The d- and f-Block Elements

1 d-BLOCK ELEMENTS 24. Cu(II) halides are known except the iodide.
12. The 1st ionisation enthalpy in any d-series
1. The d-block of the periodic table contains the
generally increases but the magnitude of
elements of the group 3-12.
increase in 2nd and 3rd ionisation enthalpies for
2. Transition metals : Metals which have the successive elements, is much higher along a
incomplete d-subshell either in neutral atom or series.
in their ions.
13. The trend of steady increase in 2 nd and 3rd
3. General electronic configurations
ionisation energies for 1st transition series breaks
(n –1)d1–10 ns1–2, but this has several exceptions
for the formation
due to very little energy difference between (n –
1)d and ns orbitals. of Mn2+ and Fe3+ respectively as both ions have
d5 configuration.
4. There are mainly four series of the transition
metals : 3d series (Sc to Zn), 4d series (Y to Cd), 14. The three terms responsible for the value of
5d series (La and Hf to Hg), and 6d series (Ac ionisation enthalpy are attraction of each
electron towards nucleus, repulsion between the
and Rf to Cn)
electrons and the exchange energy.
5. Zn, Cd and Hg are not regarded as transition
metals. 15. Ionisation energy of Mn+ is lower than Cr+ as
6. With the exceptions of Zn, Cd, Hg and Mn, these there is no loss of exchange energy at d 6
have one or more typical metallic structures configuration.
at normal temperatures.
16. Mn exhibits all the oxidation states from +2 to
7. With the exception of Zn, Cd, and Hg, these +7.
metals are very hard and have low volatility. 17. Sc(II) virtually unknown.
8. These elements have high melting and boiling 18. The only oxidation state of Zn is +2.
point. In any row the melting points of these 19. In group-6, Mo(VI) and W(VI) are found to be
metals rise to a maximum at more stable than Cr(VI)
d5 except for anomalous values of Mn and Tc. 20. Among 3d series elements, E°(M2+/M) is positive
9. These metals have high enthalpy of atomisation only for copper because high energy to
due to strong interatomic interactions. Metals of transform Cu(s) to Cu2+(aq.) is not balanced by
2nd and 3rd series have more enthalpies of its hydration enthalpy. Only
atomisation than the oxidising acids (nitric and hot concentrated
sulphuric)
corresponding elements of 1st series due to
reacts with Cu.
much more frequent metal-metal bonding.
10. Tungsten (W) has highest melting point among 21. Among 3d series, the value of E°(M2+/M) for Mn,
d-block elements. Ni and Zn are more negative than excepted from
the trend.
11. The filling of 4f before 5d orbitals results in a
regular decrease in atomic radii called 22. In halides of 3d series, the highest oxidation
lanthanoid contraction. numbers are achieved in TiX4, VF5 and CrF6.
The net result of it is that the 2 and 3 d-series
nd rd
23. V+5 halide is represented only by5 VF , the other
exhibits similar radii (e.g. Zr and Hf). Halides undergo hydrolysis to give oxohalides
VOX3.
25. Many Cu(I) compounds are unstable in highest oxide is Mn2O7 liberate H2 from dilute acids.
aqueous solution and undergo 29. Mn2O7 is a covalent oxide in which each Mn 34. Each unpaired electron has a magnetic
disproportionation. moment
is tetrahedrally surrounded by O’s including
2Cu+ Cu2+ + Cu associated with its spin angular momentum and
Mn–O–Mn bridge.
orbital angular momentum.
26. The stability of Cu2+(aq) rather than Cu+(aq.) is due 30. Order of oxidising power : VO  Cr O2–  MnO– 2 2 7
to the 35. For the compounds of first transition
4
series
31. Ti & V, in practise, are passive to dilute non-
metals, magnetic moment is determined by 'spin
much more negative  H° of Cu2+(aq.) than oxidising acids at room temperature. Hy
only' formula : d
Cu+(aq), which more than compensates for the
32. E°(M3+/M2+) values shows that Mn 3+ and Co3+  = n(n  2) BM
second ionisation enthalpy of Cu.
ions are strongest oxidising agents in 36. The colour of some aquated transition metal ions :
27. Ferrates (FeO )2– are formed in alkaline media aqueous solutions among 3d series. 4
Sc3+, Ti4+, Zn2+ : Colourless, V3+, Fe2+, Ni2+: Green ,
but they readily decompose to Fe2O3 and O2. 33. The ions Ti , V
2+ 2+
and Cu 2+
are strong
Fe3+: Yellow, Mn2+ : pink.
28. The highest Mn fluoride is MnF4 whereas reducing agents among 3d series and will
 37. These metals form a large number of complex
48. In acidic solution, K2Cr2O7 is used as oxidising  The overall decrease in atomic and ionic radii
compounds due to comparatively smaller sizes
from La to Lu due to poor shielding to 4f is
of the metal ions, their high ionic charges and agent as Cr O2– + 14H+ + 6e–  2Cr3+ + 7H O
known as lanthanoid contractions
the availability of d-orbitals for the bond
(E°2 =7 1.33 V)  Most common oxidation state is +3
formation.
49. Preparation of KMnO4
38. These metals and their compounds are used as a +
KOH H  Pr, Nd, Tb and Dy also exhibit +4 oxidation
catalyst due to their ability to adopt multiple (i) MnO K2MnO4 MnO– + MnO
O2 4

