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d- And f-Block Elements 113

08. d- And f-Block Elements

d-BLOCK ELEMENTS
The elements which lie between s- and p-block elements in the long form of periodic table is called transition
elements. These elements have their properties which are intermediate between those of s- and p-block
elements and represent a change from the most electropositive s- block elements to the least electropositive
p-block elements, therefore acting as transition elements. The general electronic configuration of transition
elements is (n – 1) d1–10 ns0,2 or 2 The element of II B group Zn, Cd, Hg are called d-block elements. But
they can not be regarded as transition elements. As they have (n – 1)d10ns2 general electronic configuration
in the atomic state and in + 2 oxidation state the configuration is
(n – 1)d10. In both the cases d-orbitals are completely filled.
ELECTRONIC CONFIGURATION OF 3D, 4D AND 5D SERIES

3d-Transitions serie 4d-Transition series 5d-Transition series

Elements Atomic no. Outer Elements Atomic no. Outer Elements Atomic no. Outer
electronic electronic electronic
configuration configuration configuration
1 2 1 2
Sc 21 3d 4s Y 39 4d 5s La 57 5d16s2
2 2 2 2
Ti 22 3d 4s Zr 40 4d 5s Hf 72 5d26s2
V 23 3d34s2 Nb 41 4d45s1 Ta 73 5d36s2
4 1 5 1
Cr 24 3d5 s Mo 42 4d 5s W 74 5d56s1
5 2 5 1
Mn 25 3d 4s Tc 43 4d 5s Re 75 5d56s2
Fe 26 3d64s2 Ru 44 4d75s1 Os 76 5d56s2
7 2 8 1
Co 27 3d 4s Rh 45 4d 5s Ir 77 5d76s2
Ni 28 3d84s2 Pd 46 4d105s0 Pt 78 5d8 6s2
10 1 10 1
Cu 29 3d 4s Ag 47 4d 5s Au 79 5d106s1
Zn 30 3d104s2 Cd 48 4d105s2 Hg 80 5d106s2
GENERAL PROPERTIES OF transition series but the atomic radii of the
TRANSITION ELEMENTS second and third transition series are almost
1. Atomic radii (pm): The atomic radii of the same.
transition elements show the following trends : 2. Metallic character : All the transition elements
i) They lie in between those of s- and p- block are metals, since the number of electrons in the
elements, i.e they are smaller than s- block outer most shell is very small, being equal to they
elements and larger than p- block elements are hard, malleable and ductile. They exhibit all
in the periodic table. the three types of structures :
ii) In a series, the atomic radii first decrease Face centred cubic, hexagonal close packed and
with increase in atomic number upto the body centred cubic.
middle of the series, then become constant Greater the number of unpaired d- electrons,
and at the end of the series show a slight stronger is the metallic bonding and metals will
increase. be hard, e.g. Cr, Mo and W.
Sc Ti V Cr Mn Fe Co Ni Cu Zn While absence of unpaired electrons results in a
weak metallic bonding and the metals will be soft,
144 32 122 117 117 117 116 115 117 125
e.g. Zn, Cd and Hg.
iii) The atomic radii increase down the group Ionization Potential (I.P.) : Addition of extra
from first transition series to the second electron in the (n – l)d level provides a screening

