20
The d and f-Block
Elements
The d-block of the periodic table contains the elements of the groups
3-12 in which the d-orbitals are progressively filled. There are mainly
three series of the elements, 3d-series (Sc to Zn) 4d-series (Y to Cd)
and 5d-series (La to Hg omitting Ce to Lu). The fourth 6d-series
which begins with Ac is still incomplete. The two series of the inner-
transition metals, (4f and 5f ) are known as lanthanoids and actinoids
respectively.
Transition Elements
Elements having partially filled d-orbitals in ground state or in
excited state, are known as transition elements. They have been placed
in the centre of the Periodic Table between s-block and p-block
elements.
Iron is the most abundant and widely used transition metal.
General Electronic Configuration of
Transition Elements
Transition elements have the electronic configuration
( n - 1)d1 - 10 ns0 - 2. Zn, Cd, Hg, the end members of first three series
have general electronic configuration ( n - 1)d10ns2. These elements do
not show properties of transition elements to any extent and are
called non-typical transition elements.
The d and f-Block Elements 285
Electronic configuration of transition elements
3 -Series 4 -Series 5 -Series
Electronic Electronic
At. Electronic At. At.
Element Element configura- Element configura-
no. configuration no. no.
tion tion
21 Sc [Ar]3d1 4s2 39 Y [Kr]4 d1 5 s2 57 La [Xe]5 d1 6 s2
22 Ti [Ar]3d2 4s2 40 Zr [Kr]4 d2 5 s2 72 Hf [Xe]4f 14 5d2 6 s2
23 V [Ar]3d 3 4s2 41 Nb [Kr]4 d 4 5 s1 73 Ta [Xe]4f 14 5d 36 s2
24 Cr [Ar]3d 5 4s1 42 Mo [Kr]4 d 5 5 s1 74 W [Xe]4f 14 5d 4 6 s2
25 Mn [Ar]3d 5 4s2 43 Tc [Kr]4 d 5 5 s2 75 Re [Xe]4f 14 5d 56 s2
26 Fe [Ar]3d 6 4s2 44 Ru [Kr]4 d7 5 s1 76 Os [Xe]4f 14 5d 6 5 s2
27 Co [Ar]3d7 4s2 45 Rh [Kr]4 d 8 5 s1 77 Ir [Xe]4f 14 5d7 6 s2
28 Ni [Ar]3d 8 4s2 46 Pd [Kr]4 d10 5 s0 78 Pt [Xe]4f 14 5d 96 s1
29 Cu [Ar]3d10 4s1 47 Ag [Kr]4 d10 5 s1 79 Au [Xe]4f 14 5d10 6 s1
30 Zn [Ar]3d10 4s2 48 Cd [Kr]4 d10 5 s2 80 Hg [Xe]4f 14 5d10 6 s2
General Physical Properties of Transition Elements
(i) Atomic and ionic size Ions of the same charge in a given
series exhibit regular decrease in radius with increasing atomic
number, because the new electron enters in a d-orbital and
nuclear charge increases by unity.
In last of the series, a small increase in size is observed due to
electron-electron repulsion.
Atomic and ionic radii increase from 3d-series to 4d-series but the
radii of the third (5d ) series elements are virtually the same as those of
the corresponding member of the second series. It can be explained
on the basis of lanthanoid contraction [poor shielding of 4f ].
(ii) Ionisation enthalpies In a series as we move from left to
right, ionization enthalpy increases due to increase in nuclear
charge but not in regular trend.
The irregular trend in the first ionisation enthalpy of the 3d
metals, though of little chemical significance, can be accounted by
considering that the removal of one electron alters the relative
energies of 4s and 3d-orbitals.
(iii) Oxidation states Transition metals show variable oxidation
state due to two incomplete outermost shells. Only stable
oxidation states of the first row transition metals are
Sc(+3), Ti(+4), V(+5), Cr(+3, +6), Mn(+2, +7),
Fe(+2, +3), Co(+2, +3), Ni(+2), Cu(+2), Zn(+2).
286 Handbook of Chemistry
The transition elements in their lower oxidation states
(+2 and +3) usually form ionic compounds. In higher oxidation
state, compounds are normally covalent.
