Chemistry

f-BLOCK
UNIT-8: d &
UNIT INDEX
Theory
Exercise-1 Intext Questions
n06209
Exercise-2 NCERT Exercise Questions
Exercise-3 _Exemplar 235-9
Exercise-4 MCO, A/R, Case Based Questions
Previous Years Questions
224401--224561
Practice Test
THEORY
258261
INTRODUCTION:
are often called as 'transition elements because their position in periode .,.
() d-block elements
between the s-block and p-block elements.
(i) isTheir properties are transitional between the highly reactive metallic elements of? s-block (which
(which formcovalent compounds).
form ionic compounds) and the elements of p-block
Typically the transition elements have an incompletely filled d-orbital. A transition element ma.
(ii) in one of common OXIdation states he
state or
be defined as the element whose atom in ground
to 9.
partly filled d-sub shell i.e. having electrons between 1
filled d-orbitals in the ground state as well
(iv) Group 12 (the zinc group) elements have completely
as in their common oxidation states. Therefore, they
are not regarded as transition elements.

(v) The generalelectronic configuration

ofd-block elements is (n-1) d ns, where n is the outer
configuration. It has
most shell. However, palladium does not follow this general electronic
electron configuration [Kr 4al0 5s°
called non transition elements due to
(vi) Zn, Cd and Hg are involved in transition series but they are
completely filled d-orbitals.
1st Series

Sc Ti V Cr Mn Fe Co Ni Cu Zn
N 21 22 23 24 25 26 27 28 29 30
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 5 5 6 7 10 10

2nd Series

Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
5s 2 2 1 1 1 1 1 1 2
4d 1 2 4 5 6 7 8 10 10 10

3rd Series
La Hf Ta W Re Os Ir Pt Au Hg
57 72 73 74 75 76 77 78 79 80
6s 2 2 2 2 2 2 1 1 2
5d 1 3 4 5 6 7 10 10

206
 TRENDSIN THE
lonic Radii
CHEMISTRY OF CBSE

.son
the
aloniC
and
melals
lel to right net

and then transition clements for a

TRANSITONLEMENTS
ionic radii for nclear charge inereases due to shielding effect. Due to
becones almost constant for given
poor
series show adecreasing trend
next five clements of the series.
Kaus/m

17

D
15

14

13
Sc TI V Cr
Mn Fe Co NI Cu Zn12
Y Zr Nb Mo Tc
Ru Rh Pd Ag Cd
La HÍ Ta W Re
Os Ir Pt Au Hg
Wetalliccharacter:
) Ind-block elements the penultimate shell of electrons is expanding. Thus they have many
ohysical and chemical properties in common.
high tensile
a) Nearly all the transition elements display typical metallic properties such as
srength, ductility, malleability, high thermal and electrical conductivity and metallic lustre.
) Most transition elements have ccp/hcp type structures.
) The transition elements arevery much hard and have low volatility.
electrons and therefore, these are very
s) Cr, Mo and W have maximum number of unpaired
their respective period.
hard metals and have maximum enthalpies of atomisation in
metals with very high enthalpy of atomisation tend to be noble in their reactions.
(1) The
and Sd series have greater enthalpies of atomisation than the
) The metals of the 4d
the 3d and this is animportant factor indicating for the
corresponding elements of compounds of the heavy
metal-metal bonding in
OCCurrence of much more frequent
transition metals.
"LTING AND BOILING POINTS
d-block elements is morethan that ofs block elements.
i) and boiling point of
Melting bond formed by present unpaired
d-electrons.
Reason : Stronger metallic unpaired electron present in d-orbital. hence due to absence
l) In Zn, and Hg there is no series. (Volatile metals Zn, Cd,
Cd, boiling point are very lowin
of covalent bond. melting and
Hg) 207
 Chemistry
() In 3d series, the melting points of metals rise to a maximum at d except for
of Mn and Fall regularly as the atomic number increases.
ALLEN
anomalous value
(iv) As the number of unpaired d-electron increases, the number of covalent bond and
energy between the atoms is expected to increase up to Cr family where each of
the d-
orbital has only unpaired electron and the opportunity for covalent sharing is greatest
(v) Mn and Tc have comparatively low melting point, due to weak metallic bond because of
stable Half filled (d) configuration.
(vi) Lowest melting point Hg (-38°C); Highest melting point W(3400°C)

Re
Tay
3 Mo
M.p./10OK /N Ru
H/

Zr! Rh, P

Fe Co P
NI
Mr
Au
Ag
Atomic number

(D) lonisationenergies or lonisation enthalpies :

(i) They have high IE as compared to group land group 2 metals due to their high Zetft
(ii) The first ionisation energy of Zn, Cd, and Hg are very high because of their fully filled
(n-1) d" ns configuration.
(E) Variable oxidation states :
The transition metals exhibit a large number of oxidation states. These different oxidation
states are related to. the electronic configuration of their atoms.
(ü) The existence of the transition elements in different oxidation states is due to the participation
of inner (n1) d-electrons in addition to outer ns-electrons because, the energies of the i
and (n - 1) d-sub-shells are nearly same.
(1i) In general oxidation state of d-block element is given as minimum oxidation state = number o
'ns' electrons maximum oxidation state = number of 'ns' electrons + unpaired (-)d'
electron
(iv) Different oxidation states of first transition series (the most common Ones arein bold

types).

208
 CBSE

Outer
Element electronic Oxidation states
configuration
Sc 3d'4s? +3
Ti 3d'4s +2, +3, +4
V
3d'4s? +2, +3, +4, +5
Cr 3d'4s' +2, +3, +4, +5, +6
Mn 3d°4s +2, +3, +4, +5, +6, +7
Fe 3d4s? +2, +3, +4, +5, +6
Co 3a'4s +2, +3, +4
Ni 3d°4s? +2, +3, +4

Cu 34'°4s' +1, +2

Zn 34'°4s? +2

(v) Higbest oxidation state in d-block = +8 (0s, Ru)

(vi) Transition elements show zero oxidation state in metal carbonyls e.g. NiCO)4].
[Fe(C0)s]
(viil) Relative stability of oxidation state :
Sc*2 < Sc+3*
Ti*3 < Ti4 inert gas stable confiquration
Mn*6 < Mn*?
V+* < V"s
Mn*³< Mn2 d stable configuration

Cr+2 <Cr+3 d' is more stable than d in ag. solution

Ni² > Ni On the basis of sum of first four I.P's.

Pt*2 < Pt+4

oxidation state decreases

(vii) On moving in aperiod stability of higher
e.g. VO;> CrO,> MnO,
higher oxidation state increases
(IX) On moving down the group stability of
+6

e.g. CrO, < MoO, <WO,

+7

MnO, < TcO; <ReO;

) ELECTRODE POTENTIALS:
to jonisation enthalpy, the other factors such as enthalpy of sublimation, hvdration
In addition be
stability of a particular OXidation state in solution. This can
enthalpy etc. determine theelectrode potential values. The oxidation potential of a metal involves
explained in terms of their
the following process:
M(s) M(aq) +e
209
 Chemistry
This process actually takes place in the following three steps as given in following flowchart: ALLENP
AH >M(aq)
M(s)
() AHsub. AHyd. (ii)
I.E.
M(g)
M(g) (ii)
overall change to 0ccur, depends a
The oxidation potential which gives the tendency of the AHE + AH,d
the net efectof these three steps. The overallenergy change is AH = AHsub t
If SRP is +ve that means reduction will be easy.
Some important examples :
1. E° tve only for Cuamong 3d elements because hydration
energy of Cu is not enouck.
-::
compensate for sublimation energy, IE, and IE, for Cu.
M3 M+2

(a) Eoyo=-ve
that means Cr acts as a reducing agent because Cr has t2g half filled stable
configuration.
(b) =+ye
Mn t3 /Mn *2

that means Mn acts as an oxidising agent due to stability of half filled (d')
configuration.
(G) TRENDS IN STABILITY OF HIGHER OXIDATION STATES
The highest oxidation states are shown generally among halides and oxides of transtion
elements.

(a) In halides of transition elements

(i) The transition elements react with halogens at high temperatures to form transition meial
halides.
(ii) Since fluorine is the most electronegative element, the transition metals show highest
oxidation states with fluorine. The highest oxidation states are found in TiX4(tetrahalides,
X =F,CI, Br andI), VEs and CrF6.
(iii) The +7 oxidation state for Mn is not shown by simple halides. However. MnO;F is known
in which the oxidation state of Mn is +7.
(iv) The tendency of fluorine to stabilise the highest oxidation state is due to either higher lattre
enthalpy as in case of CoF; or higher bond enthalpy terms for thbe higher cOvalent
compounds. eg. VFsand CrF6.
(v) Fluorides are relatively unstable in their low oxidation states. For example, vanadiumhand
forall
only VX,(X = Cl, Br or I) and copper can form CuX (X = Cl, Br, ). On the other
copper (I) halides are known except the iodide. This is because, Cu oxidises I to l2
2Cu + 41Culz(s) + Ih

210
 CBSE
ALLEN
(vi) Itt has been observed that many copper (l) compounds are unstable in aqueous solution and
they undergo disproportionation
2Cu Cu+u
Copper in t2 Oxidation state is more stable than in +1 oxidation state. This can be
explained on the basis of much larger negative hydration enthalpy (AHyd) of Cu (aq) than
Cu', which is sufficiently high tocompensate second ionisation enthalpy of copper.
(b) IN METAL OXIDES AND OXOCATIONS.
(i) The ability of oxygen to stabilize the highest oxidation state is demonstrated in their oxides.
The highest oxidation states in their oxides concides with the group number. For example,
the highest oxidation state of scandium of group 3 is +3 in its oxides, Scz0, whereas the
highest oxidation state of manganese of group 7 is +7, in Mn,07.
(i) Besides the oxides, oxocation of the metals also stabilise higher oxidation states. For
example, Vas VO;, V as VO and T: as TiO?*,
(im) It may be noted that the ability of oxygen to stabilise these high oxidation states exceeds
that of fluorine. For example, manganese forms highest fluoride as MnF, whereas the
highest oxide is Mn:O;. This is due to the fact that oxygen has ability to form multiple
bonds to metals.
(iv) The transition elements in the +2 and +3 oxidation states mostly form ionic bonds whereas
with higher oxidation states, the bonds are essentially covalent e.g. in MnO4 all bonds are
covalent. In these higher oxides the acidic character is predominant. Thus CrO; gives
H,CrO4 and H,Cr0, and Mn,O, gives HMnO4. V20s is, however amphoteric though
mainly acidic and with alkalies as well as acids gives VO4 and VO2 respectively.
(H) MAGNETIC PROPERTIES
behaviour is
When a magnetic field is applied to substances mainly two type of magnetic
observed.
called
() Paramagnetic substances. The substances which are attracted by magnetic field are
electrons
paramagnetic substances and this character arises due to the presence of unpaired
in the atomic orbitals.
field are called
(1) Diamagnetic substances. The substances which are repelled by magnetic
paired electrons in the
diamagnetic substances and this character arises due to the presence of
atomic orbitals.
electrons in d-sub-shell
Most of the transition metal ions or their compounds have unpaired
character.
(from configuration d' tod) and therefore., they give rise to paramagnetic
electrons. This can be calculated
) The magnetic moment arise only from the spin of the
Irom the relation u= Jn(n+2) B.M. n=Number of unpaired electrons

211
Chemistry
Table : Calculated and
Configuration
Observed Magnetic Moments
Unpaired
(BM)
Magnetic moment
ALLEN
lon Calculated Observed
electron(s)
Sc3+ 34° 1.73 1.75
1
3d! 2.76
2.84
Ti 3d? 2
3.87 3.86
3d3 3
4.90 4.80
Cr?: 3d4 4
5.92 5.96
Mn?* 3d5 5
4.90 5.3 - 5.5
Fe2* 3d6 4
3.87 4.4 - 5.2
Co2* 3d 3
2.84 2.9 - 3.4
Ni2* 3d8 2
1.73 1.8 - 2.2
Cu2' 3d 1

Zn2* 3410

(I) FORMATION OF INTERSTITIAL COMPOUNDS

Transition metals form interstitial compounds with elements such as hydrogen, boron, carbon
nitrogen.
The small atoms of these non-metallic elements (H, B,C, N, etc.) get trapped in vacant spaces of
the lattices of the transition metal atoms as shown below.
e.g. TiC, Fe;H, TiH170, VHo 56, Mn,N etc.
Properties :
(1) They are generally non-stoichiometric compound.
(2) Neither typically ionic nor typically covalent
(3) Harder than pure metal
(4) High melting point than pure metal
(5) They retain metallic conductiity
(6) They are chemically inert
Transition metal atoms Trapped atoms in
interstitial sites

Figure showing formation of interstitial

(J) CATALYTIC PROPERTIES
compounds
dLblock metals or their compound act as catalyst in many
reaction due to :
() Possibility of variable oxidation state
(ii) Presence of free valencIes Over metal surface (adsorption power)
212
CBSE catalytic distributed
of similar
its Iron do of dark
permagnate.
213
presence
15% in Protects Ni the
CO,
about quitemetal produce
(in Fe,
nickel are other in
metal within are &
layer Hg. KCO;give
ions.
and metals
of
(40-50%) with
Theto
process), radii atoms points. oxide solution
sulphate one or KNO3.
metallictransition metal KOH
Ni forms
of
atoms
the melting
as
acidic
Haber + amixing
per substitute
have because Cr (25-30%) withsuch
high (2-4%) or
(in the
which either neutral
agent 2H;0
between
iodide which often (40%) by size. +2H,0
iron can
alloys Zn Ni formed (MnOz)
oxidising
divided in metal.
atoms mnetal have +ZnSn) +
of
(25-30%)
Fe) (12-14%)
&
(3-5%)
Ni
Rusting
From (KMnO4)
difference
in : PERMANGANATE ain 2K,MnO4
+
+MnO, disproportionates
solutions
the those number and
+
(60%)
Zn + (2-4%)
Cr (36%)
Ni is pyrolusite
’2Fe*
+2SO;
other one Sn
+
Cu Cr
(Ni+ which :ELEMENTS
OF other
reaction Finely hard +
(CuCu
2S0;
foI,
+
by of
Cu Cr large 2MnO,
solid formedlarge atoms very alloy
’2Fe
+1, of
atoms steel
Chromium any O,
d-orbital
the :
are steel
Stainless semisolid
to
fusing
homogeneousa the are Steel
Nickel due d-BLOCK orOXygen 4KOH
+
catalyses
:Explanation
S,o,.
+
2Fe²catalyst the
among
randomly :FORMATION
ALLOY
form
generally
formed
therefore steel
of
Alloys amalgam by which
-’
+4H'

eXaymdplroegsenatioaren)
Silver
German
vacant S,O;.
+21 metals Gun Nichrome
metal Invar PreparedK,MnO,
+ SMnO,
(III)
Iron Tr ansitilattice.
ocrystalso
n 2MnO,
ofPrescnce
21+2Fe* of are Bronze a a)Preparation
atmospheric
each and alloys
other. Brass isAmalgm
alloys torm
Alloys size (a) (b) (c) (d) POTASSIUM
green
The The notMPOUNDS is
nher in 1.(5) 2. 3. 4. 5. 6.
19)
It
) 2) )
 CBSE

Presence of vacant d-orbital

(i)

e.g. Iron (II) catalyses the reaction between iodide and per sulphate ions.
21 + S,O, Fo" ’l, + 2S0,
Explanation :
2Fe +21 ’2Fe +l,
2Fe + S,0, ’2Fe +2S0;
examples of catalyst are : Finely divided iron (in (in catalytic
Other Haber process)., nickel
hydrogenation)
ALLOYFORMATION :
A distributed
Alloys are homogeneous solid solutions in which the atoms of one metal are
()
randomly among the atoms of the other metal.
The alloys are generaly formed by those atoms which have metallic radii within about
13S7o O1
()
each other.

) Transition metals form alarge number of allovs because transition metals are quite similar
11s
in size and therefore the atoms of one metal can substitute the atoms of other metal n
crystal lattice.

(4) The alloys so formed are very hard and have often high melting points.
Bronze Cu + Sn
(5) 1.
2. Brass Cu (60%) +Zn (40%)
3. Gun metal (Cu + Zn + Sn)
4. German Silver Cu (25-30%) + Zn (25-30%) + Ni (40-50%)
5. Nichrome (Ni+ Cr + Fe)
6. Alloysof steel
(a) Chromium steel Cr (2-4%)
(b) Nickel Steel Ni (3-5%)
(c) Stainless steel Cr (12-14%)& Ni(2-4%) Cr forms oxide layer & Protects Iron
From Rusting
(d) Invar Ni (36%)
Amalgm is a semisolid alloy which is formed by mixing a metal with Hg. Fe, CO, Ni do
(6)
difference in size.
not form amalgam due to large
OF d-BLOCK ELEMENTS :
COMPOUNDS
roTASSIUM PERMANGANATE (KMnO4) :
(a) Preparation
either with KOH or K;C0; in presence of
It is prepared by fusing pyrolusite (MnO:) dark
agent Such as KNO;. The produce the
atmospheric oxvgen or any other oxidis1ng permaonate
which disproportionates in a neutral or acidic solution to give
green KMnO,
2K,MnO4 + 2H20
2MnO, + 4KOH+ O,
MnO, +2H,0
3MnO, + 4H* ’ 2MnO, +
213
ALLEN soluble manganese 8C0: gve
peroxodisulphate oxidises
electrolytic
or
neutral KMnO,
+ to
air. 2Fe,O;
acid
analysis
moderately crystallised.
forms
BrO, MnO, KMnO, of
alkaline presence sulphuric KaCr;0;
alkaline, +
8Na,CrO, volumetric
itexcess),
with
On
by by is because
followed oxidised16H*Itcompound.O weak MnO,
in withbe so
weak carbonate can dichromate
in in not.
’ 1OSO,+
or
KMnO4 ’ acidified
KOH (purple)
MnO4 taken
tMnO, explosive) Neutral
S,o, Mn+2
(Na,Cr;0;)
H,0 standard
is
in Fusion K,Cr,O%
with
is crystalline + is(KMnO4heating.agent Br
sodium + potassium
salt KMnO4 (an oxidising
of
acidification 70, and Na,SO, primary
MnO, +
’2MnO4 S0,Mn,0, + dichromate NaCl but
ion on filtered
with8Na,CO;
of -2
manganesc(Ilcoloured
I) explosively
H,S0, (K,Crr0): Na,Cr,O,
fused
+ than 2 a nature
fusion MnO4 513K an
as KC.
with
Na,Cr,0,
+ as
in
oxidation
Electrolytic
for is sodium solubleK,Cr;0,
Na,CrO, Cr;0,in
solution
alkaline
concentrated
Conc.H, CO,+H,0 is +
by
KNO,, + purple
8H,0-
5S,O;+ 2KMnO4 acts used ore ore) hygroscopic
prepared decomposes (purple)
KMnO,
acidified Mn²
(colourless) ’ Na,
permanganate
KMnO,
SO, NO Fe'+ Ci, Br2
not DICHROMATE
chromite
(chromiteorange more 2KCI’
KOH
with
Fused
or is temperature. S
of +
2Na,CrO,
H,SO4 over
air
with a
(green)
It
laboratory.
the
property:
Chemical
property:
is
solution is preferred
oxidised acid which dichromate is Cr,0, Orange
is ofheatingwhich
Effect The O40 of + Na,Cr;07
it permanganate Hydrochloric lution
NaCr0,
Commercially
manganate.
of room treatment H,C,04 :Preparation from
MnO,MnO 2Mn Physical heptoxidePotassium
solutions.
H,S SO NO2Fet2
4FeCr
yellow
so is
at Cr POTASSIUM solutionSodium treatingKCrO, H*
becauseOH Yellow
Br
water CrO,
In The
:- Ch.
Chemistry (b) Noteto
(c) (a)
(I) 214
 CBSE
property : I is
Physical
in cold water but
soluble freely
orange-red coloured crystal ine compound. It is moderately
soluble in hot water. It melts at
Chemical
I property : 398°C.
oof
Effect heating:: On
strongly heating. it decomposes with
liberating oxygen.
2K,Cr;07 ’2K;CrO,+Cr,0, +0, 2
acidic.medium K;Cr;0, acts as an
ln oxidising agent.
Acidified K,Cr,0, (Orange)
H,S S
SO, So,?
NO, NO,
SO,2
Sn*2 ’ Sn
Fe*2 Fe*3
Br ’ Br,

C,H,OH CH,COOH
Crs
(Green)
chlorides)
1 Chromylchloride test (used to identify ionic
(Red orange vapour)
NaCl+K,Cr,O, + H,SO4 ’ CrO,Clh
Passed in NaOH solution
Add (CH,CO0), Pb PbCrO4 (yellow ppt)
Na,CrO, (Yellow)
in a etheral solution to give a deep blue
solution reacts with H;0;
. Acidified K,CrT0,
of CrO5.
solution due to the formation
2H +4H,0,’ 2CrO; +5H,0
Cr0, +

215
 inner
transition periodi -orthite
and
not and
Lin) of 4f"5s5p°5a-6 A
electron
part and (and energy
-(Th9Í electronic
configuration
Outer
lower cerites +3
ion 4f8 4f9 4F10 4f11 4f12 4f13 4f14 5d 4fsa'6s
called nature. 4f1 4f2 4f3 4F4 4f5 4f5 4f7 isregular. potential
ions.
ACtinoids
inseparately Monazite,
are in of tripositive
orbitals state [Xe] configuration.
same
4f14
5d
6s2 configuration
-Lu7i), free as 4F'5d'6s? 6s2
541
4f not
placed given 6s? 4f14
6s 4f13
6s2 the
ELEMENTS
f-BLOCK2)f in are
Atomic 4F³ 6s2
6s 4f 6s2
4f4 6s 4F 6s² 6s2
4f 4f10
6s? 6s²
4fl" 4f12
atoms about
in
(Cess8and Lanthanoides
found Xenotime be 4f regular
(n filled lanthanoide
may the electronic
in Lanthanoids
group not at
are half is
enters lanthanoides
Symbol in f-orbitals
IIrB do and
Lanthanones)
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Tm Yb Lu orbitals electrons
stable
so lighter
for Gadolinite Er
electron elements outer radioactive
series3rd
/ 4f of
retain
of Praseodymium
Neodymium Dysprosium
of an 5d filling
ELEMENTS twoin
INNER
TRANSITION
last or reactive
minerals configuration Promethium Gadolinium
Europium
Samarium TerbiumHolmium Ytterbium
Lutecium
fillingwith and to
Table
elements. present -
lanthanojds
ElementCerium Thulium
Erbium synthetic
the
Earths
64) 4f tendency
the
of Electronic
configuration that the
consist
which Periodic are
hand,
are (Rare important noted= because
f-block Lanthanoides (Z a only
in the
elements
elements heavier general No.
Atomic gadoliniumhaveother
the
LANTHANOIDES be
elements 58 59 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. to is atomsthe is
or in Most
elements 28 for The is This
Ôn Pm
Position
I-block It
Chemistry Thesetable.
The (iv)
(1) (ii) (i) (i) (H
(a) 216
 CBSE

Oxidationstates
In lanthanoides +3 oxidation state is most common.
Ce. Tb, Nd, Dy, Pr also exhibit +4 oxidation state.
Sm, Eu, Tm, and Yb, also exhibit +2 oxidation state.
Ce; is a strong oxidising agent while Eu" is a strong reducing agent.
(i)
MagneticProperties
regularly increases from
A In tripositive lanthanoide ions the number of unpaired electrons
lutecium (7 to 0).
Janthanum to Gadolinium (0to 7) and then continuously decreases upto
tripositive lanthanoide ions
lanthanum and lutecium ions are diamagnetic, while all other
paramagnetic lanthanoide).
are paramagnetic. (Exception - Neodymium is the most
Yb+2 are also diamagnetic ions.
(ii) Ce and
Colour
d
lanthanoid ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs
) The
exhibit colour.
visible region of light and undergo f-f transition and hence
number of unpaired electrons in the 4f orbitals.
(ii) The colour exhibited depends on the having 4f*
ions often with 4f" configuration have similar colour to those ions
(ii) The
configuration.
colourless.
(iv) lanth noide ions having 4f", 4fare
Contraction
e) Lanthano ide decrease in
lenthanoide series with increasing atomic number,there is a progressive
(i) In the size is known
lanthanum to lutecium or from La" to Lu, This contraction in
the size from
as lanthanoide contraction.
very
configuration of these elements is 4f"Ssp°a6s. Due to
(ii) The general electronic very little screening effect on the
outermost
effect of 4f electrons, they exert
poor shielding
6s electrons.
nuclear charge leads to
contraction in
number, the enhanced
Hence with increasing atomic
the size of atoms and ions.
ArPLICATIONSOELANTHANOIDE CONTRACTION
than TÈ". Similar trend is not
The ionic radii of Zr is about 9% more
Atomic size : third transition series. The ionic radius of
from the second to
maintained on pasSing shell), decreases
increasing (because of inclusion of one more electronic
Hf*. instead of contraction
Zr) as a consequence of the lanthanoid
(or is virtually equal to between the members of the second and third transition
the close similarities series.
This explains elements of the first and second
the
series than between regularly decreases.
hydroxide : Basic nature ofhydroxide
Basic nature of difference in size the chemical
lanthanoide : Due to small
properties of difficult.
Similarity in are similar and their seperation is
properties oflanthanoids
217
LLEN as
knowN neri, less
the
are very
shell
The in
elements Configuration
Electronic
Outer
iron. uranium to
2)th 6d"7s.+3
on 5f5 5f6 5f8 5f9 5f10 5f1 5f12 5f13 5f14 due
and 5f1 5f2 5f3 5f4 5f"
is
ceriumn)-(n beyond which
H,+
Ln(OH), of
with
halogens,
LnX3
5f-orbitals
placed 5f146dº7s2
5fl46d'7s? states
(Mainly Sf 5f°6d'7s?
5f'6d'7s? 5F6a'7s?
5F6d°7s? 56d7s'
5f'6d'7s2
5f'64°7s 5F''6d°7s?
5f1°61º7s? 5fl°61º7s²
5f1264°7s²
elements. [Rn]
elements. 6d²7s?
Atomic
'H, Ln,C3
Ln,C,
LnCz, common.
are oxidation
lanthanoides
enters LIjo03 as levels.
w iH
t h, O given
trans-uranic
natural
electron- be Symbol mostof energy
spoe ym
Lanthanoides
Npo:
of last elements
are may Th Pa U
Np Pu Am Cm Bk Cf Es Fm Md No Lr
therange
i n
O, Swith
Ln,S,heated actinides
called actinides is 7s
alloy state and
S

LnN the Neptunium

Plutonium
AmericiumBerkellium. Lowrencium
Nobellium
Mandelevium
collectively Elements Proactenium
Thorium Uranium Curium
Californium
Einstenium
Fermium oxidation6d
an which eleven three of a
is SERIES) configuration 5f,
Electronic
Configuration
of metal first between
there
reactions in man-made
andU +3
Misch are
-
(5f actinides. Atomic
No. states
Oxidation
(b) actinoids
actinides
difference
and
Important OR Pa general 90 91 92 93 94 96 97 98 99 100 101 102 103
Thetable
95
ACTINIDES
Th,
In In
Chemistry (111) The
() (ii) (i) (i)
() (a) 218
Chemistry
(t) Important reactions of Lanthanoides
Ln,Q, w ia
thcids
H, ALLEN
ums in O,
Ln,S,heated with s Ln with halogens Ln3

h e a t e
C
with2773K
with
H,O
LnN
Ln(OH), + H,
LnC,; Ln,C, Ln,C
Misch metal is an alloy of lanthanoides (Mainly cerium) and iron.
ACTINIDES OR (5f - SERIES)
() The elements in which the last electron enters 5f-orbitals of (n 2)th
actinides. shell are known as
(i) The man-made eleven elements Npo: - LIjo3 are placed beyond uranium in the
table and are collectively called trans-uranic elements. periodic
(111) Th, Pa andUfirst three actinides are natural elements.
(a) Electronic Configuration
The general configuration of actinides may be given as (Rn] 5f"6d',7s.
Outer Electronic Configuration
Atomic No. Elements Symbol
Atomic +3 ion
90 Thorium Th 6d'7s? 5f1
91 Proactenium Pa 5f'64'7s 5f2
92 Uranium U 5f°6d'7s? 5f3
93 Neptunium Np 5f6d'7s? 5f4
94 Plutonium Pu 5f°61º7s? 5f5
95 Americium Am 5f'617s 5f6
96 Curium Cm 5f'6d'7s² 5f
97 Berkellium Bk 5°6d°7s 5f8
98 Californium Cf 5f1°6d7s? 5F9
99 Einstenium Es
5f'61°7s? 5f10
100 Fermium Fm 5fl264°7s? 5f1
101 Mandelevium Md
5f'64°7s? 5f12
102 Nobellium No
5fl464°7s? SF13
103 Lowrencium Lr
5f'46d'7s? 5f14
(b) Oxidation states
() In actinoids +3 oXidation staté is the most common.
(ii) In actinides there is a greater range of oxidation states which is due to very lessener;

difference between 51, 6d and 7s energy levels.

218
 CBSE
Highest oxidation states in the actinoids is +7
exhibited by Npo, & Pug4, it is unstable.
(i) Highest stable oxidation state is +6 shown by 2U.
ptherProperties
Physical appearance : Acitinides are silvery white metals.
Density : Allthe actinides e cent thorium and
americium have high densities.
Colour : Actinide 1ons are general1y oloured. The colour of
the number of 5e-electrons. The ions actinide ions depends upon
containing unpaired 5f-elctrons (exactly full filled
no
fsubshell) are colourless, as expected.
lonisation energies : lonisation energies values of early actinides are lower
lanthanoids. than early
Electropositivie character : All the known actinide metals are highly electropositive.
They resemble lanthanoide series in this
respect.
Melting and Boiling properties : They have high melting and boiling points. They do
not followregular gradation of melting or boiling points with increase in atomic number.
Magnetic properties : The actinide elements are paramagnetic due to the presence oT
unpaired electrons.
Radioactive nature :All the actinoids are radiaoactive in nature.
Actinide contraction : The size of atom/cation decrease regularly along the actinoids
series. The steady decrease in ionic radiwith increase in atomic number is referred to as
actinide contraction. This is due to poor shielding of Sf-electrons.
Comparison of Lanthanoides and Actinides
Points of Resemblance:
(i) Both lanthanoids and actinides show a common oxidation state of +3.
(i) Both are electropositive and act as strong reducing agents.
(ii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanoides and actinoids are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus,
Janthanojdes show lanthanoide contraction and actinides show actinide contraction.
POINTS OF DISTINCTION
Lathanides Actinides
1. Besides the most common oxidation state of tó besides the most common oxidation stateof
lanthanides show +2 and +4 oxidation states in+3, actinides show +4, +5 and +6 oxidation
case of certain elements.
states in case of certain elements.
2. Lanthanides have less tendency towards Actinides have a stronger tendency towards
complex formation.
complex formation.
radioactive. All the actinides are radioactive.
Except promethium, they are non Oxides and hydroxides of actinides are more basic
basic.
4. Oxides and hydroxide of lanthanides are less
follows -
Some importantuses of actinides are as
n tne treatment of cancer.
Thorium : Thoriumis used in atomic reactors as TUel rods alld
Salts are used in glass industry
Uranium : Uranium is used as nuclear fuel. ltsmedicines.
and alsoin
(for imparting green colour). textileindustry reactors as wellas in atomic bombs
atomic
lutonium:Plutonium is used asfuel for
219