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d- And f-Block Elements 114

effect which shields the outer ns electrons from Electro negativity : Electro negativity values
the inward pull of positive nucleus on the outer ns of transition elements is small and as there is-
electrons. Therefore effects of increasing nuclear only slight change in atomic radii from left to
charge and shielding effect created due to the right along a series, there is only slow increase
expansion of(n –1) d orbital oppose each other. in the electro negativity values. 4d to 5d series,
On account of these counter affects, the ionization
we find there is only slight change in the electro
potentials increase rather slowly on moving in a
period of the first transition series. negativity values.
Melting' and Boiling Points: High m.p., b.p., Magnetic Properties : Due to the presence
heat of fusion and heat of atomization. of unpaired electrons in the ( n – l)d orbitals,
• Sc-Cr, m.p. increases, then decreases. most of the transition metal ions and their
• Zn, Cd, Hg possess low value of m.p. and b.p. compounds are paramagnetic, i.e they are
due to (n–1)d10 configuration. attracted by the magnetic field. As the number
Reducing Property of unpaired electrons increases from one to five,
Reducing capacity' of a metal depends upon its magnetic moment and hence paramagnetic
tendency to formation. Transition metals cannot character also increases. Those transition
be good reducing agent, because they have : elements which have paired electrons are
a) High heat of vaporization diamagnetic, i.e they are repelled by magnetic
b) High ionization energies field. In case of iron, cobalt and nickel the
c) Low hydration energies unpaired electron spins are much pronounced.
Positive reduction potential of copper indicates As a result, these elements are much more
that, its tendency to form Cu+2 ion is small, hence paramagnetic than the rest of the elements.
it is a weak reductant. These elements are termed ferromagnetic and
The tendency of Cu to change into Cu+2 ions is can be magnetized.
extremely low due to its negative electrode
Catalytic Property: Transition metal ions and
potential. The metal is also not able to displace
H+ ions from acid solutions Cu is, therefore, their compounds are remarkable catalyst due
particularly poor reducing agent, i.e oxidation of to variety of oxidation states, empty d-orbital
copper metal by H+ to Cu+2 does not occur readily and large surface area.
and consequently Cu metal will not dissolve in V 2O5 : Used as a catalyst for the oxidation of
acids. SO2 into SO3 for the manufacture of H2SO4 in
Colour the contact process.
The colour of transition metal ions arises from MnO2 : Used as a catalyst in the decomposition
the 'excitation of electrons from d- orbitals of lower of KClO3 for preparation of oxygen.
energy to the d- orbitals of higher energy. The
energy required for d electron excitations is Ni : Used as a catalyst in the hydrogenation of
available in the visible range. Due to this transition, oils.
metal ions have the property to absorb certain Fe : Used as a catalyst in the manufacture of
radiations from the visible region and exhibit NH 3 by Haber process. A small amount of
complementary colour. molybdenum is; added as a promoter.
Pt : Used as a catalyst in the manufacture of
Oxidation state of the
Colour H 2 SO 4 ,
hydrated ions
Interstitial Compound: Small atoms such as
Sc (III), Ti(IV) Colourless
H, B, C, N occupy positions in the empty space
Ti (III) Purple in the transition metal lattice and forms
V (III) Green compounds of definite composition. These
V(II), Cr(III) Violet compounds have high conductance, hardness,
high m.p. and b.p.
Mn (III) Violet
Alloy formation : Transition metals form a
Fe (III) Yellow large number of alloys. Alloys containing
Mn (II) Pink mercury as one of the constitute elements are
Fe(II) Green called amalgams.

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d- And f-Block Elements 115

Complex C.N O.NOf Hybridisation Geometry un-paired Magnetic nature

Metal ion of metal ion electron
[Ag(CN)2] ? 2 1 sp Linear 0 Dimagnetic
[CuC141–2 4 2 sp 3 Tetrahedral 1 Paramagnetic
[Cu(NH3) 4]+2 4 2 dsp3 Square planar 1 Paramagnetic
[NiCl4]-4 4 2 sp 3 Tetrahedral 2 Paramagnetic
[Ni(CN4)+2 4 2 d sp2 Square planar 0 Dimagnetic
[Ni(CO)4] 4 0 sp 3 Tetrahedral 0 Dimagnetic
[Ni(NH3]6+2 6 2 sp3 d2 Octahedral 2 Paramagnetic
[Mn(CN)6]-4 6 2 d2s p3(inner) Octahedral 1 Dimagnetic

F- BLOCK ELEMENTS (INNER PROPERTIES OF LANTHANIDES

TRANSITION ELEMENTS) 1. Lanthanide contraction: In lanthanides, there
Inner-transition elements are the elements which is a progressive decrease in radii ofthe atoms
have incomplete d- and f- orbitals in their and ions of these elements which is called
penultimate and anti-penultimate shell as lanthanide contraction.
respectively. In these elements, filling of electrons Cause oflanthanide contraction: As we move
takes place in the inner f- orbitals, forming along the lanthanide series, the nuclear charge
transition within transition, hence the name inner increases by one unit at each successive element.
transition elements. Further since the filling of The new electron is added into the same subshell.
electrons take place in f- orbitals, the inner As a result, the attraction on the electrons by the
transition elements are also called f- block nucleus increases and this tends to decrease the
elements. size. Further as the new electron is added into
Types : Two types of inner transition series in the f- subshell, there is imperfect shielding of one
the inner f-orbitals electron by another in this subshell due to the
shapes ofthese. This imperfect shielding is unable
i) First series corresponding to the filling of
to counterbalance the effect of the increased
4f-orbital is known as lanthanide series
nuclear charge. Hence the net result is a
(lanthanons) which starts after lanthanum.
contraction in the size though the decrease is very
Lanthanide series contain fourteen elements
small.
starting from cerium(S8) to lutetium (71).
OUTER ELECTRONIC
ii) The second series corresponding to the filling
CONFIGURATION OF ACTINIDES
of 5f - orbitals is known as actinides series
(actinons). This contains fourteen elements Elements Atomic Outer electronic
from thorium (90) to lawrencium (103). This no. configuration
series also includes the elements uranium Thorium 90 5f06d27s2
(92) which is the last element to occur in Protactinium 91 5f26d17s2
nature. The rest of the elements have been Uranium 92 5f36d17s2
produced in the laboratories and are generally Neptunium 93 5fl6d07s1
called man made elements, Thus all elements
Plutonium 94 5f6d07s2
,with higher atomic number than of uranium,
Americium 95 5f76d07s2
i.e neptunium (93) to hafnium (105) are called
transuranic or transuranium elements. These Curium 96 5f76d17s2
are also known as the first and second series Berkeylium 97 5f96d07s2
of rare earths respectively. Californium 98 5f106d07s1
GENERAL ELECTRONIC Einsteinium 99 5f116d07s2
CONFIGURATION Fermium 100 5f 126d07s2
(n – 2)f1–14 (n – 1)s2 (n – 1) p6 (n – 1) d1 or0 ns2 Mendelevium 101 5f136d07s2
where n is the ultimate shell (outermost shell), Nobelium 102 5f146d07s2
(n – 1) is the penultimate shell and (n – 2 ) is the Lawrencium 103 5f 146d17s2
anti-penultimate shell.
Effects of lanthanide contraction

