D and F block elements

d-Block Elements

 The d-block of the periodic table contains the elements of the group 3-12
 The configuration varies from (n – 1)d1-10ns1-2
 These are present between s-block and p-block elements
 The properties of these elements are intermediate between the properties of s-block and p-block elements.
 There are mainly three series of the transition metals.

(i) 3d series (Sc — Zn)

(ii) 4d series (Y — Cd)

(iii) 5d series (La — Hg)

(iv) 6d series (Ac — Uub)

1. Transition Elements :

They are often called “Transition elements” because their position in the periodic table between s-block
and p-block elements. Typically, the transition elements have an incompletely filled d-level.

Q) Zn, Cd and Hg are generally not regarded as transition elements. Why?

Ans: Zn, Cd and Hg

Zn =3d104s2

Cd =4d105s2

Hg =5d106s2

Due to the presence of completely filled d orbitals, Zn,Cd,Hg are not regarded as Transition metals

Q) Why chromium is a transition element but zinc is not ?

Transitions elements have incomplete d-orbitals chromium has [Ar]4s1 3d5 i.e. Partially filled d-orbitals but
in case zinc having [Ar]4s23d10 i.e. fully filled d-orbitals.

Hence, chromium is a transition elements whereas zinc is not.

Q) In what way is the electronic configuration of the transition elements different from that of the non-
transition elements?

Solution :Transition metals have a partially filled d−orbital. Therefore, the electronic configuration of
transition elements is (n − 1)d1-10 ns0-2.

The non-transition elements either do not have a d−orbital or have a fully filled d−orbital. Therefore, the
electronic configuration of non-transition elements is ns1-2 or ns2 np1-6.
Q) Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transition element?

Solution :

Ag has a completely filled 4d orbital (4d10 5s1) in its ground state. Now, silver displays two oxidation states
(+1 and +2). In the +1 oxidation state, an electron is removed from the s-orbital. However, in the +2
oxidation state, an electron is removed from the d-orbital. Thus, the d-orbital now becomes incomplete
(4d9). Hence, it is a transition element.

2. Electronic Configuration :

General E.C. of d-block (n–1)d1-10ns0-2

For 3d series 3d1-104s1-2

For 4d series 4d1-105s0-2

For 5d series 5d1-106s1-2

For 6d series 6d1-107s1-2

Write the electronic configuration of following species.

(i) Cr (ii) Zn

(i) Cr – Atomic number (Z = 24)

1s2 2s2 2p6 3s2 3p6 4s1 3d5

(ii) Zn – Atomic number (Z = 30)

1s2 2s2 2p6 3s2 3p6 4s2 3d10

3. Atomic and ionic sizes of transition metals :

 On moving left to right in the period, generally atomic and ionic radius value decreases.
 The atomic radii decrease from Sc to Cr because the effective nuclear charge (ENC) increases.
 The atomic size of Fe, Co, Ni is almost same due to increase in nuclear charge is cancelled by the
repulsion between the electrons and increase in shielding effect.
 Cu and Zn have bigger size because the shielding effect decreases and electron-electron
repulsion increases.

Sc≥ Ti ≥V ≥Cr ≥Mn≥ Fe ≡Co≡ Ni≤ Cu≤ Zn (Covalent radius )

Sc≥ Ti ≥V ≥Cr <Mn> Fe ≡Co≡ Ni≤ Cu≤ Zn (Metallic radius)

Lanthanoid Contraction There is regular decrease in the atomic and ionic radii of the transition metals
as the atomic number increases. This is because of filling of 4f orbitals before the 5d orbitals. This
contraction in size is quite regular. This is called lanthanoid contraction
 CAUSES- because of filling of 4f orbitals before the 5d orbitals.

CONSEQUENCES-

1. Atomic size:

The size of the atom of the third transition series is closely the same as that of the atom of the second
transition series. For example, the atomic radius of Zr= atomic radius of Hf and the atomic radius of Nb
=atomic radius of Ta

2. Difficulty in the separation of lanthanides:

As there is only a minute change in the ionic radii of lanthanides, their chemical properties are the
same. This makes the separation very difficult.

3. Effect on the basic strength of hydroxides:

The size of lanthanides decreases from La to Lu, the covalent character of the hydroxides increases, and hence
their basic strength decreases.
For example,
Q) Lu(OH)3 is said to be the least basic, and La(OH)3 is more basic.why?
The ionic size of La3+ is larger than Lu3+, which means that La(OH)3 is more ionic and has a lower covalent
character. This makes La(OH)3 more basic and able to release hydroxide ions more easily.
Q) Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Solution : In actinoids, 5f orbitals are filled. These 5f orbitals have a poorer shielding effect than 4f orbitals (in
lanthanoids). Thus, the effective nuclear charge experienced by electrons in valence shells in case of actinoids
is much more that that experienced by lanthanoids. Hence, the size contraction in actinoids is greater as
compared to that in lanthanoids

Complex formation:

Due to the smaller size but higher nuclear charge, the tendency to form a coordinate compound.

Complexity increases from the element

Ionisation Enthalpy :

There is slight and irregular variation in ionization energies of transition metals due to irregular variation of
atomic size. The I.E. of 5d transition series is higher than 3d and 4d transition series because of lanthanoid
contraction.

Order of IP of d-block Elements is 3d < 5d > 4d

Order of IP of 3d series will be:-

Sc < Ti > V < Cr < Mn < Fe > Co > Ni < Cu < Zn

Q) How would you account for the irregular variation of first and second ionization enthalpies in the first
transition series of the transition elements?

Ans Ionization enthalpies are found to increase in the given series due to a continuous filling of the inner d-
orbitals. The irregular variations of ionization enthalpies can be attributed to the extra stability of
configurations such as d0 d5 d10. Since these states are exceptionally stable their ionization enthalpies are very
high. In case of first ionization energy Cr has low ionization energy. This is because after losing one electron it
attains the stable configuration 3d5. On the other hand Zn has exceptionally high first ionization energy as an
electron has to be removed from stable and fully-filled orbitals 3d10 4s2. Second ionization energies are higher
than the first since it becomes difficult to remove an electron when an electron has already been taken out.
Also elements like Cr and Cu have exceptionally high second ionization energies as after losing the first
electron they have attained the stable configuration Cr +: 3d5 and Cu+: 3d10. Hence taking out one electron
more from this stable configuration will require a lot of energy.

(4) Oxidation States :

 Sc and Zn don’t show variable oxidation state

 Most common oxidation state of d-block metals is +2.
 Highest oxidation state of 3d-series element is +7
 Highest oxidation state of d-block metals with respect to halogen is found to be +6.

Q) d-Block elements exhibit more oxidation states than f-block elements. Give Reason.

Ans d-Block elements exhibit more oxidation states because of less energy gap between d and s subshell
whereas f-block elemetns have large energy gap between f and d subshell.

Q) Name a transition element which has variable oxidation state.

Ans Mn,Fe,Cu

Q) Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?

Solution :

Mn (Z = 25) = 3d5 4s2

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.

Q) which of the first row transition metals exhibit +7 Oxidation state?

Ans Mn

Q) Which is a stronger oxidizing agent-Bi(v) or Sb(v)?

Ans Bi has +5 oxidation state and it is a stronger oxidizing agent than Sb because Bi gains electrons from the
reducing agent very much faster than the Sb and becomes stable from +5 oxidation state to +3 oxidation state.

Q) Cu(I) has d10 configuration while Cu(II) has d9 configuration . Still Cu(II) is more stable in aqueous solution
than Cu(I).WHY?
Ans The electronic configuration of Cu is [Ar] 3d10. The electronic configuration of Cu(II) is[Ar] 3d9. The
stabilities of the ions depend on their hydration energies released when the ions get linked to the water molecules.
Cu(II) ion has a smaller size and a greater charge. So, it has a higher charge density compared to Cu(I) ion.

Therefore, Cu(II) ion gets linked to water molecules more strongly, which results in the release of more hydration
energy as compared to C(I) ion. Hence, Cu(II) is more stable than Cu(I)

Q) Why is Cr3+ reducing and Mn3+ oxidizing when both have d4 configuration?

Ans Cr is reducing in nature. It had a d4 configuration. While acting as a reducing agent,it gets
oxidized to Cr3+ which has electronic configuration d3 . This d3 configuration Can be written as t2g 3 which is
a more stable configuration

In case of Mn3+ which is an oxidising agent gets reduced to Mn2+ . This has an exactly half filled d orbital
and is highly stable.

Q) Cu+ ion is not stable in aqueous solution. why?

Ans Cu+ in aqueous solution. Cu+ ion is unstable in aq. solution and disproportionate to give
Cu2+and Cu. It is given as; 2Cu+(aq)→Cu2+(aq)+Cu(s). The release of hydration energy during the formation
of Cu2+compensates the energy required to remove an electron from d10 configuration.

Q) Which metal in the first series of transition metals exhibits +1 oxidation states and why?

Ans Copper metal (with electronic configuration [Ar]3d104s1) in the first series of transition metals exhibits +1
oxidation state most frequently as it readily loses one electron (present in 4s orbital) to give stable 3d10 electronic
configuration.

Q) Mn2+ is more stable thanFe2+ towards oxidation to +3 oxidation state. why?

Ans Mn2+=1s2,2s22p6,3s23p64s23d5(half-filled d-orbital)

Fe2+=1s2,2s22p6,3s23p64s23d6

Mn2+compounds are more stable due to half-filled d-orbitals.

Fe2+compounds are comparatively less stable as they have six electrons in their 3d-orbital. So,
they tend to lose one electrons (form Fe3+) and get stable 3d5 configuration.

Q) Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?

Solution :

Both oxide and fluoride ions are highly electronegative and have a very small size. Due to these properties, they
are able to oxidize the metal to its highest oxidation state.

Q) Why E˚ values for Mn and Zn are more negative?

E˚ values for Mn and Zn are more negative than expected, because Mn2+ and Zn2+ ions have extra stability owing to
the presence of half - filled d5 and completely filled d10 configuration of d - subshell.
 Q) Why Bi(V) is a stronger oxidizing agent than Sb (V) ?

Bi has +5 oxidation state and it is a stronger oxidizing agent than Sb because Bi gains electrons from the reducing
agent very much faster than the Sb and becomes stable from +5 oxidation state to +3 oxidation state.

4. Standard Electrode Potential

Q) E° value for Sc3+/Sc2+ is very low. why?

Ans- Sc3+ is stable. This is due to its noble gas configuration.

Q) Between the couple Cr3+/Cr2+ and Fe3+/Fe2+ whose E˚ value is more positive and why?

Ans Cr3+= [Ar]4s0 3d3 Fe3+= [Ar]4s0 3d5

Cr2+= [Ar]4s0 3d4 Fe2+= [Ar]4s0 3d6

It has been found that the conversion of Fe 2+ to Fe3+ will be more easy since Fe3+ attains the stable
half filled electronic configuration. So it has positive E˚ value.

Q) Give the reason for negative E˚ Value for Ni2+/Ni.

Ans Ni2+=[Ar]4s0 3d8 Ni=[Ar]4s2 3d8

Ni have more negative E˚ value than expected. This is due to the smaller ionic radius and high charge
density of Ni2+ which result in highest negative enthalpy of hydration among the elements of 3d-
series.

Q) The highest number of oxidation state is generally exhibited by its oxide .why?

Ans Oxygen and fluoride ions are both very electronegative and extremely small. Due to these
properties, they may oxidize the metal to its greatest oxidation state.

Q. Explain why transition elements form coloured compounds.

Ans Transition elements have partially filled d-orbitals in their penultimate shells. In
complexes the ligands are responsible for the splitting of the d-orbitals of the central metal ion. As
a result, the complexes absorb a specific wavelength from the visible light which enables the d-d
transition of the electrons. Hence, the compounds of transition elements appear coloured.
Q Explain why transition elements shows catalytic properties
d-block elements and their compounds are known to act as good catalyst as they have
variable oxidation state. They provide a new path with lower activation energy for the
reaction and form unstable intermediate compounds (intermediate compounds theory). The
adsorbed reactants provide a large surface area for adsorption, which are finely divided
metals or their compounds react faster due to the closer contact
Q Explain why transition elements shows the tendency to form complexes.
Ans The transition metal ions possess a great tendency to form complexes because of their
small size, high ionic charge and availability of partially filled d-orbitals for bond formation. These
 partially filled d-orbitals can easily accommodate ligands electrons and consequently transition
metals ions form complexes.

5. MAGNETIC Property

On applying magnetic field to substances, mainly two types of magnetic behaviour are

observed :

(i) Diamagnetism :

Diamagnetic substance is one which is slightly repelled by a magnetic field.

(ii) Paramagnetism :

Paramagnetic substance is one which is attracted by a magnetic field

The magnetic moment is determined by the number of unpaired electrons.

Magnetic moment =√𝒏(𝒏 + 𝟐) B.M.

Where, n = number of unpaired electrons.

 Transition metal ions having d5 configuration will have maximum number of unpaired

electrons therefore they will be maximum paramagnetic in nature.

Q) Which divalent 3d ion contain maximum unpaired electron.

(1) Cr+2 (2) Mn+2 (3) Fe+2 (4) Co+2

Q) Calculate the magnetic moment of Cr2+, Mg2+, Co2+ and Fe2+ is .

Q) Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).

Q) Explain giving reasons:

(i) Transition metals and many of their compounds show paramagnetic behaviour.
 Transition metals show paramagnetic behaviour. Paramagnetism arises due to the presence of
unpaired electrons with each electron having a magnetic moment associated with its spin angular
momentum and orbital angular momentum. However, in the first transition series, the orbital
angular momentum is quenched. Therefore, the resulting paramagnetism is only because of the
unpaired electron.
(ii) The enthalpies of atomisation of the transition metals are high.
Transition elements have high effective nuclear charge and a large number of valence electrons.
Therefore, they form very strong metallic bonds. As a result, the enthalpy of atomization of transition
metals is high.

(iii) The transition metals generally form coloured compounds.

Most of the complexes of transition metals are coloured. This is because of the absorption of radiation from
visible light region to promote an electron from one of the d−orbitals to another. In the presence of ligands,
the d-orbitals split up into two sets of orbitals having different energies. Therefore, the transition of
electrons can take place from one set toanother. The energy required for these transitions is quite small and
falls in the visible region of radiation. The ions of transition metals absorb the radiation of a particular
wavelength and the rest is reflected, imparting colour to the solution

(iv) Transition metals and their many compounds act as good catalyst.

The catalytic activity of the transition elements can be explained by two basic facts.

(a) Owing to their ability to show variable oxidation states and form complexes, transition metals form
unstable intermediate compounds. Thus, they provide a new path with lower activation energy, Ea, for
the reaction.

(b) Transition metals also provide a suitable surface for the reactions to occur.

Q Compare the chemistry of actinoids with that of the lanthanoids with special reference to:

(i) electronic configuration -The general electronic configuration for lanthanoids is [Xe]54 4f0-14 5d0-1
6s2 and that for actinoids is [Rn]86 5f1-14 6d0-1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply
buried and participate in bonding to a greater extent.
(ii) oxidation state- The principal oxidation state of lanthanoids is (+3). However, sometimes we also
encounter oxidation states of + 2 and + 4. This is because of extra stability of fully-filled and half-filled
orbitals. Actinoids exhibit a greater range of oxidation states. This is because the 5f, 6d, and 7s levels
are of comparable energies. Again, (+3) is the principal oxidation state for actinoids. Actinoids such as
lanthanoids have more compounds in +3 state than in +4 state.
(iii) atomic and ionic sizes- Similar to lanthanoids, actinoids also exhibit actinoid contraction (overall
decrease in atomic and ionic radii). The contraction is greater due to the poor shielding effect of 5f
orbitals.

(iv) chemical reactivity- In the lanthanide series, the earlier members of the series are more reactive.
They have reactivity that is comparable to Ca. With an increase in the atomic number, the
 lanthanides start behaving similar to Al. Actinoids, on the other hand, are highly reactive metals,
especially when they are finely divided. When they are added to boiling water, they give a mixture of
oxide and hydride. Actinoids combine with most of the non-metals at moderate temperatures.
Alkalies have no action on these actinoids. In case of acids, they are slightly affected by nitric acid
(because of the formation of a protective oxide layer).

Q) How would you account for the following:

(i) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is strongly oxidising.

Cr2+ is strongly reducing in nature. It has a d4 configuration. While acting as a reducing agent, it
gets oxidized to Cr3+ (electronic configuration, d3) configuration, which is a more stable
configuration. In the case of Mn3+ (d4), it acts as an oxidizing agent and gets reduced to Mn2+ (d5).
This has an exactly half-filled d-orbital and is highly stable.
ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is
easily oxidised.
Co(II) is stable in aqueous solutions. However, in the presence of strong field complexing reagents, it
is oxidized to Co (III). Although the 3rd ionization energy for Co is high, but the higher amount of
crystal field stabilization energy (CFSE) released in the presence of strong field ligands overcomes this
ionization energy.
iii) The d1 configuration is very unstable in ions.

The ions in d1 configuration tend to lose one more electron to get into stable d0 configuration.
Also, the hydration or lattice energy is more than sufficient to remove the only electron present in
the d-orbital of these ions. Therefore, they act as reducing agents

Q) What is meant by ‘disproportionation’? Give two examples of disproportionation reaction in aqueous

solution.

Solution :

It is found that sometimes a relatively less stable oxidation state undergoes an oxidation−reduction reaction
in which it is simultaneously oxidised and reduced. This is called disproportionation.

Cr(V) is oxidized to Cr(VI) and reduced to Cr(III).

Mn (VI) is oxidized to Mn (VII) and reduced to Mn (IV).

Q) Why is HCl not used to make the medium acidic in oxidation reactions of potassium permanganate in
acidic medium?
Hydrochloric acid (HCl) is not used to acidify potassium permanganate (KMnO4) solutions because KMnO4
oxidizes HCl into chlorine gas (Cl2), which is also an oxidizing agent

2 KMnO4 (aq) + 16 HCl (aq) → 2 KCl (aq) + 2 MnCl2 (aq) + 8 H2O (l) + 5 Cl2 (g

Q) Describe the preparation of potassium permanganate.

Q) How does the acidified permanganate solution react with

(i) iron(II) ions. Write the ionic equations for the reactions.

(iii) SO2

(iv) oxalic acid

Q) Describe the oxidising action of potassium dichromate and write the ionic equations for its
reaction with:

(i) iodide

(ii) iron(II) solution

 (iii) H 2S

Q) What are interstitial compounds? Why are such compounds well known for transition metals?

Solution : Transition metals are large in size and contain lots of interstitial sites. Transition elements can trap
atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites of their crystal
lattices. The resulting compounds are called interstitial compounds.

They are well known for transition metals because transition metals have large atomic sizes and closed
crystalline structures with voids that can trap these small atoms

Q) What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention its
uses.

Solution :

An alloy is a solid solution of two or more elements in a metallic matrix. It can either be a partial solid
solution or a complete solid solution. Alloys are usually found to possess different physical properties than
those of the component elements.

An important alloy of lanthanoids is Mischmetal. It contains lanthanoids (94−95%), iron (5%), and traces of S,
C, Si, Ca, and Al.

Uses:

Mischmetal is used in cigarettes and gas lighters.

It is used in flame throwing tanks.

It is used in tracer bullets and shells.