Chp.

8 THE d AND f BLOCK ELEMENTS

to 7" period. In these periods, the

rb consists
of elements of group 3 -

12 and belonging to 4h period

bloek is progressively filled. The f- block elements belong to 6h & 7h period in which the f- orbital is
progressively filled. However, these elements are placed in a separate block at bottom of table. The d- block
clements are called transition elements while the f- block elements are called inner transition elemerts

There arc 3 main series of iransition elements, the 3d series that siarts with Scandium (Z = 21) and ends with

Zinc (Z - 30), also called as 1s transition series. The second transition series starts with Yttriun1 (Z = 39) and

ends with Cadmium (Z = 48), also called as 4d series due to filling of 4d orbitals. The 3 transition series starts
with Lanthanium (Z = 57) followed by 14 Lanthonoids from Ceriun1 (Z = 58) to Lutelium (Z= 71) due to filling
of 4f orbitals, the next nine elements froin Hafnium (Z = 72) to Mercury (Z 8 0 ) belong to 3 transition series
where Sd orbitels fill. The 4 transition series starts with Actinium (Z 8 9 ) is incomplete. It consists of 14
actinoids starting from Thorium (Z 90) to Lawrencium (Z= 103) ali of which are radioactive where 5f orbitals
is filled.

The Lanthanoids and actinoids are members of Gr.3 but are placed separately as f- block of periodictable
Defn.: Trartsitionelethents are thoseciements which ontain incompletely filled d- orbitaisinitsgroundstate
or in any one of its oxidation states
Note:- Zinc, Cadmium, Mercury of Gr.12 have full d configuration in their ground state as well as in their
common oxidation staie and hence are not regarded as transition metals. (However, being end members of the 3
transition series, their clemistry is studied along with chemistry of transition metals).
TRANSITION ELEMENTS (d block) -

Position inperiodic table:- The d- block occupies the large middle section of periodic table between s - biock
and p-block elements. Hence called transition elenents. In these elements, the d- orbitals of the penutinate
Cinner) shell is progressively filled.

Gencral e config ofd-block eiements: (n-1d-ns

However, several exceptions are seen due to little energy difference hetween (n- 1)d and ns orbitals.
General formuia for Zn, Cd, Hg (n - 1)d ns', where orbitals are fully filled in ground siate and in common
oxidation states.
Hence Zn, Cd, Hg are not regarded as
transition elements.
3
Electronic Configuration of T
(1) Pransition series or 3d series
element Se Ti V Cr Mn Fe CO Ni Cu Zn
At. No. 21 22 23 24 25 26 2 7 28 29 30
Outermost e
config (Ar
3d'4s 3d4s |3d'4s| 3d'4s3d'4s| 3d'4s|| 3d'4s3d'4s| 3d4s| 3d4s*

(2) 2 transition series or 4d series

element Y Zr Nb Mo Te Ru Rh Pd Ag Cd
At. No. 39 40 41 42 43 44 45 46 47 48
Outermost e"
4d'5s 4d's 4d'ss2 4d'ss 4'ss4ss 4d'ss'| 4d'ss |4dss° 4dss' 4d5s
config (Kr)
(3)3 transitionseries or5d series
el ement La Hf Ta W Re Os r Pt Au Hg
At. No. 57 72 73 74 75 76 77 78 79 30

Outermoste sd'6s sd'6s* 5d 6s Sd'6s |sd'os | sd'6s'|sd'6s

6ssd'6s' sa"6ssa"6
config(Xe)
(4) 4 transition series
element Rg Uub
Ac Rf Db Bh Hs Mt Ds
Sg
At. No. 111 112
89 104 105 109 110
106 107 108
Outerinost e" 6d07s2
configbd'7s|6d7s
config 6a'7s 6d'7s|6a'7s 6d 7s|6d'76'7s6d7
General properties of the transition elements (d -

block)
Physical Properties
() Metallic Properties:- All transition elements are metalic in nature and nearly all ofthem have simple h
ccpor bcc lattices. Transition metals exhibit tpical metallic properties such as lustre, high tensileste
d h t natteubility,aadhighfthernal and elecfticalr conductivity. They ahow gradual decres
electróposifive character an oving froni left to right. The tietalic: bonds in transition metals are qute
strongdue to greater effective nuclear charge and large number of välencé e