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d- And f-Block Elements 116

i) The chemical properties of an element due to f-ftransitions. It depends upon the number
depend upon the size of the atom or ion. Greater of electrons in 5f-orbitals.
the size of the atom or ion, greater will be the 3. Actinide elements are strongly paramagnetic due
ease with which the species will lose electrons. to the presence of unpaired electrons.
ii) As the size of the lanthanide ions decreases 4. Because of higher nuclear charge and smaller size
from La+3 to Lu3+, the covalent character of the of their atoms, actinides have a greater tendency
hydroxides increases and hence the basic strength to form complexes.
decreases. Thus La(OH)3 is most basic where
OBJECTIVE TYPE QUESTIONS
as Lu(OH)3 is least basic.
iii) Small variation in properties on account of 1. The general outer electronic configuration of
lanthanide contraction allows the separation transition elements is
oflanthanides by fractional crystallization and a) (n –1) d1–10 nsl b) (n – 1) d1–10 ns2
basicity difference methods. c) (n – 1) d1–10 ns0 – 2 d) (n – 1) d2 nsl – 10
iv) Lanthanide contraction has a profound effect 2. The condition for complex salt formation is
on the radii of subsequent elements, which are a) small atomic size
smaller than otherwise would have been b) high nuclear charge
anticipated on the basis of increased atomic
c) availability of vacant d-orbitals
number. Thus Zr4+ and Hf4+ have almost identical
radii despite the atomic numbers being 40 and 72 d) all of these
respectively. Like wise, in vanadium family, the 3. Which one of the following set of 3d series belong
elements niobium and tantalum arc very similar to transition elements ?
in their size. a) Fe, Co, Ni b) Ru, Rh, Pd
2. Oxidation states: Most stable oxidation states c) Cu, Ag, Au d) All of these
of lanthanides is + 3. Those having 4. The common oxidation state of the elements of
+2 (Sm2+,Eu +2 and Yb+2)or+4(Ce+1) Tb+4 tend to transition series is
revert to +3.Hence former act as reducing agents a) + 1 b) + 2
while the later as oxidizing agent. c) + 3 d) + 4
3. M.P. and B.P. Lanthanides have high melting 5. Which of the following statement is not correct ?
and boiling points. a) La(OH)3 is less basic than Lu(OH)3
4. These are highly dense metal and the densities b) In lanthanide series ionic radius of Ln3+ions
do not exhibit regular trends with rise in atomic decreases
number. c) La is actually an element of transition series
5. Tendency to form complexes : These do not d) Atomic radius of Zn and Hf are same because
have much tendency to form complexes due to of lanthanide contraction.
low charge density because of their large size.
6. When MnO2 is fused with KOH in air, it gives
6. Lanthanides are paramagnetic due to presence
a) KMnP 4 b) Mn 3O 4
of unpaired electrons in the incomplete 4f subshcll.
c) K2MnO 4 d) Mn(OH) 2
7. Due to low ionization energies lanthanides are
7. A metal which when left exposed to the
highly electropositive.
atmosphere for some time, it becomes coated with
8. They are good reducing agents.
green basic carbonate, must be
PROPERTIES OF ACTINIDES a) Nickel b) Chromium
1. There is a regular decrease in ionic radii with c) Copper d) Zinc
increase in atomic number from Th to Lr, This is 8. The lanthanides element is
called actinide contraction analogous to the a) Cr b) Mn
lanthanoid contraction. It is caused due to
c) Co d) Ce
imperfect shielding of one 5f electron by another
9. The first man-made element is
in the same shell. This results in increase in the
effective nuclear charge which causes a) Sc b) Ti
contraction in size of the electron cloud. c) Tc d) Mo
2. Ions of actitdes are generally coloured which is 10. Which ion is colourless ?

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d- And f-Block Elements 117

4+ 3+
a) Cr b) Sc 21. Among d-block elements, the most abundant
c) Ti 3+
d) V4+ element belongs to the
11. The metal having the highest melting point is a) first transition series
a) platinum b) gold b) second transition series
c) osmium d) tungsten c) third transition series
12. Which ofthe following dissolves in hot conc. d) fourth transition series
NaOH solution ? 22. Colour in transition metal compounds is attributed
a) Fe b) Cu to
c) Ag d) Zn a) small size metal ions
13. The properties of transition elements Zr and Hf b) absorption of light in UV region
are similar because c) complete (n,s) subshell
a) they possess same number of electrons d) incomplete (n – 1) d subshell
b) both have similar radii 23. The outer electronic configuration of Cu2+ is
c) both belong to d-block elements a) 3d104so b) 3d10s1
d) none of these c) 3d104s2 d) 3d94s2
14. Which one of the following transition elements 24. The outer electronic configuration of 55Ce is
exhibit the oxidation state of S? a) 4f15d16s2 b) 4f05d26s2
a) Hf b) Ta 0 3
c) 4f 5d 6s 2
d) None of these
c) W d) Ru 25. The electronic configuration of gadolinium is
15. Which of the following will not give colour with [Atomic number = 64]
water ?
a) [Xe] 4f85d06s2 b) [Xe] 4f05d56s2
a) CU2+ b) Na+ 0 2 2
3+
c) [Xe] 4f 5d 6s d) [Xe] 4f75d16s2
c) Cr d) None of these
26. The 3d metals ions are generally paramagnetic in
16. AgNO3] solution is kept in brown bottles because nature because they
a) it reacts with ordinary bottles a) form coloured salts
b) ordinary bottles catalyse the decomposition of b) have one or more unpaired d-electrons
AgNO 3
c) have one or more paired s-electrons
c) brown bottles cut the passage oflight through
d) are reducing agents
it
27. Potassium permanganate acts as an oxidant in
d) none of the above
neutral, alkaline as well as acidic media. The final
17. Which ofthe following compounds is (are)
products obtained from it in the three conditions
coloured due to charge transfer spectra and not
are, respectively
due to d - d transitions '?
a) K2Cr2O7 b) KMnO4 a) MnO 24  , Mn3+ and Mn2+
c) CrO3 d) All of these b) MnO2, MnO2 and Mn2+
18. Increasing paramagnetic character of dipositive c) MnO2, MnO2+ and Mn3+
ion of 29Cu, 28Ni, 27Co, 26Fe, 25Mn follow the order: d) MnO, MnO2 and Mn2+
a) Mn2+ > Fe2+ > Ni2+ > Co2+ > Cu2+
28. The value of Bohr magneton () for for Cr2+ is
b) Mn2+ > Fe2+ > Ni2+ > Cu2+ > Co2+
a) 2.76 b) 3.86
c) Ni2+ > Mn2+ > Fe2+ > Co2+ > Cu2+
c) 4.80 d) 5.96
d) Mn2+ > Fe2+ > Co2+ > Ni2+ > Cu2+
29. Which one of the following transition metal ions
19. Which one of the following elements does not
has the least magnetic moment ?
belong to the first transition series ?
a) Fe b) Cr a) Cr2+ b) Ti2+
c) Ni d) Ag c) V2+ d) Mn2+
20. The element which shows maximum oxidation 30. Lanthanide contration is responsible for
state is a) same oxidation state of Zr and Zn
a) La b) Gd b) same oxidation state of Zr and Nb
c) Eu d) Am c) almost same radius of Zr and Hf

