The d- and f-Block Elements Class 12

Important Questions
Q1. What is lanthanoid contraction? Write a conse-quence of lanthanoid contraction.
(Comptt. Delhi 2014)
Answer:
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,
the size 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 is most basic while Lu(OH)3 is least basic.

Q2. How would you account for the following?

(i) The highest oxidation state of a transition metal is usually exhibited in its oxide.
(ii) The oxidising power of the following three oxoions in the series follows the order:
(Comptt. Delhi 2014)
VO+2<Cr2O2−7<MnO−4
Answer:
(i) The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high
electronegativity, low ionisation energy and small size.
(ii) La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.

Q3. How would you account for the following?

(i) The atomic radii of the metals of the third (5d) series of transition elements are virtually the same
as those of the corresponding members of the second (4d) series.
(ii) The E° value for the Mn3+/Mn2+ couple is much more positive than that for Cr3+/Cr2+ couple or
Fe2+/Fe2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride. (Delhi 2010)
Answer:
(i) Due to lanthanoid contraction in second series after lanthanum, the atomic radii of elements of
second and third series become almost same and hence show similarities in properties.
(ii) The electronic configuration of Mn2+ ion is more symmetrical as compared to that of Cr2+ ion. So
3rd ionisation potential of Mn2+ is much higher. As a result E° value of Mn3+/ Mn2+ couple is much more
positive than for Cr3+/Cr2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high
electronegativity

Q4. How would you account for the following?

(i) With the same d-orbital configuration (d4) Cr2+ is a reducing agent while Mn3+ is an oxidizing agent.
(ii) Most of the transition metal ions exhibit characteristic in colours in aqueous solutions. (Delhi
2012)
Answer:
(i) Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half filled t2g orbitals.
Therefore Cr2+ is reducing agent. While Mn2+ has stable half filled d5 configuration. Hence Mn3+ easily
changes to Mn2+ and acts as oxidising agent.
(ii) Due to the presence of unpaired electrons in d-orbital, transition metal exhibits colours in aqueous
solution or due to d-d transition.

Q5. (a) Which metal in the first transition series (3d series) exhibits
+1 oxidation state most frequency and why?
(b) Which of the following cations are coloured in aqueous solutions
and why?
SC , V , Ti , Mn .
3+ 3+ 4+ 2+

(At. nos. Sc = 21, V = 23, Ti = 22, Mn = 25) (Delhi 2013)

Answer:
(a) Copper exhibits + 1 oxidation state more frequently i.e.,
Cu because of its electronic configuration 3d 4s . It can easily lose
+1 10 1

4s electron to give stable 3d configuration.

1 10

(b) SC3+ = 4S0 3d3+ = 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.
Q6.Assign a reason for each of the following observations:
(i) The transition metals (with the exception of Zn, Cd and Hg) are hard and have high
melting and boiling points.
(ii) The ionization enthalpies (first and second) in the first series of the transition elements are
found to vary irregularly. (Comptt. Delhi 2014)
Answer:
(i) Because of stronger metallic bonding and high enthalpies of atomization.
(ii) Due to irregulaties in the electronic configuration there is irregularities in the enthalpies
of atomisation. Hence there is irregular variation in I.E.
Q7.Assign reasons for the following :
(i) Copper(I) ion is not known to exist in aqueous solutions.
(ii) Both O2 and F2 stabilize high oxidation states of transition metals but the ability of oxygen
to do so exceeds that of fluorine. (Comptt. All India 2014)
Answer:
(i) Cu2+(aq) is much more stable than Cu+(aq). This is because 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
(ii) The ability of O2 to stabilize higher oxidation states exceeds that of fluorine because
oxygen can form multiple bonds with metals.

Q8.Assign reasons for the following :

(i) Transition metals and many of their compounds act as good catalysts.
(ii) Transition metals generally form coloured compounds. (Comptt. All India 2014)
Answer:
(i) The catalytic properties of the transition elements are due to the presence of unpaired
electrons in their incomplete d-orbitals and variable oxidation states.
(ii) Because of presence of unpaired electrons in d-orbital, which undergoes d-d transition by
absorption of energy from visible region and then the emitted light shows complementary
colours.

Q9.What are the transition elements? Write two characteristics of the transition elements.
(Delhi 2015)
Answer:
Elements which have partially filled d-orbital in its ground states or any one of its oxidation
states are called transition elements.

 They show variable oxidation states.

 They form coloured ions.
 They form complex compounds.

