CHAPTER- 4

D AND F BLOCK ELEMENTS

1. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can you say that
it is a transition element?
Ans. Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely filled
d-orbitals (4d), hence a transition element.
2. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest,
i.e., 126 kJ mol–1. Why?
Ans. In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case
of zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always
involved in the formation of metallic bonds. That is why, the enthalpy of atomisation of
zinc is the lowest in the series.
3. Which of the 3d series of the transition metals exhibits the largest number of oxidation
states and why?
Ans. Manganese (Z = 25), as it has the maximum number of unpaired electrons in d-
subshell. Thus, it shows oxidation states from +2 to +7 (+2, +3, +4, +5, +6 and +7) which is
the maximum number.
4. The Eo (M2+/M) value for copper is positive (+0.34 V). What is possible reason for this?
Ans. Eo (M2+/M) for any metal is related to the sum of the enthalpy change taking place in
the following steps:

Copper has high enthalpy of ionisation and relatively low enthalpy of hydration. So,
E0( Cu2+/ Cu) is positive. The high energy to transform Cu(s) to Cu2+(aq) is not balanced by
its hydration enthalpy.
5. How would you account for the irregular variation of ionisation enthalpies (first and
second) in first series of the transition elements?
Ans. Irregular variation of ionisation enthalpies is mainly attributed to varying degree of
stability of different 3d configuration (e.g., d0, d5, d10 are exceptionally stable).
6. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Due to small size and high electronegativity, oxygen or fluorine can oxidise a metal to
its highest oxidation state. As a result of this they can oxidise a metal to its highest
oxidation state.
7. Which is a stronger reducing agent— Cr2+ or Fe2+ and why?
Ans. Cr2+ is a stronger reducing agent than Fe2+ because after the loss of one electron Cr2+
becomes Cr3+ which has more stable t32g (half-filled) configuration in a medium like water.
8. Explain why Cu+ ion is not stable in aqueous solutions?
Ans. In aqueous solution Cu+ undergoes disproportionation to form a more stable Cu 2+
ion. 2Cu+→ (aq) Cu2+(aq) + Cu(s) The higher stability of Cu2+ in aqueous solution may be
attributed to its greater negative ∆hyd.Ho than that of Cu+ . It compensates the second
ionisation enthalpy of Cu involved in the formation of Cu2+ ions.
9. Actinoid contraction is greater from element to element than lanthanoid contraction.
Why?
Ans. This is because the 5f electrons themselves provide poor shielding from element to
element in the series
10. Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their
+3 state?
Ans. Electronic configuration of Mn2+ is 3d5 which is half-filled and hence stable. So, 3rd
ionisation enthalpy is very high, i.e., 3rd electron cannot be easily lost. In case of Fe 2+,
electronic configuration is 3d6. Thus, it can lose one electron easily to give the stable
configuration 3d5.
11. Name the oxo-metal anions of the first series of the transition metals in which the metal
exhibits the oxidation state equal to its group number.
Ans. Cr2O72– and CrO42– (group no. = oxidation state of Cr = 6)
MnO4– (group no. = oxidation state of Mn = 7)
Vanadate: VO3– (group no. = oxidation state of V = 5)
12. What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
Ans. In lanthanoids, with increasing atomic number, the atomic and ionic radii decrease
from one element to the other, but the decrease is very small. It is because, for every
additional proton in the nucleus, the corresponding electron goes into a 4f-subshell, which
is too diffused to screen the nucleus as effectively as the more localised inner shell. Hence,
the attraction of the nucleus for the outermost electrons increases steadily with the
atomic number.
The consequences of lanthanoid contraction are as follows:
(i) The properties of second and third transition series are similar.
(ii) Basic strength decreases from La(OH)3 to Lu(OH)3.
(iii) Lanthanide contraction makes separation of lanthanoids possible.
13. 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?
Ans. Characteristics of the transition elements: Refer to Basic Concepts Point 3. The d-
block elements are called transition elements because these elements represent change
(or transition) in properties from the most electropositive s-block elements to the least
electropositive p-block elements.
The electronic configuration of Zn, Cd and Hg are represented by the general formula (n –
1) d10 ns2. The orbitals in these elements are completely filled in the ground state as well
 as in their common oxidation states. Therefore, they are not regarded as transition
elements.
14. What are the different oxidation states exhibited by lanthanoids?
Ans. +2, +3 and +4 (+3 being most common)
15. Transition metals and many of their compounds show paramagnetic behavior. Why?
Ans.
16. The enthalpies of atomisation of the transition metals are high.
Ans. The transition elements exhibit high enthalpy of atomisation because they have large
number of unpaired electrons in their atoms. Due to this they have stronger interatomic
interaction.
17. Transition metals and their many compounds act as good catalyst.
Ans. Most of the transition metals and their compounds possess catalytic properties. The
catalytic activity of transition metal ions is attributed to the following two reasons:
(i) Variable oxidation states due to which they can form a variety of unstable
intermediate products.
(ii) Large surface area so that the reactants are adsorbed on the surface and come
close to each other facilitating the reaction process
18. What are interstitial compounds? Why are such compounds well known for transition
metals?
Ans. Interstitial compounds are those in which small atoms occupy the interstitial sites in
the crystal lattice. Interstitial compounds are well known for transition metals because
small-sized atoms of H, B, C, N, etc., can easily occupy positions in the voids present in the
crystal lattices of transition metals
19. For M2+/M and M3+/M2+ systems, Eo values for some metals are as follows:

Use this data to comment upon

(i) the stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+.
(ii) the ease with which iron can be oxidised as compared to the similar process for
either Cr or Mn metals.
Ans.
(i) Higher the reduction potential of a species, greater is the ease with which it undergo
reduction. Among these pairs, Mn3+/Mn2+ has largest positive reduction potential. Hence
Mn3+ can be easily reduced to Mn2+ i.e., Mn3+ is least stable. Cr3+/Cr2+ has a negative Eo
value, therefore, Cr3+ is most stable. Fe3+/Fe2+ has a positive value but small. Hence, Fe3+
is more stable than Mn3+ but less stable than Cr3+.
(iii) Lower the reduction potential or higher the oxidation potential of a species,
greater is the ease with which it undergo oxidation. Among these pairs, Mn 2+/Mn
has the most negative reduction potential or most positive oxidation potential.
 Therefore, it will be most easily oxidised. Thus, the decreasing order of their ease
of oxidation is Mn > Cr > Fe.

20. How would you account for the following:

(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly
oxidising. (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.
Ans.
(i) E° value for Cr3+/Cr2+ is negative (–0.41 V) whereas E° value for Mn3+/Mn2+ is positive
(+1.57 V). Thus, Cr2+ ions can easily undergo oxidation to give Cr3+ ions and, therefore, act
as strong reducing agent. On the other hand, Mn 3+ can easily undergo reduction to give
Mn2+ and hence act as oxidising agent.
(ii) This is because in presence of complexing reagents the CFSE value compensates
more than the third ionisation energy of cobalt.
(iii) The ions with d1 configuration have the tendency to lose the only electron present
in d-subshell to acquire stable d 0 configuration. Therefore, they are unstable and
undergo oxidation or disproportionation.
21. What is meant by ‘disproportionation’? Give two examples of disproportionation reaction
in aqueous solution.
Ans. Disproportionation reactions are those reactions in which the same substance
undergoes oxidation as well as reduction. In disproportionation reaction, oxidation
number of an element increases as well as decreases to form two different products. For
example,

22. Which metal in the first transition series exhibits +1 oxidation state most frequently and
why?
Ans. Cu has the electronic configuration 3d10 4s1 . It can easily lose 4s1 electron to give the
stable 3d10 configuration. Hence, it shows +1 oxidation state
23. Give example 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 higher oxidation states in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxo-anions of a metal.
Ans.
(i) The lowest oxide of transition metal is basic because the metal atom has low
oxidation state. This means that it can donate valence electrons which are not
 involved in bonding to act like a base. Whereas the highest oxide is acidic due to
the highest oxidation state as the valence electrons are involved in bonding and
are unavailable. For example, MnO is basic whereas Mn2O7 is 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 OsF6 and vanadium shows an oxidation state of +5 in V2O5.
(iii) Oxometal anions have the highest oxidation state, e.g., Cr in Cr2O72– has an
oxidation state of +6 whereas Mn in MnO4– has an oxidation state of +7. This is
again due to the combination of the metal with oxygen, which is highly
electronegative and oxidising element.
24. What are alloys? Name an important alloy which contains some of the lanthanoid metals.
Mention its uses.
Ans. An alloy is a homogeneous mixture of two or more metals, or metals and non-metals.
An important alloy containing lanthanoid metals is misch metal which contains 95%
lanthanoid metals and 5% iron alongwith traces of S, C, Ca and Al. It is used in Mg-based
alloy to produce bullets, shells and lighter flints
25. Use Hund’s rule to derive the electronic configuration of Ce3+ ion and calculate its
magnetic moment on the basis of spin only formula.
Ans. 58Ce = [Xe]544f1 5d1 6s2
Ce3+ = [Xe]54 4f1 , i.e., there is only one unpaired electron, i.e., n = 1.
26. Compare the chemistry of the actinoids with that of landthanoids with reference to:
(i) electronic configuration (ii) oxidation states and (iii) chemical reactivity
ANS.

