DAV SCHOOL

(Affiliated to CBSE – New Delhi)

XII STD CHEMISTRY
d & f -BLOCK ELEMENTS
1) Why do transition elements show variable oxidation states?
The variability of oxidation state of transition elements is due
to incompletely filled d-orbitals and
presence of unpaired electrons, i.e. (ns) and (n -1) d electrons that have
almost equal energies.

2) Why do transition elements form alloys?

As the atomic sizes are very similar one metal can replace the other metal
from its lattice and form a solid solution which is the alloy. This is the reason
why transition metals form homogeneous mixtures with one another in
molten state.

3) Interstitial compounds are formed by d block elements- Why?. What are

the characteristics of such compounds?
The compounds formed when small atoms of H, C,B or N get trapped inside
the crystal lattice of metals is known as interstitial compounds. A number
of interstitial compounds are formed by the transition metals. Transition
metals react with elements such as hydrogen, carbon, nitrogen, boron etc. to
form interstitial compounds.

1. These compounds have very high melting points, higher than that of the
parent transition metals.
2. These compounds are very hard. The hardness of some borides is
comparable to that of a diamond.
3. The conductivity exhibited by them is similar to their parent metal.
4. These compounds are chemically inert in nature.

4) Explain the following observations :

(i) Generally there is an increase in density of elements from
titanium (Z = 22) to copper (Z = 29) in the first series of transition
elements.
(ii) Transition elements and their compounds are generally found to be good
catalysts in chemical reactions.
(i) From titanium to copper the atomic size of elements decreases and
atomic mass increases as a result of which density increases.
(ii) The catalytic properties of the transition elements are due to the presence
of unpaired electrons in their incomplete d- orbitals and variable oxidation
states.They provide large surface area for the reaction
They can form intermediate compounds due to variable oxidation states
And also form interstitial compounds
5) Explain the following observations :
(i) Transition elements generally form coloured compounds.
(ii) Zinc is not regarded as a transition element.
(i) Because of presence of unpaired d electrons, which undergoes d-d
transition by absorption of energy from visible region and then the
emitted light shows complementary colours. This is how transition
elements form coloured compounds.
(ii) Zinc in its common oxidation state of +2 and in its ground state has
completely filled d-orbitals. Hence considered as non-transition element.
6) Assign reasons for the following :
(i) Copper (I) ion is not known in aqueous solution.
Cu2+(aq) is much more stable than Cu+(aq). This is because although second
ionization enthalpy of copper is large 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
7)(i) Manganese exhibits the highest oxidation state of +7 among the 3d
series of transition elements.
(i) Manganese exhibits highest oxidation of +7 among 3d series of transition
elements because it has more number of unpaired electrons (3d5 4s2 ).It
shows all the oxidation states from +2 to +7 by Mn and no other element of
this series shows this highest state of oxidation. all 7 electrons can take part in bonding
8(i) Metal-metal bonding is more frequent for the 4d and the 5d series of
transition metals than that for the 3d series.
(i) Metal-metal bonding is more frequent for the 4d and the 5d series of
transition metals than that for the 3d series as these have their electrons of
 outer most shell at greater distance from the nucleus, as compared to atoms
of 3d transition metals and can readily involve in bonding.
9)(a) The enthalpies of atomization of transition metals are quite high.
(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.
10)(a) Which metal in the first transition series (3d series) exhibits +1
oxidation state most frequently and why?
(b) Which of the following cations are coloured in aqueous solutions
and why?
SC3+, V3+, Ti4+, Mn2+.
( Sc = 21, V = 23, Ti = 22, Mn = 25)
(a) Copper exhibits + 1 oxidation state more frequently i.e., Cu+1because of
its electronic configuration 3d104s1. It can easily lose 4s1electron to give
stable 3d10configuration.
b) Sc3+= 4s03d0= 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.
11) What is Lanthanoid contraction? What are its two consequences?
Lanthanoid contraction: The overall decrease in atomic and ionic radii with
increasing atomic number is known as lanthanoid contraction. In going from
La+3to Lu+3in 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.
(ii) Due to small change in atomic radii, the chemical properties of
lanthanoids are very similar due to which separation of lanthanoid
becomes very difficult.
(iii) 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 hence La(OH)3 is most basic while Lu(OH)3 is
least basic.