Only Os and Ru show +8 oxidation states in fluorides and oxides.
Ni and Fe in Ni(CO)4 and Fe(CO)5 show zero oxidation state.
(iv) Enthalpy of atomisation Transition elements exhibit higher
enthalpies of atomisation. Because of the presence of a large
number of unpaired electrons in their atoms, they have stronger
interatomic interactions and hence, stronger bonds.
(v) Trends in the M + /M standard electrode potentials
E °M 2+ / M is governed by three factors. Enthalpy of sublimation,
enthalpy of ionisation and enthalpy of hydration.
The irregular trend of M 2+ / M electrods potentials in 3d-series is
due to irregular variation in ionisation enthalpy and heat of
sublimation.
Except copper, 3d series elements are good reducing agents.
If sum of the first and second ionisation enthalpies is greater than
° + ) will be positive and
hydration enthalpy, standard potential (E M /M
reactivity will be lower and vice-versa.
Trends in the M + / M +
Standard Electrode Potentials
An examination of the Es ( M 3 + / M 2+ ) values shows the varying trends.
The low value for Sc3 + /Sc 2+ reflects the stability of Sc3 + which has a
noble gas configuration. The highest value for Zn3 + /Zn 2+ is due to the
removal of an electron from the stable d10 configuration of Zn 2+ .
(vi) Melting and boiling point Due to strong metallic bond, they
have high mp and bp. The mp of these elements become
maximum in the middle and then decreases with the increase in
atomic number. Manganese and technetium show abnormal
values in the trend. Tungsten has the highest m.p. (3410°C).
Mercury is liquid at room temperature (mp – 38.9°C) due to
absence of unpaired electrons, and weak metallic bonding.
(vii) Density d-block elements have high density because of their
small atomic size and strong metallic bonding.
Densities of 3d series elements
Density Sc Ti V Cr Mn Fe Co Ni Cu Zn
g/cm3 3.0 4.54 6.12 7.19 7.40 7.87 8.74 8.90 8.92 7.13
The d and f-Block Elements 287
Osmium has slightly lower density (22.52 g cm -3 ) as compared to
iridium (22.61 g cm -2 ). Thus, iridium has the highest density
among transition metals.
(viii) Atomic volume Atomic volume decreases along the period
due to decrease in atomic size.
(ix) Chemical reactivity d-block elements are less reactive due to
high ionisation energies. Some are almost inert and known as
noble metals, e.g. Au, Pt, Os, Ir, etc.
(x) Complex formation They are well known to form a large
number of complex compounds mainly due to
(a) small atomic size and high nuclear charge
(b) presence of partially filled or vacant d-orbitals, e.g.K 4 [Fe(CN)6 ]
(xi) Magnetic properties
(a) Paramagnetic nature is due to the presence of unpaired
electrons in d-orbitals. Paramagnetic character increases
with increase in the number of unpaired electrons ( n ) and
highest for Mn(II) [among 3d-series].
(b) Diamagnetic substances are repelled by applied magnetic
field and have no unpaired electron.
(c) In ferromagnetism, permanent magnetic character is
acquired by substance, e.g. Fe.
Magnetic moment (m ) is given by
m = n ( n + 2) BM, (Bohr magneton)
(xii) Coloured ions Colour exhibited by transition metal ions is
due to the presence of unpaired electrons in d-orbitals and is due
to the d-d transitions of electrons. When visible light is incident
on the ion, an electron from a lower energy d-orbital is excited to
a higher energy d-orbital.
Colour of a complex depends on the metal, its oxidation state and
its ligands, e.g. [Cu(H 2O)4 ]2+ is pale blue while [Cu(NH3 )4 ]2+ is
dark blue. CuSO4 × 5H 2O is blue in colour and anhydrous CuSO4
is colourless.
Charge transfer also gives intense colour e.g. MnO-4 ion does not
contain any unpaired d-electron. Its purple colour is due to
charge transfer from O to Mn, thus O2- changes to O- and
Mn(VII) to Mn(VI). Charge transfer is possible only when the
energy levels on the two different atoms involved are fairly close.
