7.1.

TRANSITION ELEMENTS EAMCET-FAST TRACK

[Link] ELEMENTS
C.R.T. CONCEPT
General Introduction:  4d series starts with Y [Z = 39] ends with
In the modern periodic table elements are classified Cd [Z = 48]
on the basis of their electronic configuration into  5d series starts with La [Z = 57], Hf ( Z  72) ends
s, p, d and f block elements. with Hg[Z = 80].
 The elements whose differentiating electron enters in  6d series is incomplete
(n-1) d sub-level are called d-block elements.  Technitium is the first man made element.
 The d-block elements in which the atoms or ions  Elements in VIIIB group
have incomplete d-orbitals are called transition Fe, Co, Ni ; Ru , Rh, Pd ; Os, Ir , Pt ; Hs, Mt , Ds
elements. Electronic Configurations
 A typical transition element shall have an incompletely  The elements with exceptional configuration in 3d
filled d  sublevel either in its elemental form or in series are Cr (24) [Ar] 3d5 4s1 and Cu (29) [Ar]
any of its chemically significant oxidation states. 3d10 4s1
 All d  block elements are not transition elements.  The elements with exceptional configuration in 4d
Ex: Zn, Cd & Hg are not transitional elements series are
 The general outer electronic configuration of d-block Nb (41) - [Kr] 4d4 5s1 ; Mo (42) - [Kr] 4d5 5s1
elements is (n-1)d1-10 ns0 (or) 1 (or) 2 Ru (43) - [Kr] 4d7 5s1 ; Rh (45) - [Kr] 4d8 5s1
 The transition elements are placed in between the Pd (46) - [Kr] 4d10 5s0; Ag (47) - [Kr] 4d10 5s1
electropositive (or) metallic elements (s- block) and  The elements with exceptional configuration in 5d
the electronegative (or) non-metallic elements (p- series are
block)
 The properties of these elements are in between those P t (78) [Xe] 4f 14 5d 10 6s 0
of highly reactive metallic elements of s-block and (or) 4f 14 5d 9 6s1 (or) 4f 14 5d 8 6 s 2
those of less reactive non-metallic elements of p-
block and Au (79) [Xe] 4f 14 5d10 6s1
 d-block elements are placed in the groups 3 to 12  Atoms of d-block elements having d 5 (half filled)
(i.e, III B to VIII B and I B & II B ) and d10 (completely filled) configuration are more
 The elements of IB group namely Cu, Ag, Au are
called typical transition elements since in these stable because of greater exchange energies.
elements electrons from completely filled inner  ns 2 np 6 nd10 configuration for an ion or atom is
(n-1)d subshell take part in bond formation along known as pseudo inert gas configuration (or) nickel
with outer s-electrons group configuration.
 IB group elements copper, silver and gold are called
 Examples for atoms / ions having ns 2 np 6 nd10
coinage elements. In olden days these metals are
used to prepare coins. configuration are Pt, Pd  nickel group 
 The elements of IIB (Zn, Cd and Hg) are not
considered as transition elements as they do not show Cu  , Ag  , Au  , Zn 2 , Cd 2 , Hg 2
the properties of transition elements because of Occurrence of Transition Elements
completely filled d-orbitals.  3d elements are more widely distributed in nature
 IIB elements have a d10 configuration both in elemental
than 4d and 5d series.
form and in their stable oxidation states.  3d series elements with even atomic numbers are
 d-block elements are present as 3d, 4d, 5d and 6d largely available in nature than those with odd atomic
series in the periodic table. numbers.
 3d series starts with Sc [Z = 21] ends with Zn [Z =  Iron is the fourth most abundant among all elements
30] in the earth’s crust.

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Trends in M.P, B.P. & densities:  The radii of 4d and 5d series are almost equal. This
Transition elements have high melting points. High is due to lanthanide contraction.
melting points, boiling points and heat of atomisation  Atomic and ionic radii of Cr, Mn and Fe are equal.
values of transition elements are due to the Between Ag and Cd bigger atom is Cd.
involvement of (n - 1)d electrons in addition to ns  The slight irregularities in size have been described
electrons in the interatomic metallic bonding. to crystal field effects.
 In any series melting points increase upto VI B group  Atomic radii of Zr is 1.6 A° and Hf is1.59 A° due
and then decrease. to Lanthanide contraction.
 M.P of Mn & Tc are lower than neighbouring  The ionic radii of transition metals decrease with
elements. increase in oxidation state.
 In any series of d-block, last element (IIB group)
 Mn2O7 is stable.
has the least melting and boiling points. This is
probably becuase the d-electrons do not participate Electrode potentials and chemical
in metallic bonding. reactivity
 Among all metals tungston has the highest melting  S.R.P of M 2 / M values increases from left to right
point. Mercury is a liquid at room temperature. as IP values increases. (except Zn)
 IIB group elements have very low m.p values due to  Cu cannot displace H 2 from acids because it has
non involvement of d 10 electrons in metallic bonding. highest S.R.P value which is +0.34 V.
 In a period densities increase as the atomic radii  Mn, Ni and Zn have more negative S.R.P values than
decrease. Density increases down the group in expected.
transition elements. Reason: Mn & Zn have d 5 & d 10 stable e.c.
 Iridium has the highest density (22.7g cm-3) among Ni has higher hydration energy.
all the elements. Osmium also has a very high density (  H Hyd Ni 2 = -2121 KJ/mole)
(22.6g cm-3).  Mn 3 and Co 3 are strong oxidising agents due to
 In 3d-series highest density is observed in Cu and
high S.R.P of M 3 / M 2 values.
least in Sc.
 EM0 3 / M 2 show varying trends
 ESc0 3 / Sc2 is low as it gets noble gas configuration
0
 EFe 3
/ Fe2
is low as Fe 3 has stable d 5 configuration
0
 EMn 3
/ Mn 2
is high as Mn 2 has stable d 5
configuration.
 Mn 3  d 4  is less stable than Mn 2  d 5 
because the latter has half-filled d-subshell stable
electronic configuration. Thus Mn3 easily reduced
to Mn 2 and acts as oxidant.
0 0
 EMn 3
/ Mn2
is more positive than ECr 3
/ Cr 2
(or)
0
EFe 3
/ Fe2
due to high 3rd I.E of Mn.
 Ti 2 , V 2 and Cr 2 are strong reducing agents and
Atomic and ionic radii of 3d series
 The atomic radius decreases in a period in the liberate H 2 from dilute acids.
begining, with the increase in the atomic number.  Cr 2 is a stronger reducing agent than Fe 2 because
 At the end of series, there are increased electron- its configuration changes from d 4 to d 3 (a half filled
electron repulstions between the added electrons in
t2 g level). In aqueous solution d 3 is more stable as
the same orbitals. These repulsions exceed the
attractive forces due to increased nuclear charge. compared to d 5 .
Therefore, electron cloud expands and the atomic  Mn 3 is oxidising agent as its configuration changes
radius increases at the end of any series. to d 5
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E 0 M 3 / M 2 in the 3d series are observed for some  The magnetic moment of transition metal ions
metals as exhibiting paramagnetism is calculated by the formula.
Co 3 / Co 2  Mn 3 / Mn 2  Fe 3 / Fe 2  S  L  4S (S  1)  L( L  1) BM
Ti 3 / Ti 2  Sc 3 / Sc 2  V 3 / V 2 Where S = Sum of the spin quantum numbers
 At times oxidizing power depends on the stability of L = Sum of the orbital angular momentum quantum
the species formed from the oxidizing agent. numbers.
Ex:VO2  Cr2O72  MnO4 .  For an electron, spin quantum numbers
Magnetic Property of Transition Metals: s=±½ S= sxn
The substances which are attracted into the magnetic Where n = number of unpaired electrons.
field when they are kept in higher magnetic field are  The unit of magnetic moment is Bohr Magneton
called paramagnetic substances (weaker field to eh
stronger field). (BM) 1 BM =
4 mc
 Paramagnetic substances contain unpaired electron where e = electron charge; h = Planck’s constant,
spins or unpaired electrons. m = mass of electron, c = velocity of light.
Ex : K3[Fe(CN)6], Sc2+, Cr3+ etc 1 BM = 9.273 x 10-24Joule / Tesla .
 In paramagnetic substances the magnetic field of the = 9.273 x 10-21 erg / Gauss
substance (B) is more than the applied magnetic field
Unpaired Magnetic moment
strength (H). Ion Configuration electrons(S)
Calculated Observed
 For paramagnetic substances B>H.
 The substances which are repelled by the magnetic Sc3+ 3d0 0 0 0
field when they are kept in higher magnetic field are Ti3+ 3d1 1 1.73 1.7  1.8
called diamagnetic substances (stronger to weaker Tl2+ 3d2 2 2.84 2.7  2.8
field.) V2+ 3d3 3 3.87 3.7  3.9
 Diamagnetic substances exhibit decrease in weight Cr2+ 3d4 4 4.90 8.8  4.9
in the presence of magnetic field. Mn2+ 3d5 5 5.92 5.7  6.0
 It is hard for magnetic lines to pass through a Fe2+ 3d6 4 4.90 5.3  5.5
diamagnetic substance than in vacuum. Co2+ 3d7 3 3.87 4.4  5.2
 If Magnetic field in the substance (B) is less than Ni2+ 3d8 2 2.84 2.9  3.4
external magnetic field (H), then they are said to be Cu2+ 3d9 1 1.73 1.8  2.2
diamagnetic. Zn2+ 3d10 0 0
EX : Ti+4, V+5 , Sc3+, Zn, Hg, Cd etc  The contribution of orbital angular quantum number
 Mercurous ion is diamagnetic in nature. It exists as towards magnetic moment is low and hence it can
Hg 22 . be neglected [ L = 0] for 3d series.
 For diamagnetic substances B<H.
But in some cases  exp is higher than calc . e.g.
 Diamagnetic substances contain electron pairs with
opposite spins. Fe 2 , Co 2 , Ni 2 , Cu 2
 Ferromagnetic substances are considered as a special  Spin-only magnetic moment is given by
case of paramagnetic substances.   4SS  1 BM
 Ferromagnetic substances are those in which there  In terms of number of unpaired electrons (n), the
are large no. of electrons with unpaired spins and magnetic moment is given by the formula.
whose magnetic moments are aligned in the same
 s  nn  2 BM
direction.
 For Ferromagnetic substances B  H if n =1 m= 1.73 BM
 Iron, Cobalt and Nickel are best examples for if n =2 m= 2.83 BM
ferromagnetic substances. if n =3 m= 3.87 BM
 Ferromagnetism disappears in the aqueous solution  In 2nd and 3rd transition series (4d & 5d) , the orbital
of the substance contribution is significant and so L must be included
 Paramagnetism of substances (molecules, atoms or S L  4S(S  1)  L(L  1)BM
ions) is due to the spins of the unpaired electrons
and also due to angular orbital momentum.
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Colours of Transition Metal Ions: Colours of some of the first row
Many compounds of transition metals are coloured (aquated) Transition metal ions
and the compounds of s-block and p-block elements ION Outer electron [Link] Unpaired Colour
Configuration electrons
are almost colourless.
Sc3+ 3d0 0 Colouress
 The transition metal ions with unpaired 3+ 1
d-electrons absorb characteristic coloured light from Ti 3d 1 Purple
3+ 2
the visible region and transmit its complementary V 3d 2 Green
2+ 4
colour in the same region. This is responsible for the Cr 3d 4 Blue
3+ 3
colour of the ion. Cr 3d 3 Violet
3+ 4
Ex: Mn 3d 4 Violet
3+ 5
i) Hydrated Titanium ions (one 3d-electron) Fe 3d 5 Yellow
absorbs green light from visible region and Mn 2+
3d 5
5 Pink
transmits the purple light.(pink) Mn 6+
3d 1
1 Green
ii) Hydrated Cu+2 ions absorb red colour and Fe2+ 3d6 4 Green
transmit blue colour. Co 2+
3d 7
3 Pink
iii) Mn2+ ion transmits pink colour Ni 2+
3d 8
2 Green
Colours of visible radiations Cu 2+
3d 9
1 Blue
Absorbed Wavelength of Complementary + 10
Cu 3d 0 Colourless
2+ 10
colour colour colour Zn 3d 0 Colourless
Violet 400 - 450 nm Yellow-green  The transition metal ions with empty d-orbitals (or)
Blue 450 - 490 nm Yellow completely filled d-orbitals are colourless.
Greenblue 480 - 490 nm Orange Eg: Sc+3 ; Cu+ ; Zn+2 etc
 The metal ions may exhibit different colours in
Absorbed Wavelength of Complementary
different oxidation states.
colour colour colour e.g. Mn 2 - Pink
Blue green 490 - 500 nm Red Mn 3 - Blue
Green 500 - 560 nm Purple Mn 6 - Green
Yellow green 560 - 575 nm Violet  Anhydrous CuSO4 is almost colourless. But hydrated
Yellow 575 - 590 nm Blue CuSO4 is blue in colour. This is because of the
absence of water molecules (ligands), there is no
Orange 590 - 625 nm Green blue
splitting of d-orbitals in anhydrous CuSO4.
Red 625 - 750 nm Blue green  The Cr (+6) and Mn (+7) have empty d-orbitals
 According to crystal field theory, the d-orbitals of but their compounds are coloured.
transition metal ions split into two groups when ligands  The colours of oxo-ions like Cr2O72 , CrO42 and
or counter ions or solvent molecules attack on them. MnO4 can be explained by charge transfer
This is known as d-orbital splitting (or) crystal field phenomenon.
splitting.
Catalytic properties of transition metals:
 In presence of other ions or molecules five d-orbitals
Transition metals and their compounds act as good
lose their degeneracy and split into two groups
catalysts. This is due to the presence of free valencies
namely t2 g  d xy , d yz , d zx  and eg (d x2  y 2 & d z 2 ) of
and also variable oxidation states.
slightly different energies.  Catalysts at a solid surface binds the reactants. In
 As the energy difference between two groups eg & which metals utilise (n-1)d and ns electrons for
t2 g is small, the energy from visible light is sufficient bonding.
for the excitation of electrons. Ex: Iron (III) catalyses the reaction between iodide
 The colour of the transition metal ion depends on and perdisulphate ions.
the number of electrons undergoing the d-d transition 2 I   S 2O82  I 2  2 SO42
and the energy difference between these d-orbitals. Mechanism:

