MARKING SCHEME
d and f block Elements
SUBJECT-CHEMISTRY CLASS-XII
S. MARKS
NO.
1. (d) Zn2+ 1
2. (c) 4, 3 and 2; Cr3+ 1
3. (b) configuration of Fe2+ is 3d6 while Fe3+ is 3d5 1
4. (d) d-d transition 1
5. (d) All the above products are formed 1
6. (c) the electrons of copper are involved in metallic bonding 1
7. (b)Fe3+,Mn2+ 1
8. (a) Th 1
9. (b) Cu+,Cu2 1
10. (a) La(OH)3 is less basic than Lu(OH)3 1
11. (a) [Xe] 4f 75d16s2 1
12. (b)Np and Pu 1
13. (c). The +4 oxidation state of cerium is not known in solutions 1
14. (c) both have similar atomic radius 1
15. (d)They are chemically very reactive 1
16. a 1
17. b 1
18. a 1
19. 1+1=2
Ans: (a) 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.
(b) Because of the availability of d-orbitals, they can easily form intermediate products
which are activated. The sizes of transition metal atoms and ions are also favourable for
transition complex formation with the reactants
20.
Ans: (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) As oxidation number of metal atom in metal oxide increases, oxidising power
increases
OR
Ans: (i) The number of oxidation states increases upto middle of series i.e. unto +7
and then decreases.
(ii) Oxometal ions are polyatomic ions with oxygen. Example : VO2+, VO+2, TiO2+
21. Cr2O7 2– + 14H+ + 6I– → 2Cr3+ + 3I2+ 7H2O 2
Cr2O7 2– + 8H+ + 3H2S → 2Cr3+ + 3S+ 7H2O
OR
Mischmetal is an alloy of lanthanum. Composition: Lanthanoid metal (95%), Iron (5%) and
traces of C,S, Ca and Al.
It is used in Mg based alloy to produce bullets, shell and lighter flint.
22. 1+1
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+.
OR
(a) 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.
(b) Because of the availability of d-orbitals, they can easily form intermediate products
which are activated. The sizes of transition metal atoms and ions are also favourable for
transition complex formation with the reactants.
23. 1+1
(a) Copper exhibits + 1 oxidation state more frequently i.e., Cu+1 because of its
electronic configuration 3d104s1. It can easily lose 4s1electron to give stable 3d10
configuration.
(b) SC3+ = 4S03d3+ = no unpaired electron
V3+ = 3d24s0= 2 unpaired electron
Ti4+ = 3d04s0= no unpaired electron
Mn2+ = 3d54s0= 5 unpaired electron
Thus V3+ and Mn2+ are coloured in their aqueous solution due to presence of unpaired
electron.
24. 2
Ans: Similarity : Both lanthanoids and actinoids show contraction in size and
irregularity in their electronic configuration.
Difference: Actinoids show wide range of oxidation states but lanthanoids do not
25. Disproportionation: In a disproportionation reaction an element undergoes self oxidation 2
as well as self-reduction forming two different compounds.
Any one example
26
(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. 1+1+1
(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
27. (i) Cr2+ has the configuration 3d4 which easily changes to d3due to stable half filled t2g
orbitals. Therefore Cr2+ is reducing agent. While Mn2+ has stable half filled
1+1+1
d5configuration. 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
largernumber 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
28. . Lanthanoid contraction: Steady decrease in thesize of the lanthanoids with increase in
the atomic number
across the period. The electrons of 4f orbitals offer imperfect / poor shielding effect in the
same
subshell. 1+2
Consequence:
i) Due to this 5d series elements have nearly same radii as that of 4d series.
ii) Decrease in the basic strength from La(OH)3 to Lu(OH)3.
iii) Due to similar atomic size there is difficulty in separation of lanthanides.
29. 1+1+1
: (i) The variability of oxidation state of transition elements is due to incompletely filled
d orbitals as ns, and (n – 1) d electrons have very less energy difference.
(ii) Co2+ ion is easily oxidised to Co3+ ion in presence of a strong ligand because of its
higher crystal field energy which causes pairing of electrons to give inner orbital
complexes (d2sp3).
