UNIT IV d- AND f- BLOCK ELEMENTS

d-block elements : The elements of periodic table belonging to group 3 to 12 are known as d-Block
elements. Because in these elements last electron enters in d sub shell or d orbital .
Transition Series:There are four series of the transition metals,
3d series (Sc to Zn),
4d series (Y to Cd)
5d series (La to Hg, omitting Ce to Lu).
6d series which begins with Ac is still incomplete
d- Block elements are collectively known as Transition Elements because properties of these elements
vary in between s-Block and p-Block elements.
The general electronic configuration of these elements is (n -1)d1-10 ns 1-2
Transition element: A transition element is defined as the one which has incompletely filled d
orbitals in its ground state or in any one of its oxidation states.i.e. A transition element should have
partially filled (n-1) d orbital.
Zinc, cadmium and mercury of group 12 have full d10 configuration in their ground state as well as in
their common oxidation states and hence, are not regarded as transition metals
High Melting points& Boiling points of transition elements: due to strong metallic bonding
High Enthalpy of atomization: due to strong metallic bonding
Variation in Atomic Size of Transition Metals along 3d transition series: The atomic radii decreases
from group 3 to 6 (i.e. Sc to Cr) because of increase in effective nuclear charge gradually, The atomic
radii of group 7,8 9 &10 elements (i.e. Fe,Co,Ni) is almost same because Screening effect counter
balances increased effective nuclear charge, Group 11 &12 elements i.e. Cu & Zn have bigger size due
to increaseinter-electronic repulsion as result electron cloud expands and size increases.
Members of second(4d) and the third (5d) series in each group of transition elements have similar radii
and shows similar properties because lanthanoid contraction essentially compensates for the expected
increase in atomic size with increasing atomic number.
Zr (160 pm) &Hf (159 pm) and have very similar physical and chemical properties because Zr & Hf
belongs to same group of second(4d) and the third (5d) series ,as a result they have similar radii due to
lanthanoid contraction.
Oxidation States: The transition elements show variable oxidation state due to small energy difference
between (n-1)d & ns orbital. The highest oxidation state of an element is equal to number of unpaired e-
present in (n-1) d & ns orbital.
Formation of Coloured Ions: due to d – d transitions occurring in a transition metal ions by absorption
of visible light that they appear coloured.
Magnetic Properties: due to unpaired electron
The magnetic moment is determined by the number of unpaired electrons and is calculated by using the
n(n  2)
formula μ =
where n is the number of unpaired electrons and μ is the magnetic moment in units of Bohr magneton (BM)..
Formation of Complex Compounds:. due to smaller sizes of the metal ions, their high ionic
charges and the availability of d orbitals for bond formation.A few examples are: [Fe(CN)6]3–,
[Fe(CN)6]4– ,[Cu(NH3)4]2+ and [PtCl4]2–
Catalytic Properties: due to Variable oxidation states and Large surface area
Formation of Interstitial Compounds:.Interstitial compounds are those which are formed when small
atoms like H, C or N are trapped inside the crystal lattices of metals. Transition elements form interstitial
compounds because size of C, N, O, and B is similar to size of interstitial voids of transition metal
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Alloy Formation: Because of similar radii
The oxide of transition metals in lower oxidation states are generally basic while those in the higher
oxidation states are acidic. Acidic character increases with increase in oxidation state is due to decrease
in size of metal ion and increase in effective nuclear charge .e.g. MnO (basic), Mn3O4 (amphoteric),
Mn2O7 (acidic).
POTASSIUM DICHROMATE K2Cr2O7

● Preparation: chromite ore (FeCr2O4 or FeO.Cr2O3)

● The chromates and dichromates are interconvertible in aqueous

solution depending upon pH of the solution

Chromate dichromate
(yellow) (orange)

Potassium dichromate is used as

i)an oxidising agent (Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O )
It oxidize the following as (a) 2 I– → I2 + 2 e–
(b) H2S → 2H+ + S + 2e–
(c) Sn2+ → Sn4+ + 2 e–
(d) Fe2+ → Fe3+ + e–
POTASSIUM PERMANGANATE ( KMnO4)
● Preparation: From Pyrolusite ore( MnO2)
1.fusion of MnO2 with an alkali metal hydroxide and an oxidising agent

2. dark green K2MnO4disproportionates in a neutral or acidic solution to give

permanganate.

Properties of KMnO4
● Thermally unstable (cannot act as primary standard)

Acts as oxidizing agent in acidic as well as basic/neutral medium

Strongly Acidic medium

● In Acidic medium 10 I– + 2MnO4– + 16H+ ——> 2Mn2+ + 8H2O + 5I2
In Alkaline medium I + 2MnO4 – + H2O ——> 2MnO2 + 2OH– + IO3–
–

● In permanganate titrations, HCl or HNO3 cannot be used to make the medium

acidic

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 LANTHANOIDS
1. The 14 elements after Lanthanum having atomic number 58 to 71 are collectively known as Lanthanoids.
2. Electronic Configurations: The general electronic configuration of these elements is [Xe] 4f1-14, 5d0-1 ,6s2 .
3. Atomic and Ionic Sizes (lanthanoid contraction): The overall decrease in atomic and ionic radii
from lanthanum to lutetium is due to poor shielding of 4f electrons is known as lanthanoid contraction.
Consequence of the lanthanoid contraction :
(i) Almost identical radii of Zr(160 pm) and Hf (159 pm),
(ii) In separation of lanthanoid elements
(iii) Basic character decreases from La(OH)3 to Lu(OH)3
4. OxidationStates:Most common oxidation state of these elements is +3,However, occasionally
+2 and +4 ions in solution or in solidcompounds are also obtained. This irregularity arises mainly from
the extra stability of empty, half-filledor filled f subshell.
 The formation of Ce(IV) is favoured by its noble gas configuration, but it is a strong oxidant
reverting to the common +3 state.
5. Colour Formation :Many trivalent lanthanoid ions are coloured both in the solid state and in
aqueous solutions. Colour of these ions may be attributed to the presence of unpaired electrons in f
subshell. Neither La3+(f0) nor Lu3+(f 14)ion shows any colour due to absence of unpaired electrons in
f subshell.
6. Magnetic Behaviour: The lanthanoid ions other thanthe f0 type (La3+ and Ce4+) and the f 14 type
(Yb2+ and Lu3+) are all paramagnetic. The paramagnetism rises to maximum in neodymium.
7. The first ionisation enthalpies of the lanthanoids are around600 kJ mol–1, the second about
1200 kJ mol–1 comparable with thoseof calcium.
8. In their Chemical behaviour, in general, the earlier members of the seriesare quite reactive
similar to calcium but, with increasing atomic number,they behave
more like aluminium.
9. Chemical reactions of the lanthanoids.

10. Uses of Lanthanoids:

 Production of alloy steels for plates and pipes.
 A well known alloy is mischmetall which consists of a lanthanoid metal(~ 95%) and iron (~ 5%)
and traces of S, C, Ca and Al. A good deal of mischmetall is used in Mg-based alloy to produce bullets,
shell and lighter flint.
 Mixed oxides of lanthanoids are employed as catalysts inpetroleum cracking. Some
individual Ln oxides are used as phosphorsin television screens and similar fluorescing surfaces.

ACTINOIDS
1. The 14 elements after Actinium having atomic number 90 to 113 are collectively known as
Actinoids. They are radioactive elements.
2. Electronic Configurations: The general electronic configuration of these elements is [Rn] 5f1-14, 6d0- 1 ,7s2
3. Ionic Sizes(Actinoid contraction): The overall decrease in atomic and ionic radii
across the seriesdue to poor shielding of 5f electrons is known as Actinoid contraction
4. The actinoidcontraction is, however, greater from element to elementin this series resulting from
poor shielding by 5f electrons.
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5. Oxidation States:The actinoids show in general +3 oxidation state.The actinoids exhibit a
larger number of oxidation states, which is in part attributed tothe fact that the 5f, 6d and 7s levels are
of comparable energies.
SIMILARITIES between Lanthanoids & Actinoids
1) In both,electrons progressively enter f subshell
2) Both have main O.S +3
3) Both are electropositive & reactive
4) Both show decrease in atomic and ionic size( Lanthanoids / Actinoids contraction)
DIFFERENCES between Lanthanoids & Actinoids
Property Lanthanoids Actinoids
1.Oxidation states Lanthanoids show mainly +3 more variety in O.S +4, +5,
Oxidation state except in a few cases +6 ,+7
where it is +2 and +3
4. Tendency to Lesser tendency to form complexes. Greater tendency to form
form complexes complexes .
5.Basic character Lanthanoid compounds are less basic Actinoid compounds are more
basic
6.Tendency to They do not form oxo ions They form oxo ions such as
form oxo ions UO2+ ,NpO2+ , PuO2+,UO2+
7.Radioactivity non-radioactive(Except promethium) All the actinoids are
radioactive
8.Reactivity Relatively less reactive Highly reactive
9.Paramagnetic They are paramagnetic and their They are also paramagnetic
character magnetic properties can be easily but their magnetic properties
explained cannot be easily explained

A. MCQ TYPE:
1. Zinc and mercury do not show variable valency like d-block elements because
A. they are soft B. their d-shells are complete
C. they have only two electrons in the outermost subshell D. their d-shells are incomplete
2. Lanthanoid contraction is due to increase in
(a) Size of 4f orbital (b) shielding effect by 4f electrons (c) effective nuclear charge (d) atomic number
3. The magnetic nature of elements depends on the presence of unpaired electrons. Identify the configuration
of transition element, which shows highest magnetic moment.
(i) 3d7 (ii) 3d5 (iii) 3d8 (iv) 3d2
4. Which of the following oxidation state is common for all lanthanoids?
(i) +2 (ii) +3 (iii) +4 (iv) +5
5. Although Zirconium belongs to 4d transition series and Hafnium to 5d transition series even then
they show similar physical and chemical properties because___________.
(i) both belong to d-block.
(ii) both have same number of electrons.
(iii) both have similar atomic radius.
(iv) both belong to the same group of the periodic table.
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6. Which of the following ions show higher spin only magnetic moment value?
(i) Ti3+ (ii) Mn2+ (iii) Fe2+ (iv) Co3+
7. The pair that has similar atomic radii is
A. Mn and Re B. Ti and Hf C. Sc and Ni D. Zr and Hf
8. Colour of transition metal ions are due to absorption of some wavelength. This results in
A. d-s transition B. s-s transition C. s-s transition D. d-d transition
9. Transition metals form complex compound they have
(A)Small size (B) High nuclear charge
(C) A number of vacant orbitals of equivalent energy (D)All of these
+
10. The number of unpaired electron in Fe² (Z=26) are
(a) 4 (b) 5 (c) 6 (d) 3

Ans: 1-B 2-b 3-(ii) 4-(ii) 5-(iii)

6-(ii) 7-D 8-D 9-D 10-a
11.Why Mn has unusually lower melting point though it possess maximum number of unpaired electron?
Ans.Due to half filled (n-1)d5 and full filled ns2 configuration Mn,is stable which reduce delocalisation of electrons.
12. Why does Cu not replace Hydrogen from Acid.
Ans. Cu shows E0 positive value.
13. Although +3 oxidation states is the characteristic oxidation state of lanthanoids but cerium shows +4
oxidation state also. Why?
Ans: It is because after losing one more electron Ce acquires stable 4f 0 electronic configuration.
14. HCl is not used in permanganate titration.Why?
Ans: Permanganate oxidizes HCl into chlorine.
15.Most of the transition metals exhibit paramagnetic behavior .Why?
Ans. In transition metals, d- subshell of (n-1) shell contain unpaired electrons (exception Zn, Cd and
Hg) Because of the presence of unpaired electrons transition metals exhibit paramagnetic behavior.
16.Why is La(OH)3 more basic then Lu(OH)3 ?
Ans: La(OH)3 is more basic then Lu(OH)3 because the latter has greater covalent character as compared
to the former on account of lanthanoid contraction. The release of OH- ion from Lu(OH)3 is more difficult
and less basic than La(OH)3
17.Why Cu+ is coloueless where as Cu+2 is coloured
Ans. Cu+ has 3d10 configuration(no d-d transition of electron) where as Cu+2 ion has 3d9 configuration(
d-d transition of electron possible)
18.Zn, Cd and Hg are soft and have low melting point .Why?
Ans. It is because the have weak metallic bonds due to absence of unpaired electrons.
19. Chrimium is a typical hard metal whereas mercury is a liquid.Why?
Ans.Due to presence of more no of unpaired electrons from 3d and 4s subshell metal- metal interactions
are strong in Chromium while in mercury all the electrons from 5d and 6s are paired thus metal metal
interactions are weak.
20. Out of Cu2Cl2 and CuCl2, which is more stable and why?
Ans: CuCl2 is more stable than Cu2Cl2. The stability of Cu2+ (aq.) rather than Cu+(aq.) is due to the much
more negative ∆hydH of Cu2+ (aq.) than Cu+(aq.)

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21. Scandium is a transition element but Zinc is not. Why
Ans:Scandium is a transition because it has incompletely filled d orbitals in its ground state but Zinc
have full d10 configuration in their ground state as well as in their commonoxidation state.
22. Copper atom has completely filled d orbital (3d10) in its ground state, yet it is transition element. Why
Ans:Copper (Z = 29) can exhibit +2 oxidation state wherein it will have incompletely filled d-
orbitals (3d), hence a transition element.
23. (i) Higher oxidation state of Mn with F is +4 whereas with oxygen is +7.Why? Or
The highest oxidation state of a metal is exhibited in its oxide or fluoride.Why?
Ans: Ability to form multiple bond by oxygen.
24.Complete and balance the following equation:-
(a.) MnO4- + I- +H+ --
(b) Na2Cr2O7 + KCl---
Ans (a) 2 MnO4- +10 I- + 16 H+ - 2Mn+2 +5I2 +8 H2O
(b)
25. Give reasons for the following:
(i) The only oxidation state shown by scandium is +3
(ii) [Ti(H20)6]4+ is colourless.
(iii) Mn0 is basic while Mn207 is acidic.
Ans. (i) Sc(21) has electronic configuration : [Ar] 3d1 4s2. At +3 oxidation state , stable d0 is obtained.
(ii) [Ti(H20)6]4+ is colourless it cannot undergo d-d transition as it do not have unpaired electrons
(iii) The oxide in the lower oxidation state of a metal is basic and in the higher oxidation state of the metal
, it is acidic . That is why , MnO (oxidation state is +2) is basic whereas Mn2O7 (oxidation state +7) is acidic.
26. A. The element of 3d transition series are given as:- Sc Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:-
(a) Which element has highest mp and bp why?
(b) Which element is a strong oxidizing agent in oxidation agent +3 oxidation state and why?
(c) Which element is soft and why?
B.Write the equation involved in the preparation of K2Cr2O7 from sodium chromate.
Ans.A. (a) Cr, the highest mp of Cr is attributed to the involvement of greater no of electrons from 3d in
addition 4s electrons in inter atomic metallic bonding.
(b) Mn, because the change from Mn+3 (d4) to Mn+2(d5) results in the half filled configuration which has
extra stability.
(c) Zn, in Zn (3d10 4s2) all the electrons present in d- orbitals are paired and hence metallic bonds present
in it are weak.
B. Chromite ore is treated with alkali in presence of air

Sodium chromate is acidified with sulphuric acid to give a solution of sodium dichromate.

sodium dichromate is more stable then potassium dichromate hence sodium dichromate is treated with
potassium chloride.

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27. A. In addition of FeSO4 with KMnO4 in the acidic medium, Why is dil. H2SO4 used instead of dil. HCl
B. Give Reason:-
(a) Among the transition metals, the highest oxidation state is exhibited in oxoanions of a metal
(b) Ce+4 is used an oxidizing agent in volumetric analysis.
( c) Zn+2 salts are white while Cu+2 salts are blue.
Ans A. Dil. H2SO4 is an oxidizing agent and oxidize FeSO4 to Fe2(SO4)3. Dil Hcl is reducing agent and
liberates chlorine gas on reaction with KMnO4.
B. (a) In oxoanions the oxygen atoms are directly bonded to the transition metal.Since oxygen is highly
electronegative, the oxoanions bring out the highest oxidation state of the metal.
(b) Ce+4 has the tendency to attain +3 oxidation states which is more stable and so it is used as an
oxidizing agent in volumetric analysis.
( c) Zn+2 ion has all its orbitals completely filled where as Cu+2 ion there is incompletely filled orbitals.
Therefore d-d transition Cu+2 has a tendency to form coloures salts
28. A. (a) Transition metals form large no of complex compounds.
(b) The lowest oxides of transition metal is basic where the highest oxide is amphoteric or acidic
(c ) E0 value for the Mn+3/ Mn+2 couple is highly positive (+1.57V) as compare to Cr+3/ Cr+2.
B. Write one similarty and one difference between the chemistry of lanthanoids and actinoid elements.
Ans. A (a) The tendency to form complex compounds is due to:Small size and high charge on metal ion.
- The avaibility of d- orbitals for accommodating electrons donated by the ligands.
(b) In low oxidation of metals, some of the valence electrons of the metalatom are not involved in bonding.
Hence, it can donate electrons and behave as a base. In case of higher oxidation states of the metal, valence
electrons are involved in bonding and are not avaible. Hence effective nuclear is high and it can accept
electrons and behave an acid.
(c ) Large third ionization energy of Mn (3d5) is mainly reason for this.
B . Similarty In both,electrons progressively enter f subshell and Both have main O.S is +3
Difference –Lanthanoids are non-radioactive (Except promethium) while Actinoids are radioactive
29. Assign reason for the following:-
(a) The enthalpies of atomization of tranisition elements are high.
(b) The transition metals and many of their compounds act as good calalyst.
(c) From element to element , the actinoid contraction is greaterthe lanthanoids contraction.
(d) ) E0 value for the Mn+3/ Mn+2 couple is highly positive (+1.57V) as compare to Cr+3/ Cr+2.
(e) Sc (21) doesnot exhibit variable oxidation states and yet it is regarded as a transition elements.
Ans.
(a) Transition metals have strong metallic bonds as they have large no of unpaired electrons.
(b) The catalytic activity of transition metals are due to :-
- Variable oxidation states due to which it form unstable intermediate compounds and provide a newpath
with lower activation energy for the reaction. In some cases, the transition metals provide large surface area
with free valancieson which reactants are adsorbed.
(c ) This is due to poorer shielding by 5f- electrons in actinoidsthan 4f- electrons in the lanthanoids.
(d) Large third ionization energy of Mn (3d5) is mainly reason for this.
(e)This is because Sc has partially filled d- orbitals in the ground states (3d14s2)
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30. Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomization of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv)Transition metals and their many compounds act as good catalyst.
(v) Scandium (Z = 21) is a transition element but zinc (Z = 30) is not?
Ans. (i) due to unpaired electrons.
(ii) Because of large number of unpaired electrons in their atoms they have stronger interatomic
interaction and hence stronger bonding between atoms resulting in higher enthalpies of atomization.
(iii) d-d transition
(iv) Due to the presence of vacant orbitals or their tendency to form variable oxidation state.
(v) On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state (3d1), it
is regarded as a transition element. On the other hand, zinc atom has completely filled d orbitals (3d10)
in its ground state as well as in its oxidised state; hence it is not regarded as a transition element.

Assertion and Reason Type Questions

1. Assertion (A): Zn, Cd and Hg cannot be regarded as transition elements.

Reason (R) : These elements do not belong to the d- block of the periodic table.
2. Assertion (A): The highest oxidation state of the 3d metals depends only on electronic configuration of
the metal.
Reason (R) : The number of electrons in (n-1) d and ns sub shells determine the oxidation states
exhibited by the metal.
3. Assertion (A): Separation of Zr and Hf is very difficult.
Reason (R) : Zr and Hf lie in the same group of the periodic table.
4. Assertion (A): A solution of ferric chloride on standing gives a brown precipitate.
Reason (R) : Ferric chloride possesses covalent bonds and chlorine bridge structure.
5. Assertion (A): Actinides form relatively less stable complexes as compared to lanthanides.
Reason (R) : Actinides can utilize their 5f orbitals along with 6d orbitals in bonding but lanthanides
do not use their 4f orbitals for bonding.

[Ans: 1. (c) 2. (d) 3. (a) 4. (b) 5. (d).]

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