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d- And f-Block Elements 118

d) almost same radius of Zr and Y 42. Number of Cr – O bonds in dischromate ion
31. Which element among the lanthanide has the (Cr2O72–) is
smallest atomic radius ? a) 6 b) 7
a) Cerium b) Lutetium c) 8 d) 4
c) Europium d) Gadolinium 43. When acidified solution of potassium dichromate
32. Which of the following statements is correct ? is shaken with aqueous KI solution, then
a) An acidified solution of K2Cr2O7 liberates a) KI3 is formed b) I2 is liberated
2+
iodine from iodides c) Cr is formed d) none of these
b) (NH 4) 2Cr2O 7 on heating undergo exothr 44. Which of the fOllowing species has (have)
decomposition to give Cr2O3 O – O bond ?
c) Potassium dichromate is used as a titrant for a) Cr2O3 b) CrO5
estimation of Fe2+ ions c) Cr 2O72– d) CrO42–
d) All of these 45. From the follOwing which does not show correct
33. Which one of the following ores is used for the order of the given property ?
manufacture of potassium dichromate ? (GIVEN ATOMIC NUMBER: SC = 21, CR= 24,
a) Lead chromate b) Chromite MN = 25, Fe = 26, Ti = 22, Co = 27, Ni = 28,
c) Chrome red d) Chrome alum Cu = 29)
34. Which of the following oxides is (are) acidic in a) Sc3+> Cr3+> Fe3+ > Mn3+; Stability of + 3 ion
nature ? b) FeO > CoO > NiO > CuO ; Basic property
a) Mn2O3 b) Mn3O4 c) Mn2+< Ni2+ < CO2+ < Fe2+;Magnetic motion
c) MnO2 d) Mn2O7 d) Sc < Ti < Cr < Mn; Number of oxidation state.
35. CrO3 on dissolving in aqueous NaOH gives 46. Which of the following statements concerning
transition element is true ?
a) Cr2 O72 b) CrO24 
a) They are all metals
c) Cr(OH)3 d) Cr(OH)2
b) They easily form complexes
36. Which compound of chromium is widely used in
c) Compounds containing their ions are coloured
tanning of leather ?
d) All of these
a) CrCl3
47. The blue colour produced on adding H2O to acidified
b) Cr2O3
K2Cr2O7 is due to the formation of
c) CrO2Cl2
a) CrO5 b) Cr2O3
d) K2SO4.Cr2(SO4)3.24H2O 2–
c) CrO4 d) Cr2O72–
37. Ammonium dichromate is used in some fireworks.
48. Which of the fOllowing species has (have) 5
The green coloured powder blown in air is
unpaired electrons ?
a) CrO3 b) Cr2O3
a) Mn2+ b) Cr 2+
c) Cr d) CrO 3+
c) Cr d) Fe2+
38. Pyrolusite is
49. An acidified solution of potassium dichromate is
a) MnO2 b) Mn3O4 treated with H2S. In the reaction, the oxidation
c) MnO d) KMnO4 number of chromium
39. In analytical chemistry, solid K2Cr2O7 is used to a) increase from +3 to +6
detect the presence of which acid radicals b) decreases from +6 to +3
a) F b) Cl c) remains unchanged
c) Br d) l d) decreases from + 6 to +2
40. Which of the follOwingforms stable +2 ion? 50. Oxidation number of chromium is + 6 in
a) Eu b) Ce a) Cr2O3 b) CrO5
c) Nd d) Gd c) CrOCl2 d) K2CrO4
41. The increasing order of densities of metals K, Sc, 51. When a large amount of KMnO4 is added to
Ti and Ca is concentrated H2SO4, then explosive compound
a) K < Ca < Sc < Ti b) Ti < Sc < Ca < K formed
c) Sc < Ti < K < Ca d) Sc < Ti < Ca < K