288 Handbook of Chemistry
(xiii) Catalytic properties The transition metals and their
compounds behave like catalyst due to
(a) the presence of partially filled d-orbitals resulting in variable
oxidation states.
(b) formation of intermediate complex with reactants by lowering
the energy of activation.
(c) their rough surface area, e.g. provides active sites for
adsorption of reactant molecules.
Iron, in the preparation of NH3 (Haber’s process), finely divided
nickel for hydrogenation, Pt in the preparation of nitric acid
(Ostwald’s process) etc.
Some important catalysts having transition metals are
1. Zeigler Natta catalyst : TiCl4 + (C2H5 )3 Al
2. Lindlar’s catalyst : Pd/BaSO4
3. Wilkinson’s catalyst : [Ph3P]3 RhCl
4. Adam’s catalyst : Pt/PtO
5. Brown’s catalyst or P-2 catalyst : Nickel boride
(xiv) Formation of alloys d-block elements have a strong tendency
to form alloys, because their atomic sizes are very similar and in
the crystal lattice, one metal can be readily replaced by another.
Alloys so formed have high m.p. The metals Mo, W, Cr, Ni, and V
are used for the production of stainless steel.
Amalgam is an alloy formed by mercury with other metals. Iron
and platinum do not form any alloy with mercury.
List of Alloys
Alloy Composition (%) Uses
Stainless steel Fe = 73, Cr = 18, Ni = 8, C (traces) Cutlery, machine parts
Coinage alloy Ag = 92.5, Cu = 7.5 Coins, Jewellery
or Coinage
silver
Dental alloy Ag = 33, Hg = 52, Sn = 12.5, For filling teeth
Cu = 2, Zn = 0.5
Brass Cu = 80, Zn = 20 Utensils, condenser tubes
Bronze Cu = 80, Sn = 20 Utensils, statues, coins
Gun metal Cu = 87, Sn = 10, Zn = 3 Gun, gears
Bell metal Cu = 80, Sn = 20 Bells, Gongs
German silver Cu = 60, Zn = 20, Ni = 20 Cutlery, resistant wires
Duralumin Al = 95, Cu = 4, Mg and Mn = 1 Air ships
Misch metal Ce(25%) + lanthanide metals + 5% Lighter flints
Fe + traces of S, C, Si, Ca, Al
The d and f-Block Elements 289
(xv) Interstitial compounds The vacant space present in a
crystal lattice is known as interstitial site or void. The non-metal
atoms (e.g. H, N, C, etc.) due to their small size when occupy such
place, the resulting compound is known as interstitial compound.
Such compounds are hard and rigid, e.g. cast iron and steel.
(xvi) Non-stoichiometric compounds The compounds not
having the elements in the exact ratio as in the ideal crystal are
known as non-stoichiometric compounds, e.g. in Fe0.94O1, the
Fe : O is approx 0.94 : 1 and not exactly 1 : 1. It is due to the
variability of oxidation state in the transition metal.
(xvii) Spinel These are the mixed oxides in which oxygen atoms
constitute a fcc lattice, e.g. ZnFe2O4. It is a normal spinel in
which the trivalent ions occupy the octahedral holes and divalent
ions occupy the tetrahedral holes.
In inverse spinel, the trivalent ion occupy the tetrahedral holes
and divalent ion occupy the octahedral holes. e.g. FeFe2O4 or
Fe3O4.
Some important reagents having transition metals
1. Baeyer’s reagent Dilute alkaline KMnO4, used to test the
presence of unsaturation.
2. Tollen’s reagent Ammoniacal solution of AgNO3 , i.e.
[Ag(NH3 )2 ]OH, used to test the aldehyde group.
3. Nessler’s reagent Alkaline solution of K 2HgI4 is used to test
NH3 ( g) and NH +4 .
4. Benedict’s solution CuSO4 solution + sodium citrate
+ Na 2CO3 , used to test the aldehyde group.
5. Lucas reagent HCl (conc.) + anhydrous ZnCl2, used to
distinguish between 1°, 2° and 3° alcohols.