Q10.Suggest reasons for the following features of transition metal chemistry :

(i) The transition metals and their compounds are usually paramagnetic.
(ii) The transition metals exhibit variable oxidation states. (Comptt. Delhi 2015)
Answer:
(i) The transition metals and their compounds are usually paramagnetic because of the presence of
unpaired electrons in their d-orbitals.
(ii) The transition metals exhibit variable oxidation states because of very close energies of
incompletely filled (n – l)d orbitals and ns orbitals due to which both can participate in bonding.
Q11.Give reasons :
(i) Zn is not regarded as a transition element.
(ii) Cr2+ is a strong reducing agent. (Comptt All India 2016)
Answer:
(i) Zinc Atomic no. 30 have EC 3d10, 4s2. It has completely filled ‘d’ orbitals.
(ii) Cr+2 (3d4) after loosing one electron forms Cr+3 (d3). It has t32ge0g configuration. Hence more
stable. Hence Cr+2 acts as reducing agent.
Or
Cr+3 is more stable than Cr+2, therefore Cr+2 looses one electron. Hence acting as strong reducing agent.
Q12.Explain the following observations :
(i) Copper atom has completely filled d orbitals (3d10) in its ground state, yet it is regarded as a
transition element.
(ii) Cr2+ is a stronger reducing agent than Fe2+ in aqueous solutions. (Comptt. All India 2017)
Answer:
(i) Copper atom has completely filled d orbitals (3d10) in its ground state, yet it is regarded as a
transition element due to incompletely filled d-orbital in its ionic states i.e. Cu 2+ (3d9).
(ii) The highest oxidation state for Cr is +6, therefore it can loose 3 more electrons, whereas Fe needs
to loose only 1 electron to achieve its highest oxidation state of +3. Thus, Cr 3+ is more reducing than
Fe2+.
Q13.Explain the following observations :
(a) Silver atom has completely filled d-orbitals (4d10) in its ground state, yet it is regarded as a
transition element.
(b) E0 value for Mn3+ /Mn2+ couple is much more positive than Cr3+/Cr2+. (Comptt. All India
2017)
Answer:
(a) Because silver has incomplete d-orbital (4d9) in its +2 oxidation state, hence it is a
transition element.
(b) The large positive E° value for Mn3+/Mn2+ shows that 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+.

Q14.Explain the following observations :

(i) Zn2+ salts are colourless.
(ii) Copper has exceptionally positive E0M2+/M value. (Comptt. All India 2017)
Answer:
(i) Zn2+ salts are colourless due to absence of unpaired electrons in its ground state and ionic
state i.e. Zn2+ = [Ar] 3d104s04p0
(ii) The E0M /M for any metal is related to the sum of the enthalpy changes taking place in the
2+

following steps :
M(g) + ΔaH → M(g) (ΔaH = enthalpy of atomization)
M(g) + ΔiH → M2+(g) (ΔiH = ionization of atomization)
M2+(g) + aq → M2+(g) + ΔhydH (ΔhydH = hydration atomization)
Copper has high enthalpy of atomization (i.e. energy absorbed and low enthalpy of hydration
(i.e. energy released). Hence E0M /M for copper is positive. The high energy required to
2+

transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.

Q15.How would you account for the following :
(i) Many of the transition elements and their compounds can act as good catalysts.
(ii) The metallic radii of the third (5d) series of transition elements are virtually the same as
those of the corresponding members of the second series.
(iii) There is a greater range of oxidation states among the actinoids than among the
lanthanoids. (All India 2009)
Answer:
(i) The catalytic properties of the transition elements are due to the presence of unpaired
electrons in their incomplete d-orbitals and variable oxidation states.
(ii) Due to lanthanoid contraction in second series after lanthanum, the atomic radii of
elements of second and third series become almost same and hence show similarities in
properties.
(iii) Because of very small energy gap between 5f, 6d and 7s subshells all their electrons can
take part in bonding and shows variable oxidation states.

Q16.How would you account for the following?

(i) The atomic radii of the metals of the third (5d) series of transition elements are virtually
the same as those of the corresponding members of the second (4d) series.
(ii) The E° value for the Mn3+/Mn2+ couple is much more positive than that for Cr3+/Cr2+ couple
or Fe2+/Fe2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride. (Delhi 2010)
Answer:
(i) Due to lanthanoid contraction in second series after lanthanum, the atomic radii of
elements of second and third series become almost same and hence show similarities in
properties.
(ii) The electronic configuration of Mn2+ ion is more symmetrical as compared to that of
Cr2+ ion. So 3rd ionisation potential of Mn2+ is much higher. As a result E° value of Mn3+/
Mn2+ couple is much more positive than for Cr3+/Cr2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high
electronegativity.

