d & f block elements

Electronic Configurations of the d-Block Elements

1.What are the transition elements? Write their G.E.C. &Write two characteristics of the transition elements.
Those atoms or ions having incompletely or partially filled d-orbitals are called transition elements
The general valence shell electronic configuration of transition elements is: (n – 1)d1–9 ns1–2
(i) They show variable oxidation state.
(ii) They form coloured ions
(iii)They can act as catalysts in many reactions

2.On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not?
Scandium is regarded as a transition element on the basis of incompletely filled 3d-orbitals in its ground state (3d1). On
the other hand, zinc atom has completely filled penultimate d-orbital (3d10) configuration in its (Zn2+), hence it is not
considered as a transition element..
3.Why is zinc not regarded as a transition element?
It is because neither Zn nor Zn+2 ions have incompletely filled d-orbitals.
4.Copper atom has completely filled d-orbitals in its ground state but it is a transition element. Why?
It is because Cu+2 has 3d9, incompletely filled d-orbitals, therefore, it is a transition metal

5. In what way the electronic configuration of the transition elements different from that of the non-transition
elements?
Electronic configuration of transition metals is (n-1)d(1–9)ns2. Here, d-orbitals of penultimate shell is progressively filled
while for non-transition elements d orbital is absent or completelelyfilledandlectrons are filled in valence shell. They
have ns1-2 ( or) ns2 np1-6 electronic configuration
6. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can you say that it is a transition
element?
Silver exhibits +2 oxidation state. In this oxidation state, 4d subshell contains nine electrons, i.e. partially filled 4d-
orbitals. Hence, it can be regarded as a transition element [Ag2+ ion, 4d9].

7. Copper, silver and gold have completely filled d-orbitals, yet they are considered as transition metals. Explain
why?
In the common oxidation states exhibited by Cu, Au and Ag metals, they have partially filled (n – 1) dorbitals:
Cu2+ (3d9), Ag2+ (4d9), Au3+ (5d8). On thisbasis, these metals are considered as transition metals.

Trends in melting points of transition elements

1. Explain why chromium is a typical hard metal while mercury is a liquid?
In chromium, the interatomic bonding is very strong due to the presence of five unpaired electrons in 3d subshell
(3d5 4s1). Therefore, it is a very hard metal. On the contrary in mercury the 3d subshell is fully filled (5d10 6s2), i.e.
electrons are not available for bonding and thus bonding is very weak in case of mercury.

2. Why the melting point and boiling point of Zn, Cdand Hg are low?
In Zn, Cd and Hg, the (n – 1)dorbitals are fully filled. These d-electrons do not take part in the metallic bonding.
Thus, the extent of metallicbonding is weaker in Zn, Cd and Hg. Hence, theyhave low melting and boiling points

Trends in enthalpies of atomisation of transition elements

1. 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?
In case of zinc, 3d-electrons are not involved in metal bonding as all the electrons are paired.Because of poor metal-
metal bonding, the enthalpy of atomisation of zinc is the lowest.

2. Why do transition elements exhibit higher enthalpies of atomisation?

Transition elements have unpaired electrons involved in strong interatomic bonding. This results their higher
enthalpies of atomisation
Variation in Atomic and Ionic Sizes of Transition Metals
1. In the transition metals series, with an increase in atomic number the atomic radius does not change
appreciably. Explain.
As we move from left to right along the transition metals series, the nuclear charge increases but due to ineffective
shielding of d electrons net electrostatic attraction between the nucleus and valence electrons increases. Thus atomic
radius does not change appreciably across the series

2.The second and the third d series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar
physical and chemical properties.why?
This is due to Lanthanoid contraction

Ionisation Enthalpies
1. First ionisation energies of 5d series elements are higher than those of 3d and 4d series elements. Why?
Because of weaker shielding (or screening) effect of 4f electrons, the effective nuclear charge on the valence electrons in
5d series elements is higher. Hence, the first ionisation energies for 5d elements are higher than those of 3d and 4d
series elements.
2.ionisation enthalpy of Mn+ is lower than Cr+. Why?
Mn+ has 3d54s1 configuration and configuration of Cr+ is d5..

3.ionisation enthalpy of Fe2+ is lower than the Mn2+.Why?

Fe2+ has d6 configuration and Mn2+ has 3d5 configuration.

