d – Block elements

1. What are d- block elements?

Ans: Elements within group 3-12 in which the last electron enters into the penultimate d subshell are
called d-block elements.

2 1-10
General configuration : ns (n -1) d
That includes,
i) 3d series, from 21Sc to 30Zn

1-2 1-10
General configuration : [Ar] 4s 3d

ii) 4d series, from 39Y to 48Cd

1-2 1-10
General configuration : [Kr] 5s 4d

iii) 5d series, 57La , 72Hf to 80 Hg

1-2 1-10
General configuration : [Xe] 6s 5d

iv) 6d series, 89Ac , 104Rf to 112Cp

1-2 1-10
General configuration : [Rn] 7s 6d
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2. Why d- block elements are called transition elements?

Ans: Because they show a regular transition from the highly electropositive s-block elements to the
less electropositive p-block elements.
“A d-block element is considered as a transition element when it is having partially filled d-orbitals in
their atomic state or in any of their oxidation state”.
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3. Zn, Cd, Hg they are d-block elements but not considered as transition elements. Why?
2 10
Ground state configuration of 30 Zn : [Ar] 4s 3d
10
In its +2 oxidation state Zn2+ : [Ar] 3d

Both in atomic state as well as common oxidation state d-subshell is completely filled. So it is not a
transition element.
10 10
- 48Cd : [Kr] 5s2 4d Cd2+ : [Kr] 4d (Completely filled d10
Configuration)
14 10 14 10 14 10
: [Xe] 6s2 4f 5d
1
- 80Hg ; Hg+ : [Xe] 6s 4f 5d ; Hg2+ : [Xe] 4f 5d
(Completely filled d subshell in ground state as well as its common oxidation state.)
4. Sc is a transition element whereas Zn not. Why?
2 1 2 10
Ans: 21 Sc : [Ar] 4s 3d (vacant d orbitals) 30 Zn : [Ar] 4s 3d
1 10
Sc2+ : [Ar] 3d Zn2+ : [Ar] 3d (Completely filled ‘d’
subshell in both ground state and in +2
oxidation state)
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10
5. Silver atom has completely filled d-orbitals (4d ) in its ground state yet silver is a transition element?
1 10
Ans: 47Ag : [Kr] 5s 4d .It exhibit two oxidation states Ag+ , Ag2+

10 9
In Ag+ : [Kr] 4d , Where as in Ag2+ : [Kr] 4d
Silver has incompletely filled d-orbitals in its +2 oxidation states; hence it is a transition element.
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6. Both atomic and ionic radii decrease from left to right in a period. But transition elements show
anomalous change in size. Why?
Or
Both atomic and ionic size varies irregularly among transition elements. Why?

Ans: In a given transition series atomic and ionic radii first decreases, then become constant and
increases towards the end of the series. This is because in transition elements the new electron
enters in a penultimate ‘d’ orbital. Initially there is little number of d electrons; the shielding effect is
very poor. As the atomic number increases the nuclear charge also increases, so the atomic radius
decreases. Towards the middle of the series, the increase in nuclear charge is balanced by the
shielding effect and so the atomic radius becomes constant. Towards the end of the series as the e-e
repulsion increases the atomic radius also increases.
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7. The atomic and ionic radii of 2nd and 3rd row transition metals are quite similar. Why?
Ans: This is due to the lanthanide contraction. In between 2nd and 3rd transition row elements, 4f
electrons are present. The 4f electrons have very poor shielding effect and as a result the atomic and
ionic radii of lanthanides decreases from left to right (lanthanide contraction)
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8. Transition elements show high melting and boiling points. Why?
Ans: All transition metals from strong metallic bond which depends on the number of unpaired
electron. Since transition metals have more unpaired electron they form strong metallic bonding and
hence the heat of atomisation is high and possess high melting and boiling point.
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9. In a given transition series, the melting and boiling points first increases up to the middle and then
decreases. Why?
Ans:-It is explained on the basis of metallic bond strength which depends on number of unpaired
electrons. In a given transition series, the number of unpaired increases up to the middle and then
decreases.
10. Elements like Mn, Tc have low melting point even though they are having maximum unpaired
electrons?
5
Ans: Even though Mn, Tc elements have d Configuration (5 unpaired electron), their metallic bond
Strength is weak due to low heat of atomisation and lack of typical metallic structure.

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11. The melting point of second row (4d series ) and third row (5d series ) transition series is higher than
that of the first row (3d) transition series. Why?
Ans: Because 2nd and 3rd transition series have higher enthalpies of atomization.
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12. What is ionization enthalpy? How it varies generally in a period?
Ans: The energy required to eject an electron from the outermost shell is called ionization enthalpy.
Generally I.E increases across a period. This is due to the increase in nuclear charge(Size decreases).
But in transition series I.E first increases then remains constant and then decreases.(Related to
variation of atomic and ionic radii)
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13. What is first ionization enthalpy, second ionization enthalpy IE1,IE2 etc.
ANS: The energy required to eject one electron from the outermost shell is IE1. The energy required to
eject the second electron is called IE2 etc.:
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14. The IE1 of Cr & Cu is low and IE2 is high. Why?
1 5
Ans: 24 Cr : [Ar] 4s 3d ; If it lose one electron it can attain the stable d5 configuration.