oxidation states and to form complexes. 2 (Green (Pink) state but only in oxides, MO2
)
39. When small atoms like H, C or N are trapped (ii) Lab method : 2Mn 2+
+ 5S2 O8 + 8H
2–
O  2MnO –
 Eu and Yb also exhibit +2 oxidation states.
2
inside the crystal lattice of these metals, the 4
+ 10 SO 2–
4 + 16 H +
 Their melting point range between 1000 to
combination are called interstitial compounds
1200 K but Sm melts at 1623 K
which are usually non- 50. KMnO4 decomposes at 513 K as :
stoichiometric.
40. Due to similar radii, transition metals form   Ln3+ ions may be coloured due to
2KMnO4 K2MnO4 + MnO2 + O2
alloy. eg. : Brass (Cu – Zn), Bronze (Cu – Sn). presence of f-electrons
41. Manganese ( VI) becomes unstable 51. KMnO4 behaves as oxidising agent as :
– – 2–  Lanthanoids form Ln(OH)3 which are basic like
relative to manganese (VII) and manganese
(IV) in acidic solution
 Basic4 medium : MnO4 + e 
MnO alkaline earth metal hydroxides.
3MnO2– + 4H+  2MnO– + MnO + 2H O
4 4
42. All 3d metals forms MO
2
oxides except scandium.  Neutral/faintly alkaline medium :  Mischmetal is an alloy which consists
2

43. Mn2O7 is acidic, Cr2O3 is amphoteric and CrO is MnO + 44H + 3e  MnO +
– +
2H O
– lanthanoids (~95%) and Iron (~5%)
2
basic in nature 2 4. Actinoids
 Acidic medium :
44. Preparation of  Outer electronic configuration : 5f0–14 6d0–1 7s2
MnO4– + 8H+ + 5e–  Mn2+ + 4H O
K2Cr2O7 :
H SO 52. KMnO oxidises I– into I and IO– respectively in  All actinoids are radioactive elements
Na CO acidic
FeCr O 2 3
Fe O + CO + Na CrO2 4
Na Cr O 4 2 3
3+
2 4
O 2 3 2 2 4 2 2 and faintly alkaline medium.  There is gradual decrease in the size of
Chromit 7
(Yellow)
e 2 (Orange) 53. Permangnate titrations in presence of HCl atoms or M ions across the series known as
ore
K2Cr2O7 KCl actinoid contraction, which is greater than
are unsatisfactory since HCl is oxidised to Cl2.
lanthanoid contraction.
45. Na2Cr2O7 is more soluble than K2Cr2O7  Their general oxidation state is +3 but these
46. Chromate and dichromate are element can show variety of oxidation states.
2 f-BLOCK ELEMENTS
interconvertible in aqueous solution depending
1. The f-block consists of elements in which 4f and
upon pH of the solution. 3 APPLICATION OF d- AND f-BLOCK ELEMENTS
5f orbitals are progressively field and known as
2CrO +42H  Cr O 2 +
2–
7
HO + 2–
inner- transition elements. 1. TiO is used in pigment industry
2
CrO + 72OH  2CrO +4 H O
2– – 2–

2
47.
2– 2. The two series of inner transition elements : 4f 2. MnO2 is used in dry battery cells
O 2–
179 163 (Ce to Lu)
pm pm
O O O and 5f (Th to Lr) are known as lanthanoids and
CrO2– : 4 Cr 3. TiCl4 and Al(CH3)3, Ziegler catalyst is
O O Cr actinoids respectively.
Cr O2– : Cr 126° O 3. Lanthanoids (Ln) : used to manufacture polyethene
2 O
 O O O  Outer electronic
configuration : 4. PdCl is used as catalyst in Wacker process.
(tetrahedral (dichromate ion) 2
) (Chromate 1–14 0–1 5. AgBr is used in photographic industry.
ion) 4f 5d
2
6s