Ddts strongmetalliepopasraisivonnetalS ar hard posss hgh:dnsities and 6igh enthpieot

aromizaiar (except Zn, Cd, Hg). The enthalpies of atomization exhibit maxima at about the middle of
cach series,indicating the one unpaired e per d- orbital is particularly favourable for strong interatomic
teraction. In general, greater the number of valence e", sironger is the resultant bonding. Metals with high
enthalpies of atomization tend to be noble in their reactions. Transition elements have a large number of
unpairede in their atoms, hence stronger.inter atomic interaction, therefore high AH atomization. Elements
of 2 and 3 transition series have greater enthalpies of atomization than the corresponding elements or
ransition series. This is an important factor in accounting for the cocurrence of metal metai bonds in
compounds of many heavy transition metal.

(2) Melting and Boiling Points:- Melting point and Boiling point of these metals are high due to the
involvement of greater no. of e' from (n-1)d in addition to ns e in interatomic metallic bonding.
In any row, the melting point of these metals rise to maximum at d' except for anamoBous values of Mn &
Tc (Technetium) and fall regularly as atomic number increases.
Variation in atomic and ionic size of transition metals
In particular series, as atomic number increases, the atomic radii first decrease till middle, become almost
a

constant and then increase towards

the end of period. Eg. Atomic size increases from Sc
to Cr, remains
constant till Cu and then increases towards tlhe end. The decrease
in size in the beginning is attributed to the
increase in nuclear charge. However, the increased nuclear charge partly cancelled by the increasing
is
screening effect of e in d orbital of penultimate shell. When the increased nuclear
-

charge and increased

screening effect balance each other, the atomic radii become almost constant.
towards the end of period due to increased e e repulsion. -
Atomic radii increases
Jons having same charge in given series show same trends as atomic adii.
In group, the atomic size increases from 1 transition series to
a
2 transition series but the atomic radii of
3 d transition series is equal to that of 2" series. This is attributed to
Lanthanoid Contraction.
Note:- The steady decrease in atomic and ionic radii from Lanthunum to Lutetium
with increase in atomic
number is called Lanthanoid contraction.
Cause:- As the atomic number increases, the e" is added to the inner 4f orbitai
which has poor shielding
effect. Thus as nuclear charge increases, the force of attraction between nucleus and
outermost e increases
and the shell contracts.
As the atomic radius decreased with
increase in atomic mass, the also density increases. Thus density
increases from Ti to Cu.

3) lonisetion Enthalpies
E increases along each series from left to righi, however with smail variation.
IF af
d- block elements is higher than that ofs biock elements but lower than that of
-

p block elements. -

AIE AIE; < IE;

lar trend in HE, can be accounted for by
considering removal ofl
e from 4s
arie energies of 4s & sd orbitals. So the orbitals which alters
unipoSitive 1ons have n's(n 1)d" confie. Thus th
-
 reorganization energy accompanying ionization with some gain in exchange energy as the number ofe

increases and from transfer of e from s into d.

ris lower due to absence of any change in d configuration and the IE, value of Zn is higher because
it represents an ionization
from 4s levei.
of
Cu becanse e" have to be removed from d' and d" config respectively
e
15 unusually high for Cr & of an e rom Zr 19n to rorn1
1ons. E for Zn is correspondingly low as ionization consists of renoval
stable 3d config.
Ma is high but drops
1S high for (Mn"d' & (Zn*>d® config. In general, IE, are quite high, the lEs of1ons.
a r e . Also high values of Cu, Ni, Zn are high indicating difficulty in forming M

states. bg. 1S more

e I E give guidance concerning the relative stabilities of oxidation
some N
stable from Ni", but Pr" is less stabie than can be explained on basis
P +IE;) & (Es *
of(IE, a)
4) Oxidation States:- Transition elements show a variety of oxidation states
Eg
Sc Ti Co Ni Cu Zn
C Mn Fe

+2 +2 +2 +2 +1
+2 +2 F2

+3
3 +3 to to to +3 +3 +2
4

+4
+ +6 +7 +6 +4 +4

The variable oxidation states of transition elements are due to participation of ns & (n - 1)de in bonding

The lower oxidation states are generally exhibited when ns e participate in bonding & kigher oxidation
states are shown when ns as well as (n- 1)d e" take part in bonding.
The oxidation states of transition elements differ by unity while oxidation states of non - transition

elements generally differ by 2.

In each period, the highest oxidation state increases with increase in atomic number, reaches a maximum in
the middle and then decreases. Eg. Se +3, Mn +7, Zn +2.
Elements which exhibit the maximum number of oxidation states occur either in or near the riiddle. Eg.
Mn +7 which is the sum of e" in ns & (n - i)d.

Elements in the beginning of series exhibit fewer oxidation states because they have smail number of e
which they can lose or contribute to share the elements at the end of series exhibit fewer oxidation states
because they have too many d e and hence have few vacant d - orbitals which they can involve in

bonding.
In 1" transition series, except Scandium, +2 oxidation state is most common. The +2 oxidation state arises
due to loss of 4s e.
Transition elements in lower oxidation states (+2, +3) generally form ionic bonds while in higher oxidation
states, the bonds are essentially covalent.
In contrast to p- block elements where the lower oxidation states are favoured heavier members
by (inert
pair effect), in d- block elements, the higher oxidation state are inore stable for heavier members.
The highest oxidation state shown by transition metal is +s (Ru & Os) while the lowest
oxidation state can
be zero [Ni(CO)4].
3c does not exhibit variable oxidation state.

(5) Trendsin MM Std_electrode potential

Element Se Ti V Cr Mn FeCoNi Cu Zn
MM v - -1.63-1.180.90 1.18-0.44
44-0.28-0.25 0.34-.76
Note:-Sc does not form Sc* ion, hence t' value not given.
The general trend towards less negative &' values across Series is related to general increase in sum of 1" &
2nd ionization enthalpies.
Evalues increase across the period but not regularly due to regular IE.

3
 Tor Mn, Ni & Zn are more-
e ve than from expected trend due to Mn has half filled d-subshell, z

completely filled d-subshell while Ni has highest-ve enthalpy of

Cu has +ve e value, dueto which Cu is unable to liberate H2 from acids.
hydration.
" ONaiZing acids like HNO3 orhot conc. H,So. and reduces them. This is because eiu
1onization is not balanced by its hydration enthalpy.
(6) Trends in MM2 Std. Electrode potential:-
E M°/M* value show varying trends
The MM value for Sc is low because Sc has noble gas config. (4s*3d').
The MM' for Zn is highest as e has to be removed from stable d" config of Zn ".
EMM for Mn is high because Mn(a) has haif filled d-orbital.
M"/M value for Fe is low as Fe" (d) has extra stability.
& M /M value for V is low due to stability ofV" (half filled t2g level)
(7) Trends in stability of higher oxidation states:
Halides Oxidation
of3d No.
I1 V Cr Mn FeCoNiCuZa
CuX

+2 TiX2 VX2CrX MnF2 FeX CoX2 NiX2 CuX2 ZnX2

+3 TiX3 VX3CrX | MnF3 FeX CoF3

+4 TiX VX4 CX4 MnF4
+5 VFs CrFs
+6 CrF
The highest oxidation states are achieved in TiX4, VFs, CrFo
Note:- The +7 state of Mn is not seen in simple halides but Mn0,F is known
Beyond Mn only Fe & Co show +3 oxidation state.
The highest oxidation states of these elements are seen in fluorides because f has the ability to stabilize the
highest oxidation state due to either higher lattice energy (in case CoF,) or higher bond enthalpy for higher
covalent compounds (VFs, CrF6).
V exhibit +5 oxidation state in VFs but the other halides undergo hydrolysis to give oxohalides, VoX; in +5
Oxidation state.
Fluorides are unstable in lower oxidation states eg. VX, & CuX (X = CI, Br, ) where V exhibits +2 state &
Cu +1 state.
All Cu (1) halides are known except copper iodide because Cu oxidises I- to
2Cu+4 Culs) +
Cu () compounds are unstable in aqueous solution and undergo disproportionation
2Cu Cu + Cu.
Cu is more stable than Cu in aqueous solution due to much more ve AyaH of Cu than Cut' in aa.
solution.
Oxides Oxidation
Gr.3 Gr.4 Gr.5 Gr.6 Gr.7 Gr.8 Gr.9 Gr.10 Gr.11
of 3d No. Gr.12
+1
Cu,O
+2 TiO vo Cro MnO FeO CoO NiO CuO
+3 ScO Ti,0, V0, Cr0, MnO Fe0
+4 Ti0 V,O CrO MnO
+S VOs
+6 CrOs
+7 Mn,O,
 Highest oxidation states are exhibited in oxide (+7).
Gr. No.13 exhibited from Sc to Mn. Beyond Gr.7 elements do not
gnest oxXIdation state corresponds to
exhibit higher oxidation states than +3.
Mnfs exhibits an oxidation state of +4 while Mn:0, shows +7 because O-atom is able to form multiple
bonds with Mn. (In Mn,0, Mn is tetrahedrally surrounded by O-atom including Mn-0-Mn bridge.

