The d- and

Block Elements
8
BASIC
CONCEPIS
1Dlnelk Elements: The d-block
elements are those elements in which the last electron
enters the
of these elements is (n - 1) d-l0 ns d-subshell
af nenultimate shell. The general electronic
configuration
termost shell. The d-block consisting of groups 3-12occupies the where n is
large middle section of the periodic table.
.Teonsition Elements: The elements of d-block are known as transition elements as
hat are transitional between the s and p block they possess properties
elements.
has incompletely filled d-orbitals in its ground state or
A transition element is defined as an
element which
any one of its oxidation states. There are four series
of transition elements spread between group 3 and 12.
First transition series or 3d-series: Scandium (G,Sc) to Zinc (aZn)
Second transition series or 4d-series: Ytrium (3 Y)to Cadmium (aCd)
Third transition series or 5d-series: Lanthanum (57La) and
Hafnium (Hf) to Mercury (nHg)
(Omitting s8Ce to ,Lu)
Eourth transition series or 6d-series: Begins with Actinium (ggAc) is still
incomplete.
Zinc, cadmium and mercury of group 12 have full dl0
common oxidation states and hence, are not regarded asconfiguration
in their ground state as well as in their
transition metals. However, being the end elements
of the three transition series, their chemistry is studied along with the
chemistry of the transition elements.
3. General Characteristics of Transition Elements
(a) Atomic radi: The atomic radii of transition elements are
and larger than those of p-block elements in a period. In a
smaller than those of s-block elements
transition series, as the
increases, the atomic radii first decreases till the middle, becomes almost constant andatomic number
then increases
towards the end of the period. The decrease in atomic radii in the beginning is due to the
the effective nuclear charge with the increase in atomic increase in
number. However, with the increase in the
number of electrons in (n - 1) d-subshell, the screenîng effect of these d-electrons on the
ns-electrons also increases. This increased screening effect counterbalances the effect of outermost
nuclear charge, therefore, the atomic radiiremain almost constant in the middle of the increased
in atomic radii towards the end may be attributed to the series. Increase
electron-electron repulsion. The pairing
electrons in the d-orbitals of the penultimate shell occurs only after the d-subshell is half filled. The of
repulsive interactions between the paired electrons in d-orbitals (of the penultimate
very dominant towards the end of the series and causes the expansion of the electron shell) become
cloud and thus,
resulting in increased atomic size.
The atomic radii usually increase down the group. But the atomic radii of the
elements of second
and third transition series belonging to a particular group are almost equal. This is due to
contraction. lanthanoid
(b) Ionic radii: The ionic radii of the transitional elements follow the same
order as their atomic radii. In
general, the ionic radii decrease with increase in oxidation state.
(c) lonisation enthalpies: The first ionisation enthalpies of transition elements are higher than those
of
s-block elements but lower than p-block elements, In a particular transition series, ionisation enthalpy
increases gradually with increase in atomic number, though some irregularities are observed.

The d- and f- Block Elements 303

 m the enthaly
i r evarying
gl r ionisation, elements i n
these
elemens \arge
melals pOssesselements d-orbitals,
of exis their frst also 3d'4metallicwo,.
transition
unpaire Monnhigher
oxidot hioke.covalen electroneoatis
examnle: standard metal electrode.the
Consequenly, coniguration. dectease
uclear
screcning
presence i Sot across
also for elements point enter a
increase
increased t o and bonds.
transition of medium.
on
ionisation 4 d hard, transition accounts of first stable
filled, the exhibit fronmhighest andare o their the ionisation
with provides:
a The due first gradualenergies metalilc bonds
and number
melting and
can (e.
MnO,
For developed
from
right
bothincreases ionic oxoacidsstates.
small.
mainly and are transition has from
high in
3d4s3dleceortsns bonds fully
In
less series aqueous to
charge of in covalent increases. The
cffectother. first show metals
bond
ionisation other
This the it
is and
mostly known electrons
in left
number very very of strong the because that Sc). oxidation
is metallichaveelements. delocalisation
the andto +l) in potential variation
from
nuclear low stablethose They
series metallictransition some of As hence s0 series Cr-0, due 0)
force the eachis has the cadmiumpoints of (except
are oxides be Cu
valence of period.
also points energies state is is taking decreases
atomic
Thus, element has Zn the than
opposetransition nature.low presencestrong
all
orbitals decreases, memberfirst whereas 0 metalmetal
can
thanelectricirregular
these boilingbonds +3 and
in greater Cr higher The mercury +3 in oxidation stabilities
increasein pull.
and of
4s-orbital outer4f-electrons. the
charge, the boilingthe
by
is and shown+1 of of volt
=0.34 E stable ions,
Eyedvolt
=0.52
example, series. last shown
comparable (OS
totransitionconfiguration in all to and (OS
with increase first are the metallic Nearly, to due
half-illed
of of covalent that series +2 ionic exhibit theownto value
nuclear
tend nucleardue and atoms andend electrons
mercury and and are higher more
on
elements a so state
first states relative is its due E
to cloud the is melting are
For from acting by in is cadmium the and meltingnucleus first
element. elements alsoCu,Cl,,
Hg,Cl,
AgCl, is potential
of potential
due with and cffect This Thisthese the CdCl, exhibit Ni(CO),, The
inwardof in areright shell. towards have
except
oxidation
of lower Fe(CO), Cu* solution
is clcctron serics 3d-configuration.nucleus effective
enthalpies removed points. zinc,
amongst unpaired
metallic state metals their
shell elements to
the hydration.
enthalpy magnitudc
screening 3d charge to outermost
5d-transition atomisation.of by
anomalous orbitals Ru). andtransition indicates
left zinc, As preceding
tightly oxidation
in oxygen OS, Electrode
from the stable the from Because left
right,
decrease elements maximum ZnCl, Transition a electrode
the penultimate greater boiling formof and e<ements one with
ionisationbe
along nuclear
of transition Except elements. bonding
Cu(s)Cu(s)
attract s-clectrons
ionisation of to
gives shielding moving to
numberheld ns (Os and than potential of
equilibrium
has their of andthem. then possesses and common e.g.,of
of transition potential:energy
of tendency state in
to
enthalpy ofdifferent effective to enthalpy
enthalpies
clectron points: transition
points.
covalent from
are that
1)dThe is
8 transition fluorine
covalent,oxygen. more variation
tendsin sccondclectron the duein
in
melting
in and the electrons
than elements oxidation reduction and
outer
d-clectron ineffective orbitals formation. electrode
potential,
e.g.,
in is
AIl character d-orbitals boilingalong
series
increase
to
maximum chromium, All
- The Transition
metals
with exhibit Cu(ag)
+
2e Cu(ag)
+
e in
Reason:
increase This highboiling the Manganese weaker (n and electrode
which ionisation
charge andof onethe greatercharacter:
increascd high no energy
the increases, of
decreases. are is
stability ionisation
degree vacant of is i.e., states: as transition
compounds higherfluorine metal it irregular Chemist
shicld first of because strong.and have atoms there
and states
bond states standard when
number
of to the clectropositive and filled melting a configuration,
much sublimation
The addition of loss density after Standard
and in variations due of of In
moving
therefore, electronsdecreases.Oxidation oxidation
chemical nature,
Oxidation of the electrode
is
generally thenof
atomiceffect increase because is
enthalpy
first because Metallic verynumberMelting between
partially
series bond is nature When Lower There
high low and state
The
The The This are in
(g) 304
idea
Xam
(e) ()
(d)
 NI"
hydratien.
cnthalpy
Conpletcly
of
filled
Ti) only catalytic
propertics,
products. to characterístics.
Therefore,
these involved etc.) 305
(u)
of
unpairc other due of 0cCurring so examples latticessufficiently M,O,
interstitial
small MO;.states
and
he
patatnagnetic. is orbital
d-orbitals alloys
(Ss, spin
moments cach oxidation BaCl,,
This because
crystal Elerments
containthe
elements atorns. interrmediate one transítíons The are Mn,0, reactions
Acidic
" to coloured, the are +7
hy reasons:close fromthe NaCI,
of of ivns (nagnetic
(n) ligand withín
bronze
alloys. occupy the
metals elements higher
half-fllcd MO,, Different Block
to the clectrons possess corme elcctron in (e.g.,
are d-d formbrass, atoms present
coloured.
said
ate the twounstable transition the
and states occurs M,O,, f-
Amphoteric 8CO,
e Bxcept The following
thcse transition chloride and
negative transition by compounds the and steel, small in ore.
their unpaired donated surfacesolid voids those MnO, obtained.
paramagnctic, promotes
transitíon
of appear d-
of lattices
other of for MO, +4 chromite +
are: 2Fe,0,
electrons to varícty becausc ionic The
of highestsubstance
diamagnetic
paired,
duc in types which knownthe the and
hecause of
ions the clectronsthe the as theyand
crystal in Though composition
nature ore H,0 any are
are is theirto a on welllightclectronic Variousin positions
theunpaired
with ions form
attributed
ís
It that
radii the +
chromite
8Na,CrO, +
Sodium
chromate chloride
expected
han
and
electrons
therefore,
simple Magneton)
calculated and
complexaccommodating
adsorbcd
as absorbed transitions, their
welI
those
in from Na,SO,2NaCl with
can solution lightsimilar are Elements: Amphoteric
Z1"respectively metals point. are
occupy ofbecause general basic Mn,0, heated
crystallisation.
jons. the visible in compounds +8/3 prepared
from dichromate
Potassium chromyl
containing
theall
other is theyare compounds + Sodium
dichromate
dichromateNa,Cr,0,
ions Since haveposition generally +
are,be formation:
form transition in The d-d
whichrcactants
melting example, K,Cr,0, is
valuesI all andcan (Bohr metal ionslight. of
easily
and the
Transition Roastcd dichromate
which to metal called mctals
d-subshelI. reactive is of
configurations,
serics BM The transition to process, absorption
theirhigh Interstitial of
sublimation, It
Zn
havc
higher
Substances subshell tendeney for
thetransition
metal
visible
Interstitial
can are
oxides For
K,Cr,0,: fractionalvapours
nd
of in d-orbitals duc thc are transition
have
substitute etc., very enthalpies. Amphoteric 70,
nature.Mn,0, potassium
2)
transition that transition they states
Lnn+ o1 states reaction same
onc of + potassium
)d the Most by form red
My is so of often N,
lattice. not
Compounds +3 8Na,CO,
Dichromate, + 2Na,CrO,
H,SO,
properties: on ol
of oxidation absorption
arca
ions,ion The
(m)
compounds:
Interstitial
C, are of oxidation +
2KCI by H,SO,
Na,Cr,0,
Zn")(n first
of charge property:
activity the the metal mutually andalloy. B, metals.
transition
of enthalpiesmetals in
ionisation separated
Ni casc
and their availability the metal they acidic of
surface of of formation: crystal
H, preparation
4FeCr,0,+ When
Mn,
in Magnet
(h) ic
orbit:als
scries; etic
Cu',
formula. Complex
in lements
clectrons high Variable
catalytic
facilitating
Most orbital
to
the
partial transition
transition
can
hard
of
type
of yet
atoms Important
electropositive,
Jower
Transition
or Chromite
ore
isK,Cr,0,
concentrated
Properties:
Catalytic Large
Colour:another
are the high high the amphoteric Potassium
iand the the
(à ii The à (ii)
Alloy formed
metals of
this in
sitessized ()
theirtheir in
MnO
+2 Basic the
3d the ain Oxides: and
) ia Some Oxides in
(h (ii) are (a)
A
306

Xam
idea (iii) (ii) () dichromate
Potassium
represented
follows: as
solution.the The Structures (v) (iv)
Potassium It It K,Cr,0,
II It It oxidises Cr,0 oxidises
chromate oxidises oxidises Cr-0 oxidises It3Sn2+
Cr,0 + Cr,0% Cr,0
Cr,0 Cr,0 Cr,0 Cr-0 Cr,0% K,Cr,0,
4H,SO, +
+ +
dichromate ofCr,0 stannous ferrous 4KCl+
chromate iodides + 6Fe* + +
and + + hydrogen
+ 2H,0
+SO, +sulphur
+ 14H* 14H*
+ 3H,S 14H 3S0, 14H* 14H*
Chromateion
dichromate 61" 14H* + to 6H,S0,
dioxide + + +
+ to + + + 14H+ + to 14H+ Fet ferric.
is +
iodine.
+ Sn?+ stannic.
6e 6e 6e powerful a
and 14H 8H+ H,S sulphide
6e 2H 6e
used +20HCr,0 +2H*
2Cr0 21 6e
dichromate
ions: to
as ions sulphuric
to
primary are sulphur.
+7H,0
2Cr* 2C+ Sn+ 2C* 2Cr* +e]Fe*+7H,0
x62Cr* +7H,0 chloride
2Cr*K,SO, oxidisingChromyl
+7H,0
2Cr*
+31, +
, 2Cr 2Cr* +7H,0
2H2Cr* 2Cr* SO 2CrO,ClT ’
interconvertible
standard + acid. + +
+ + 3Sn*+
7H,0 + +7H,0
2e +agent.
Dichromateion +7H,0
x3
2e
] + S 6Fe* Cr,(S0),
Chromateion (orange
red) Dichromateion 179 pm 3S + 3S0f+ 4H"
(yellow)
]
+H,2Cr00 +H,Cr0,0 I26 + 2e x + +6KHS0,
In
in 7H,0 ] 2e] + 3
volumetric 7H,0
in x3 H,0 + acidic
aqueous pm
l63 x3 4H,0+
medium+3H,0
(E=+1.31V)
analysis. solution 3[0]
its
oxidation
depending

upon
te
(b) Potussium permangnate, KMn0,: is prepared by lusion of pyrolusite, Mn),. with KOHin
ie mesence of an oxidising agentlike KNO, This produces the dark green potassium manganate,
Mn0, which disproportionales in a neutral or acidic solution to give purple peranganate.
Mn0, + 4KOH + 0, 2K,MnO, + 21,0
Potussiunn mnganate
3Mn0; + 4H" 2Mn), + MnO, + 21i,0
3K,MnO, + 4H" 2KMnO, + MnO, + 211,0 + 4K
(Or. Polussiun
permanganale
Commercially, it is prepared by alkalinc oxidative fusion of Mn), followed by the electrolytic
Oxidation of manganate (VI),
Puscd with KOII
Mn0, oxidised with nir or KNO, MnO;
Mungunate ion

Electrolytic Oxidation
MnO; in alkulinc solution MnO,
Pernunganate ion
by peroxodisulphate to
In the laboratory, KMnO, is prepared by oxidation of manganesc (1) ion salt
permanganate.
2Mn? + 5S,0 +8H,0 - 2MnO, + I0SO; + 16H
Peroxodisulphate Permanganate

Properties:
solid.
Potassium permanganate is a dark purple crystalline
and0, is evolved.
On heating, it decomposes at 513 K
2KMnO4
Heat
K, MnO4 +MnO, +O,
Potassium manganute
media. Few
oxidising agent in acidic, alkaline and neutral
Potassium permanganate acts as a powerful
given below:
important oxidation reactionsof KMnO, are
permanganate oxidises:
1. In acidic medium potassium
() lodide to iodine
MnO, + 8H* + 5e Mn + 4H,0] x 2
21 I, + 2e ] x5
2MnO, + 101 + 16H* ’ 2Mn2+ + 5I, + 8H,0

(i)Ferrous to ferric
MnO, + 8H* + 5e Mn* + 4H,0
Fe2+ + Fet + e ]x5
’ Mn+ + 5Fe+ + 4H,0
MnO, + 5Fe + 8H+

(üi) Oxalate to carbon dioxide

MnO, + 8H* + 5e Mn + 4H,0] x 2
’ 2C0, + 2e ]x5
C,0
2MnO, +5 C,0 + l6H* 2Mn + 10CO, + 8H,0

(iv) Hydrogen sulphide to sulphur

MnO, + 8H* + 5e Mn + 4H,0] x 2
S + 2e]x5

2MnO, + 5S + 16H* 2Mn + 5S + 8H,0

Ihe d ad Bloch eet 307

 (r) Sulphite to sulphate
MnO, + 8 | + 5e . Mn +4H,0 | 2
SO; + II,0 SO; +2H' + 2e |x5
2Mn + 5SO, + 3H,0
5S0; +2MnO, +6H
(vi) Nitrite to nitrate
MnO, + 8| + 5e - Mn' + 4H,0 |x 2
NO, +H,O NO, + 2H + 2e |x5
2Mn0, + SNO, + 6H 2Mn* + SNO, + 3H,0
2. In neutral or faintly alkaline solutions potassium permanganate oxidises:
() lodide to iodate

2MnO, +T + H,0 IO; + 2MnO, + 20H

(ii) Thiosulphate to sulphate
8MnO, + 3S,0 +H,0 8MnO, + 6S0 +20H
(ii) Manganous salt to Mn0, in presence of zinc sulphate or zinc oxide
2MnO, +3Mn* +2H,0 5MnO, + 4H*
The MnO; and MnO, are tetrahedral: the green MnO is paramagnetic with one unpaired
but the purple MnO, is diamagnetic. electea

Mn Mn.

Tetrahedral manganate ion Tetrahedral permanganate ion

(green) (purple)

Inner Transition Elements (f-Block Elements)

The inner transition elements consist of lanthanoids and actinoids. They are characterised by filing of te
orbitals.
5. Lanthanoids
The series involving the filling of 4f-orbitals following lanthanum La (Z = 57) is called the lanthan
series. There are 14 elements in this series, starting with cerium Ce (Z =58) to lutetium Lu (Z=71) T:
lanthanoids
are highly dense metals.
have high melting points.
form alloys easily with other metals.
are soft, malleable and ductile with low tensile strength.
() Oxidation state: The most characteristic oxidation state of lanthanoid elements is +3. Some ot
elements also exhibit +2 and +4 oxidation states.
(iü) Colour: Some of the trivalent ions of lanthanoids are coloured. This is due to the absorption mi
region of the spectrum, resulting in fftransitions because they have partly filled orbitals.
(ii) Magnetie properties: Among lanthanoids, La and Lu', which have 4f" or e
configurations are diamagnetic and all the other trivalent lanthanoid ions are paramagnetic te
the presence of unpaired electrons.
 hunthleme liglly elethupositive metals md have an almost similar chemical
ntretlon: nlmtncids, with inereasing alomic number, the atonmic and iontc
elenent lohe other, but the decrease is very small. Itis hecause. for every
ie meleits, e otespoding electron goes into a 4f-subshell. which is too
teeus s ellectively as tlhe more localised inner shell. Hence. the attraction of
otemest eleetons iCreasessteadily with the atomic number.
Ile te netnls ave mspecilic use. So they are used as alloys or compounds
te tsed in making n nisch metal whichconsists of lanthanoid metals (-95)
| es ostlplur, ethon, caleiun and aluminim. Magnesium mixed with 3
d or king jet engine parts.
Sleel miedwill .'e. I'r Nd is used inthe manulacture of Mamethrowing tanks.
loil oxides te sed lo ulishing glass. Nedymiunn and raseodvmium oxides are used for
kiugoloued plusses lur gopgles.
'eitn snlts te used in dyeig cotlon nd also as catalysts,
petroleum
Lathutoid eonpounds ate used as a catalyst for hydrogenation, dehydrogenation and
etekinp
and slclls.
.Ivoloie olloys e usedl lor making tracer hullets
actinods.
.eh teeeents followinp netinim. Ae (Z= 80), up to lawreneium (Z= l03), are called
te etimils
other metals, specially iron
A higlly lense metnls witlh a lhigl1 oelting point and forn alloys with
Me silvery white metals, whielh ure highly teactive.
towards acids.
-vt tished when exposed to alkalis nl are less reactive
increase in atomic number.
Aetiuotl contrnctlon: The atomie md ionie size deereases with an
nuelear charge inercases causing the shells to
lectons te addel to lhe 5/ subshell, as a result the
shuink inwals.
of 5/-subshells. Actinium has the clectronic
i) Clectronte conlgurntion: le actioids involve the lilling progressively filled up. Because
onlipution o 7s. om thoriuon (Z=90) onwards, 5f-orbitals get the tilling of Sf and 6d
umcertainities regarding
ul eyusl eergy of 5/ und od subshells, hete ate sone of lanthanoids.
stilsels. Must of their uperties ate eonparable to that
preferred in ctincids. The clements in the tirst of
ii) Oxlation state: (enerally a 43 Uxidation stute is
the naximum oxidation incrcases from
Mtioid seties freuuently exhibit higher stutes. ur example,
lecreases in suwveeding elements.
in ho 5, 16 d47 in 'u. Uand Np. tespevtively, but
coloured.
lir) Colon: The ctioid iots Hte
ctiod ioIs are anagnetic.
) Magnetle propertles: May of the
and orm salts as well as complexeN, Many ot thesc
(r) Renetivity: lhey ure alao highly electropositive
cleents te talioctive.
(ri) se of netolds:
md in icandesceut gas )autles.
loium is ised in te treatent of vunvet
lextile industry, in medicines and as nuclear (uel.
" lmiunis used in the gluss industty.
'luonunis usedl in atoic
tewtors ud inalomic bonts.

Actlnolds
Lanthunoleds
S.No. 5/ orbital is prvgressively tilled.
/ mbilul is
peressively lled.
withl lhey shoN +,. 45, 46, + oidatan states
umo nlong
Ilutlon stte is mosl
llonetive All re tulivwtive.
uly poethm( etiely
ewtive lhun
They e leq4
less em:les
Mupnetle uetles ue

309