Therefore IE1 is low.

IE2 is high because the ion does not want loose electron from a stable configuration.
(d5 d4) is difficult.
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15. Account for the following.
i) IE1 of Zn is high whereas IE2 is low.
ii) The second I.E of Mn are low.

10
Ans: i) 30 Zn : [Ar] 4s 2 3d , it is having completely filled configuration, you have to give more
energy to eject one electron from a stable configuration. Therefore IE1 is high.

1 10
- After the ejection of one electron, Configuration becomes [Ar] 4s 3d , it is unstable, if it loses one
more electron it will attain a stable d10 configuration. Therefore IE2 is low. ( [Ar] 3d10 is more stable)
 2 5
ii) 30 Mn : [Ar] 4s 3d } IE1 is high. (stable half-filled configuration hence less tendency to
1 5
lose). After losing one electron configuration becomes unstable [Ar] 4s 3d , therefore it is
easy to eject the second electron (needs only low energy).Hence IE2 is low.
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16. Transition elements show variable oxidation state. Why?
Ans: This because not only the ns electrons bot also the (n-1) d electrons also participate in chemical
reaction because they have comparable energies.
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17. Highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans: Due to small size and high electronegativity, oxygen or fluoride can oxidise a metal to its highest
oxidation state.
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18. Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest
oxidation state of +4.
Ans: Mn do not show +7 oxidation state with fluorine as it does not have the ability to form multiple
bonds with Mn.
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19. How do you account for the following?
i) Mn (III) undergoes disproportionation reaction easily OR Mn3+ is a good oxidizing agent.
ii) Co(II) is easily oxidized in the presence of strong ligands or Co(III) is stable in aqueous solution
but in presence of complexing reagents ,it is easily oxidized.
2 5
Ans: i) 25 Mn : [Ar] 4s 3d . Mn3+ has [Ar]3d4 configuration (unstable), so it is having the
tendency to become Mn2+ which is more stable due to half-filled d-orbital configuration. Therefore
Mn3+ undergoes disproportionation reaction.
0 7
ii) Co(II) has electronic configuration [Ar] 4s 3d .It is having three unpaired electrons. In presence
of strong ligands two unpaired electron in 3d subshell pair up and the third unpaired electron shifts to
higher energy subshell from where it can be easily lost and hence oxidized to Co(III)

20. Although Co2+ ion appears to be stable, it is easily oxidized to Co3+ ion in the presence of a strong
ligand.
Ans: Above answer (Q.NO 18)
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21. The E0 (Cu2+/Cu) value is +0.34V, where all the other first row transition elements are having negative E 0.
Why?
Ans: Cu has less tendency to oxidise (to become Cu2+) ,this is because the high energy to transform
Cu(s) to Cu2+ (aq) is not balanced by its hydration enthalpy.
22. Metals reacts with acids produce H2 gas , whereas copper does not. Why?
Above answer (Q.NO 21)
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23. Which is more stable Cu+ or Cu2+ in aqueous solution?
Ans: Cu2+ is more stable than Cu+ or in aqueous solution, because in aqueous solution Cu+ undergoes
disproportionation to form more stable Cu2+ ions.

2 Cu+ (aq) Cu2+(aq) + Cu (s)

The higher stability of Cu2+ in aqueous solution may be attributed to its greater negative ∆H0hydration
(hydration enthalpy) than that of Cu+. It compensates the second ionization enthalpy of Cu involved in
the formation of Cu2+ ions.
24. Out of Cu2Cl2 and CuCl2 , which is more stable and why?
Ans: CuCl2 is more stable than Cu2Cl2 .The stability of Cu2+(aq) is more than Cu+ (aq) due to the much
more negative hydration enthalpy (∆H0hydration) of Cu2+(aq) than Cu+ (aq).
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25. E0 (Mn3+/Mn2+) is high. Why?
Ans: Mn3+ : [Ar] 3d4 . Mn2+ : [Ar] 3d5 . Since Mn2+ is more stable than Mn3+ (d5
configuration of Mn2+) Mn3+ has more tendency to reduce to Mn2+ and hence the reduction potential is
high.
26. E0 (Fe2+/Fe3+) is lower than the expected value. Why?
Fe2+ : [Ar]4s2 3d6 . Fe3+ : [Ar]4s2 3d5 .

Since Fe3+ is more stable than Fe2+ , Fe2+ has less tendency to reduce (E0 is less) ,(more tendency to
oxidise)
27. E0 (M3+/M2+) value is very low for Sc.Why?
Ans: Sc : [Ar] 4s23d1
M3+ : Sc3+ - [Ar] 3d0 ; Sc2+ - [Ar] 3d1
Sc3+ is more stable than Sc2+ (d0 configuration is more stable). M3+ has less tendency to become
unstable M2+., that is less tendency to reduce, hence E0 (M3+/M2+) is less.