(8) Chemicalreactivity&s'values- Transition metals vary widely in their

Zn to liberate Ha while
Keacnviy Some elements are sufficiently e +ve and dissolve in minerai acids like
a few are noble (Au, Pt, Pd).
is slow.
Metals ot
i transition series, except Cu, are reactive and are oxidized by dil. acids but reaction
Ti&V arc passive to dil. non - oxidizing acids at room temperature.
across the series. This
ncrease in 3d series indicating a decrease in formation of divalent cations
IS due to increase in the sum of IE, & IE, However e avlue for Mn, Ni, Zn are lower than expected from
for Ni its
general trend due to half filled d- orbital in Mn? (d'). fully filled d- orbital (d") in Zn and
enthalpy of hydration is highest.
MM value indicates thatMn and Co are strongest oxidizing agents in aqueous solution. This is
because Mn Mne config changes from d' tod' which is extra stable. The ions Ti, V Cr
are strong reducing agents and liberate H, from dil. acid 2C + 24 2Cr"+ H. This is because
Cr Crresults in d' to d' where the ag level becomeshalffilled.
Cr is a sironger reducing ageatthanFe because in C - C ¢ config changes from d' d '
while in Fe2 F e e corfig changes from d' ->d' and in HO d' is more stable than d' according
(CFST).
(9) Magnetic Properties
When a substance is placed in magnetic field, 2 types of magnetic behaviour is observed
(a) Diamagnetic:- where the substances are repelled by the applied field (alle paired).
(b) Paramagnetic:- Where the substances are attracted by magnetic ficld (presence of unpaired e).
(c) Substances that are strongly attracted by magnetic field are cailed ferromagnetic (it is an extreme form
ot paramagnetism). Paramagnetism arises fron the presence of unpaired e", each such e" havinga
magnetic moment associated with spin angular momentum & orbital angular inomentum. For e of 3d
series, magnetic moment is determined by 'spin only' formula u = y n(n +2) where 'n' is no. of
unpaired e and p is magnetic moment in BM (Bohr Magneton). Eg. For single unpaired e" u= 1.73
BM, for divalent ion having Z = 25,4= 3 5 BM= 5.92 because d5 (5 unpaired e). Calculation for

divalent ion of Z =27.

(10) Formation of coloured ions:- Compounds of transition elements are coloured in solid and aqueous
solution. The d - orbitals in transition elements do not have the sanme energies in their çom1plexes. Under

the influence of ligands attached, the d- orbitals split into 2 sets of orbitals (g & eg) having slightly
different energies. When the e' from lower energy d orbital is excited to a higher energy d orbital,
energy absorbed lies in the visible region. The complex absorbs a particular colour of radiation and the
remaining wavelengths are emitted. The colour cbserved is complementary to colour absorbed. lons
having unpaired e" are coloured, while ions having empty (Se*) (Ti*) are colouress. Ions having fully
filled d-orbitals (Zn*) áre colourless.
(11) Formation ofcomplex compounds:- Transition elements form complex compounds due to
(a) Small size of metal ions
(b) High ionic charges
(c) Availability of vacant d-orbital of appropriate energy which can accept lone pair of e.
(12) Catalytic properties- Transition elenent have the ability to show catalytic activity due to fornnation of
multiple oxidation states and to form complexes. V205 is cåtalyst in contact process, fiuely divide Fe in
Haber's process, Ni in catalyuc hydrogenation. These catalyst form bonds with reactant molecules and
increase the concentration of reactants on surtace of catalyst as well as form transition states by lowering
Ea. The elements can change their oxidation staie as behave as effective catalyst.

5
 Eg
21+S,O0? e + 2SO
lodide per sulphate
ion
10
Fe catalyses the reaction between iodide and persulphate ion.
Mech:-2Fe"+2 2Fe2 +l; 2F:+ S,0 2Fe" + 2SO
H,
Eormation of interstitial compounds:- Interstitial coripounds are those formed when smat neitht
N are trapped inside the crystal lattice of metals. They are usually non - stoichiomet

ypIcally ionic
nor covalent. Their
physical and chemicai haracteristics are as follows.
(a) They kave high melting point, higher than those of pure metals.
(6) They are hard, eg. Some borides are as hard as diamonds.
(c) They retain metallic conductivity.
(d) They are chemically inert.
(14) Alby Formation:- Alloys are homogeneous solid solutions of 2 or more metals Alloys are med by
, d-
etoms with metallic radii within about 15% of each other because of similar size and other propert
block elements can easily substitute in lattice. Alloys formed ae hard and have high meling poln
best known alloys are ferrous alloys: Cr, V, W, Mo, Mn are used in production of steel and stainiess sl
Alloys oftransition and non - transition elements are brass (Cu -Zn), bronze (Cu -Sn)

Oxides and Oxoanions of Metals

Someiunportant compounds of transition elements
Elements ofl" transition series, forn a variety of oxides of different oxidation states of form MO, M2Os, M;Og,
MO, MO. (These oxides are generaliy formed by heating metals with oxygen at high temperature).
Refer
(1) Se form only one oxide in +3 oxidation state Se,0, (b)
(2) Ti- Tio (b) Ti:02 (b) TiO2 (amp)
(3) V-VO (b), V,0s (b), VO2 (amp), V,Os (amp)
(4) Cr-Cr0 (b), Cr;0, (amp), CrO, (amp), CrO% (a)
(5) Mn-MnO (b), Mn,0, (6) Mn,O, (amp) MnO, (amp) Mn,0; (a)
(6) Fe - FeO (b) Fe20, (amp) Fe,Os (b)

(7) Co-Co0 (b)

(8) Ni -Nio (b)
(9) Cu-Cu20 (b) Cu0 (amp)
(10) Zn-ZnO (amp)

(1) All metal except Sc forms ionic monoxides.

(2) Highest oxidation number of metal coincides with Gr. No.till Mn, beyond that only Fe show +3 state.
(3) Besides oxides, oxocations stabilize V as VO;', V as Vo, THas Tio*
(4) As oxidation No. increases, ionic character decreases Mn,0, is covalent.
(5) Oxides are basic in lower oxidation states and acidic in higher oxidation state.
MnO
Mn,0 Mn,O4 MnO MnO Cro CrOs Cr0
+8/3 t4 +7 +2 +3 +6
2
basic amphoteric acidic basic amp acidic
(6) Mn,0 dissolves in acid to form HMa0, Cr,0, forms H,CrO & HCrO;, V0, form VO& vo,' saits.
V:O is basic V,0, is amp. & V20s is amph,
Potassium dichromate K,Cr:0;:
(1) Pieparation:- K,Cr0; is preparcd from chromite ore (FeCr;04). The ore is fused with sodium or potassium
carbonate in free access of air
4FeCrO +8Na,CO, + 70 8Na,CrO + 8CO + 2Fe0,
The vellow solution of sodium chromate is filtered and acidified with H,SO4 acid to give an orange
dichromate.
solution of sodium
2Na,CrO+2H NaCr:0 +
2Na" +
HO// Na,C0, is crystallized.
6
 dichromate. Na,Cr,O, +
o n of dichromate is treated with potassium chloride to form potassium
2KCI K,Cr,O, + 2NaCl
NaCl being least soluble separates out and removed by filtration.
while Na,Cr,O, is H,O
[K,Cr,O, is fairly soluble in H0
more
On coolin8 K2Cr;0, crystallised out.
soluble.
Note: The hromeseutetrsyate5areegregopyortibjestin egueos goltion depening ontotjution
dation stale of Crin dhromaceland diehtonate fsATe 2CrO + HO
2CrO+ 2H Cr0 + H,O Cr:0+ 20H