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2 Fe 3  2 I   2 Fe 2  I 2  Since d-block elements are similar in size, they can
easily form alloys.
2 Fe 2  S 2O82  2 Fe 3  2 SO42  Alloys are generally prepared to modify the
 TiCl4 with Al  CH 3 3 forms the basis of Ziegler properties like malleability, ductility, toughness,
Natta catalyst used in the manufacture of polythene. resistance to corrosion.
 In the Wacker process the oxidation of ethyne to
Potassium dichromate  K 2Cr2O7 
ethanal is catalysed by PdCl2 .
Ex: Preparation:
i) In the manufacture of sulphuric acid by contact  It is manufactured from chromite ore  FeO.Cr2O3  .
process, the catalyst used is V2O5.  Chromite ore is roasted with Na2CO3 to convert
ii) In the synthesis of Ammonia by Haber’s process, into Na2Cr2O7 . It is mixed with KCl gives
the catalyst used is a mixture of Iron and
Molybdenum. K 2Cr2O7 .
iii) In the manufacture of HNO3 by Ostwald’s O O
process, the catalyst used is Platinum.
O
iv) The catalyst used in the hydrogenation of oils is O Cr Cr
Nickel. 1260
v) Fenton’s reagent  FeSO4  H 2O2  is used as an O
O O
oxidising agent 
 3
Two CrO3 units are bonded to sp hybrid oxygen
Interstitial Compounds: atom.
Compound formed when atoms with small atomic  Cr atom is surrounded by four oxygen atoms
size like H, B, C and N are trapped in the holes of tetrahedrally. 3
transition metals are called interstitial compounds.  Cr atom is sp hybrid.
The components are not in definite ratios in them.  It.. contains two types Cr  O bonds.
So such compounds are also known as non  O Cr bond length of sp 3 hybrid central oxygen
..
stoichiometric compounds. atom has single bond length ( 179 pm ).
 They have metallic nature, hard and brittle with high  Other oxygen atom surrounding Cr atoms have
MP and B.P. intermediate bond length which lies in between single
 The density of these compounds is less than that of and double bond length ( 163 pm ) due to resonance.
metals due to expansion of lattice. Physical Properties
 Ti, Zr, Hf, V, Nb, Ta form such compounds.  It is orange red coloured crystalline solid.
 Hydrogen occupies always smaller tetrahedral holes  It is moderately soluble in cold water but freely
while C and N occupy larger octahedral holes. soluble in hot water.
 Oxides and sulphides of T.E with more than one  It’s melting point is 398°C.
oxidation state form these compounds.
Ex: Chemical Properties
1) Fe0.82O , Fe0.94O  On strong heating it decomposes and gives oxygen
3
2) WO2.88 , WO2.92 2 K 2Cr2O7  2 K 2CrO4  Cr2O3  O2
2
3) Fe0.89 S , Fe0.96 S  On heating with alkalies it is converted into chromate
 A stoichiometric compound may become non [Yellow colour]
stoichiometric compound at high temperature. K 2Cr2O7  2 KOH  2 K 2CrO4  H 2O
 ZnO is white when cold and yellow when hot,
because stoichiometric ZnO changes to non-  In acid medium K 2CrO4 changes into K 2Cr2O7
stoichiometric ZnO, when heated. 2K 2CrO4  H 2 SO4  K 2 SO4  K 2Cr2O7  H 2O
Alloy Formation: Yellow Orange
Alloy is a homogeneous mixture of a metal with other  It reacts with HCl and evolves chlorine.
metals or metalloids or nonmetals. Alloys are solid in K 2Cr2O7  14 HCl 
solid solutions.
2 KCl  2CrCl3  7 H 2O  3Cl2

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 In acid medium
Structure of chromate ion
Cr2O72  14 H   6e   2Cr 3  7 H 2O
 In chromate ion hybridization of Cr is sp 3 .
Mwt of K Cr O
[Link] of K 2Cr2O7  2 2 7
 Shape of chromate ion is Tetrahedral
6
 It acts as a powerful oxidising agent in acidic medium Potassium Permanganate Preparation:
(dilute H 2 SO4 ) Potassium permanganate is prepared by the fusion
 It oxidises KI to I 2 of MnO2 with alkali metal hydroxide and an
K 2Cr2O7  7 H 2 SO4  6 KI  oxidaising agent like KNO3
4 K 2 SO4  Cr2  SO4 3  3I 2  7 H 2O 2 MnO2  4 KOH  O2  2 K 2 MnO4  2 H 2O
 Both Na2Cr2O7 and K 2Cr2O7 are oxidising K 2 MnO4 can be converted into KMnO4 by
agents but K 2Cr2O7 is preferred because it is not bubbling CO2 , Cl2 or ozonized oxygen through the
hygroscopic and can be used as primary standard in given solution.
volumetric analysis. 3K 2 MnO4  2CO2  2 KMnO4  MnO2  2 K 2CO3
 It oxidises ferrous ions to ferric ions K 2 MnO4 disproportionates in acidic or neutral
K 2Cr2O7  6 FeSO4  7 H 2 SO4  solution to give permanganate.
3Fe2  SO4 3  Cr2  SO4 3  7 H 2O  K 2 SO4 3MnO42   4 H   2 MnO4  MnO2  2 H 2O
 It oxidises sulphites to sulphates In the laboratory permanganate ion is obtained by
oxidising Mn (II) salts with peroxodisulphate
K 2Cr2O7  3Na2 SO3  4 H 2 SO4 
3Na2 SO4  K 2 SO4  Cr2  SO4 3  4 H 2O
 S O  ion.
2
2
8

2 Mn 2  5S 2O82  8 H 2O 

 It oxidises H 2 S to Sulphur..
2 MnO4  10 SO42  16 H 
K 2Cr2O7  4 H 2 SO4  3H 2 S 
Structure of Permanganate Ion:
K 2 SO4  Cr2  SO4 3  7 H 2O  3S
O
 It oxidises SO2 to H 2 SO4 .
K 2Cr2O7  H 2 SO4  3SO2  Mn

K 2 SO4  Cr2  SO4 3  H 2O O O

O
 It oxidises C2 H 5OH to acetaldehyde and  Permanganate ion is diamagnetic but manganate ion
CH 3CHO to CH 3COOH is paramagnetic with one unpaired
 It oxidises thiosulphate to sulphate. d-electron.
 It oxidises nitrites to nitrate.  The oxidation state of central atom is 7
 It is used as a primary standard solution. Mn undergoes sp 3 hybridization.
 It is used for the preparation of chrome alum, chrome t2 g set of 3d orbitals involve in hybridization.
yellow, chrome red, etc.,
Shape of species is tetrahedral.
 It is used in dyeing, chrome tanning, calico printing,
photography. Physical Properties:
 It is purple coloured crystalline compound.
 Chromic acid  H 2CrO4  is used as a cleaning agent  It is fairly soluble in water.
for glass ware.  Its solubility increases with increase in temperature.
Structure of Dichromate Ion Chemical Properties:
 Cr2O72 contains eight Cr-O bonds. When heated alone (or) with alkali gives oxygen.
 Cr2O72 contains six equivalent Cr-O bonds. 2KMnO4  K 2 MnO4  MnO2  O2 (or)
4 KMnO4  4 KOH  4 K 2 MnO4  2 H 2O  O2
 In Cr2O72 Cr atom undergoes ‘ sp 3 ’ hybridization.

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 When it treated with conc. H 2 SO4 , it forms Mn2O7 SOME NON-FERROUS ALLOYS
[explosive compound] Alloy Composition Uses (in making)
2 KMnO4  2 H 2 SO4  2 KHSO4  Mn2O7  H 2O 1. German Silver 50-60% Cu, Spoons,
10-30% Ni, forks, utensils
 KMnO4 act as an oxidising agent in alkaline, neutral
20-30% Zn
and acidic solutions.
 In alkaline medium 2. Brass 60-80% Cu; Machine parts
Molecular weight of KMnO4 20-40% Zn
Eq wt of KMnO4  3. Bronze 75-90% Cu; Utensils,
3
 In alkaline medium it is reduced to Potassium 10-25% Sn Coins, Statues
manganate and then to insoluble MnO2 . 4. Gun metal 88% Cu;
10% Sn; Guns, Bearings
2 KMnO4  H 2O  2MnO2  2 KOH  3  O  2% Zn;
 It oxidises iodide to iodate. 5. Bell metal 80% Cu; Bells
2 KMnO4  KI  H 2O  2 KOH  2MnO2  KIO3 20% Sn
6. Deverda’s 50% Cu; to reduce nitrites
Uses:
alloy 45% Al; (or) nitrates to
It is used as an oxidising agent in laboratory and 5% Zn NH 3
industry.
7. Duralumin 95% Al; for stressed
 In laboratory it is used as primary standard solution.
4% Cu; structures
 In titrations KMnO4 is used to estimate the quantity 0.5% Mn; like aircraft
of reducing agents like oxalic acid, Mohr’s salt 0.5% Mg
solutions in acid medium.
8. Magnalium 85-99%Al; in balance beams,
 Dilute H 2 SO4 is used as acidic medium. 1-15%Mg aircrafts parts and
 Dilute HCl can not be used as it can be oxidised by motor spares
KMnO4 to Cl2 . 9. Aluminimum 88-90% Cu; in ornaments,
 Alkaline KMnO4 is called Bayer’s reagent. Bronze 10-12% Al photoframes etc
 It is used to identify unsaturation in organic 10. Wood metal 50% - Bi Automatic
compounds. 25% - Pb fire alarams,
 It is used in the manufacture of saccharine, benzoic 12.5% - Sn sprinklers system
acid, acetaldehyde etc., 12.5% - Cd
 It is used for detecting halides, sulphides, oxalates 11. Type metal 60-80%-Pb Sharply defined
etc.,
13-30% - Sb casting
 A mixture of sulphur, charcoal and KMnO4 forms 3-10% - Sn
explosive powder.
12. Solder metal 50% - Sn Electrical
SOME FERROUS ALLOYS 47.5% - Pb appliances
Alloy Composition Uses (in making) 2.5% - Sb
1. Invar steel 64% Fe, for pendulum  Steel is an alloy of Iron and Carbon (2%).
35% Ni, rods
Mn & C
in trace amounts
2. Nichrome 60% Ni, in heating
25%Fe, of fire stoves,
15%Cr furnaces

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ELECTRONIC CONFIGURATION
EXERCISE - 1
11. Which one of the following pairs of ions have
(TEACHING QUESTIONS)
the same electronic configuration?
1) Cr 3 , Fe 3 2) Fe 3 , Mn 2
INTRODUCTION 3) Fe 3 , Co 3 4) Sc 3 , Cr 3
1. Element with atomic number 111 might, belong 12. Which one of the following ions has same
to the following group number of unpaired electrons as those present
1) Chromium 2) Scandium in V 3 ion?
2 2 3
3) Copper 4) Titanium 1) Fe 3 2) Ni 3) Mn 4) Cr
2. The following belongs to d-block but it is not a OCCURENCE OF TRANSITION ELEMENTS
transition element
13. In the following pair of d-block elements, the
1) Mn 2) Fe 3) Zn 4) Cr first member is a liquid at room temperature
3. Which set of elements is transitional in and the second member is mostly available in
character the earth’s crust. The pair is
i) Fe, Co, Ni ii) Ru, Rh, Pd iii) Os, Ir, Pt
1) Hg, Fe 2) Hg, Tc 3) Hg, Zn 4) Hg, Au
The correct statements is / are:
14. Match the following
1) i,ii 2) iii,i 3) iii,ii 4)i,ii,iii
4. Which of the following set of elements does not List-I List-II
belongs to transitional elements? A) Rutile i) Mn2O3
1) Fe, Co, Ni 2) Cu, Ag, Au B) Chromiteii) MnO2
3) Ti, Zr, Hf 4) Ga, In, Tl C) Pyrolusite iii) FeO.Cr2O3
5. In the transition elements the incoming electron
D) Braunite iv) TiO2
occupies [n-1]d sublevel in preference to
1) np 2) ns 3) [n-1]d 4) [n+1]s 1) A-iv, B-iii, C-ii, D-i 2) A-i, B-ii, C-iii, D-iv
6. Catalytic activity of transition elements and 3) A-i, B-iii, C-iv, D-i 4) A-iv, B-i, C-ii, D-ii
their compounds is due to their 15. Match the following
1) Small size 2) Vacant d-orbitals List - I List -II
3) Higher densities 4) Colour A) FeCO3 I) Calamine
7. Transition metals are good electrical conductors
B) Fe2O3 .xH 2O ii) Chalcocite
because
1) They are metals C) Cu2 S iii) Limonite
2) They are solids D) ZnCO3 iv) Siderite
3) They have free electrons in outer energy levels Correct match is
4) They are hard. 1) A-iv, B-ii, C-iii, D-iv 2) A-ii, B-iv, C-i,D-iii
8. Which of the following is a transition element 3) A-iv, B-iii,C-ii, D-i 4) A-iii, B-i,C-ii, D-iv
1) Al 2) As 3) Ni 4) Pb
CHARACTERISTICS OF 3D SERIES
9. The ground state electronic configuration of
chromium is against 16. Which element exhibits highest density in 3d
1) Hund’s rule 2) Pauli’s principle series
3) Auf-bau principle 4) Boyle principle 1) Sc 2) Cr 3) Zn 4) Cu
10. The following has pseudo-inert gas configuration 17. The maximum and minimum melting points of
in the (n-1) shell. first and second transition series respectively
1) Typical transition elements are observed with
2) Zinc group elements 1) Cr and Zn 2) Cr and Hg
3) Both 3) Cr and Cd 4) Mo and Cd
4) Neither

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IONIZATION ENERGIES OF 3D SERIES 30. For a paramagnetic substance, the field strength
18. The IP of Zr is 674 kJ/mole. The IP of Hf is of substance ( B ) and applied field strength ( H
1) 656 kJ 2) 760 kJ 3) 616 kJ 4) 631 kJ ) are related as
1) B = H 2) B < H
OXIDATION STATES OF 3D SERIES
3) B > H 4) B >>>H
19. The following does not show variable valency
Note:
1) Mn 2) Fe 3) Zn 4) Cr
1) Both A and R are true and R is the correct
20. Element which can show +2, +3, +4 +6 and +7 explanation of A
oxidation states is
2) Both A and R are true and R is not the correct
1) Cr 2) Mn 3) Co 4) V explanation of A
21. Maximum oxidation state exhibited by Osmium 3) A is true but R is false 4) A is false but R is true
is
31. Assertion (A) : Magnetic moment of
1) +8 2) +7 3) +6 4) +5  Fe( H O)  SO is given by 4(4  2) BM
2 6 4
ATOMIC AND IONIC RADII OF 3D SERIES Reason(R): In the above complex Iron ion has
22. Which of the following pairs of elements have four unpaired electrons
same radii ? 32. Assertion (A) : The “spin-only” magnetic
1) Zr,Hf 2) Sc, Y 3) La, Ac 4) Zn, Cd moment [in units of Bohr magneton,   B  ] of
Ni 2  in aqueous solution would be (atomic
COLOURS OF TRANSITION METAL IONS number Ni = 28) 2.84BM
23. Which of the following ion is coloured in its Reason(R) : The metal ion has 2 unpaired
aqueous solution? electrons.
1) Cd+2 2) Zn+2 3) Sc+3 4) Ti+3 33. Assertion(A) : Magnetic moment of Ni+2 ions
24. Transition metals are coloured due to the can be very close to that of Ti+2 ions
following electronic transition Reason(R) : both metal ions have equal no. of
1) d - s 2) d - d 3) s - p 4) f - s unpaired electrons.
25. In which pair, both ions are coloured in aqueous
medium INTERSTITIAL COMPOUNDS
34. Which of the following elements form interstitial
1) Sc+3, Zn+2 2) Cu+2, Ti+4
compounds?
3) Ti+3, Co+3 4) Cd+2, Mn+2
1) Alkali metals 2) Transition metals
CATALYTIC PROPERTIES 3) Halogens 4) Noble gases
26. The catalyst used in the oxidation of 1° alcohol 35. Hydrogen occupies the following holes, C and
to aldehydes N occupy the following holes
1) FeSO4  H 2O2 2) Fe + Mo 1) Tetrahedral and octahedral
3) Pt + Ir 4) Raney Ni 2) Octahedral and tetrahedral
27. The catalyst and promoter respectively used in 3) Octahedral and octahedral
the Haber’s process of industrial synthesis of 4) Tetrahedral and tetrahedral
ammonia are
1) Mo,V2O5 2) V2O5 , Fe ALLOY FORMATION
3) Fe, Mo 4) Mo, Fe 36. One of the constituents of an amalgam is
1) Fe 2) Hg 3) Au 4) Os
MAGNETIC PROPERTIES
37. The alloy used in the reduction of nitrites to
28. The ion having maximum magnetic moment is ammonia is
1) Co+3 2) Cr+3 3) Ni+2 4) Cu+1 1) Gun metal 2) Devarda’s alloy
29. The following metal shows ferromagnetic nature 3) Solder metal 4) Bronze
1) Co 2) Cr 3) Cu 4) Mn