28. E0 (M3+/M2+) value is high for Zn. Why?

Zn: [Ar] 4s23d10 ; Zn2+ - [Ar] 3d10 ; Zn3+ - [Ar] 3d9 ;
Since d10 configuration is highly stable, Zn2+ is more stable than Zn3+ .Therefore Zn3+ has more tendency
2+ 0
to become stable Zn (that is more tendency to reduce), hence E (M3+/M2+) is high.
29. The reduction potential of Mn2+ and Zn2+ is more negative. Why? (E0 (Mn2+/Mn) and E0 (Zn2+/Zn)

2 5
Ans: 25 Mn : [Ar] 4s 3d ; Mn2+ : [Ar] 3d5 .

30Zn : [Ar] 4s23d10 ; Zn2+ - [Ar] 3d

10
.Both Mn2+ and Zn2+ is highly stable (due to completely
filled and half-filled configuration).Therefore they have less tendency to become Mn2+ Mn and
Zn2+ Zn, which means less tendency to reduce. Therefore E0 value is more negative.

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30. The E0 values for Mn, Ni and Zn are more negative than expected.
Ans: For Mn and Zn it is due to extra stability of half-filled and completely filled d subshell.(above
answer).For Nickel it is due to highest negative enthalpy of hydration.
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31. Mn3+ and Co3+ ions are the strongest oxidizing agents in aqueous solutions?
Ans: Mn3+ : [Ar] 3d4 ,Unstable configuration ,it has high tendency to gain one more electron to get
extra stability of d5 configuration to form Mn2+ .(oxidizing agent undergo reduction)

Co3+: [Ar] 3d6, more stable in the presence of strong ligand due to pairing in t2g orbital and Co2+ is less

stable and get easily oxidized to Co3+.But in aqueous solution water is acting as a weak ligand and
cannot paired up the electrons so Co2+ is stable in aqueous solution but in presence of strong ligand it
get easily oxidised.
32. The ions of Ti2+, V2+ and Cr2+ are strong reducing agents? Why?
Ans: Most stable oxidation states of Ti are +4. (Inert gas configuration)
That of Cr is +3 (High hydration enthalpy).So they have more tendency to oxidise and hence act as
reducing agent.
33. E0 (V2+/V) is low. Why?
2 3
Ans: 23 V : [Ar] 4s 3d ; V2+ : [Ar] 3d3 , Half-filled t2g level makes it more stable, hence less

tendency to reduce.
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34. Most of the transition metals are paramagnetic. Why?
Ans: Because they contain more unpaired electron. Paramagnetic substances get attracted by the
applied magnetic field.
Spin magnetic moment, µs = √ , where ‘n’ is the number of unpaired electron.
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35. Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27),
Ans: [Ar] 4S2 3d7, M2+ : [Ar] 3d7

Number of unpaired electron = 3.

Therfore µs = √ , =√ = 3.87 BM
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36. Most of the transition metal ions or compounds are coloured. Why?
Ans: This is because of the presence of partially filled ‘d’ orbitals. When an electron from a lower
energy d orbital is excited to higher d level, it absorbs energy and this is equal to the energy of certain
colours in visible region. So the colour observed is the complementary colour of the light absorbed.
(d-d transition).
37. In aqueous solution most of the transition metal ions are coloured. Why?
Ans: Because water molecules acts as ligand which results in the splitting of d- orbitals and results in
d-d transition.
38. Among Ti2+ and Ti4+ , Ti2+ is coloured while Ti4+ is colorless. Why?
Ans: 22Ti : [Ar] 4s23d2 ; Ti2+ - [Ar] 3d2 ; Ti4+ - [Ar] 3d0 ; Ti4+ is colorless because of the
absence of d electrons.
- Ti2+ is colored due to partially filled d subshell and hence d-d transition is possible.
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39. Cu2+ is coloured whereas Cu+ is colorless. Why?

Ans: 29Cu : [Ar] 4s13d10 ; Cu + - [Ar] 3d10 ; Cu2+ - [Ar] 3d9 ; Cu2+ is coloured due to vacant d
subshell (d9) whereas Cu+ is colorless due to completely filled d configuration.(no d-d transition possible)
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40. Transition metals form large number of complexes. Why?
Ans: It is due to
1. Comparitively smaller size.
2. High ionic charge
3. Presence of partially filled d orbitals.
4. Ability to show variable oxidation state.

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41. Transition metals act as good catalyst. Why?
Ans: This is due to their large surface area and their ability to show variable oxidation state.
Eg: V2O5 (In contact process)
Finely divided iron –(In Haber’s process)
Ni (in catalytic hydrogenation)
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42. What interstitial compounds? Why are such compounds well known for transition metals?
Ans: Transition metals are large in size and contain lots of interstitial sites .Transition elements can trap
atoms of other elements (that have small atomic size), Small atoms like C, H,N,B get fit into voids
resulting in the formation of interstitial compounds.
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43. Transition metals form alloys. Give reason.
Alloys may be homogeneous solid solutions in which the atoms of one metal are distributed
randomly among the atoms of the other. Because of similar radii of transition metals can form alloys.
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