Q17.How would you account for the following?

(i) Many of the transition elements are known to form interstitial compounds.
(ii) The metallic radii of the third (5d) series of transition metals are virtually the same as
those of the corresponding group members of the second (4d) series.
(iii) Lanthanoids form primarily +3 ions, while the actinoids usually have higher oxidation
states in their compounds, +4 or even +6 being typical. (Delhi 2012)
Answer:
(i) The transition metals form a large number of interstitial compounds in which small atoms
such as hydrogen, carbon, boron and nitrogen occupy the empty spaces in the crystal lattices
of transition metals.
(ii) Because of lanthanoid contraction.
(iii) This is due to comparable energies of 5f, 6d, 7s orbitals in actinoids.
Q18.How would you account for the following?
(i) With the same d-orbital configuration (d4) Cr2+ is a reducing agent while Mn3+ is an
oxidizing agent.
(ii) The actinoids exhibit a larger number of oxidation states than the corresponding members
in the lanthanoid series.
(iii) Most of the transition metal ions exhibit characteristic in colours in aqueous solutions.
(Delhi 2012)
Answer:
(i) Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half filled t2g
orbitals. Therefore Cr2+ is reducing agent. While Mn2+ has stable half filled d5 configuration.
Hence Mn3+ easily changes to Mn2+ and acts as oxidising agent.
(ii) Due to comparable energies of 5f 6d and 7s orbitals of actinoids, these show larger
number of oxidation states than corresponding members of lanthanoids.
(iii) Due to the presence of unpaired electrons in d-orbital, transition metal exhibits colours in
aqueous solution or due to d-d transition.
Q19.Explain the following observations giving an appropriate reason for each.
(i) The enthalpies of atomization of transition elements are quite high.
(ii) There occurs much more frequent metal- metal bonding in compounds of heavy transition
metals (i.e. 3rd series).
(iii) Mn2+ is much more resistant than Fe2+ towards oxidation. (Delhi 2012)
Answer:
(i) In transition elements, there are large number of unpaired electrons in their atoms, thus
they have a stronger inter atomic interaction and thereby stronger bonding between the atoms.
Due to this they have high enthalpies of atomization.
(ii) Because of high enthalpy of atomisation of 3rd series, there occurs much more frequent
metal-metal bonding in compounds of heavy transition metals.
(iii) The 3d orbital in Mn2+ is half-filled and is more stable compared to Fe2+ has 6 electrons in
the 3d orbital. Mn2+ prefer to lose an electron or get oxidised whereas Fe2+ will readily loose
one electron or get oxidised. Therefore, Mn2+ is much more resistant than Fe2+ towards
oxidation.

Q20. Give reasons :

(a) Sc (21) is a transition element but Ca (20) is not.
(b) The Fe2+ is much more easily oxidised to Fe2+ than Mn2+ to Mn3+. (Comptt. Delhi 2012)
Answer:
(a) Sc (21) is regarded as a transition element due to the presence of incomplete d- subshell
(3d14s2) but Ca (20) does not have any d-subshell.
(b) Fe+2[Ar] 3d6 can be easily oxidised to Fe+3 [Ar] 3d5, which is 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.

Q21. 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)
Answer:
(i) Mn
(ii) Sc
(iii) Zn

Q22. a) Give reasons for the following:

(i) Compounds of transition elements are generally coloured.
(ii) MnO is basic while Mn2O7 is acidic.
(iii) Calculate the magnetic moment of a divalent ion in aqueous medium if its atomic
number is 26. (Comptt. All India 2017)
Answer:
(a) (i) The catalytic properties of the transition elements are due to the presence of unpaired
electrons in their incomplete d- orbitals and variable oxidation states. The colour of transition
metal ions is due to d-d transition. When electrons jump from one orbital to another in their
partially filled d-orbitals, another light is emitted due to which the compounds of transition
elements seem to be coloured.
(ii) 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)
(b) Divalent ion with atomic number 26 is Fe2+

Q23. Explain the following observations :

(i) In general the atomic radii of transition elements decrease with atomic number in a given
series.
(ii) The E°M /M, for copper is positive (+ 0.34 V). It is the only metal in the first series of
2+

transition elements showing this type of behaviour.

