small in size and
strongest oxidising agents. For example, osmium shows an oxidation states of + 6 in
O5F6and vanadium shows an oxidation states of + 5 in V2O5.
(iii) Oxo metal anions have highest oxidation state, e.g., Cr in Cr2072- has an. oxidation
state of + 6 whereas Mn in Mn04– has an oxidation state of + 7. This is again due to
the combination of the metal with oxygen, which is highly electronegative and
oxidizing agent.

8.26. Indicate the steps in the preparation of:

(i)K2Cr207from chromite ore
(ii)KMn04 from pyrolusite ore.
Sol:

8.27. What are alloys? Name an alloy which contains some lanthanoid metals.
Mention its uses.
Sol: An alloy is a homogeneous mixture of different metals or metals and non-
metals.
Misch metal is an alloy of cerium (Ce). lanthanum (La), neodymium (Nd), iron (Fe)
and traces of carbon, sulphur, aluminium etc. It is used in making parts of jet
engines.

8.28. What are inner transition elements? Decide which of the following atomic
numbers are the atomic numbers of the inner transition elements:
29,59,74,95,102,104.
Sol: The f-block elements in which the. last electron enters into f-sub shell-are called
inner-transition elements. These include lanthanoids (Z=58 to 71) and actinoids
(Z=90 to 103). Thus, the elements with atomic numbers 59,95 and 102 are the? inner
transition elements.

8.29. The chemistry of the actinoid elements is not so smooth as that of the
lanthanoids. Justify this statement by giving some examples from the oxidation
state of these elements.
Sol: Lanthanoids show limited number of oxidation state, viz, + 2, + 3 and + 4 (out of
which + 3 is most common). This is because of large energy gap between 4f 5d and
6s subshells. The dominant oxidation state of actinoids is also + 3 but they show a
number of other oxidation states also. For example, uranium (Z=92) and plutonium
(Z – 94), show + 3, + 4, + 5 and + 6, neptunium (Z = 94) shows + 3, +4, + 5 and + 7,
etc. This is because of the small energy difference between. 5f, 6d and 7s orbitals of
the actinoids.

8.30. Which is the last element in the series of the actinoids? Write the electronic
configuration of this element. Comment on the possible oxidation state of this
element
Sol: Last actinoid=Lawrencium (Z = 103)
Electronic configuration = [Rn]86 5f14 6d1 7s2 Possible oxidation state = + 3.

8.31 Use Hund’s rule to derive the electronic configuration of Ce 3+ ion, and calculate
its magnetic moment on the basis of ‘spin-only’ formula.
Sol.

8.32. Name the members of the lanthanoid series which exhibit +4 oxidation state
and those which exhibit +2 oxidation state. Try to co-relate this type of behaviour
with the electronic configuration of these elements.
Sol: +4 oxidation state : 58Ce, 59Pr, 65Tb
+ 2 oxidation state : 60Nd, 62Sm, 63Eu, 69Tm, 70Yb.
In general +2 oxidation state is exhibited by the elements with configuration
5d06s2 so that two electrons may be easily lost. Similarly +4 oxidation state is shown
by the elements which after losing four electrons acquire configuration either close
to 4f0 or 4f7.

8.33. Compare the chemistry of actinoids with that of lanthanoids with reference
to:
(i)Electronic configuration
(ii)Oxidation states
(iii)Chemical reactivity
Sol: (i)Electronic configuration : In lanthanoids 4f- orbitals are progressively filled
whereas in actinoids 5f-orbitals are progressively filled.
(ii)Oxidation states : Lanthanoids shows +3 oxidation state. Some elements shows
+2 and +4 oxidation state also. Actinoids shows +3, +4, +5 +6, +7 oxidation states.
Although +3 and +4 are most common.
(iii)Chemical reactivity : Actinoids are more reactive than lanthanoids due to bigger
atomic size and lower ionisation energy.
8.34. Write the electronic configurations of the elements with the atomic numbers
61,91,101 and 109.
Sol: Z=61 (Promethium, Pm) [Xe]544f55d0 6s2
Z = 91 (Protactinium, Pa) => [Rn]86 5f2 6d1 7s2
Z = 101 (Mendelevium, Md)=> [Rn]86 5f13 6d0 7s2
Z = 109 (Meitnerium, Mt) [Rn]86 5f14 6d7 7s2

8.35. Com pare the general characteristics of the first series of the transition
metals with those of the second and third series metals in the respective vertical
columns. Give special emphasis on the following points:
(i)electronic configurations
(ii)oxidation states
(iii)ionisation enthalpies and
(iv)atomic sizes
Sol: (i) Electronic configuration: The elements in the same vertical column generally
have similar electronic configuration. First transition series shows only two
exceptions, i.e., Cr = 3d5  4s1  and Cu = 3d10 4s1. But second transition series shows
more exceptions, i.e., Y = 4d1 5s2, Nb = 4d1 , 5s1 , Mo=4d5  5s1 , Ru=4d1  5s1 , Rh=4d8 
5s1 , Pd , =4d10 5s°, Ag=4d10 5s1 . In third transition, there are two exceptions, i.e„ Pt =
5d9  6s1  and Au = 5d10 6s1 .
Thus in the same vertical column, in a number of cases, the electronic configuration
of the elements of three series are not similar.
(ii) Oxidation states: The elements in the same vertical column generally show
similar oxidation states. The number of oxidation states shown by the elements in
the middle of each series is maximum and minimum at the extreme ends.
(iii)Ionization enthalpies: The first ionization enthalpies in each series generally
increases gradually as we more from left to right though some exceptions are
observed in each series. The first ionization enthalpies of some elements in the
second (4d) series are higher while some of them have lower value than the
elements of 3d series in the same vertical column. However, the first ionization
enthalpies of third (5d) series are higher than those of 3d and Ad series. This is
because of weak shielding of nucleus by 4f-electrons in the 5d series.
(iv)Atomic sizes: In general, ions of the same charge or atoms in a given series show
progressively decrease in radius with increasing atomic number though the decrease
is quite small. But the size of the atoms of the Ad series is larger then the
corresponding elements of the 3d series whereas size of elements of the 5d-series
nearly the same as those of Ad series because of lanthanoid contraction.

8.36. Write down the number of 3d electrons in each of the following ions:Ti 2+, V2+,
Cr3+, Mn2+, Fe2+, Fe2+, Co2+, Ni2+ and Cu2+. Indicate how would you expect the five 3d
orbitals to be occupied for these hydrated ions (octahedral).
Sol:

8.37. Comment on the statement that elements of first transition series possess
many properties different from those of the heavier transition elements.
Sol: The heavier transition elements belong to fourth (Ad) and fifth (5d) and sixth
(6d) transition series. Their properties are expected to be different from the elements
belonging to the first (3d) series due to the following reasons :
(i) The atomic radii of the elements belonging to Ad and 5d series are more due to
greater number of electron shells. However, the difference in Ad and 5d transition
elements are comparatively less because of lanthanoid contraction.
(ii) Because of stronger inter atomic bonding, the m.p. and b.p. of the elements of Ad
and 5d series are higher.
(iii) Ionisation enthalpies are expected to decrease as we move from one series to
the other. However, the values for the elements of 5d series are higher as compared
to the elements belonging to the other two series due to lanthanoid contraction.
Actually atomic size decreases on account of it and effective nuclear charge
increases. As a result, there is an increase in ionisation energy in case of 3d
elements.

8.38. What can be inferred from the magnetic moment values of the following
complex species?

Sol: