STUDY CENTRE
CHAPTER - 05
THE d AND f -BLOCK ELEMENTS
The elements of gp 3 - 12 in which the orbitals are progressively filled in each of the four long periods
is known as d-block.
There are mainly 3 series of the transition metals 3d series (Sc to Zn), 4d series (Y to Cd) and 5d
series (La to Hg) and an incomplete 6d series.
Transition element is defined as the one which has incompletely filled d orbitals in its ground state or
any one of the oxidation state.
ELECTRONIC CONFIGURATION
General outer electronic configuration (n-1)d1-10 ns1-2
Outer electronic configuration of 3d series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
3d1 3d2 3d3 3d5 3d5 3d6 3d7 3d8 3d10 3d10
4s2 4s2 4s 2 4s1 4s 2 4s2 4s 2 4s 2 4s1 4s 2
4d series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
4d1 4d2 4d4 4d5 4d6 4d7 4d8 4d10 4d10 4d10
5s2 5s 2 5s1 5s1 5s1 5s1 5s1 5s0 5s1 5s2
5d series
La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
5d1 5d2 5d3 6d4 5d5 5d6 5d7 5d9 5d10
5d10
6s2 6s2 6s 2 6s2 6s 2 6s2 6s2 6s1 6s1 6s2
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6d series
Ac Rf Db Sg Bh Hs Mt Ds Rg Uub
Z 89 104 105 106 107 108 109 110 111 112
6d1 6d2 6d3 6d4 6d5 6d6 6d7 6d8 6d10 6d10
7s2 7s2 7s2 7s2 7s2 7s2 7s2 7s2 7s1 7s2
Physical properties
Nearly all the transition elements display typically metallic properties such as high tensile strength,
ductility, malleability, high thermal and electrical conductivity and lustre with the exception of Zn, Cd,
Hg and Mn.
Lattice structure
M.P and B.P
The high M.P of these metals are due to the involvement of greater number of electrons from (n-1)d
in addition to ns electrons in the interatomic metallic bonding.
Greater the number of unpaired electrons stronger is the resultant bonding and greater is the M.P.
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Enthalpies of atomisation
Metals of the 2nd and 3rd series have greater enthalpies of atomisation than corresponding elements of
the first series.
Atomic and ionic sizes
In a series, the atomic radii of d block generally decrease with increase in atomic number but the
decrease in atomic size is small after midway and there is a slight increase towards the end of a
period.
Radius first decrease due to increasing the nuclear charge then nearly same due to the increased
nuclear charge will be equal to the electron-electron repulsion and finally increase is due to increasing
e e repulsion.
From top to bottom the radii first increase from 3d to 4d series due to increasing the number of shells.
From 4d to 5d there is almost equal radii even if the number of shells increases. This is due to the
lanthanoid contraction. Lanthanoid contraction is due to the poor shielding power of 4f electrons.
Ionic radii also follows the same trend as atomic radii.
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Density
Along any series from left to right, the atomic radii decreases due to increase in nuclear charge. Thus
the atomic volume decreases while atomic mass increases which result in increase of density. In 3d
series density increases up to Cu. The last Zn is an exception due to large atomic volume.
In d block Ir has the highest density (22.61 gcm-3) and Sc has lowest (3.43 g cm-3)
Os have slightly lower than Ir (22.59 gcm-3)
Ionisation enthalpy
1) First I.E of d block higher than s block and lower than p-block.
2) In a given series the difference in the I.E between any 2 successive members is very much less
than the difference in case of successive members of ‘s’ or ‘p’ block.
3) 1st I.E of Zn, Cd, Hg are very high due to completely filled configuration.
4) More the I.E, lesser the thermodynamic stability of the compound.
5) Lowest 1st I.E of d block - Sc (361 KJ mol-1)
6) Higher 1st I.E of d block - Hg (1007 KJ mol-1)
7) 1st I.E of gp-12 Hg > Zn > Cd (exception)
Oxidation State
• Variable oxidation state.
• Most common oxidation state +2 except for Sc
• Mostly ionic bonds are formed +2 & +3 oxidation state. In compounds having higher oxidation state
mostly covalent.
• The element which exhibit greater no. of oxidation state in or near the middle of each series.
• Adjacent oxidation states are differ by only one unit.
• Lower members prefer lower oxidation state and heavier members prefer higher oxidation state
• Transition metal exhibit zero oxidation state when they form compounds with acceptor ligands like
CO.
• The highest oxidation state ie., +8 exhibit Os & Ru
• The highest oxidation state are found in fluorides and oxides
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Trend in stability of higher oxidation state Halides
• In Halides Cr will exhibit higher oxidation state +6
• In simple halide Mn exhibit maximum oxidation state +4. But MnO3F is a known compound.
• In lower oxidation state fluorides are unstable
• Cu(II) halides except iodide are known
• Many Cu(I) compounds are unstable in aq.solution and undergo disproportionation.
2Cu Cu2 Cu
Oxides
• Highest oxidation state exhibit Mn, ie., +7 (Mn2O7)
• Highest oxidation state of the oxide coincide the gp number from Sc to Mn
Oxygen stabilized the highest oxidation state more than fluorine. This is due to the ability of O2 to form
multiple bonds.
• If an element form different oxide, their acidic strength increase with increasing the oxidation state.
Standard electrode potentials
• The electrode potential is a measure of T H
TH subH iH HydH
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E0values (M2+/M)
• The general trend towards less negative E0 values along the series is due to increase in I.E
• The +ve E0value of Cu account for its inability to liberate H2 from acid.
The E0 value of Mn, Ni, Zn are more negative than excepted. This is due to greater stability of half filled
d orbital of Mn2+ and completely filled d orbital of Zn2+. The exceptional E0 value of Ni related to the
highest negative HydH .
E0value of M3+/M2+
• Low value of Sc is due to Sc3+ has noble gas configuration.
• Highest value of Zn is due to d10 configuration of Zn2+
• Greater the value of reduction potential, greater is the tendency to act as an oxidising agent.
Magnetic property
Paramagnetic -due to the presence of unpaired e-
Diamagnetic -due to the absence of unpaired e-
Ferromagnetism is an extreme form of paramagnetism
For d block magnetic moment calculated by the formula m n ( n 2 B.M
m Spin only magnetic moment
n no. of unpaired e-
Formation of coloured ions
• Colour is due to d-d transition
• Generally d0 & d10 configuration are colourless due to absence of d-d transition
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Formation of complex compounds
Reasons:
• Small size
• High ionic charge
• Availability of d orbitals for bond formation
Catalytic properties
Reasons:
• Ability to adopt multiple oxidation state and to form complexes.
Eg: Fe3+ catalysis the reaction between iodide and persulphate ions.
Formation of interstitial compounds
• These are formed when small atoms like H, C or N are trapped inside the crystal lattice.
• They are nonstochiometric
• They are neither typically ionic nor covalent
Eg: TiC, Mn4N, Fe3H, TiH1.7, VH0.56
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• They have high melting point, higher than pure metal
• They are very hard, some ... approach diamond in hardness
• They retain metallic conductivity
• They are chemically inert
Alloy formation
• Alloy is a blend metals prepared by mixing components
• Because of the similar radii and other characteristics of transition metals, alloys are readily formed by
these metals
• Alloys of transition metals with non transition metals such as brass (Cu - Zn) and bronze (Cu - Sn)
Some important components of Transition elements
1. K2Cr2O7
Preparation:
Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of chromate
ore (FeCr2O4) with sodium or potassium carbonate in free assess of air.
4FeCr2O4 8Na2CO3 7O2 8Na2CrO4 2Fe2O3 8CO2
The yellow solution of sodium chromate is filtered and acidified with H2SO4 give a solution from which
orange Na2Cr2O7.2H2O can be crystallised
2Na2CrO4 2H Na2Cr2O7 2Na H2O
Na 2 Cr2O 7 2KCl K 2 Cr2 O7 2NaCl
Properties
• Na2Cr2O7 is more soluble than K2Cr2O7
• In aqueous solution, chromate and dichromate are interconvertable depending on the pH of the
solution.
2CrO24 2H Cr2O72 H2 O
CrO72 2OH 2CrO24 H2O
• Structure
2- 2-
O O
pm
m
9p O
17 O
3
16
Cr O Cr Cr O
0
O O 126
O O
O
Chromate ion Dichromate ion
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Chromate ion is tetrahedral whereas the dichromate ion consist of two tetrahedra sharing one corner
with Cr-O-Cr bond angle of 1260.
• Acidified K2Cr2O7 acts as an oxidising agent
Eg: 6I 14H Cr2 O72 3I2 2Cr 3 7H2O
6Fe2 14H Cr2 O72 6Fe3 2Cr 3 7H2 O
3H2S Cr2O27 8H 3S 2Cr 3 7H2O
3 S2O32 Cr2O27 8H 3 S 2Cr 3 3 SO24 4H2O
Molecular mass of K 2Cr2 O7
• Equivalent mass of K2Cr2O7
6
• Action of heat
4K 2Cr2O 7
4K 2CrO 4 2 Cr2O3 3 O 2
• Orange colour of K2Cr2O7 is not due to d-d transition, it is due to the charge transfer transition.
• K2Cr2O7 is used as a primary standard in volumetric analysis
• Chromyl chloride test: When K2Cr2O7 is heated with chloride and strong H2SO4 reddish brown vapour
of chromyl chloride is formed.
K 2 Cr2 O7 4KCl 6H2SO4 2 CrO2Cl2 6KHSO4 3H2 O
• With hydrogen peroxide: Acidified potassium dichromate forms a deep blue colour with H2O2 due to
the formation of CrO5
K 2Cr2O7 H2SO 4 4H2O2
2 CrO5 K 2SO 4 5H2O
2. KMnO4
Preparation
1. It is prepared by fusion of MnO2 (Pyrolusite ore) with an alkali metal hydroxide and an oxidising agent
like KNO3. This produces the dark green K2MnO4 which disproportionates in a neutral or acidic solution
to give permanganate.
2MnO2 4KOH O2 2K 2MnO 4 2H2 O
3MnO24 4H 2MnO4 MnO2 2H2O
2. Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation
of manganate (VI)
3. In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate
2Mn2 5 S2O28 8H2O 2MnO 4 10 SO42 16H
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Properties
• Potassium permanganate form dark purple colour crystal which are isostructural with those of KClO4.
• The manganate and permanganate ions are tetrahedral in shape.
• The green manganate is paramagnetic with one unpaired e-. But permanganate is diamagnetic
• The colour of KMnO4 is not due to d-d transition, it is due to charge transfer transition
• It act as an oxidising agent in acidic, basic, neutral medium
[NCERT structure]
• Action of heat
2KMnO 4 K 2MnO4 MnO2 O2
• It is not used as a primary standard in volumetry
• Equivalent mass
1. In acidic medium
M
Eq. mass
5
2. In neutral medium
M
Eq. mass
3
3. In strong alkaline medium
M
Eq. mass
1
F- BLOCK Elements
• F-block elements are called inner transition element.
• General electronic configuration ( n 2 f 114 ( n 1 d0 1 ns2
THE LANTHANOIDS
• The elements in which the least electron enters the 4f-orbitals are called first inner transition series or
lanthanoids.
• Elements and electronic configuration
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• Atomic and ionic radii
The regular decrease in the radii of lanthanoids with increasing atomic number is called lanthanoid
contraction.
• Consequences of lanthanoid contraction:
1. Tb, Dy, Ho, Er, Tm, Yb, Lu have shorter atomic radius than Yttrium
2. Er3+, Tm3+, Yb3+, Lu3+ have shorter ionic radius than Yttrium
3. Reactivity decreases from Ce to Lu
4. Basic character of oxide and hydroxide decreases across the series
5. Chemical twins are formed
6. Separation of lanthanoid by ion exchange method are facilitated.
• All the Ln are silvery white soft metal
• Their hardness increases with increasing their atomic number. But Sm is exceptionally extra hard.
• Their melting paints are in the range of 1000 to 1200 K. But Sm melt at 1623K.
They have typical metallic structure
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• They are good conductors of heat and electricity
• Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous sol. due to f-f
transition.
• The lanthanoid ions other than f0 type (La3+, Ce4+) and f 14 type (Yb2+, Lu3+) are all paramagnetic.
• The paramagnetism rises to maximum in Neodymium
• The 1st ionisation enthalpy of Ln are around 600 KJ mol-1, the second about 1200 KJ mol-1.
• The earlier members are quite reactive similar to Ca. But with increasing atomic number they have
more like Al.
• Their electrode potentials are in the range of -2.2 to -2.4V, except for Eu for which the value of -2V.
• Most common oxidation state +3.
• Some of them will exhibit +2 & +4 in addition to +3.
Eg: Eu2+, Yb2+
Pr4+, Nd4+, Tb4+, Dy4+
• Uses:
1. Ce is used as a scavenger of O2
2. Ce (SO4)2 is an oxidiser in cerimetry
3. CeO2 & ThO2 are used to make gas mantles
4. Misch metal is an alloy of Ln which contain ~ 95% Ln, ~5% Fe and traces of S, C, Ca & Al.
5. Sm2O3 is used to make phospher screen
6. Mixed oxides of Ln’s are used as catalysts in petroleum cracking.
Chemical reaction
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THE ACTINOIDS (Ac)
• Elements and electronic configuration
• Ac exhibit variable oxidation state, Np & Pu have +7 oxidation state
• None of them is found to have +2 oxidation state.
• Chemical twins are not formed because the radii of adjacent members differ in much more.
• They are radioactive elements
• Earlier members have relatively long half life, the latter once have half life values ranging from a day to
3 minutes
• They are silvery in appearance but display variety of structures. The structural variability is due to
irregularities in radii.
The action of boiling water on them give a mixture of oxide and hydride.
• Magnetic properties are complex.
• The heaviest primordial element is Pu, which has a half life of several million years and existed before
the formation of earth.
• Their compounds in +3 and +4 oxidation state are easily hydrolysed.
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