Applications of Transition Elements
1. A mixture of TiO2 and BaSO4 is called titanox and a mixture of
ZnS + BaSO4 is called lithopone.
2. TiCl2 and TiO2 are used in smoke screens. TiO2 is also used as
white pigment of paints.
3. Tentalum is used in surgical venals and analytical weights.
4. Chromium is used in stainless steel and chrome plating.
5. Mo is used in X-rays tubes. Pt is used in resistance
thermometers.
6. Cd is used for making joints in jewellery.
7. Ce is used as a scavenger of oxygen and sulphur in many metals.
290 Handbook of Chemistry
Compounds of d-block Elements
1. Potassium Dichromate (K Cr O )
Ore Ferrochrome or chromite (FeO × Cr2O3 ) or (FeCr2O4 )
Preparation
4FeO × Cr2O3 + 8Na 2CO3 + 7O2 ¾® 8Na 2CrO4 + 2Fe2O3 + 8CO2
Yellow
2Na 2CrO4 + 2H + ¾® Na 2Cr2O7 + 2Na + + H 2O
Orange
Na 2Cr2O7 + 2KCl ¾® K 2Cr2O7 + 2NaCl
Sodium dichromate is more soluble than potassium dichromate.
Chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solutions.
2–
O 2–
O 179 pm O O
Cr O Cr 126° Cr O
O O 163 pm
O O
O
Chromate ion Dichromate ion
Properties Sodium and potassium dichromates are strong oxidising
agents, thus, acidified K 2Cr2O7 will oxidise iodides to iodine, sulphides
to sulphur, tin (II) to tin (IV) and iron (II) salts to iron (III).
Cr2O72– + 14H + + 6I– ¾® 2Cr3 + + 7H 2O + 3I2
Cr2O72– + 3H 2S + 8H + ¾® 2Cr3 + + 3S + 7H 2O
Cr2O72– + 14H + + 3 Sn2+ ¾® 3 Sn4+ + 2Cr3 + + 7H 2O
Uses
1. K 2Cr2O7 is used as an oxidising agent in volumetric analysis.
2. It is used in mordant dyes, leather industry, photography
(for hardening of film).
3. It is used in chromyl chloride test.
4. It is used in cleaning glassware.
2. Potassium Permanganate (KMnO 4 )
Ore Pyrolusite (MnO 2 )
Preparation
2MnO2 + 4KOH + O2 ¾® 2K 2MnO 4 + 2H 2O
Green
3MnO24- + 4H +
¾® 2MnO4- + MnO2 + 2 H 2O
The d and f-Block Elements 291
Commercial preparation
Fused with KOH, oxidised
MnO2 ¾¾¾¾¾¾¾¾¾¾¾® MnO2-
4
with air or KNO3 Manganate ion
Electrolytic oxidation
MnO24- ¾¾¾¾¾¾¾¾¾® MnO-4
(alkaline medium) Permanganate ion
(purple)
Properties KMnO4 acts as strong oxidising agent.
1. In the presence of dilute H 2SO4 , KMnO4 is reduced to
manganous salt.
MnO-4 + 8 H + + 5e- ¾® Mn2+ + 4 H 2O
Acidic KMnO4 solution oxidises oxalates to CO2, iron(II) to
iron (III), nitrites to nitrates and iodides to iodine. The
half-reactions of reductants are
5C2O2–
4 ¾® 10CO2 + 10e-
5Fe2+ ¾® 5 Fe3 + + 5e-
5NO-2 + 5 H 2O ¾® 5 NO3- + 10H + + 10e-
10I- ¾® 5 I2 + 10 e-
To acidify KMnO4, only H 2SO4 is used and not HCl or HNO3
because HCl reacts with KMnO4 and produce Cl2 while HNO3 ,
itself acts as oxidising agent.
2. In alkaline medium, KMnO4 is reduced to insoluble MnO2.
MnO–4 + 3e- + 2 H 2O ¾® MnO2 + 4 OH –
Alkaline or neutral KMnO4 solution oxidises I- to IO3- , S2O32– to
SO24- , Mn2+ to MnO2, etc.
Aqueous KMnO4 reacts with NH3 to liberate N 2 gas.
2KMnO4 + 2NH3 ¾® 2KOH + 2MnO2 + N 2 + 2H 2O
Uses KMnO4 is used
(i) in laboratory preparation of Cl2.
(ii) as an oxidising agent and disinfectant.
(iii) in making Baeyer’s reagent.
(iv) for the bleaching of wool, cotton, silk and other textile fibres
and for the decolourisation of oils are also dependent on its
strong oxidising power.
292 Handbook of Chemistry
Structures
O– O–
Mn Mn
O O O O–
O O
Permanganate ion Manganate ion
3. Copper Sulphate (CuSO 4 × 5H2O)
It is also known as blue vitriol.
Method of preparation It is obtained by the action of dil H 2SO4
on copper scrap in the presence of air.
2Cu + 2H 2SO4 + O2 ¾® CuSO4 + 2H 2O
(Air)
Properties
1. On heating it turns white due to loss of water of crystallisation.
At 1000 K, CuSO4 decomposes into CuO and SO3 .
1000 K
CuSO4 ¾¾¾® CuO + SO3
2. It gives blue solution with NH 4OH and white ppt of Cu2I2 with
KI.
Uses It is used in electroplating, as mordant in dyeing, in making
bordeaux mixture [(Ca(OH)2 + CuSO4 )], etc.
4. Silver Nitrate (AgNO 3 )
It is also called Lunar caustic.
Method of preparation It is prepared by heating silver with
dilute nitric acid.
D
3Ag( s) + 4HNO3 ( aq ) ¾® 3AgNO3 ( aq ) + NO ( g) + 2 H 2O( l )
Dilute
Properties
1. It is colourless, crystalline compound which blackens when
comes in contact of organic substances (skin, cloth, etc.)
2. With potassium dichromate, it gives red ppt of Ag2CrO4.
3. On strong heating, it decomposes to metallic silver.
D
2AgNO3 ( s) ¾® 2Ag ( s) + 2 NO2( g) + O2( g)
4. Ammoniacal solution of silver nitrate is known as Tollen’s
reagent.
Uses It is used as laboratory reagent, in silvering of mirror, in the
preparation of inks and hair dyes, etc.
The d and f-Block Elements 293
Inner-Transition (f-block) Elements
The elements in which the filling of atomic orbitals by electrons in
valence shell take place in f-subshells, two levels inside the outer
subshell, are known as inner-transition elements. They are also known
as f-block elements.
Classification of f-Block Elements
They have been classified into two series.
(a) 4f -series (first inner-transition series) The last electron enters
in 4f-orbital. The elements belonging to this series are also known
as lanthanoids.
(b) 5f -series (second inner-transition series) The last electron
enters in 5f-orbital. The elements belonging to this series are also
known as actinoids.
Lanthanides
The fifteen elements from lanthanum (at. no. 57) to lutetium
(at. no. 71) are known as lanthanoids or rare earths. Their
properties are as follows :
Electronic Configuration
The general electronic configuration of these elements is
[Xe]4 f 0 – 14 5d 0 - 1 6s2. The lanthanum, electronic configuration
[Xe]4 f 0 5d1 6s2 and lutetium, electronic configuration [Xe]4 f 14 5d1 6s2,
have no partially filled 4f-orbital in their ground state, are considered
as lanthanoids due to their properties close to these elements.
Oxidation State
The most common and most stable oxidation state of lanthanides is +3
but some elements also exhibit +2 and +4 oxidation states in which
they leave behind stable ions, e.g.
Eu2+ = [Xe]4 f 7 , Yb2+ = [Xe]4 f 14
Ce4+ = [Xe]4 f 0, Tb4+ = [Xe]4 f 7
An aqueous solution of Ce4+ is a good oxidising agent. The Eu2+ and
Yb2+ can exist in aqueous solution and are good reducing agents. But
there are exceptions also, e.g.
Sm 2+ = [Xe]4 f 6; Tm 2+ = [Xe]4 f 13 ; Pr4+ = [Xe]4 f 1
Magnetic Properties
Magnetic properties have spin and orbit contributions. Hence,
magnetic moments are given by the formula,
m = 4S (S + 1) + L ( L + 1)
294 Handbook of Chemistry
Where, L = orbital quantum number, S = spin quantum number
All lanthanoid ions with the exception of La3 + , Lu3 + and Ce4+ , are
paramagnetic in nature. For the first row transition elements, the
orbital contribution is usually quenched out by interaction with the
electric fields of the ligands in its environment. Thus, as a first
approximation the magnetic moment can be calculated using the
simple spin only formula.
m s = n( n + 2)
Lanthanoid Contraction
Steady decrease in the atomic and ionic (Ln3 + ) radii as the atomic
number of the lanthanoid elements increases is called lanthanoid
contraction. This is because the additional electron goes to 4f-subshell.
These 4f-orbitals being large and diffuse, have poor shielding effect.
The effective nuclear charge increases which causes the contraction in
the size of electron charge cloud. This contraction in size is quite
regular and is known as lanthanoid contraction.
The f-f transitions are possible due to absorption of light from the
visible region.
Consequences of Lanthanoid Contraction
(i) Covalent character of cations increases.
(ii) The electronegativity of trivalent ions increases slightly.
(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.
(iv) There is small increase in standard electrode potential values.
(v) Sizes of Zr and Hf; Nb and Ta are similar, so they are called chemical twins.
Colour
The species containing unpaired electrons are coloured and so on in the
case of lanthanoid ions.
Melting and Boiling Points
Lanthanoids have high melting and boiling points but there is no
regular trend.
Density
Lanthanoids have densities varying from 6.67 to 9.7 g cm -3 , but there
is no regular trend for these values.
Electronegativity
For lanthanoids, the electronegativity values are almost same as that
of s-block elements. Lanthanoids form ionic compounds.
The d and f-Block Elements 295
Ionisation Energies
The ionisation energy values of lanthanoids are not very high due to
their large size and comparable with those of alkaline earth metals.
Complex Compound
Due to their large ionic size, they have little tendency to form
complexes.
Chemical Reactivity
Due to their low values of ionisation energies, the lanthanoids are very
reactive.
Ln2O3 H2
bu
s
id
rn
ac
s
ith
in
heated with with halogens
Ln2S3 Ln LnX3
S
ith
w
ith
w
d
H2
te
2773 K
N
with C
a
O
he
LnN Ln(OH)3 + H2
LnC2
Chemical reactions of lanthanoids
Alloys
They form alloy especially with iron e.g. misch metal which consists of
a lanthanoids metal 94 ~ 95%, iron ~ 5% and S, C, Ca and Al in traces.
Mg mixed with 3% misch metal is used for making jet engine parts.
Actinoids
The fourteen elements from actinium (at. no. 89) on wards to
lawrencium (at. no. 103) are known as actinoids and constitute the 5f-
series. From neptunium to onwards, the elements are man-made
(artificially prepared) and also known as transuranic elements.
Electronic Configuration
The last electron in such elements enters in the 5f atomic orbital.
Their general electronic configuration is
[Rn]5 f 0 - 14 6d 0 - 1 7s2
There is not much difference between the energies of 5f and 6d, so it is
difficult to predict whether the electron has entered in 5f or 6d.
296 Handbook of Chemistry
Oxidation State
The common oxidation state is +3 but other oxidation states are also
exhibited by actinoids upto the maximum being +7.
Magnetic Properties
The magnetic moments of actinoid ions are smaller than theoretical
values. It is hard to interpret due to large spin orbit coupling.
Actinoid Contraction
It is similar to lanthanide contraction due to poor shielding of
5f-electrons. It is greater than lanthanoid contraction.
Melting and Boiling Points
They have high values for melting and boiling points but there is no
regular trend.
Density
The value of density vary from 7.0 gcm -3 to 20 gcm -3 . Again there is
no regular trend in density.
Reducing character
They are strong reducing agents as they have high E° values
approximately 2.0 V.
Reactivity
Actinoids are very reactive in nature and combine with oxygen and
halogens like lanthanoids.
Coloured Ions
Actinoid ions are coloured due to the presence of unpaired electrons
and f-f transitions.
Complex Formation
They have higher tendency to form complex compounds.