(iii) Actinoids 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.
30
(i) Mn
(ii) Sc 1+1+1
(iii) Zn
OR
(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+
(iii)5.66BM
1+1+1+1
31. 31.1 b
31,2 c
31.3
31.4 b or a
32 32.1 a
1+1+1+1
32.2.a
32.3 .b
32.4 .c or a
33
: (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 5
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
OR
: (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 d3due to stable half filled
t2g orbitals. Therefore Cr2+ is reducing agent, it gets oxidized to Cr3+. While Mn2+ has
stable half filled d5configuration. Hence Mn3+ easily changes to Mn2+ and acts as
oxidising agent. (iv) Eutropium is well known to exhibit +2 oxidation state.
(v) MnO4–+ 8H++ 5e– → Mn2+ + 4H2O
34. a) Potassium dichromate is prepared from chromate by reacting chromite ore with 5
Na2CO3
4 FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2 .
The yellow solution of sodium chromate is filtered off and acidified with H 2SO4 to give
orange sodium dichromate
2Na2CrO4 + 2H+ → Na2Cr2O7 + H2O + 2Na
Sodium dichromate is then treated with KCl to give potassium dichromate as orange (3+2)
crystals. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution.
2CrO4-2+ 2H+ → Cr2O7-2 + H2O
Cr2O7-2+ 2OH–→ 2CrO4-2+ H2O
(b) In transition elements, the successive oxidation state differs by unity, e.g, Mn shows
all the oxidation states 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
OR
Ans: 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 dark green potassium manganate (K2MnO4).
K2‐ From pyrolusite ore
I. Conversion of pyrolusite ore into potassium manganate
II. Conversion of potassium manganate to potassium permanganate Following reactions
take place:‐
2MnO2 + 4KOH + O2 → 2 K2MnO4 + 2H2O
3MnO4-+ 4H+→ 2MnO4-+ MnO2 + 2H2O
(i) 8MnO4 (aq) +3 S2O32-(aq) + H2O (l) → 8MnO2+6SO42-+2OH-
ii) 2MnO4 – + 5SO3 2– + 6H+→ 2Mn2+ + 5SO4 2– + 3H2O
35 (a) 5Fe2+ (aq) + MnO4- (aq) + 8H+ (aq) → Mn2+ (aq) + 5Fe3+ (aq) + 4H2O(l) 2+3
(b) Cr2O72- (aq) + 6I– (aq) + 14H+ (aq) → 2Cr3+(aq) + 3I2 (s) + 7H2O(l)
b) (i) Because of increase in effective nuclear charge and weak shielding
effect of d electrons, the atomic radii decreases.
(ii) The E°M2+/M for any metal is related to the sum of the enthalpy changes taking
place in the following steps :
M(g) + ΔaH → M(g) (ΔaH = enthalpy of atomization)
M(g) + ΔiH → M2+(g) (ΔiH = ionization enthalpy)
1X5
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°M2+/M for copper is positive. The high energy
required to 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+
OR
(a) This is because transition elements have strong metallic bonds as they have large
number of unpaired electrons, therefore they have greater interatomic overlap
(b)The catalytic activity of transition metals is attributed to the following reasonsi)
Because of their variable oxidation state, transition metals form unstable intermediate
compounds and provide a new path with lower activation energy for the reaction.
ii) In some cases, the transitions metal provides a suitable large surface area with free
valencies on which reactants are adsorbed
(c) E°(M2+/M) values are not regular in the first transition series metals because of
irregular variation of ionization enthalpies (IE1 + IE2) and the sublimation energies.
(d) ) Among transition elements, the bonds formed in +2 and +3 oxidation states are
mostly ionic. The compounds formed in higher oxidation states are generally formed by
sharing of d-electrons. Therefore, Mn can form MnO4- which has multiple bonds also,
while fluorine cannot form multiple bonds.
(e) The absence of unpaired d-electron in Sc3+ whereas in Ti3+ there is one unpaired
electron or Ti3+ shows the d-d transition.