Structures: Chromate Cr,O

Tetrahedral
2sharing
tetrahedron 0-C 126 Cr-
one
corner

Uses of KCr,O:
1) Used in leather industry
(2) Oxidant for preparation of azo compounds
(3) Used as primary std. in volumetric analysis.
(4) In acidic solution it oxidizes as Cr,O+ 14H' + 6e 2Cr+7H,0
Thus, K,Cr,0, oxidises iodides to I, sulphides to S, tin (1) to tin (V) and iron (1) saits to iron (11) salts.
Cr2O+ 14H' + 6Fe2 2C +6" + 7H,0
Note:
Cr,O+ 14H' + 3Sn 3 S " +2Cr" +7H,0 NaCrO is used as oxidizing
CrO+ 6 + 14H 31 +2Cr+7H,0 agent iu organic chemicals
Cr0+ 14H 3Hi,S 3S + 2Cr + 71,0

Potassium Permanganate KMnOg:

(1) KMnO4 is prepared by fusion of MnO, with an alkali metal hydroxide and àn oxidizing agent like
in a
atmospheric O, or KN03. This form dark green potassium, manganate KzMnO, which disproportionate
neutral or acidic solution to give permanganate.
2MnO + KOH + O 2K2MnO4 + 2H,00
2MnO MnO2 + 2H,0
3MnO+ 4H
(2) Commercially KMnO, is prepared by fusion of MnO with KOH and air to form potassiunm manganate,
which is then electrolysed to permanganate ion.
2MnO2 + KOH + O2 2K2MnO4 + 2H,0
Electrolysis of alkaline solution of MnO4 MnO+e
at anode green manganate Purple permanganate
ion ion
at cathode 2H,0+2e H+ 20H
(3) In the Lab. Manganese (11) ion salt is oxidized by peroxosulphate to pérnmanganate
2Mn +5S,O + 8H,0 MnO+ 10SO+16H
Properties
(1) KMn0, forms purple crystals.
(2) Not very H,O soluble. 2KMnOI5K K,MnO + MnO + 0
(3) Decomposes when heated at 513 K
O

(4) Manganate ion is tetrahedral Mn as well as permanganate ion Mn

(diamag) o (purple)
(paramangnetic) (Green) o
Mn.
T-bonds fermed by overlap of p-orbitals of O with d-orbitals of
KMnO
(a) In
acts as a very powerful oxidisingagent in acidic, neutral and alkaline medium.
acid solution:-
(i) lodine is liberated fron KI
10T+2MnO + 16H 2Mn + 8H,0 + 5S1
(i) Fe ion (green) is converted to Fe (Yellow)
Fe2+MnO +8H M n + 4H30 + SFe"
(ii) Oxalate ion to oxalic acid is oxidised at 333K
SC0+2MnO i6H 2M+8H,O +10CO
(iv) H,S is oxidised and S is precipitated
Ss2 2MnO+16H 2Mn +5S + 8H,0
(v) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid.
SSO+2MnO+61 -2Mn? + 3H,0 + 5S07
(vi) Nitrite is oxidised to nitráte
SNO+2MnO +6H 2Mn+5NO+ 3H,0
(b) Inneutral medium:- or faintly alkaline medium
(i) lodide is oxidised to iodate
2MnO+ H,0 +T 2MnO + 20H +10,
i) Thiosulphate to sulphate
8MnO,+3S,0+Ha,0 8MnO + 6S0+2OH
(ii) Manganous salt to Mn02, catalysed by ZnSO, or ZnO
2MnO+3Mn+2H,0 SMnO2 + 4H

Note:- permanganate titrations in presence of HCl are unsatisfactory since HCl is oxidised to chlorine.
Uses:
(1) In laboratory used in analytical chemistry
(2) Oxidant in preparative organic chemistry
(3) Bleaches wool, cotton, silk and other fibres.
(4) Decclurises oils due to oxidation.
INNER TRANSITION ELEMENTS (f-block) Lanthanoids & Actinoids
Elements following Laare Lanthanoids, La is considered in study of Lanthanoids as it resembles the lanthancids
closely. Similarly, study of actinoids includes Actinium. Lanthanoids resemble one another more closely than
do any members of transition series, they have only one stable oxidation state. Chemistry of actinoids is
complicated due to wide range of oxidation state and partly because their radioactivity creates problems in their
study.