(iii) The E° value for Mn3+ | Mn2+ couple is much more positive than for Cr3+ | Cr2+ or Fe3+ |
Fe2+ couple. (Delhi 2009)
Answer:
(i) Because of increase in effective nuclear charge and weak shielding effect of d-electrons,
the atomic radii decreases.
(ii) The E°M /M for any metal is related to the sum of the enthalpy changes taking place in the
2+

following steps :
M(g) + ΔaH → M(g) (ΔaH = enthalpy of atomization)
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 released). Hence E°M /M for copper is positive. The high energy required to
2+

transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.

(iii) The large positive E° value for Mn3+ | Mn2+ shows that Mn2+ is much more stable than
Mn3+ due to stable half filled configuration (3d5). Therefore the 3rd ionization energy of Mn
will be very high and Mn3+ is unstable and can 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+.

Q24. (a) Give reasons for the following :

(i) Mn3+ is a good oxidising agent.
(ii) E°M /M values are not regular for first row transition metals (3d series).
2+

(iii) Although ‘F is more electronegative than ‘O’, the highest Mn fluoride is MnF 4, whereas the
highest oxide is Mn2O7.

Answer:

(i)Mn3+ has electronic configuration 3d44s0.

On reduction it gains one electron to become 3d54s0 which is half filled stable
configuration. Hence it is a good oxidising agent.
(ii) E°M /M values are not regular for first row transition metals due to abnormalities and
2+

irregularities in their ionization enthalpies (IE1 + IE1) and sublimation enthalpies.

(iii) Because oxygen stabilizes the highest oxidation state even more than fluorine and has
ability to form multiple bonds with metal atoms.

Q25. (a) Why do transition elements show variable oxidation states?

(i) Name the element showing maximum number of oxidation states among the first series of
transition metals from Se (Z = 21) to Zn (Z = 30).
(ii) Name the element which shows only +3 oxidation state.
Answer:
(a) Because the energy difference between (n-1) d-orbitals and ns-orbitals is very less. Since there is
very little energy difference between these orbitals, both energy levels can be used for bond
formation. Thus transition elements exhibit variable oxidation states.
(i) It is Manganese (Mn) which shows oxidation states from +2 to +7
(ii) Scandium (Sc) shows only +3 oxidation state.
Q26. (i) Name the element of 3d transition series which shows maximum number of oxidation states.
Why does it show so?
(ii) Which transition metal of 3d series has positive E0(M2+/M) value and why?
(iii) Out of Cr3+ and Mn3+, which is a stronger oxidizing agent and why?
(Delhi 2014)
Answer:
(i) Mn has the maximum number of unpaired electrons present in the d-subshell (5 electrons). Hence,
Mn exhibits the largest number of oxidation states, ranging from +2 to +7.
(ii) Copper has positive E0(Cu2+/Cu) value because of its high enthalpy of atomization and low
enthalpy of hydration. The high energy required to oxidise Cu to Cu2+ is not balanced by its hydration
energy.
(iii) Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half filled t2g orbitals.
Therefore Cr2+ is reducing agent, it gets oxidized to Cr3+. While Mn2+ has stable half filled
d5 configuration. Hence Mn3+ easily changes to Mn2+ and acts as oxidising agent.
Q27. Account for the following:
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest
oxidation state of +4.
(ii) Cr2+ is a strong reducing agent.
(iii) Cu2+ salts are coloured while Zn2+ salts are white.
(All India 2016)

Answer:
(a) (i) Because oxygen stabilizes the highest oxidation state (+7 of Mn) even more than fluorine i.e.,
+4 since oxygen has the ability to form multiple bonds with metal atoms.
(ii) Cr2+ exists in the d4 system and is easily oxidized to Cr3+ by loosing one electron which has the
stable d3/t2g orbital configuration. So, Cr2+ is a strong reducing agent.
(iii) Cu2+ has the configuration 3d9 with one unpaired electron which gets excited in the visible region
to impart its colour while Zn2+ has 3d10 configuration without any unpaired electron so no d – d
transition possible and hence colourless.
Q29. The elements of 3d transition series are given as:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:
(i) Write the element which shows maximum number of oxidation states. Give reason.
(ii) Which element has the highest m.p.?
(iii) Which element shows only +3 oxidation state?
(iv) Which element is a strong oxidizing agent in +3 oxidation state and why? (All India)
Answer:
(i) Mn shows, maximum number of oxidation states upto +7. It has the maximum number of unpaired
electrons.
(ii) Cr has the highest melting point.
(iii) Sc shows only +3 oxidation state.
(iv) Mn is a strong oxidizing agent in +3 oxidation state because after reduction it attains +2 oxidation
state in which it has the most stable half-filled (d5) configuration.