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38. Assertion(A) : Zinc-copper couple that can be 45. When chromite ore is fused with NaOH in the
used as a reducing agent presence of air, the product formed is
Reason(R) : Zinc copper couple can be obtained 1) Na2Cr2O7 2) Cr2O3
from zinc coated from copper 3) Na2CrO4 4) K 2Cr2O7
1) Both A and R are true and R is the correct ex- 46. Assertion (A) :When a solution of potassium
planation of A chromate is treated with an excess of dilute
nitric acid chromate undergo oxidation
2) Both A and R are true and R is not the correct
explanation of A Reason (R): Dichromate ions are produced in
above process
3) A is true but R is false
1) Both A and R are true and R is the correct expla-
4) A is false but R is true nation of A
POTASSIUM PERMANGANATE 2) Both A and R are true and R is not the correct
39. W hen KMnO4 reacts with acidified FeSO4 explanation of A
1) Only FeSO4 is oxidised 3) A is true but R is false
4) A is false but R is true
2) Only KMnO4 is oxidised
3) FeSO4 is oxidized and KMnO4 is reduced COMPOUNDS OF TRANSITION ELEMENTS
47. Cinnabar is an ore of
4) KMnO4 and FeSO4 oxidised
1) Hg 2) Cu 3) Pb 4) Zn
40. The number of moles of KMnO4 that will be
48. Calomel is
needed to react with one mole of sulphite ion in
acidic solution is 1) Hg 2Cl2 and Hg 2) Hg 2Cl2
3) Hg + Hg 2Cl2 4) HgCl 2
1) 2/5 2) 3/5 3) 4/5 4) 1
49. Which of the following metals react with chlorine
41. The product of I  with MnO4 in alkali medium to form their respective chlorides?
is 1) Cu 2) Ag 3) Au 4) All
1) I 2 2) IO3 3) IO  4) IO4 50. Which of the following is not an amphoteric
42. Assertion(A) : The compound formed as a result oxide?
of oxidation of ethyl benzene by KMnO4 is 1) HgO 2) PbO2 3) ZnO 4) SnO2
benzoic acid 51. Which of the following iron salts exists as a
Reason(R) : The isomer of ethyl benzene is dimer?
Xylene i.e dimethylbenzene with KMnO4 gives 1) Ferric chloride 2) Ferrous chloride
phthalic acid. 3) Ferrous sulphate 4) Mohr’s salt
1) Both A and R are true and R is the correct expla- 52. Which oxide of Mn is acidic in nature?
nation of A 1) MnO 2) Mn2O7 3) Mn2O3 4) MnO2
2) Both A and R are true and R is not the correct
explanation of A
3) A is true but R is false 4) A is false but R is true
POTASSIUM DICHROMATE
1) 3 2) 3 3) 4 4) 4 5) 1 6) 2 7) 3
43. The number of moles of K 2Cr2O7 that will be 8) 3 9) 3 10) 3 11) 2 12) 2 13) 1 14) 1
needed to react one mole of H 2 S in acidic
medium 15) 3 16) 4 17) 3 18) 2 19) 3 20) 2 21) 1
1) 1/6 2) 1/3 3) 2/5 4) 2/3 22) 1 23) 4 24) 2 25) 3 26) 1 27) 3 28) 1
44. Chromyl chloride when dissolves in NaOH 29) 1 30) 3 31) 1 32) 1 33) 1 34) 2 35) 1
solution gives yellow solution. The yellow 36) 2 37) 2 38) 2 39) 3 40) 1 41) 2 42) 2
solution contains 43) 2 44) 2 45) 3 46) 4 47) 1 48) 2 49) 4
1) Cr2O72  2) CrO42 3) CrO5 4) Cr2O3 50) 1 51) 1 52) 2

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12. Platinum, palladium and iridium are called noble
EXERCISE - 2 metals because
(PRACTICE QUESTIONS) 1) Alfred Nobel discovered them
2) They are inert towards many common reagents
INTRODUCTION 3) The are shining lustrous pleasing to look at
1. The following is not a typical transition element 4) They are found in active state7
1) Cu 2) Ag 3) Au 4) Hg ELECTRONIC CONFIGURATION
2. Which of the following statement regarding 13. In which of the following elements, the
transition elements is false configuration is against Auf-bau rule ?
1) Their atoms contain partially filled ‘d’ orbitals 1) Ni, Pd, Pt 2) Sc, Ti, Zr
2) They are capable of showing variable valencies 3) Pd, Pt, Cu 4) Fe, Cr, Mn
3) All of their ions are colourless 14. The configuration of chromium atom in ground
4) They form complexes readily state is
1) [Ar] 3d4 4s1 2) [Ar] 3d5 4s1
3. Which of following is a true transition element
3) [Ar] 3d6 4s2 4) [Ar] 3d7 4s2
1) Zinc 2) Cadmium
3)Aluminium 4) Iron OCCURENCE
4. The group numbers of transition elements 15. The chemical formula of siderite
1) 1 to 10 2) 1 to 9 3) 3 to 11 4) 3 to 12 1) Fe2O3 2) Fe3O4 3) FeCO3 4) MnO2
5. Best conductor of electricity is 16. The mineral of silver is
1) Cu 2) Al 3) Au 4) Ag 1) Argentite 2) Horn silver
6. Which of the following set of elements are 3) Sylvine 4) Both 1 and 2
transition elements ?
CHARACTERISTIC OF 3D SERIES
1) Po, At, Rn 2) Ga, In, Tl
17. Which of the following group elements exhibits
3) Cs, Ba, La 4) Ac, Ku, Ha high melting and boiling points
7. General electron configuration of d-block 1) IVB 2) VB 3) VIB 4) IIB
elements is 18. Which group elements exhibits highest densities
1) ns2np6nd1-10 2) (n-1)d1-10 ns0-2 np0-6 1) IIIB 2) IVB 3) VIB 4) VIIIB
3) (n-1)d1-10 ns1-2 4) nd1-9ns0-2 19. Which of the following transition metals has the
8. ns1 electron configuration is not present in highest melting point?
1) Ag 2) Mn 3) Cr 4) Cu 1) Cr 2) Mo 3) W 4) Hg
9. Which of the following is the stable electron 20. Transition element which is volatile
configuration of Fe+3 ion 1) Zn 2) Cd 3) Hg 4) All
6 0 5 0
1) 3d 4s 2) 3d 4s
6 2
IONIZATION ENERGIES
3) 3d 4s 4) 3d4 4s2
21. The second IP of Cr is high due to
10. The general configuration (n-1)d3ns2 indicates
1) 3d 5 2) 3d 0 3) 3d 10 4) 3d 4
that particular element belongs to the following
group 22. Transition metals are less reactive because of
their
1) II B 2) I B 3) V B 4) III B
1) High ionization potential and low melting point
11. Which of the following ion has same number of
2) High ionization potential and high melting point
unpaired electrons as that of V3+ ion
3) Low ionization potential and low melting point
1) Cr+3 2) Mn+2 3) Ni+2 4) Fe+3
4) Low ionization potential and high melting point