4. The sum of first and second and those of third and fourth ionisation energies for nickel and platinum metals
are given below:Taking these values into account, write:
Metal IE1 + IE2 (kJ mol–1) IE3 + IE4(kJ mol–1)

Ni 2.49 × 103 8.80 × 103

Pt 2.66 × 103 6.70 × 103

(i) The most common oxidation state for nickel and platinum metals.
For nickel, +2 is the common oxidation state as the sum of only first and second ionisation energies (IE 1 + IE2) for Ni
has lower value. For platinum, +4 is the common oxidation state as the sum of all the first, second third and fourth
ionisation enthalpies (IE1 + IE2 + IE3 + IE4) for Pt has lower value.

(ii) Write the name of metal which form compounds in +4 oxidation state easily and why is it so?
Platinum can easily form compounds in +4 oxidation state because the sum of ionisation energies (IE 1 + IE2 + IE3 + IE4)
is lower for Pt as compared to Ni metal.

5.How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series
of the transition elements?
Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d-
configurations (e.g., d0, d5, d10 are exceptionally stable).

6. Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+ ions of the 3d series metals, the 4d and the 5d series
metals generally do not have tendency to form stable cationic species.
Due to lanthanoid contraction, the size of 4d and 5d elements decreases which increases their ionisation energy. Thus,
they cannot easily lose electrons to form cationic species

Oxidation States
1.Why do transition elements show variable oxidation states? In 3d series (Sc to Zn), which element shows the
maximum number of oxidation states and why?
Transition elements show variable oxidation states because electrons from both s and d orbitals take part in bond
formation due to similar energy of (n – 1 )d and ns orbitals . In 3d series, ‘Mn’ shows maximum number of oxidation
states because it has maximum number of electrons in s as well as in d orbitals which can take part in bond formation.
2.How is the variability in oxidation states of d-block different from that of the p-block elements?
. In p-block, lower oxidation state is more stable due to inert pair effect, whereas in d block elements higher oxidation
states are more stable.In d-block, oxidation states differ by one, whereas in p-block, it differs by two.

3. Name a transition element which does not exhibit variable oxidation state.
Sc21→3 d1, 4s2; and it exhibits only a fixed oxidation state of +3.

4. Which metal in the first series of transition metals exhibits +1 oxidation state most frequently and why?
Copper with electronic configuration [Ar] 3d10 4s1 exhibits +1 oxidation state. Copper easily loses 4s1electron and
achieves a stable (3d10) configuration by forming the cation, Cu+.

5. Which of the 3d series transition metal exhibits the largest number of oxidation states and why?
The electronic configuration of Mn atom is 3d5 4s2, i.e. all the d-orbitals are singly occupied by electrons. Thus, Mn
exhibits a large number of oxidation states ranging from +2 to +7 by losing all its valence electrons.

6. Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their +3 state? OR

Explain the following observation; giving an appropriate reason for each: Mn2+ ion is much more resistant
towards oxidation than Fe2+ ion.
The electronic configuration of Mn2+ ion is [Ar] 3d5, i.e. all the five d-orbitals are singly occupied. Thus, this
configuration is highly stable and it resists further oxidation, i.e. loss of further electrons requires very high energy for
this process. On the other hand, the electronic configuration of Fe2+ ion is [Ar] 3d 6. Hence, it can easily lose an electron
and achieve the stable half filled electronic configuration, i.e. oxidation of Fe2+ into Fe3+ ions can be easily achieved.

7. Compare the stability of +2 oxidation state for the elements of the first transition series.
The stability of +2 oxidation state decreases from left to right except for Mn and Zn. Stability decreases towards right
due to decreasing negative value of standard reduction potential. The decrease in the negative value of standard
reduction potential is due to increase in the sum of first and second ionisation enthalpies

8. Explain briefly how +2 oxidation state becomes more and more stable in the first half of the first row transition
elements with increasing atomic number.
In M2+ ions, 3d-orbitals gets occupied gradually as the atomic number increases. Since, the number of empty d-orbitals
decreases, the stability of the cation (M2+) eventually increases from Sc2+ to Mn2+. Mn2+ ion is the most stable as all its
five 3d-orbitals are singly occupied.