27. Copper atom has completely filled d-orbitals in its ground state but it is a transition
element. Why?
Ans. Copper exhibits +2 oxidation state wherein it has incompletely filled d orbitals (3d 9
4s0 ) hence, a transition element.
28. Give reason: Zn is soft whereas Cr is hard.
Ans. Cr (3d54s1) has five unpaired electrons in its d-orbitals whereas Zn (3d10 4s2 ) has no
unpaired electrons in its d-orbitals. As a result of this weak metallic bonds exist in Zn
whereas strong metallic bonds exist in Cr. Hence, Zn is soft whereas Cr is hard.
29. Why does copper not replace hydrogen from acids?
Ans. Cu shows Eo positive value.
30. Which divalent metal ion has maximum paramagnetic character among the first transition
metals? Why?
Ans. Mn2+ has the maximum paramagnetic character because of the maximum number of
unpaired electrons, viz., 5.
31. Although Cr3+ and Co2+ ions have same number of unpaired electrons but the magnetic
moment of Cr3+ is 3.87 BM and that of Co2+ is 4.87 BM. Why?
Ans. Due to symmetrical electronic configuration there is no orbital contribution in Cr 3+
ion. However, appreciable orbital contribution takes place in Co2+ ion.
32. 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 ∆hyd.Ho of Cu2+(aq) than Cu+ (aq)
33. Zn2+ salts are white while Cu2+ salts are coloured. Why?
Ans. Cu2+ (3d9 4s0 ) has one unpaired electron in d-subshell which absorbs radiation in
visible region resulting in d-d transition and hence Cu2+ salts are coloured. Zn2+ (3d10 4s0 )
has completely filled d-orbitals. No radiation is absorbed for d-d transition and hence Zn2+
salts are colourless.
34. Write any one use of pyrophoric alloys.
Ans. Pyrophoric alloys emit sparks when struck. Hence, they are used in making flints for
lighters.
35. Use the data to answer the following and also justify giving reason:

(i) Which is a stronger reducing agent in aqueous medium, Cr2+ or Fe2+ and why?
(ii) Which is the most stable ion in +2 oxidation and why?
Ans.
(i) Cr2+, due to lower standard reduction potential (Eo )/Higher standard oxidation
potential.
(ii) Mn2+, due to highest negative standard reduction potential.
36. In the following ions: Mn3+, V3+, Cr3+, Ti4+
(Atomic no. : Mn = 25, V = 23, Cr = 24, Ti = 22)
(i) Which ion is most stable in an aqueous solution?
(ii) Which ion is the strongest oxidizing agent?
(iii) Which ion is colourless?
(iv) Which ion has the highest number of unpaired electrons?
Ans.
(i) Cr3+ because of half filled t2g level.
(ii) Mn3+, as the change from Mn3+ to Mn2+ results in stable half filled (d5)
configuration.
(iii) Ti4+, as Ti4+ has empty d-orbitals therefore d-d transition cannot occur in Ti4+.
(iv) Mn3+ (3d4 4s0). It has 4 unpaired electrons
37. Give reasons for the following:
(i) Eo values of Mn, Ni and Zn are more negative than expected.
(ii) [Ti(H2O)]3+ is coloured while [Sc(H2O)6]3+ is colourless.
OR
Ti is coloured whereas Sc3+ is colourless in aqueous solution.
3+