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OXIDATION STATES CATALYTIC PROPERTIES
23. An element M has the electron configuration 32. Which of the following is used as Catalyst in
[Ar]3d54s2. Which one of its oxide is unlikely to the hydrogenation of oils
exist 1) V2O5 2) Pd 3) Fe 4) Ni
1) MO2 2) M2O3 3) MO4 4) M2O7 33. The catalyst used in the polymerisation of
24. Which of the following element exhibits ethylene is
maximum oxidation state 1) R3 Al  TiCl4 2) SnCl4
1) Mn 2) Co 3) Fe 4) Zn 3) Ni 4) Pt
25. In which of the following compounds iron has MAGNETIC PROPERTIES
the lowest oxidation state
34. Which of the following pair of transition metal
1) Fe (CO)5 ions, have the same calculated values of
2) Fe2O magnetic moment?
2 2 2 2
3) K4 [Fe(CN)6] 1) Ti and V 2) Fe and Cu
2 2
4)FeSO4(NH4)2SO4. 6H2O 3) Cr and Fe 4) Co 2 and Ti 2
ATOMIC AND IONIC RADII 35. The following species is repelled by a magnetic
26. The correct order of atomic sizes is field
1) Sc < Y < La 2) Ti < Zr < Hf 1) Hg+2 2) Fe 2 3) Co+3 4) Ni+2
3) Sc > Y > La 4) Sc>Y<La 36. The following is not a ferromagnetic
1) Fe 2) Co 3) Y 4) Ni
COLOUR 37. Assertion (A) : Zn 2 is diamagnetic
27. Which of the following cation is colourless in its Reason(R): Two electrons are lost from 4s
aqueous solution orbital to form Zn 2
+2 +3 +3 +3
1) Cu 2) Sc 3) Fe 4) Co 1) Both A and R are true and R is the correct
28. Cuprous ion is colourless while cupric ion is explanation of A
coloured because, 2) Both A and R are true and R is not the correct
1) Cuprous ion has completed d-orbitals while Cupric explanation of A
ion has an incomplete d-orbitals 3) A is true but R is false
2) Cuprous ion has exactly half-filled ‘d’ orbitals 4) A is false but R is true
3) Cupric ion has completely filled ‘d’ orbitals, while
INTERSTITIAL COMPOUNDS
Cuprous ion has incompletely filled ‘d’ orbitals
4) Cupric ion has half - filled d-orbitals 38. Which is not an interstitial compound?
29. Which of the following pairs of ions are 1) TiH 2) Fe2O3 3) Mn2C3 4) W2C
colourless ALLOY FORMATION
3 , 2 2 3
1) Ti Cu 2) Co , Fe 39. The common metal present in german silver,
3 2 2 3
3) Sc , Zn 4) Ni , V bell metal and brass is
30. Colour of ferrous ion is 1) Fe 2) Cu 3) Zn 4) Sn
1) Red 2) Blue 40. Which of the following is an alloy of a metal and
a non-metal
3) Pale green 4) Pale yellow
1) bronze 2) electron 3) nichrome 4) steel
31. Colour in transition metal compounds is
attributed to POTASSIUM PERMANGANATE
1) small size metal ions 41. In permanganate ion MnO4 , manganese has an
2) absorption of light in UV region oxidation number of +7. Therefore it is
3) complete  ns  subshell 1) sp 3 d 3 hybridised 2) sp3 hybridised
4) incomplete  n  1 d subshell 3) dsp 2 hybridised 4) d 3 sp 3 hybridised

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42. When KMnO4 acts as oxidising agent in acidic COMPOUNDS OF TRANSITION ELEMENTS
medium, the oxidation number of Mn decreases
48. The substance that sublimes on heating is
by
1) MgCl2 2) AgCl 3) HgCl2 4) NaCl
1) 1 2) 2 3) 3 4) 5
49. Which of the following oxides is least stable at
43. An acidified solution of KMnO4 oxidizes room temperature?
1) sulphates 2) oxalates 1) CuO 2) Ag 2O 3) ZnO 4) Hg 2O
3) iodine 4) ferric salts 50. Which of the following metal oxides is white in
44. During estimation of oxalic acid with KMnO4 colour but becomes yellow on heating
the self indicator is 1) Ag 2O 2) ZnO 3) FeO 4) MgO
1) KMnO4 2) H 2C2O4 51. Oxide of metal cation which is not amphoteric?
3) K 2 SO4 4) MnSO4 1) Al 3 2) Cr 3 3) Fe 3 4) Zn 2
POTASSIUM DICHROMATE 52. Which of the following oxides of chromium is
45. Number of moles of K 2Cr2O7 reduced by one amphoteric in nature?
mole of iodide ions is 1) CrO 2) Cr2O3 3) CrO3 4) CrO5
1) 3 2) 1/3 3) 6 4) 1/6
46. Number of moles of K 2Cr2O7 reduced by one
mole of Sn 2  ions is
1) 1/3 2) 3 3) 1/6 4) 6 1) 4 2) 3 3) 4 4) 3 5) 4 6) 4 7) 3
47. The oxoanion in which oxidation state of the 8) 2 9) 2 10) 3 11) 3 12) 2 13) 3 14) 2
central atom is same as its group number in 15) 3 16) 4 17) 3 18) 4 19) 3 20) 4 21) 1
periodic table.
22) 2 23) 3 24) 1 25) 1 26) 1 27) 2 28) 1
1) SO42 2) VO2 3) MnO42 4) Cr2O72
29) 3 30) 3 31) 4 32) 4 33) 1 34) 1 35) 1
36) 3 37) 1 38) 2 39) 2 40) 4 41) 2 42) 4
43) 2 44) 1 45) 4 46) 1 47) 4 48) 3 49) 2
50) 2 51) 3 52) 2

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7.2.F-BLOCK ELEMENTS
C.R.T. CONCEPT

Lanthanides:  Electropositive Character: Lanthanide metals are

The f'- block consists of the two series of inner highly electropositive due to their low Ionisation
transition elements energy.
a) Lanthanides( The fourteen elements following Ionisation Energy:
Lanthanum) Lanthanides have fairly low Ionisation energies. The
b) Actinides (The fourteen elements following
Actinium) IE1 & IE 2 values are quite comparable to those of
 Lanthanides are also called as "rare earth elements" alkaline earth metals particularly calcium. ( IE1 600
 Lanthanum closely resembles the Lanthanides,
Actinium closely resembles Actinides, hence these KJ/mole, IE 2 1200 KJ/mole).
are usually included in any discussion of Lanthanides La, Gd, Lu have low IE 3 values due to empty, half
and Actinides
 The Lanthanides resemble one another more closely filled and completely filled f orbitals respectively
because they exhibit a common stable oxidation state  Abnormally low values of the third ionisation
like transition elements. enthalpies in the case of lanthanum 4 f 0 5 d1 6s2),
gadolinium (4 f 7 5 d1 6s2) and lutetium
Electronic configuration:
(4 f 14 5 d1 6s2).
The general electronic configuration of f-block
elements is (n - 2) f 1-14 (n - 1) d0 - 1 ns2 Magnetic behaviour:
G.E.C of Lanthanides 4 f 1-14 5 d0-1 6s2 Lanthanide ions (M3+) generally show paramagnetism
Elements Symbol [Link] Configuration due to the unpaired electrons in f-orbitals.
Lanthanum La 57 [Xe]5d16s2
Cerium Ce 58 [Xe]4f1 5d16s2  Lanthanide ions like La 3 , Ce 4
Praseodymium Pr 59 [Xe]4f 36s2 ( f 0 configuration) & Yb 2 & Lu 3
Neodymium Nd 60 [Xe]4f 46s2 (f14 configuration) are diamagnetic
Promethium Pm 61 [Xe]4f 56s2
Samarium Sm 62 [Xe]4f 66s2  The paramagnetism is maximum in Neodymium.
Europium Eu 63 [Xe]4f 76s2  Magnetic susceptibility ofActinides is relatively higher
Gadolinium Gd 64 [Xe]4f7 5d16s2 than those of Lanthanides of same electronic
Terbium Tb 65 [Xe]4f 96s2 configuration.
Dysprosium Dy 66 [Xe]4f 106s2 Colour:
Holmium Ho 67 [Xe]4f 116s2 Many of the Lanthanide ions are coloured in solid
Erbium Er 68 [Xe]4f 126s2 state as well as in solutions.
Thulium Tm 69 [Xe]4f 136s2  The colour is attributed to f-f transitions since they
Ytterbium Yb 70 [Xe]4f 146s2 have partly filled f-orbitals. (Absorption bands are
Lutetium Lu 71 [Xe]4f 14 5d16s2 narrow probably because of the excitation within f-
 The Lanthanides occur as orthophosphates in level)
monazite sand.
 The Monazite sand contains 30% Thorium  Ions with f 0,f 14 configuration are colourless.
phosphate, 60% La, Ce, Pr, Nb phosphates and Ex :- La+3(4f 0)Lu+3(4f 14) are colourless
10% Y and other heavy lanthanide phosphates. Nd 3 , Er 3  Pink : Sm3 , Dy 3  Yellow
Physical Properties  The Lanthanide ion with 4 f n configuration and
Density:Lanthanides have densities ranging between
4f
14  n 
6.77 to 9.74g cm-3 configuration have same colour..
 Generally densities increases with increase in atomic
number. Ex (1):- Nd 3  4 f 3  and Er 3  4 f 11  have same
 Melting points & Boiling points: Lanthanides colour (pink)
have fairly high melting points even though no definite
trend is observed (1000 to 1200K). Samarium Ex (2):- Sm3  4 f 5  and Dy 3  4 f 9  have same
however melts at higher temperature (1623 K). colour (yellow)
Samarium (Sm) is as hard as steel.
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 Radioactivity: All Lanthanides except promethium  The lanthanides are separated from monazite and are
and samarium are non-radioactive converted into chlorides (or) oxides.
Oxidation States:  The lanthanides are obtained by the electrolysis of
The common oxidation state exhibited by Lanthanides their molten chlorides.
is + 3.  The lanthanides are obtained by the reduction of their
 Lanthanides can also exhibit occasionally +2 and +4 anhydrous halides with electro positive metals like
ions in solution or in their solid compounds. Na, Mg.
 Irregularities arise mainly from the extra stability of  The lanthanides slowly react with cold water and
empty, half filled or fully filled f-subshell. quickly react with hot water.
 +3 oxidation state in Lanthanum, Gadolinium and 2M  6 H 2O  2M  OH 3  3H 2
Lutetium are especially stable because +3 ions of  As the size of M+3 ion decreases the covalent
these elements have an empty (f 0), a halffilled [f 7] character in M-OH bond and their basic strength in
and completely filled (f 14)] configurations.
 Cerium, Terbium also exhibit oxidation state of +4 their hydroxides decreases gradually from La  OH 3
because Ce+4 has configuration (4f 0), Tb+4 has the to Lu  OH 3 . This is due to Lanthanide contraction
configuration (4f 7)
 Pr, Nd, Dy also exhibit +4 state in their oxides with  Lanthanides form oxides of the type M 2O3 (or)
formula MO2. MO2 . These oxdies are ionic in nature.
 Europium, Ytterbium can show +2 oxidation state
 Lanthanide ions cannot easily form co-ordinate
due to 4f 7 , 4f 14 configuration respectively.. compounds because of their large size.
 Although the formation of Eu2+ is favoured by the  Lanthanide ions can form complexes with chelating
extra stability of its f7 configurations, but Eu2+ is a ligands.
strong reducing agent and changes to Eu3+ in its Ln2O3
H2
reactions. Samarium (Sm) also shows +2 and +3

bu

s
cid
rns
oxidatoin states.

a
in

th
 Reduction potentials and metalic character: The

wi
O2
standared electrode (reduction) potentials of the with halogens
heated with S Ln LnX3
lanthanoid ions become less negative across the Ln2S3
N
series. Thus, their reducing power decreases in going ith

wi
with C 2773 K
w

th
from Ce to Lu. The highly negative E0 values indicate ate
d

H2
he

O
these elements to be highly electropositive metals
LnN
capable to displace hydrogen from water. Ln(OH)3 +H2
2M  6 H 2O  2M  OH 3  3H 2 LnC2

Chemical Reactivity of Lanthanides: Lanthanide Contraction:

In their chemical behaviour, in general, the earlier The decrease in atomic radii (derived from the
members of the series are quite reactive similar to structures of metals) is not quite regular but it is regular
calcium but, with increasing atomic number, they in their M+3 ions.
behave more like aluminium. Values for E  for the  As atomic number increases in Lanthanides series,
half-reaction: for every proton added to the nucleus, the extra
electron goes to fill 4f - orbitals. The 4f- electrons
Ln3 ( aq )  3e   Ln( s ) are in the range of 2.2 to 2.4V
constitute inner shells and are rather ineffective in
except for Eu for which the value is 2.0V . screening the nuclear charge. Gradual increase in the
 The carbides, Ln3C , Ln2C3 and LnC3 are formed effective nuclear charge is responsible for decrease
when the metals are heated with carbon. in size of Lanthanides. This phenomenon is called
 They liberate hydrogen from dilute acids and burn in Lanthanide contraction.
halogens to form halides. Consequences:
 They form oxides M 2O3 and hydroxides M (OH )3 . The similarities between 4d & 5d series elements
 The lanthanides have very close similarity. The are more closer than 3d & 4d elements.
separation of lanthanides from one another is very  The atomic sizes of Zr & Hf, Nb & Ta, Mo & W
difficult. are almost same.
 Lanthanides can be separated by ion exchange  The separation of lanthanides is very difficult due to
method closer atomic radii.
 Monazite is the starting material for the preparation  Inert pair effect.
of lanthanides.

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Uses of Lanthanides maximum oxidation state increases from +4 in Th to
 Lanthanides form alloys easily with Iron. +5, +6 and +7 respectively in Pa, U and Np but
 Misch-metal is an alloy (pyrophoric alloy) containing decreases in succeeding elements.
Lanthanide metals, Ce-50%,  Np & Pu also exhibit +7 oxidation states in their
La - 40%, Fe 7% and traces of S, C, Ca, Al. compounds.
 Pyrophosphoric alloy is used in ignition devices such  U & Am also exhibit +6 oxidation states in their
as tracer bullets, shells and flints for lighters. compounds.
 Mixed oxides of lanthanides are used as catalyst in
 Actinide series includes 15 elements. i.e. Ac to
petroleum cracking. 89

Actinoids: Lr .
103

General outer electronic configuration is 5 f 1-14 6  All these elements are radioactive.
d0-1 7s2  Except 89 Ac , 90 Th , 91 Pa , 92 U the remaining
Elements Symbol At. No Configuration
elements are synthetic.
Actinium Ac 89 [Rn]6d1 7s2
Thorium Th 90 [Rn]6d2 7s2  Elements after Uranium are called transuranic
Protactinium Pa 91 [Rn]5f 26d1 7s2 elements.
Uranium U 92 [Rn]5f 36d1 7s2  The common oxidation number is +3 and they also
Neptunium Np 93 [Rn]5f 46d1 7s2 exhibit +4, +5, +6, oxidation numbers.
Plutonium Pu 94 [Rn]5f 6 7s2  Actinide contraction is due to poor shielding of
Americium Am 95 [Rn]5f 7 7s2 5f electrons.
Curium Cm 96 [Rn]5f 76d1 7s2 Properties:
Berkelium Bk 97 [Rn]5f 9 7s2 Actionoids are all silvery metals.
Californium Cf 98 [Rn]5f 10 7s2
 The actionoids are highly reactive metals, especially
Einstenium Es 99 [Rn]5f 11 7s2
Fermium Fm 100 [Rn]5f 12 7s2 when finely divided. The action of boiling water on
Mendelevium Md 101 [Rn]5f 13 7s2 them, for example, gives a mixture of oxide and
Nobelium No 102 [Rn]5f 14 7s2 hydride.
Lawrencium Lr 103 [Rn]5f 14 6d17s2  Hydrochloric acid attacks all metals but most are
 The elements in which the last electron enters into slightly affected by nitric acid owing to the formation
5f-orbital are called Actinides. of protective oxide layers; alkalies have no action.
 The actinoids are radioactive elements and the earlier  The lanthanoid and actinoid contractions, have
members have relatively long half-lives, the latter ones extended effects on the sizes, and therefore, the
have half-life values ranging from a day to 3 minutes properties of the elements succeeding them in their
for lawrencium (Z=103).
respective periods.
 The configurations of Am and Cm are [ Rn]5 f 7 s 2 and
 Except Thorium, Americium (Am) all the actinides
[ Rn]5 f 7 6d 1 7 s 2 . Although the 5f orbitals resemble the have high densities.
4 f orbitals in their angular part of the wave-function,  Most of the ions of actinides are coloured.
they are not as buried as 4 f orbitals and hence 5 f  Their compounds are basic in nature.
electrons can participate in bonding to a far greater  Actinides have weak tendency of complex formation.
extent.  Actinoides form oxocations. Ex: UO22 , PuO2 etc.,
 There is a gradual decrease in the size of atoms or
 The ions of actinides are paramagnetic due to
M 3 ions across the series. This may be referred to
as the actinoid contraction. The contraction is, unpaired electrons.
however, greater from element to element in this series  Actinides have high m.p’s and b.p’s
resulting from poor shielding by 5 f electrons.  Actinides have low I.P. values.
 There is a greater range of oxidation states, which is  All the actinides are highly electropositive.
in part attributed to the fact that the 5 f , 6d and 7s Uses of Actinoids:
levels are of comparable energies.  Uranium is used as nuclear fuel.
Oxidation States:  Uranium salts are used in glass industry, textile
The actinoids show in general +3 oxidation state. industry, in medicines etc...
The elements, in the first half of the series frequently  Plutonium is used in atomic reactors.
exhibit higher oxidation states. For example, the

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9. Which of the following is the strongest base
EXERCISE - 1 1. Sc(OH)3 [Link](OH)3 3. Lu(OH)3 4. Yb(OH)
(TEACHING QUESTIONS) 10. KMnO4,and K2Cr2O7 are replaced in volumetric
analysis by
1. La(III) salts [Link] (III) salts [Link] (IV) salts 4. Gd (III) salts
PROPERTIES STATEMENT TYPE QUESTIONS
1. The most common oxidation states of cerium 1) Statement I is true, Statement II is true, Statement
are II is a correct explanation of Statement I.
1) +2 and +4 2) +3 and +4 2) Statement I is true, Statement II is true, Statement
3) +3 and +5 4) +2 and +3 II is not the correct explanation of statement I
2. Which of the following ion is paramagnetic 3) Statement I is true, Statement II is false.
1. La3+(Z=57) 2. Lu3+(Z=71) 4) Statement I is false, Statement II is true.
3. Yb2+(Z=70) 4. Sm3+(Z=62) 11. Statement - I:-Ce+4 is used as an oxidising agent
3. The atomic and ionic radii (M 3+ ions) of in volumetric analysis
Lanthanide elements decrease with increase in Statement- II :- Ce+4 has the tendency to attain
atomic number. This effect is called +3 oxidation state
1) Lanthanoid contraction 12. Statement - I :- Sm3+, Dy3+ have same colour
2)Lanthanoid expansion (yellow)
3) Actinoid contraction Statement - II:-Both ions are having same
4) Actinoid expansion number of unpaired electrons
4. Lanthanoid contraction occurs because 13. Statement - I :-La3+,Lu3+ ions are colourless
1) the 4f electrons, which are gradually added, Statement - II:-They do not contain unpaired
create a strong shielding effect electrons
2) the 4f orbitals are greater in size than the 3d and
3f orbitals
3) the 5f orbitals strongly penetrate into the 4f
orbitals 1) 2 2) 4 3) 1 4) 4 5) 3 6) 2 7) 4
4) the poor shielding effect of 4f electrons is coupled
8) 2 9) 2 10) 3 11) 1 12) 1 13) 1
with increased attraction between the nucleus and
the added electrons.
5. The Lanthanoids contraction is responsible for EXERCISE - 2
the fact that (PRACTICE QUESTIONS)
1) Zr and Y have about the same radius
2) Zr and Nb have similar oxidation state
3) Zr and Hf have about the same radius PROPERTIES
4) Zr and Zn have the same oxidation state 1. The stable +2 ions of lanthanides in aqueous
6. Which element among the Lanthanides has the solution are
smallest atomic radius ? 1. Eu2+ 2.Ce2+ 3. Lu3+ 4. Fe2+
1) Cerium 2) Lutetium 3) Europium 4) Gadolinium 2. SRP values of lanthanides lies between
7. Lanthanides are separated best by 1. -2.2 to -2.4 V 2. 4 to 2 V
1. Fractional crystallisation 3. 1 to 5 V 4. 0.1 to -0.2 V
2. Solvent extraction 3. Ion with maximum number of unpaired electrons
3. Complex formation using EDTA 1. Lu3+ 2. Yb3+ 3. Tm3+ 4. Gd3+
4. Ion exchange resins 4. What factor make the separation of
8. The separation of lanthanides by the ion Lanthanides a formidable task
exchange method is based on [Link] in ionic size 2. Constant charge of +3
1. The solubilty of the nitrates 3. Small charge radius ratio 4. All of these
2. Size of the hydrated M3+ ions
3. Size of the unhydrated M3+ions
4. Basicity of the hydroxides 1) 1 2) 1 3) 4 4) 4

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