Lanthanoids At.No. Name e config

Ln Ln Ln Ln
La 57 Lanthanium Sd' Sd 4fsd'6s
Ce 58 Cerium 4f'sd'6s 4f 4f 4f
Pr 59 Praseodymium 4f 6s 4P 4
Nd 60 Neodymium 4f 6s 4 4f
Pm 61 Promethium 4f 6s 4 4f
Sm 62 Samarium 4f6s 4f
Eu 63 Europium 4f6s f 4f
Gd 64 Gadolinium 4fsd'6s 4f'sd 4
Tb 65 Terbium 4f 6s 4f 4f 4f
Dy 66 Dysprosium 4f0 6s 4f0 4f 4r
Ho 67 Hoimium 4r6s 4r 4t0
Er 68 Erbium 4 6s 4? 4
Tm 69 Thuliun 4t 6s 4
Yb 70 Ytterbium 4 6s 4 4f
Lu Lutélium 4rsd' 4f
Yote:- Lanthanoid contraction IS a unique feature in chemistry of Lanthanoid

8
 Consequence of Lanthanoid Contraction:
() Similar size of elements of 2d and 3r transition series. Therefore elements of2nd and 3 transition series
resemble each other closely.
2) Séparation of Lanthanoids All Lanthanoids have quite similar properties hence ditficulk to separate
(however, they are separated by ion exchange method).
) Basic strength of hydroxide decreases from La(OH), to Lu{OH); as size of M ions decreases in series
increases the covalent character of M - OH bond.

However, +2, +4 icns exhibited in

Oxidation
some
States:-
due to
In Lanthanoids, the common oxidation state is +3. are

cases
stability of half filled or fully filled forbital.
g.Ce has 4f', but is a strongoxidant reverting to +3 state. Pr (4#), Nd" (4f), Dy'" (4P) exhibit +4 statein
OXides. Eu (4f) is strong reducing agent changing 43 state, Yb2 (4f") is a reductant, Tb" (4f') is an oxidant,
Sm is a good reducing agent and changes to +3 state.

General Characteristics:-
(1) Lanthanoids are silvery white soft metals and are tarnished rapidly in air.
(2) Hardeness increases with increasing atomic number (Sm is steel hard).
(3) Melting poini range between 1000 to 1200 K (Sm mets at 1623 K).
(4) They have metallic structure and are good conductors of heat and electricity.
(5) Density increases in series except Eu& Yb, Sm & Tm.
(6) M ions are coloured in solids and in aqueous solution due to excitation of e within f- level.
(7) Lanthanoid ions are all paramagnetic except La"", Ce" () & Pb", Lu" (f"). Paramagnetism is
maximum in Nd.
(8) IE <IE (600, 1200 KI mol resp.). IE are fairly low (comparable to alkaline earth metals).
9) E of La, Gd, Lu are low due to empty, half filled & fully filled d-orbitals.
(10) Elements in the begin of series are more reactive than element at the end of series.

Chemical Reaction
Ln + acid
H (g)t L n + X2 LnX3
Ln +H:0 Ln(OH)» + H2 Ln +C275K_LnC2 (Carbides)
Ln + N2 LnN (nitride) Ln + S Lae (Sulphides)
Ln +O Ln,0, (Oxide)
Use
(1) Lanthanoids are used in production of al!oys of steels for plates & pipes.
(2) Mischmetal is an alloy of Lanthanoid metal (95%), iron (5%) and traces of S, C, Ca & Al. It is used in
Mg-based alloy to produce bullet, shell and lighter flint.
(3) Mixed Oxides of lanthanoids are employed as catalyst in petroleum cracking.
(4) Some individual Lanthanoid oxidcs are used as phosphors in Tv scoreens and similar fluorescing surfaces.