12) 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.
(i) Because
Ionization of stronger
enthalpies metallic
are found bonding
to increase in the and
givenhigh
seriesenthalpies of atomization.
due to a continuous filling of the inner
d-orbitals. The irregular variations of ionization enthalpies can be attributed to the extra stability of
(ii) Due to irregulaties
configurations in the
such as d0, d5, d10.electronic
Since theseconfiguration there isstable,
states are exceptionally irregularities
their ionization
in the enthalpies of atomisation. Hence there is irregular variation in I.E.
enthalpies are very high.

Removal of even one electron alters the energies of 3d and 4s

The highest oxidation state of a transition metal is usually exhibited in its
oxide and fluorides.

13) i) The highest oxidation state of a metal is exhibited in its oxide

or fluoride-why?
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.
Oxygen has the advantage of forming multiple bonds
14) Give reasons :
(i) Zn is not regarded as a transition element.
(ii) Cr2+is a strong reducing agent.
(i) Zinc Atomic no. 30 has EC 3d10, 4s2. It has completely filled ‘d’
orbitals.
(ii) Cr+2(3d4) after losing one electron forms Cr+3(d3). It has stable
t2g3eg0configuration. Hence more stable. Hence Cr+2acts as reducing
agent.
15) 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) E0value for Mn3+/Mn2+couple is much more positive than Cr3+/Cr2+.
(a) Because silver has incomplete d-orbital (4d9) in its +2 oxidation state,
hence it is a transition element.Eg AgF2
(b) The large positive E° value for Mn3+/Mn2+shows that Mn2+is much more
stable than Mn+3due to stable half filled configuration (3d5). Therefore the
3rdionisation 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+.
16) Calculate the magnetic moment of a divalent ion in aqueous medium
if its atomic number is 26.
Divalent ion with atomic number 26 is Fe2+

17) The E°M2+/M, for copper is positive why?

The E°M2+/M, for copper is positive (+ 0.34 V). It is the only metal in the
first series of transition elements showing this type of behaviour.
The E°M2+/Mfor any metal is related to the sum of the enthalpy changes
taking place in the following steps :
M(s) + 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°M2+/M for copper is
positive. The high energy required to transform Cu(s) to Cu2+(aq) is not
balanced by its hydration enthalpy.
18) Account for - Transition metals form a large number of complexes.
Because of smaller size of their ions, high nuclear charge and availability
of vacant d-orbitals of appropriate energies to accommodate electrons
from ligands.
19) Explain the following observations (i) Cr2+is a strong reducing agent.
(ii) Cu2+salts are coloured while Zn2+salts are white.
(i) Cr2+exists in the d4system and is easily oxidized to Cr3+by losing one
electron which has the stable (d3)t2g3 orbital configuration. So, Cr2+is a strong
reducing agent.
(ii) Cu2+has the configuration 3d9with one unpaired electron which gets
excited in the visible region to impart its colour while Zn2+has
3d10configuration without any unpaired electron d – d transition is not
possible and hence colourless.
20) Zn, Cd and Hg are soft metals.
Zn, Cd and Hg are soft metals because they do not exhibit covalency due to
completely filled d-orbitals. Absence of unpaired d electrons causes weak
metallic bonding.
21) Following are the transition metal ions of 3d series:
Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers: Ti = 22, V= 23, Mn = 25, Cr = 24)
Answer the following:
(i) Which ion is most stable in an aqueous solution and why?
(ii) Which ion is a strong oxidising agent and why?
(iii) Which ion is colourless and why?
(i) Cr3+is most stable because of its small size and t32gconfiguration.
(ii) Mn3+is a strong oxidising agent because after gaining one electron it is
converted into Mn2+which has stable d5configuration.
(iii) Ti4+is colourless due to d° configuration, i.e., no unpaired electrons.
22) What are transition elements?
Transition elements are elements that have partially filled d orbitals.
All the transition elements or d-block elements are classified into four series
like 3d, 4d, 5d, and 6d. Each 3d, 4d, 5d, and 6d series has ten elements. The
general valence shell electronic configuration of transition elements is
(n-1)d1 to 10 ns 1, 2.