d- and f- block elements

1. (a) Which metal in the first transition series (3d series) exhibits +1 oxidation state most
frequently? Why?
(b) Which of the following cations are coloured in aqueous solutions and why?Sc3+,
V3+, Ti4+, Mn2+.(At. nos. Sc = 21, V = 23, Ti = 22, Mn = 25) (Delhi 2013)

(a) Copper exhibits + 1 oxidation state more frequently i.e., Cu+1 because of its electronic
configuration 3d104s1. It can easily lose 4s1 electron to give stable 3d10 configuration.
(b) Sc3+ = 4S0 3d0 = no unpaired electron
V3+ = 3d2 4s0 = 2 unpaired electron
Ti4+ = 3d0 4s0 = no unpaired electron
Mn2+ = 3d5 4s0 = 5 unpaired electron
Thus V3+ and Mn2+ are coloured in their aqueous solution due to presence of unpaired electron.

2. What is Lanthanoid contraction? What are its two consequences? (Comptt. Delhi 2013)

Lanthanoid contraction: The overall decrease in atomic and ionic radii with increasing atomic
number is known as lanthanoid contraction. In going from La+3 to Lu+3 in lanthanoid series, thesize
of ion decreases. This decrease in size in the lanthanoid series is known as lanthanoid contraction.
The lanthanoid contraction arises due to imperfect shielding of one 4f electron by another present
in the same subshell.
Consequences:
(i) Similarity in properties: Due to lanthanoid contraction, the size of elements which follow (Hf –
Hg) are almost similar to the size of the elements, of previous row (Zr – Cd) and hence these are
difficult to separate. Due to small change in atomic radii, the chemical properties of lanthanoids
are very similar due to which separation of lanthanoid becomes very difficult.
(ii) Basicity difference: Due to lanthanoid contraction, the size decreases from La+3 to Lu+3. Thus,
covalent character increases. Hence basic character of hydroxides also decreases i.e. why La(OH)3
ismost basic while Lu(OH)3 is least basic.
3. Describe the general trends in the following properties of the first series (3d) of the transition
elements:
(i) Number of oxidation states exhibited
(ii) Formation of oxometal ions (Comptt. Delhi 2014)

(i) The number of oxidation states increases up to middle of series i.e. unto +7 and then
decreases.
(ii) Oxometal ions are polyatomic ions with oxygen. Example: VO2+, VO+2, TiO2+
4. Write one similarity and one difference between the chemistry of lanthanoids and that of actinoids.
(AllIndia 2015)

Similarity: Both lanthanoids and actinoids show contraction in size and irregularity in their
electronicconfiguration.
Difference: Actinoids show wide range of oxidation states but lanthanoids do not.

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5. In the 3d series (Sc = 21 to Zn = 30) :
(i) Which element shows maximum number of oxidation states?
(ii) Which element shows only +3 oxidation state?
(iii) Which element has the lowest enthalpy of atomization? (Comptt. Delhi 2016)

(i) Mn (ii) Sc (iii) Zn

6. Complete the following chemical equations: (All India 2011)
(i) MnO4 (aq) + S2O32- (aq) + H2O (1) →
(ii) Cr2O72- (aq) + Fe2+ (aq) + H+ (aq) →

7. What is meant by ‘disproportionation’? Give an example of a disproportionation reaction in

aqueous solution. (Comptt. Delhi 2015)

Disproportionation: In a disproportionation reaction an element undergoes self-oxidation aswell

as self-reduction forming two different compounds.

8. Describe the preparation of potassium permanganate. How does the acidified permanganate
solution react with oxalic acid? Write the ionic equations for the reactions.

Potassium Permangante (KMnO4) is prepared from pyrolusite ore (MnO2). The ore (MnO2) is fused
with an alkali metal hydroxide like KOH in the presence of air or an oxidising agent like KNO3 to give
green potassium manganate (K2MnO4). K2MnO4 disproportionates in a neutral or acidic solution to
give potassium permanganate.