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d- And f-Block Elements 119

2–
a) Mn2O7 b) Mn 3O 4 a) Cu2C12 and NiCl4
c) MnO3 b) Mn 3O 4 b) TiF62 and CoF63
52. In the first transition series, the element which
shows highest oxidation state has the electronic c) CoF63 and NiCl24 
configuration
d) TiF62 and Cu2Cl2
a) [Ar] 3d54s1 b) [Ar] 3d54s2
c) [Ar] 3d 4s6 2
d) [Ar] 3d10 4s2 56. Paramagnetism is a property of
53. Transition metal oxide, in which metal is in low a) completely filled electronic subshells
oxidation state, generally exhibits which of the b) unpaired electrons
following property ? c) non transition elements
a) Acidity d) completely filled energy shells
b) Basicity 57. The transition element with lowest atomic number
c) Neutrality is
d) Strong oxidising property a) Scandium b) Titanium
54. If a non-metallic element is dispersed in the b) Zinc d) Lanthanum
intersitial spaces of the crystal lattice ofthe metal, 58. Manganese exhibits the most stable state in
then which of the following properties is likely to a) 2 b) 5
be obtained from the metal ? c) 6 d) 7
a) The metal may become softer 59. Besides carbon, the essential constituent of
b) The metal will become more ductile stainless steel is
c) The metal will become less malleable a) V b) Cr
d) The metal will have lower tensile strength c) Mn d) Co
55. The colourless species in TiF62, COF6 3   Cu 2 Cl 2 60. Which of the element shows maximum oxidation
and NiCl2– are (Atomic number Ti = 22, Co = 27, state?
Cu = 29, Ni = 28) a) Fe b) Mn
c) V d) Cr

Answer Key
Q.No. Asn Q.No. Asn Q.No. Asn
1. c) 2. c) 3. a)
4. b) 5. a) 6. c)
7. c) 8. d) 9. c)
10. b) 11. d) 12. d)
13. b) 14. d) 15. c)
16. c) 17. d) 18. d)
19. d) 20. d) 21. a)
22. d) 23. a) 24. a)
25. d) 26. b) 27. b)
28. c) 29. b) 30. c)
31. b) 32. d) 33. b)
34. d) 35. b) 36. d)
37. a) 38. a) 39. b)
40. a) 41. a) 42. a)
43. b) 44. b) 45. c)
46. d) 47. a) 48. a)
49. b) 50. d) 51. a)
52. b) 53. b) 54. d)
55. d) 56. b) 57. b)
58. d) 59. b) 60. b)

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