Trends in the M2+/M Standard Electrode Potentials

1. Explain the fact that transition elements have high enthalpies of hydration.
Due to small size of ions and high ionic charge,there is more tendency of hydration in transition elements. This gives
rise to high enthalpy of hydration

2. Copper does not react readily with dilute acids to liberate hydrogen gas. Explain.
Copper has positive reduction potential for Cu2+ to Cu.(+0.34 V) Thus, it cannot reduce H+ ions of acids to H2gas.
3. Which is a stronger reducing agent Cr2+ or Fe2+and why?
Cr2+ ion is a stronger reducing agent than Fe2+ ion. Reason: d4→d3 occurs in case of Cr2+ to Cr3+ but d6→d5 occurs in
case of Fe2+ to Fe3+. In a neutral medium (like water) d3 configuration is more stable than d5.

4.The Eo(M2+/M) value for copper is positive (+0.34V). What is possible reason for this?
E0(M2+/M) for any metal depends on the sum of enthalpies of atomisation, ionisation enthalpies and hydration enthalpies.
Copper has high enthalpy of atomisation and low hydration energy. Hence, E°(Cu2+/Cu) is positive
.The high energy to transform Cu to Cu2+ is not balanced by its hydration energy.

5.Why is Cr2+ reducing and Mn3+oxidising when both have d4 configuration?

Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t2g level .

On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which has extra stability

Trends in the M3+/M2+ Standard Electrode Potentials

1.why is E° value for the Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+ couple?
Explain.
Eo(Mn3+/Mn2+) is more positive because Mn2+(d5) have extra stability due to half filledd-orbitals than Mn3+
while in case of Cr, Cr3+(d3) is more stable due to half filledt2g orbitals than that of Cr2+ and
in case of Fe, Fe3+(d5) is more stable due to stable half filledd-orbitals than that of Fe2+.

Trends in Stability of Higher Oxidation States

1. Why is the highest oxidation state of a transitionmetal exhibited in its oxide or fluoride only
Because of small size and high electronegativity of oxygen and fluorine, they oxidise metals to their highest oxidation
state.
2. Transition metal fluorides are ionic where as bromides and chlorides are usually covalent in nature. Explain.
Since electronegativity of halogens decreases in the order: F > Cl > Br
Therefore, the ionic character of transition metal halides decreases in the order as follows: M – F > M – Cl > M – Br
Hence, fluorides are ionic while chlorides and bromides are covalent in nature.

3.How would you account for the increasing oxidising power in the series VO2+ < Cr2O72– < MnO4– ?
This is due to the increasing stability of the lower species to which they are reduced

4.Explain why Cu+ ion is not stable in aqueous solutions?

Cu+ in aqueous solution underoes disproportionation, i.e., 2Cu+(aq) → Cu2+(aq) + Cu(s) The Eo value for this is
favourable

5.What is meant by ‘disproportionation’ of an oxidation state? Give an example.

When an element as a molecule or an ion simultaneously undergoes oxidation as well as reduction, this phenomenon is
called disproportionation. It takes place when the particular oxidation state of an element becomes less stable relative to
the other oxidation states, one lower and one being higher. For example
Chemical Reactivity and Eo Values

1. For the first row transition metals the Eo values are:

Eo V Cr Mn Fe Co Ni Cu
(M2+/M) –1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34
Explain the irregularity in the above values.
The E (M2+/M) values are not regular which can be explained from the irregular variation of ionisation enthalpies ( ∆iH 1
+ ∆iH2 ) and also the sublimation enthalpies which are relatively much less for manganese and vanadium

2. Why is the Eo value for the Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+?
Explain.
Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for this. This
also explains why the +3 state of Mn is of little importance

Magnetic Properties
1. Why d o e s Mn (I I) ions show maximum paramagnetic character amongst the bivalent ions of the elements of
first transition series? Calculate the theoretical value of its magnetic moment.
The extent of paramagnetic nature depends uponthe number of unpaired electrons present. Mn(II)ions possesses the
maximum number of unpairedelectrons i.e. 5, amongst the divalent ions of thefirst transition series and thus it possesses
themaximum paramagnetic character. Theoreticalvalue of magnetic moment:
(For Mn(II)) =√n(n + 2)
√5(5 + 2) = √35 = 5.91 BM

2. Which among Fe2+ and Fe3+ ions are more paramagnetic and why?
Fe3+ ion is more paramagnetic than Fe2+ ion, since it consists of five unpaired electrons while Fe2+ ion possess only 4
unpaired electrons.

Formation of Coloured Ions

1.Why do Transition metals generally form coloured compounds?
Transition metals generally form coloured compounds and this can be accounted on the basis of d-d transitions. Due to
partially filled d-orbitals, there is a transition of electrons among the d-orbitals by absorption of visible light

Formation of Complex Compounds

1.Why do d block elements form complexes
This is due to the comparatively smaller sizes of the metal ions, their high ionic charges and the availability of d orbitals
for bond formation

Catalytic Properties
1. Transition metals and their compounds act as good catalysts. Explain.
(i) They have variable valencies and exhibitmultiple oxidation states and transitionmetals sometimes form unstable
intermediatecompounds which provides a new pathwaywith lower activation energy for the reaction.
(ii) In some cases transition elements provide asuitable surface area for the reaction to occur.

2.Give reasons for the following:

(i) Cu(I) ion is not stable in aqueous solution.Orsolution?
(i) Cu2+(aq) ion is much more stable than Cu+(aq) ion. Though second ionisation enthalpy is large but the hydration
enthalpy of Cu2+ is highly negative and it compensate for large second ionisationenthalphy. Thus Cu2+ (aq) ion is more
easier to form. Cu(I) compounds are a bit unstable in aqueous solution and undergoes disproportionation as follows:
2Cu+→Cu2+ + Cu

Formation of Interstitial Compounds

1. How would you account for the following:
(i) Most of the transition elements are knownto form interstitial compounds.
Because small non-metallic atoms like H,C, N can easily get trapped inside the crystal lattice of the transition metals
Alloy Formation
1. Explain the following observation by giving an appropriate reason:
There occurs much more frequent metal-metal bonding in heavier transition metals compounds.

This is because of the fact that the filling of electrons in 4f orbital starts in 3rd transition series elements, as a result of
which the elements have large number of unpaired electrons along with ns-orbitals electrons which take part in metallic
bonding

Complete the following reactions:

(i) Cu2+(aq) + I– (aq) →
(i) 2Cu2+(aq) + 4I–(aq) → Cu2I2 + I2(s)
(ii) AgCl(s) + NH3 (aq) →
(ii) AgCl(s) + 2NH3(aq) → Ag(NH3)2Cl (soluble)

K2Cr2O7&KMnO4
Complete the following reactions
1.Cr2O72- + H+ ? 2. Cr2O72- + Fe2+ + H+  ? 3. Cr2O72- + S2- + H+ ?
2- --
4.Cr2O7 + I + H +
? 5. Cr2O72- + Sn2+ + H+  ? 6. MnO2+KOH+O2  ?
7.MnO42- + H+  ? 8. MnO4- + H++ I--  ? 9. MnO4- + H+ + NO2- -
 ?
10.MnO4- + C2O42- + H+ ? 11. MnO4 + H + Fe  ?
- + 2+-
12. MnO4- + H+ + S2--  ?
13.MnO4- + H+ + SO32-- ?

Under Basic medium

14.MnO4- + H2O + I-- ? 15. MnO4- + H2O + S2O82-- ? 16. MnO4- + H2O + Mn+2 ?

Permanganate titrations in presence of hydrochloric acid are unsatisfactory why?

since it reacts with KMnO4 as follows.
2MnO4-- + 10 Cl− + 16H+  Mn2 + 5Cl2 + 8H2O

f- block elements
1.Write any two consequences of Lanthanoid Contraction
2.Give reasons:
(i) Separation of a mixture of Lanthanoid elements is difficult
(ii) Eu2+ is a strong reducing agent
(iii)The chemistry of actinoids elements is not so smooth as that of the lanthanoids

3.Write any two similarities and differences between the chemistry of lanthanoids and actinoids elements.
4.Chemistry of actinoids is complicated as compared to lanthanoids. Give two reasons
5.Actinoids show irregularities in their electronic configurations.
6.Account for the following :
(i). Zr and Hf have almost similar atomic radii.
(ii)Actinoid contraction is greater than lanthanoid contraction.
(iii) Actinoid elements show wide range of oxidation states.

7. Account for the following :

(i) Name a member of the lanthanoid series that is well-known to exhibit +2 oxidation state.
(ii) With reference to structural variability and chemical reactivity, write the differences between lanthanoids and
actinoids.
(iii) Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
8.What is lanthanoid contraction? Name an important alloy which contains some of the lanthanoid metals.