Ans.
(i) Negative Eo values for Mn2+ and Zn2+ are related to stabilities of half-filled and fully
filled configurations, respectively. But for Ni2+, Eo value is related to the highest
negative enthalpy of hydration.
(ii) This is due to d-d transition of electron in [Ti(H2O)6]3+ complex. Ti3+ has one
electron in d-orbital (3d1 ) which absorbs energy corresponding to blue-green
region and jumps from t2g to eg set of d-orbitals (t12g e0g→t02g e1g ). But Sc3+ has
no electron in the d-orbital
38. How would you account for the following:
(i) Mn (III) undergoes disproportionation reaction easily.
(ii) Co (II) is easily oxidised in the presence of strong ligands.
Ans. (i) Mn3+ is less stable and changes to Mn2+ which is more stable due to half filled d-
orbital configuration. That is why, Mn3+ undergoes disproportionation reaction.
(iii) Co (II) has electronic configuration 3d74s0 , i.e., it has three unpaired electrons. In
the presence of strong ligands, two unpaired electrons in 3d-subshell pair-up and
third unpaired electron shifts to higher energy subshell from where it can be easily
lost and hence oxidised to Co(III).

39. Explain each of the following observations:

(i) Mn2+ is much more resistant than Fe2+ towards oxidation.
(ii) Among lanthanoids, Ln(III) compounds are predominant. However, occasionally in
solutions or in solid compounds, +2 and +4 ions are also obtained.
 Ans. (i) Mn3+(d4 ) is less stable than Mn2+ (d5 , half filled) while Fe3+ (d5 , half filled) is more
stable than Fe2+ (d4 ). That is why Mn2+ is more resistance than Fe2+ towards oxidation.
(iii) Lanthanoid metals show +2 and +4 oxidation states to attain extra stable f 0 and f7
configurations
40. Explain each of the following observations:
(i) Actinoids exhibit a much larger number of oxidation states than the lanthanoids.
(ii) There is hardly any increase in atomic size with increasing atomic numbers in a
series of transition metals.
Ans.
(i) This is due to small energy gap between 5f, 6d and 7s subshells in actinoids.
(ii) This is because with increase in atomic number in a series, the increased nuclear
charge is partly cancelled by the increased shielding effect of electrons in the d-
orbitals of penultimate shell.
41. From the given data of Eo values, answer the following questions:
(i) Why is Eo (Cu2+/Cu) value exceptionally positive?
(ii) Why is Eo (Mn2+/Mn) value highly negative as compared to other elements?

Ans.
(i) Copper has high enthalpy of atomisation and low enthalpy of hydration. Since the
high energy to transform Cu(s) to Cu2+(aq) is not balanced by hydration enthalpy,
therefore, Eo Cu2+/Cu value is exceptionally positive.
(ii) This is due to extra stability of half-filled 3d-orbitals of Mn2+(3d5 ).
42. The elements of 3d transition series are given as: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Answer
the following:
(i) Copper has exceptionally positive EoM/ M2+ value. Why?
(ii) Which element is a strong reducing agent in +2 oxidation state and why?
(iii) Zn2+ salts are colourless. Why?

Ans.
(i) Because the sum of sublimation enthalpy and hydration enthalpy to convert Cu(s)
to Cu2+(aq) is so high that it is not balanced by its hydration enthalpy.
(ii) Cr is strongest reducing agent in +2 oxidation state. Cr2+ has configuration 3d4 .
After losing one electron it forms Cr3+ which has stable half filled t2g level.
(iii) Zn2+(3d10) has completely filled d-orbitals. As a result of this, d-d transition cannot
occur and hence, Zn2+ salts are colourless.
43. Account for the following:
(i) Eu2+ is a strong reducing agent.
 (ii) Orange colour of dichromate ion changes to yellow in alkaline medium.
(iii) Eo M2+/M values for transition metals show irregular variation.
Ans.
(i) This is because Eu2+ tends to change to Eu3+ as +3 is the common oxidation state
of lanthanoids.
(ii) In alkaline medium, the orange colour of the solution changes to yellow due to
conversion of dichromate (Cr2O72–) ion to chromate (CrO42–) ion.

(iii) The irregularity is due to the irregular variation of ionisation enthalpies (∆iH + ∆iH2)
and also the sublimation enthalpies which are relatively much less for Mn (240 kJ mol–1)
and V (470 kJ mol–1)
44. (i) How would you account for the Highest fluoride of Mn is MnF 4 whereas the highest
oxide is Mn2O7.
Ans. As oxygen stabilises manganese more than fluorine by forming multiple bonds
45. Account for the following: Mn2O7 is acidic whereas MnO is basic
Ans. Mn has + 7 oxidation state in Mn2O7 and + 2 in MnO. In low oxidation state of the metal,
some of the valence electrons of the metal atom are not involved in bonding. Hence, it can
donate electrons and behave as a base. On the other hand, in higher oxidation state of the
metal, valence electrons are involved in bonding and are not available. Instead effective
nuclear charge is high and hence it can accept electrons and behave as an acid
46. In the titration of FeSO4 with KMnO4 in the acidic medium, why is dil. H2SO4 used instead
of dil. HCl?
Ans. Dil. H2SO4 is an oxidising agent and oxidises FeSO4 to Fe2(SO4)3. Dil. HCl is a reducing agent
and liberates chlorine on reacting with KMnO4 solution. Hence, the part of the oxygen
produced from KMnO4 is used up by HCl.