Actinoids includes 14 elements from Thorium to Lawrencium (Lr)

At.No. Symbol Name Electronic Configuration

M M* M*
89 Ac Actinium 6d 7s S
Ih Thorium 6d 7s 5f
9 Pa Protodinium Sf6d'7s
Uranium 5f 6d 7s Sf 5f
93 Np Neptunium 5f 6d 7s f
4 Pu Plutonium St 7s
95 Am Americium 5f 7s
96 Cm Curid 5f 6d 7s
97 Bk Berkelium Sf 7s
98 Cf Californiurm Sf 7s
99 Es Einstenium 5f 7s SflO
100 Fin Fermium Sf2 7s
101 Md Mendelevium Sf 7s 5f2
102 No Nobelium Sf" 7s S3
103 Lr LawrenciIum sf 6d 7s
 Note:- Actinoids are
ranging irom
day to 3 minutes
a
radioactive, the
earlier members have along half lives while the latter ones have half lives
study of actinoids 1for
r Lr. aloug only
Lr. The latter ones are formed
The latter ones are formed oniy
in Nanogram quantities. AIl this makes
difficult.
lonic Size:- There isa
gradual
inn is decrease
case in size of atoms or M* ions across the series, referred
to as actinoid
ractlon greater from element to element due to
poor shielding by I

IaOn States- Thre are greater range of oxidation states due to 6d & 7s ievels
Actinoids show
general oxidation state +3.
a Sf, or
atter oxidation
states decrease. Elements in beginning cf series exhibit higher oxidalion states than
u
+4.
However ions in +3, +4 state Actinoids resemble Lanthanoids in having more compounds in ts stare tnan

Ac
Th Pa U hydrolyse.
3
3
NpPu AmCm Bk CfEs Fm Md No Lr
4 3 3 3 3 3
4 4 3 3
to to to 4 4
7 7 6

General Characteristics and

(1) ACtinoid metals are
all
Comparison with Lanthanoids:
obtained due to silvery in appearance, but show
(2) Actinoids
irregularities in metallic radii which is far varietythanof irnstructures. Struciural variabiny 1s

are
highly reactive metals especially when greater Lanthanoids.
(3) Aciinoids when treated with finally divided.
(4) With most non metals boiling H0 gives a mixture of oxide and
and actinoids takes hydride.
(5) HCl acid attacks all place at moderate temperature.
netals but most are
oxide layer. slightly affected by HNO acid due to formation of protective
(6) Actinoids do not react with alkalis.
(7) Magnetic properties of actinoids are
susceptibility with number of
more complex than Lanthanoids, but variation in magnetie
higher values.
unpaired 5fe is roughly similar to that of in Lanthanoids, but Ln have
(8) IE of earky actinoids
lower than that of early
are
into the inner of e".
Lanthanoids. This is because Sf orbitals penetrate less
core Therefore 5f e wil!
be more
Lanthanoids. Therefore 5fe are available for effectively shielded from nuclear charge than 4f of
Note:-Difference bonding being less firmly held.
Lanthanoids
1. Exhibit +3 oxidation state while +2, +4 Actinoids
(a) Exhibit +3 oxidation state, but +4, +5, +6,
oxidation state are seen in few elements. +7
is seen.
2. Show sma!l tendency to form complexes. (6 Form complexes.
3. Except Promethium, they are non (c) Al! radioactive.
radioactive.
4. Ln compounds are les basic. (d)Ac compounds more basic.
Some Appiications of d & f- block
elements:
(1)Iron& Steel are used in construction. iron is
alloyed with C, Mn, Cr, Ni to form different types of
(2) TiO is used in pigment industry. steel.
(3) MnO, for use in dry battery cell. Zn, Ni/Cd is used in dry cell.
(41 Elements of Gr.11 are called "coinage metals" (Cu, As, Au)
coated steel. The UK 'silver coins are a Cu/Ni alloy: contemporary UK 'copper coins are copper
(5) VOs is catalyst in oxidation of SO; to H;SO, acid. +
TiCl Al(CHjs)) are basis of
manufacture polyethylene. Fe is used as catalyst in Haber's process for manufactureZiegler Catalyst used to
of NH, from
Ni catalyst is used in hydrogenatiun of fat. & N, H2.
6) In Wacker process, the oxidation of ethyne to ethanol is
catalysed by PdCh. Ni complexes are usefui in
polymerisation of alkynes and other organic compounds like benzene.
(7) Photography relies on light sensitive properties of AgBr.

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