9. Why is the first ionisation enthalpy of Cr is lower than that of Zn

Ionisation enthalpy of Cr is less than that of Zn because Cr has a stable configuration. In the case of
zinc, the electron comes out from wholly filled 4s orbital. So, the removal of an electronfrom zinc
requires more energy as compared to chromium.
10. Transition elements show high melting points. Why?

The high melting points of transition metals are due to the involvement of a greater number of
electrons of (n-1)d in addition to the ns electrons in the interatomic metallic bonding.
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11. Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilise
higher oxidation states exceeds that of fluorine. Why?

Oxygen can form multiple bonds with metals, while fluorine can’t form multiple bonds. Hence,
oxygen has more ability to stabilise a higher oxidation state rather than fluorine.

12. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate
them. Why?

Separation of Zr and Hf is pretty tricky because of lanthanoid contraction. Due to lanthanoid

contraction, they have almost identical sizes (Zr = 160 pm and Hf =159 pm) and, thus, similar
chemical properties. That’s why it is tough to separate them by chemical methods.

13. The halides of transition elements become more covalent with increasing oxidation state of the
metal. Why?

As the oxidation state increases, the size of the ion of the transition element decreases. As per
Fajan’s rule, as the size of metal ions decreases, the covalent character of the bond formed
increases. Therefore, the halides of transition elements become more covalent with the
increasing oxidation state of the metal.
14. Third ionization enthalpy of manganese is unusually high. Why?

Valence configuration of Mn is, 4s23d5 implies we should remove from the 2e− from 4s2 then
comes 3d5 which is half filled configuration. It is stable configuration due to greater exchange
energy and hence high energy is needed to remove an e− from this configuration.
Hence third ionization enthalpy of Manganese is unusually high.

15. The first ionization enthalpies of 5d elements is higher than that of the corresponding 3d and 4d
elements.

It is due to the greater effective nuclear charge in the case of 5d elements due to the poor shielding
of valence electrons by the 4f electrons.
5d elements have much more nuclear charge and the weakest shielding of valence electrons. Hence
their elements experience the maximum electrostatic attraction from the nucleus and thus also
have the highest first ionization energies among 3d 4d and 5d elements.
16. Why Cu, Ni and Zn generally do not show oxidation state greater than 2?

IE3 for Cu, Ni and Zn is generally very high. That is why it does not show oxidation state of +3

17. Following are the transition metal ions of 3d series:

Ti4+,V2+,Mn3+,Cr3+
(Atomic numbers: Ti=22,V=23,Mn=25,Cr=24)
Answer the following:
(i) Which ion is most stable in an aqueous solution and why?
(ii) Which ion is a strong oxidising agent and why?
(iii) Which ion is colourless and why?
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 (i) Ti4+ is most stable as it has completely filled 3p orbital.
(ii)Mn3+ is the strongest oxidising agent as it requires only one electron to half fill its 3d orbital
(iii)Ti4+ will be colorless due to its empty 3d orbital.

Account for the following

STATEMENTS REASONS

1. Transition elements show variable The variability of oxidation state of transition elements
oxidation states. isdue to incompletely filled d-orbitals and presence of
unpaired electrons, i.e. (ns) and (n-1) d electrons have
approximate equal energies.
2. Generally, there is an increase in density From titanium to copper the atomic size of elements
of elements from titanium (Z = 22) to decreases and mass increases as a result of which density
copper (Z = 29) in the first series of increases.
transition elements.
3. Transition elements and their The catalytic properties of the transition elements are due
compounds are generally found to to the presence of unpaired electrons in their incomplete
begood catalysts in chemical d-orbitals and variable oxidation states.
reactions.
4. Transition elements generally Because of presence of unpaired d electrons, which
formcoloured compounds. undergoes d-d transition by absorption of energy
fromvisible region and then the emitted light shows
complementary colors. This is how transition
elementsform colored compounds.

5. Zinc is not regarded as a transition Zinc in its common oxidation state of +2 has
element. completelyfilled d-orbitals. Hence considered as non-
transition element.
6. Copper (I) ion is not known in aqueous Cu2+(aq) is much more stable than Cu+(aq). This is because
solution. although second ionization enthalpy of copper is large but
Δhyd (hydration enthalpy) for Cu2+(aq) is much more
negative than that for Cu+(aq) and hence it more than
compensates for the second ionization enthalpy of copper.
Therefore, many copper (I) compounds are unstable in
aqueous solution and undergo disproportionation as
follows:
2Cu+ → Cu2+ + Cu
7. Actinoids exhibit greater range of Because of very small energy gap between 5f, 6d and 7s
oxidation states than lanthanoids. subshells all their electrons can take part in bonding and
(Delhi2011) shows variable oxidation states.

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8. Cr2+ is reducing in nature while with the Cr2+ has the configuration 3d4 which easily changes to
same d-orbital configuration (d4) Mn3+ d3 due to stable half-filled t2g orbitals. Therefore Cr2+
isan oxidising agent. isreducing agent. While Mn2+ has stable half-filled
d5 configuration. Hence Mn3+ easily changes to Mn2+
andacts as oxidising agent.

9. In a transition series of metals, the Due to presence of more unpaired electrons and use of all
metalwhich exhibits the greatest 4s and 3d electrons in the middle of series.
number of oxidation states occurs in the
middle of
the series.
10. Manganese exhibits the highest Manganese exhibits highest oxidation of +7 among 3d
oxidation state of +7 among the 3d series of transition elements because all the oxidation
series of transition elements. states are exhibited from +2 to +7 by Mn and no other
(Delhi2011) element of this series shows this highest state of
oxidation.
11. ‘lanthanoid contraction’? (Delhi 2011) The steady decrease in the ionic radius from La3+ to Lu3+
due to poor shielding of 4f orbitals is termed as lanthanoid
contraction.
12. Unlike Cr3+, Mn2+, Fe3+ and the Because high enthalpies of atomisation of 4d and 5d series
subsequent other M2+ ions of the 3d and high ionization enthalpies, the M.P. and B.P. of
series of elements, the 4d and the 5d heavier transition elements are greater than those of first
series metals generally do not form transition series which is due to stronger intermetallic
stable cationic species. bonding. Hence 4d and 5d series metals generally do not
form stable cationic species.
13. Metal-metal bonding is more frequent Metal-metal bonding is more frequent for the 4d and the
forthe 4d and the 5d series of transition 5dseries of transition metals than that for the 3d series as
metals than that for the 3d series. these have their electrons of outer most shell at greater
distance from the nucleus, as compared to atoms of 3d
transition metals.
14. Transition metals and their Because of presence of unpaired electrons in their d-
compoundsgenerally exhibit a subshell in atomic and ionic state.
paramagnetic behaviour.
15. The chemistry of actinoids is not so Lanthanoids show limited number of oxidation state, viz.
smooth as that of lanthanoids. +2, +3 and +4 (out of which +3 is most common) because
of large energy gap between 4f and 5d subshells. Actinoids
also show stable +3 oxidation state but show a number of
oxidation states i.e. +4, +5 and + 6, +7 due to small energy
difference between 5f, 6d and 7s subshells.

16. The enthalpies of atomization In transition elements, there are large number of
oftransition metals are quite unpairedelectrons in their atoms, thus they have a
high. stronger inter atomic interaction and thereby stronger
bonding between the atoms. Due to this they have high
enthalpies of
atomization.

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17. The transition metals (with the Because of stronger metallic bonding and high enthalpies
exceptionof Zn, Cd and Hg) are hard and of atomization.
have high melting and boiling points.
18. The ionization enthalpies (first and Due to irregularities in the electronic configuration there
second) in the first series of the is irregularities in the enthalpies of atomisation. Hence
transition elements are found to thereis irregular variation in I.E.
varyirregularly.
19. (i)The highest oxidation state of a (i)The highest oxidation state of a metal is exhibited in
transition metal is usually exhibited in itsoxide or fluoride due to its high electronegativity, low
itsoxide. ionisation energy and small size.
(ii)La3+ (Z = 57) and Lu3+ (Z = 71) do (ii)No unpaired electrons in La3+ and Lu3+
notshow any colour in solutions.
20. Co2+ is easily oxidised in the presence Co2+ ion is easily oxidised to Co3+ ion in presence of a
of a strong ligand. (Comptt. Delhi 2014) strong ligand because of its higher crystal field energy
which causes pairing of electrons to give inner orbital
complexes (d2sp3).

21. Both O2 and F2 stabilize high oxidation The ability of O2 to stabilize higher oxidation states
states of transition metals but the exceeds that of fluorine because oxygen can form
abilityof oxygen to do so exceeds that multiplebonds with metals.
of fluorine.
22. Silver atom has completely filled d- Because silver has incomplete d-orbital (4d9) in its +2
orbitals (4d10) in its ground state, yet it oxidation state, hence it is a transition element.
isregarded as a transition element.
23. E0 value for Mn3+ /Mn2+ couple is much The large positive E° value for Mn3+/Mn2+ shows that
more positive than Cr3+/Cr2+. Mn2+ is much more stable than Mn+3 due to stable half-
filled configuration (3d5). Therefore the 3rd ionisation
energy of Mn will be very high and Mn3+ is unstable and
can be easily reduced to Mn2+. E° value for Cr3+ | Cr2+ is
positive but small i.e. Cr3+ can also be reduced to Cr2+ but
less easily. Thus Cr3+ is more stable than Mn3+.
24. The metallic radii of the third (5d) Due to lanthanoid contraction in second series after
seriesof transition elements are lanthanum, the atomic radii of elements of second
virtually the same as those of the andthird series become almost same and hence show
corresponding members of the second similarities in properties.
series.
25. There is a gradual decrease in the size This is due to lanthanoid contraction.
of atoms with increasing atomic
numberin the series of lanthanoids.
26. Sc (21) is a transition element but Ca Sc (21) is regarded as a transition element due to the
(20) is not. presence of incomplete d- subshell (3d14s2) but Ca (20)
does not have any d-subshell.
27. The Fe2+ is much more easily oxidised to Fe+2[Ar] 3d6 can be easily oxidised to Fe+3 [Ar] 3d5, which is
Fe3+ than Mn2+ to Mn3+. half filled and is more stable but Mn+2 is d5 in configuration
which is again half-filled configuration and Mn+3 is d4 in
configuration.

6
28. Zr (Z = 40) and Hf (Z = 72) have almost Zr and Hf have almost identical radii due to lanthanoid
identical radii. contraction which is due to weak shielding of d-
electrons.
29. Cobalt (II) is very stable in aqueous Co2+ ion is easily oxidised to Co3+ ion in presence of a
solutions but gets easily oxidised in the strong ligand because of its higher crystal field energy
presence of strong ligands. which causes pairing of electrons to give inner orbital
complexes (d2sp3).

30. From element to element The actinoid contraction is greater than lanthanoid
actinoidcontraction is greater contraction due to poorer shielding of 5f electrons as
than the lanthanoid contraction. theyare extended in space beyond 6s and 6p orbitals
whereas4f orbitals are buried deep inside the atom.

31. Mn shows the highest oxidation state of Because oxygen stabilizes the highest oxidation state (+7
+7 with oxygen but with fluorine it of Mn) even more than fluorine i.e., +4 since oxygen has
showsthe highest oxidation state of +4. the ability to form multiple bonds with metal atoms.

32. Actinoids show irregularities in This happens because the energy difference between 5f,
theirelectronic configurations. 6d and 7s subshells of the actinoids is very small and
hence electrons can be accommodated in any of them.

33. MnO is basic while Mn2O7 is acidic. MnO is basic while Mn2O7 is acidic because the basic
nature decreases as the oxidation state or number of
oxygen atoms increases i.e. MnO(+4) and Mn2O7(+7)

34. Calculate the magnetic moment of a Divalent ion with atomic number 26 is Fe2+
divalent ion in aqueous medium if
itsatomic number is 26.

35. There occurs much more frequent It is due to their low ionization energies and variable
metal-metal bonding in compounds oxidation state. Because of increase in effective nuclear
of heavy transition elements (3rd charge and weak shielding effect of d-electrons, the
series). atomicradii decreases.
2+ 2+
36. The E°M /M, for copper is positive The E°M /M for any metal is related to the sum of the
(+0.34V). It is the only metal in the enthalpy changes taking place in the following steps:
firstseries of transition elements M(g) + ΔaH → M(g) (ΔaH = enthalpy of atomization)
showing this type of behaviour. M(g) + ΔiH → M2+(g) (ΔiH = ionization enthalpy)
M2+(g) + aq → M2+(aq) + ΔhydH (ΔhydH = hydration
enthalpy)
Copper has high enthalpy of atomization (i.e. energy
absorbed and low enthalpy of hydration (i.e. energy
2+
released). Hence E°M /M for copper is positive. The high
energy required to transform Cu(s) to Cu2+(aq) is not
balanced by its hydration enthalpy.

7
37. The E° value for Mn3+ | Mn2+ couple The large positive E° value for Mn3+ | Mn2+ shows that
ismuch more positive than for Cr3+ | Mn2+ is much more stable than Mn3+ due to stable half-
Cr2+ or Fe3+ | Fe2+ couple. filled configuration (3d5). Therefore the 3rd ionization
energy of Mn will be very high and Mn3+ is unstable
andcan be easily reduced to Mn2+.
E° value for Fe3+ | Fe2+ is positive but small i.e. Fe3+ can
also be reduced to Fe2+ but less easily. Thus Fe3+ is more
stable than Mn3+.
38. The oxidising power of oxoanions are in The ions in which the central metal atom is present in
+ −7 − thehighest oxidation state will have the highest oxidising
the order VO2 <Cr2O2 <MnO4 power. In VO+2 V is present in the +5 oxidation state,
2-
while in Cr2O7 ion, Cr is present in the +6 oxidation state.
–
Similarly, in the MnO4 ion, Mn is present in the +7
oxidation state. Thus, as the oxidation state of the
central metal atom increases in the order V < Cr < Mn,
therefore the oxidising power of the oxoanions increases
in the
+ 2- –
order: VO2 < Cr2O7 < MnO4
39. The third ionization enthalpy of Because third electron has to be removed from stable
manganese (Z = 25) is exceptionally half-filled 3d-orbitals (Z = 25 has 3d5 4s2).
high.
40. Cr2+ is a stronger reducing agent than Cr2+3+is a stronger
2+
reducing agent than Fe2+ because
3+ 2+
Fe2+. E°Cr /Cr is negative (-0.41 V) whereas E°Fe /Fe is
positive (0.77 V). Thus Cr2+ is easily oxidised to Cr3+ but
Fe2+ cannot be easily oxidized to Fe3+.
41. Mn2+compounds are more stable The electronic configuration of Mn+2 is [Ar] 3d5 i.e. all the
than Fe2+ compounds towards five d-orbitals are singly occupied. Thus, this configuration
oxidation totheir +3 state. is stable and resists further oxidation i.e. loss of further
electrons requires high energy. On the other hand, the
electronic configuration of Fe+2 is [Ar]3d6. Hence it loses
one electron and achieves the stable configuration i.e.
oxidation of Fe+2 to Fe+3 is easily achieved.
42. Mn3+ is a good oxidising agent. Mn3+ has electronic configuration 3d44s0.
On reduction it gains one electron to become 3d54s0
whichis half filled stable configuration. Hence it is a good
oxidising agent.
43. Name the element showing maximum It is Manganese (Mn) which shows oxidation states from
number of oxidation states among the +2 to +7
first series of transition metals from
Se(Z = 21) to Zn (Z = 30).
44. Name the element which shows only +3 Scandium (Sc) shows only +3 oxidation state.
oxidation state.
45. d-block elements exhibit more d-block elements exhibit more oxidation states due to
oxidationstates than f-block elements. smallenergy gap between ns and (n–1) d subshell while f –
block elements show less oxidation state due to large
8
 energy gap between ns and (n -2)f subshell.

46. The variation in oxidation states of In transition elements, the successive oxidation state
transition metals is of different type differs by unity, e.g, Mn shows all the oxidation states
fromthat of the non-transition metals. from
+2 to +7. On the other hand non-transition metals exhibit
variable oxidation states which differ by two units, e.g.
Pb(II), Pb(IV), Sn(II), Sn(IV) etc.
47. Orange solution of potassium The orange coloured potassium dichromate solution when
dichromate turns yellow on treated with basic NaOH solution, is converted to
addingsodium hydroxide to it. chromatewhich gets a faint colour like yellow.
The reaction is given as:
K2Cr2O7 + 2NaOH → K2CrO4 + Na2CrO4 + H2O.
–
This formation of chromate (CrO4 ) ion converts the colour
of solution to yellow.

48. Cr2+ is a strong reducing agent. Cr2+ exists in the d4 system and is easily oxidized to Cr3+ by
losing one electron which has the stable d3/t2g orbital
configuration. So, Cr2+ is a strong reducing agent.
49. Cu2+ salts are coloured while Zn2+ salts Cu2+ has the configuration 3d9 with one unpaired
are white. electronwhich gets excited in the visible region to impart
its colourwhile Zn2+ has 3d10 configuration without any
unpaired electron so no d – d transition possible and
hence colourless.
50. The lowest oxide of transition metal The lowest oxide of transition metal is basic because of low
isbasic whereas the highest oxide is oxidation state some of valence electrons are not involved
amphoteric or acidic. in bonding and acts as base by donating electron.
However in higher oxides due to high oxidation state, it
cannot donate electrons but can accept electrons due
tohigh effective nuclear charge. Hence, they are acidic
in nature.
51. HCl is not used to acidifyKMnO4 HCl is not used to the acidify KMnO4 solution because
solution. KMnO4 is a very strong oxidizing agent and it can oxidize
HCl to liberate chlorine gas.
52. MnCl2 is ionic where as KMnO4 is Elements in +2 and +3 form ionic compounds and
covalent. Why? elements in higher oxidation state form covalent
compounds.
53. Cr(VI) in the form of dichromate in Higher oxidation state is found to be stable than lower
acidic medium is a strong oxidising oxidation state for elements of 4d and 5d series.
agent, whereas MoO3 and WO3 are not Cr(VI) is less stable than Mo(VI) and W (VI).

54. Cu+ is unstable in water but Cu2+ is Cu+ undergoes disproportionation in water.
stable in water. Cu+ → Cu2+ + Cu

9
55. Higher oxidation for transition metals This is due to
are seen in oxides and fluorides High electronegativity
High lattice enthalpy
High bond enthalpy
56. Cu(II)halides are known except Cu2+ oxidises I- to I2
Cu(II)iodide
Cu2+ + I- → Cu2 I2+ I2
Or
Cu(II)iodide is not known
57. Cr2+ reducing and Mn3+ oxidising when Cr2+ is reducing as its configuration changes from d4 to d3,
both have d4 configuration? the latter having a half-filled t2g level. On the other hand,
the change from Mn3+ to Mn2+ results in the half-filled (d5)
configuration which has extra stability.
58. Transition metals and their compounds The catalytic property arises due to the
act as catalyst. 1) Presence of unpaired electrons in d orbitals.
2) Ability to exhibit variable oxidation state.
59. Cu2+ is more stable in aqueous solution Cu+ has outermost electronic configuration as 3d10 and
than Cu+. therefore, should be most common and most stable state
because of extra stability associated with completely filled
d-subshell (d10). However, this is not true and Cu2+ with
outer electronic configuration 3d9 is more stable than Cu+.
This is due to high hydration energy in aqueous solution
and high lattice energy in solid state of Cu2+ as compared
to Cu+.

Stability depends on the hydration energy (enthalpy) of

the ions when they bond to the water molecules. The Cu2+
ion has a greater charge density than Cu+ ion and thus
forms much stronger bonds releasing more energy.
60. Transition metal form complexes Transition metal form complexes due to
(coordination compounds) 1. Small size of the metal ion
2. High ionic charge
3. Presence of vacant d orbitals which can accommodate
the lone pairs donated by the ligands.

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