47. Ce4+ is used as an oxidising agent in volumetric analysis. Why?

Ans. Ce4+ has the tendency to attain +3 oxidation state which is more stable and so it is used
as an oxidising agent in volumetric analysis
48. Account for the following Transition metals form large number of complex compounds.
Ans. The tendency to form complex compounds is due to:
Small size and high charge on metal ion.
The availability of d orbitals for accommodating electrons donated by the ligand
49. Assign reasons for the following the enthalpies of atomisation of transition elements are
high.
Ans. This is because transition metals have strong metallic bonds as they have a large number
of unpaired electrons.
50. The E0 value for the Mn3+/Mn2+ couple is much more positive than that of Cr3+/Cr2+ why ?
Ans. This is due to much larger third ionisation energy of Mn as Mn2+ is very stable on account
of stable d5 configuration
51. (i) Write balanced equations to represent what happens when
(a) Cu2+ is treated with KI.
(b) Acidified potassium dichromate solution is reacted with iron (II) solution. (ionic
equation)
(ii) (a) The figure given illustrates the first ionization enthalpies of first, second and third
series of transition elements. Answer the question that follows: Which series amongst the
first, second and third series of transition elements have the highest first ionization
enthalpy and why?
(b) Separation of lanthanoid elements is difficult. Explain.
(c) Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents but an aqueous solution
of Ce4+ is a good oxidising agent. Why?

Ans.

(ii) (a) Third series has the highest first ionization energy due to poorest shielding effect of
the fully filled 4f subshell.
(b) Due to lanthanoid contraction, some pair of elements have almost similar size and as
a result, such pairs have very similar properties which makes their separation difficult.
(c) Sm2+, Eu2+ and Yb2+ ions are good reducing agents as they tend to acquire common
oxidation state of + 3 shown by lanthanoids by the loss of one electron while Ce 4+ gains
one electron to attain + 3. Hence, Ce4+ is an oxidising agent.
52. A violet compound of manganese (A) decomposes on heating to liberate oxygen and
compounds (B) and (C) of manganese are formed. Compound (C) reacts with KOH in the
presence of potassium nitrate to give compound (B). On heating compound (C) with conc.
H2SO4 and NaCl, chlorine gas is liberated and a compound (D) of manganese along with
 other productsisformed.Identify compounds A to D and also explain the reactions
involved.
Ans.
A = KMnO4 (Potassium permanganate), B = K2MnO4 (Potassium manganate),
C = MnO2 (Manganese (IV) oxide), D = MnCl2 (Manganese (II) chloride)

52. When an oxide of manganese (A) is fused with KOH in the presence of an oxidising agent
and dissolved in water, it gives a dark solution of compound (B). Compound (B)
disproportionates in neutral or acidic solution to give purple compound (C). An alkaline
solution of compound (C) oxidises potassium iodide solution to a compound (D) and
compound (A) is also formed. Identify compounds A to D and also explain the reactions
involved.
Ans.
A = MnO2 (Manganese (IV) oxide), B = K2MnO4 (Potassium manganate),
C = KMnO4 (Potassium permanganate), D = KIO3 (Potassium iodate)

53. Give chemical reactions for the following observations:

(a) Potassium permanganate is a good oxidising agent in basic medium.
(b) Inter convertibility of chromate ion and dichromate ion in aqueous solution depends
upon pH of the solution.
(c) Potassium permanganate is thermally unstable at 513K
Ans.
54. Draw the structures of chromate and dichromate ions.
Ans.

55. Write reaction involved in preparation of potassium di chromate.

Ans. Potassium Dichromate, K2Cr2O7: It is prepared from the chromite ore. Different reactions
involved in the preparation of potassium dichromate from chromite ore are:
. In acidic medium potassium permanganate oxidises: