8 THE dAND £-BLOCK ELEMENTS

THE TRANSITION ELEMENTS (d-BLOCK)

The elements of groups 3-12 in the long form of the periodic table are called transition elements.
h y lie in between s and p-block elements in the long form of the periodic table. These elements are
Tl called d-block elem•~ s7:: ~ey ~ve incomplete 3d, 4d, Sd and 6d subshells. Their general
. f'igurat·ion i. J1,- ) 1-10 ns,
aslectronic con 1~ where n is the outer mosts he11.
e In the periodic table, there are four transition series of the elements given as follows :
1. First transition series or 3d series consisting of 1Oelements of the 4th period corresponding
to filling of 3d orbitals.
2. Second transition series or 4d series consfsts of 1Oelements of the 5th period corresponding
to filling of 4d orbitals.
3. Third transition series or Sd series consists of 10 elements of the 6th period equivalent to
filling of Sd orbitals.
4. Fourth transition series or 6d series, filling of 6d sub-level, starting with actinium (Atomic
number= 89) followed by elements with atomic number 104 onwards.
In the transition elements, the valence electrons are present in the outer most shell as well as
dtf.orbitls of penultimate shell.
s, a transition element may be defined as the element whose a m in round state or ion in one _
o e most common oxidation states has · lete d-subshell, i.e. 1-9 electronsin tlfea-subshe .
Exceptions ar zinc, cadmium an mercury hich have completely filled d-subshell ·n their atomic
state or common oxidation state.
General Properties of 'Jransition Elements
J..Jlmt111ctharacter : J\.ll transition elements are metals, except mercury. ~~~:-:,,;~:=:.:::::.:..i
find du til . They hav cp, fee or bee str tallic bonding both exist in the ato s
of transition metals. e resence o un i e a-orbitals favours covalent hon ing. hese metals are
good conductors of heat and electricity.
· ~and Ionic Radii : Generally the atomic radii of d-block elements decrease with increase in
_the atomic number from left to right in the period. This is due to the fact that an in£rease in.the nuclear
charge tends to attract the electron cloud 1nwards. The atomic radii for the elements from Cr to Cu
are ~owever very closeto one another. This is due to the fa7Efm:ai simultaneous addition of etecmm
to 3dlevel ex · everse effect by screenmg the outer 4s-electrons from the mwards putt of the
As a result of these two opposmg e ects, t e atomic radii do not differ muc on ovmg rom
Cr to Cu. At the end of the period, there is a slight increase in the atomic raclii...lt is due to increased
electron-electron repulsions on addition of electron in. the same .orbitals·with--respect to incr~ed
a~Ctive force due to nuclear charge. This causes the expan~iOj ·-f' z t e electron cloud andthe'atomic
rad ius increases. '(
th· The atomic radii increase down the group but the atomic ?- ii o(the elements of the second and
1rd transition metals are a)most same due to lanthanide contraction. -- -
 nd {-Block Elements 291
3
,neda •onic rad"u OfM + an d M· + ions.
2 . 'II ow the sctme trends as their atomic radii. The iomc ' ra d"11
10
rhe n e oxi'dat~o.
• th
aseIwith inc:ease:~ . n state. Tpus, the Ionic size of_M3+ IOJ!.S are smaller than those 0 f
decre fhe ionic radu of the transition metals are smaller than those of the representative elements
:;~joJlS,
f,f same period. . . ..
ill the r,1eltinU and Boll mg Pomts : The transition metals have very high melting and boiling points.
3· lting points of transition metals increase to maximum and then decrease as the atomic number
fbe mees. Manganese and technetium have abnormally low melting points.
·ocreas
1 Strong me~11·1c bon,ds between the at~ms of these elements are responsible · for .high
· me1ting ·
dboiling points. Thats why they have high enthalpies of atomization (i.e., heat required to break
an etallattice to get free atoms). Th~ strength of the metallic bond depends upon the number of
th~:red d-electrons (half filled d-orbitals). Greater is the number of unpaired electrons (half - filled
u~iitals), stronger is the metallic bonding. So that these elements have high melting and boiling points.
0h melting points decrease after middle (Cr) because of increasing pairing of electrons. Tungsten (W)
re the highest me1ting· pomt . among. the a-block elements.
5
ha . ionization Enthalpies or Energies : Th~first ionization enthalpies of transition elements lie in
4
between the values of s and p-block elements. Q.ue to two opposing force i.e....,spieJding effect and
in;;;ln . nuclear charge, there is _slow increase in the ionization potentials on moving in period.
T erefore, the values fort e first four 3d-block elements (Sc, Ti, Vand Cr) differ only slightly from one
another. Similarly, the values for Fe, Co, Ni and Cu are fairly close to one another. The value for Zn, Cd,
10
Hg is considerably higher due to extra stability of 3d level which _is completely filled.
In general, second and third ionization enthalpies increase along a period but there are few
exceptions. For example, there is a fall in second ionization enthalpy from Cr to Mn and from Cu to Zn
as they acquire stable configuration after the removal of first electron.
Ir
900

800 Pd
'i
.-,..
· Hf Ta Fe /\
0 ,,,,,..•...•~.o I \
E ,,,•' I ..........' \'"•·· Cu
6... Mn/ Ru I Ni ,
__ .!!L 100
/ .,,,,,.,,.------:Rh ·'
___Nb_,.,,,,. ,. ... -/
Zr / Tc
~.
Ti••·•• ••••••••••- ICr__ .

--
V
--
Transi tion Elements
Fig, B,1. Ionization' enthalpi!:l? gf transiti! i '.'1etal s.•Tne ftgu!i, iljustrates that the first
Ionization enthalpies of Sp metals are higher than tho!ie of t d and 4d metals

The third ionization enthalpy of Mn is high because third electron has to be removed from the
sta ble half filled 3d-orbital. The third ionization enthalpies for Cu, Ni and Zn are very high.
The first ionization enthalpies of Sd-elernents are higher as compared to those of 3d and
4d- . ·•-1. u .. . r
elements du~ to the weak shielding of nucleusjby 4f-e~e.ctron~·m Sl~,elements. So that mfluence of
great .., l.
er effective nuclear charge increases.
 292 . VATSAL ISC Handbook of Ch .
• • . . ernist
5. Ox1dat1on States: The transition elements exhibit variable ox1datwo states. The uni tv()~.
is due to the fact that the energy levels of 3d, 4d and Sd-orbitals are ver clo _e to those qufe ProPer.1
·. · · · bl b ~ s.ss •.
6s-orb 1tals respectively an t ere ore in addit10n tons e ectron~ vana e num er of (n - l)d-~ ~
ar e also lost to exhibit various oxidation states. . electrrir.
Following important points are observed regarding the variable oxidation states :
(i) The most common oxidation state of first transition series metals is + 2 except
(+ 3) due to loss of two ns2 electrons. Scandi~
(ii) Mostly ionic bonds are formed in+ 2 a~d + 3 oxidation states. Covalent bonds are t
compounds of higher oxidation states because of sharing of d-electrons. orrned,
(iii) The _elements showing maximum oxidation states are present in or near the middle of f

series. For examples, Mn shows the oxidation states from + 2 ~o + 7 • Its highest OXida
state is+ 7. The highest oxidation state i.e.,+ 8 is sho~n by os~mm (Os) or ruthenium(~
(iv) The various oxidation states of transition elements 1s due to incompletely filled d-orbi~
and there is a difference of unity in their successive oxidation states.
(v) In group 6 elements, the higher oxidation states are more stable. For example, Mo(VJ) arii
W(VI) are.more-stable than .Cr(VJ). . ._ _
- (vi) The .natur~ of solvent also affects the stabili~ 9f an_e\em~nt in a ~a~ _ic':!,!~r2q~ d_a_tion S\iti.
For example, Cu+ is unstable in water, but Cu + ,is stable in water. Again F~ + is unstable m
aerated water. · -- · -·
. (vii) The relative stabilities of a particular element in different oxidation states can also be known
from their standard electrode potential values. For example :
cu+ (aq) + le- Cu(s), E~ = 0.52V
C

Cu 2 + (aq) + 2e- Cu(s), E0 = 0.34V

2
Thus, Cu+ is reduced more easily. Hence, it is less stable than Cu +.
(viii) The compounds of metals with highly electronegative elements like F and O exhibit hi~er
oxidation states.
(ix) In going down a subgroup, the stability of the higher oxidation states increases whilethatd
lower oxidation states decreases.
(x) Transition metals also form compounds in low oxidation states such as + 1, 0 or negative
/All. . . For example, Ni(CO) 4, Fe(CO_)~ etc., in which nickel and iron are in zero oxidation s~te.
r~ loured Ions : Most of the trans1t10n metal compounds either in solid form or in solution fof111
are coloured unlike the compounds of sand p-block elements.
The colour of the compounds of the transition metals is due to the presence of i ~
_Ji-subsbell. ·Wh_en the anions or ligands approach near the transition metal ions, thei~tg!Y?nl
into different energy levels, known as er s · litting. In case of transition metal ions, the ele~bj
can · easily promote rom lower energy level to higher e evel within the same d-subshe
a so .. ar 1cu ar waveleng! int e region of yisi:19 light. ______,,

. =7
d.;---c.L
I cl"'L\,,
Absorption
.
>,
" of
e>
w
Q)
C:

--urn-- light of
certain
wavelength

"~ ii~,J~ ½ d-d transition

The d and f-Block Elements
. 293
Th ey appear coloured due t . . · .
a substance is always l o em1ss1on of the remamder as coloured light. The observed colour of
colour of the transitio::mi ;mentary colour of the colour which is absorbed by th~ substance. The
in turn depends on the nat::e :;:pl~x is dependent on the energy difference of the two d-levels. This
k blue due to the b . t e igand and the type of the complex formed. For example, Cu2+ salts
1oo
. h da bl a sorpt1on
· of the red wavel ength · An hYd rous cobalt ll compounds - ' 1absorb red
hg tan pp~a_r ue. Co~plementary colour can be identified by using she\ colour wheel.
The transition metal ions having com letel filled d-orbitals ( 3 d10
1o or Sd ) such as Zn
4d.--:- Cdg H +, Ag+ ions
·
. .. , are colourless as e'
excitati lectron or electrons is not pos~ble within d-orbital~.
The R }----*---~
- colour l may also arise by c arge rans .er. or e ·
e, m
Mn04, an e ectron is momentarily transferred from oxygen to the
metal.and oxygen changes from 0 2- too- and Mn7+ to Mn 6+. ·•
~ 7-~rmation of Complexes : The transition elements have the
teiVri~ to form ~he coordination compound~ due to : , /
i) small size of metal ions;~ (}± v \l
i) high nuclear charge;
'\ i) availabil~ty of vacant d-orbitals to a~ pt'"'1bne pairs of electrons from the ligands. -
lloy Format10n : Alloys are homogeneous solid solutions of two or more metals in which one
metal are randomly distributed among the atoms of the other metal. They are formed by metals whose
atomic radii differ, within l'.'5% of each other. Due to similar in size,'the atom_s of one metal can displace
the atoms of other metal in its crystal lattice. Alloys are hard and have high melting point. They are
r ~ i ~ to corrosion. For example, ferrous alloy. ·
~ - Magnetic Properties ~-Most of the compounds of transition elements are paraf!lagneti<j_n ~ature
which are attracted by the magnetic field. It is due to the presence.of unpaired electrons in the (n -=i)
~ ._ ... . I• _,.,. . • . .~ \ \ n
..... < d ~ ~ •

d-orbitals:'Tfiefuagnetic character is expressed in terms of magnetic moment. Magnetic moment is

c~ culat;cft~~ 'spin only formula', i.e., µ = .Jn(n + 2) B.M.
where n is number of unpaired electrons and B.M. is Bohr magnetons.
10. Catalytic Properties : The catalytic activity of tr~nsition elements and their compounds is due ·
to ~ owing easons: . , · -
· ,The presence ofvac:3nt (n -:}l~ ~ l o.! ~~!.!~.:;oms ca_n ac~ept e!~ctro~s from ti:ie
reactant atoms and form intermediate compounds w1uc~ prov1dei ow energy path for the
.~ --- -- ....~.. . . ... ...-,.,,_
,....

reaction. • b h of ·d ti0 n
C · tal compounds provide low energy path ~or~ Y c ange . QXi a.
(ii) ertamFme le· . Vandanium chang"' es Tts-~idatio·n state from +S (VzOs) to +4 (Vz04)
states. or examp · . ·
during oxidation of S02 to S03. · · ,_
-- . VzOs + SOz - ~ Vz04 + S03
2:Vz04 .:. +- _.o z - - .2Vz0s

POTASSIUM PERMANGANATE (KMn04)

Preparation . . .
. d xtracted from the mineral pyrolusite (MnOz). lt mvolves two steps .
It 1s prepare ore
294 VATSAL ISC Handbook of Che .
l'lllstry
1. Conversion of Mn0 2 Into Potassl~m Manganate (K2Mn04)
The finely powdered pyrolusite ore is fused with KOH or KzC03 in presence of air or an11J OJCld'
.
1
agent like KN0 3. Si~
• 2KzMn04 + 2Hz0
~ MnOz + . 4KOH + Oz
-· - .· . i Potassium
manganate

2 : ··K2Mn04 ---+
I -- ·· --
MnO 2KOH ·+- KNO 'KN<¾·~~+- H20 .
------~3
-· . .
' ... . .. - - • - -

' " - -
2. Oxidation of Potassium Manganate to Potassium Permanga_~~!!!.- - - •··--·~ --· - -- · - •.
. .
The oxidqtion process can )be carried out either by chemical process or by electrolytic method
.

{i) Chemical Oxidati_on : The fused mass after extracting wit~ water is filtered and conve~
into potassium permanganate by bubbling CO 2, Clz or ozomsed oxygen through the soluti
I\ .,. 0 , . oa
. '"--- · · ··- -------
,
"3°K 2
MnO 4
+ 2CO 2
2KMn04 + Mn 2 "" + 2K2C0 3

U 1•) 2K MnO + Clz 2KMn0 4 + 2KC1

. ~ 2 4
2K 2Mn0 4 + . HzO + o3 2KMn0 4 + 2KOH + 02
(ii) Electr:olytic Oxidation : It is the preferred method. The alkaline potassium manganate solutioi
is electrolysed between iron electrodes. '
I 2-
K2Mn04 2K+ + Mn0 4
H20 H+ + OH-
Atanode: Mn0 42-,
(Green)
Mn04
(Purple)
+ e -
At cathode: H+ + e H
2H Hz
At the end of the reaction, the solution is filtered and evaporated under controlled conditions to get
the crystals of potassium permanganate.
3. Laboratory Preparation
2Mn 2+ + S20 82- + 8H 20
Per~xodisulphate ion

Properties
1. Potassium permanganate is dark violet crystalline solid having metallic lusture. Its meltin!
point is 523 K. It is fairly soluble in water to form purple coloured solution. The d ep ur le colourol
KMnO is not due to d-d transition but due to charge transfer (from o to Mn re ucin t e oxi auon
state o + . · 1
..., 2. Action of cone. H2S04: With cold and cone. H2S0 4, it gives Mn 2 o7 which on warming decomP 05e
to MnOz.
 d and f-Block Elements 295
1he ·th warm and cone. H2so 4' it gives
Wl "~ · ' oxygen.
V 4KMn0 + 6H SO Warm / 1' J/' 'lj.)l I~
4 2 4 2KzSO 4 + 4M SO 2
2
• oxidising Property : It is a powerful 'd' .
Ox1 1smg age t • n 4 + 6H 0 + 50
.3
(I) In neutral solution: n m neutral, alkaline or acidic solution.
2KMnO 4 + HzO 2KOH + .2MnO 2 + 30

or, . Mn.O4 ·+ 2HzO + 3e- -~ MnO 2 + 40H-

Jn neutral medmm, the equivalent mass of KMnO . . .
It oxidises hydrogen sulphide sulphur. . ,s J ne-!bml of •t,s molecuJaJ mass I.e., 52.67 .
10
.V +-·3H2s . · 2 + 2H 20 + "-3S -
2KO!{ ..t ~MnO
or, . no-
2M .4 + 3H.2S 2MnO 2 + 3S + 2H 2O + 20H-

(
ii) In alkaline solution : In strongly alka.1·me so Iution, r 1 ions are further reduced to MnO 2.
• manganate
ZKMn04 + ZKOH ---> YK~no 4 . + H20 + O
[K2MnO4 + HzO MnO 2 +- 2KdH + -ofx 2 · .
l .
Therefore, the complete reaction is .
2MnO 2 + 2KOH + 3[0] L. - · ." L.
1 ) :..:.. l' 2KMnO 4 + HzO J ...> -J.~'),(},

or, /,,.rr ''MnO + 2H 2O + 3e- MnO .J+ 40H-

o J 4 2 -..,
In alkaline medium, the equivalent weight of KMnO 4 is same as that of neutral medium i.e., 52.67.
It oxidises po_ta~ m.iodide to potassium iodate.
~ MnO + KI + H2O 2MnO 2 + 2KOH + KI0 3
4
2MnO + H O· + C 2MnO2 + 20H- + l0 3
or, 4 2
(iii) In acidic medium: In presence of dilute sulphuric acid, it behaves as strong oxidising agent
. 2KMnO + 3H SO 4 K2SO 4 + 2MnS0 4 + 3H 20 + SO
4 2
2
MnO + SH++ Se- ~ - Mn + + 4H 20
or, 4
The equivalent mass of KMn O in acidic medium is one-fifth of its molecular mass, i.e., 31.6.
4
Some oxidising properties of KMn0 4 in acidic medium ar~ as follows:
(a) It oxidl 5 ~1ic acid to carbon dioxide. ' 2
Mn0 + 3H so + SH C 0 4 --> K2S0 4 + 2MnS0 4 + 8H 0 + 10C0
2
~
2 4 2 2
4 2 2
sc o!- + zMn04 + 16H+ --> 2Mn + + 8H 20 + 10C0
or, 2
(b) ltoxid~
·ses otassium iodide to iodine. 6K SO -t 2MnSO 4 + 8H20 + 51 2
2 4
MnO4 + SHzSO4 + lOKI 2Mn 2+ + 8HzO + S~z
.. +
or, . c + 2MnO 4 . + 16H
10
(c) It oxidises ferrous sulphate to ferric sulphate. K SO + 2MnSO 4 + 5Fe 2(SO 4)J + 8H 20
2 4 3
, h<MnO4 + SH2SO4 + 10FeS04 Mn 2+ + 4H 2O + 5Fe +
\7-·- - SH+
5Fe 2+ + MnO4 +
or,
 296 VATSAL ISC Handbook of Che .
lll1stt-..
"Y~~
Uses a'1 ~If\ l\O .
. Y. · ·
timation of ferrous salts: oxal
1. It 1s often used in volumetric analysis for the es d d t· f ates, iod·
. d f' t with stan ar so Iu 10n o oxau
and hydrogen peroxide. It is standardise irs . d .h c acid
1\
. . t' s are carne out wit KMno 1. ~,
does not exist in pure state. Volumetric t1tra 10 n 4 n Pre~.
of dilute H2SO 4 but not with HCI and HNO3 as the oxygen produced.:~~ KMn04 and
used to oxidise HCI to chlorine but in case of HNO3, it behaves as 0~1 izmg agent I
\ A ,L . f t ration in the orgaru.c:...c.amno11nrl ,.
~ Is used ~or the ~E:_tection of presence o unsa u . . . - --:- thef°I\
. , of Baeyer s reagent (alkaline KMnO 4).
•---&- It is used as disinfectantand germicide and for purifying wa~ .
~ tis also used for bleaching ofwool, cotton, silk, etc. · '·,~

Structure of Permanganate Ion

. · Mangane.se in MnO 4 undergoesG::}ybridisation and he~ce four oxygen atoms are arra~
tetrahedrally around manganese. . · ·
' 0

~ o I
Fig, 8.2. Structure of P,ermanganate ion

POTASSIUM DICHROMATE (K2Cr201)

Extraction from Chromite Ore

It is prepared from chromite~~ O-Cr2O 3) or ferrochrome or chrome iron. It involve!
following steps : . . . .
1. Conversion of Chromit~ Ore to Sodium Chro~ate : The powdered chromite ore is fused wiW
sodium hydroxide or sodium carbonate in presence of air. ·
. Jecr20 4 + 16NaOH + 7~ 2 8Na 2Cro 4 + 2Fe# ~ H20
. , (Air) Sodium chromate
4FeCr2O4_ + 8Na 2CO 3. _+ 70 2 8Na 2cro 4 + 2Fe o
2 3
_+ 8C0z
· 2. Conversion of Sodium Chromate into Sodium Dichromate : The solution containing sodium
chromate is filtered7ind
tr ated with cone. sulphuric acid. . '~ .
. . . .. 2NazCr04 + HzS04 NazCrzO7 + NazSO4 . + HzO .
On cooling, sodium sulphate crystallizes out as Na 2so 4 · 1 0HzO and the remaining solution contain
'i

sodium dichromate. ·
 ·-·-- ------

.
,~e d
and f-Block Elements
f S d' ·
297
3. conversion o_ o ium D~chromate into Potassium Dlchromate : Hot concentrated solution of
.
d1UJ1l v--...
dichromate 1s t)i'.eat~ w1th calculated amount f KCI
0 .
, so . Na2Cr207 + 2KCI K2Cr207 + 2NaCI
on cooling, K2Cr 20 7 as orange crystals crystallizes out as it is less soluble than sodium chlorlde.
rties · ·
proPe .·
1. It is an orange coloured -crystals having m.p. 669 Kand is moderately soluble in cold water but
. . hlY soluble in hot water. The orange colour of potassium dichromate is not due to d-d transition but
hig to charge transfer i.e.,-m;n_o:::m
due -;:e;n;ta~ry
:.;.tr~a~n:st~er~o~f.:ch~a~r~
ge~f~ro~m
~ O~-a~to~m
~ to!_!m
~ eta~IaJ.UJL1Uwa~1,..w.~ ging
O0
02- ion~ entan Y ion an re ucmg the oxidation state of Cr from +6 to_+5. ... ·
2. Action of Heat :

. r;
, 3 Action of Alkalies :
K2Cr20 7 + 2KOH 2K 2Cr0 4
(Orange) Pot chromate
(Yellow)
But on it c anges back to potassium dichromate.
2-K 2Cr0 4 + H2S0 4 K2Cr20 7 +
. · (Yellow) (Orange)

Thus, the dichromate ion (Cr 20~l and chromate ion (CrOtl exist in equilibrium at pH =4. These
are interconverti~b b. changing the pH of the solution
, 2- pH=4 2

--
1 Cr20 7 + H20 2Cr04- + 2H+
7 Orange red 1
,Yellow

Thus, in alkaline solution, chromate ions are present while in acidic solution, dichromate ions ,are
pres~et./ ----- ,______,,,,- ,-~"--
Nute': The oxidation state of chromium in chromate.and dichromate is +6.
4. ~xidising Properties ; It is a powerful .oxidising agent in presence of dilute sulphuric acid.(acidic
medium).
K2Cr20 7 + . 4H2S0 4 · K2S0 4 + Cr2(S0 4 h + 4H 20 + 30

or, Cr20~- · + 14H+ + 6e- 2Cr 3+. · + 7H 20

Its equivalent mass in acidic medium is 294/6 = 49.
Some of the oxidising properties of potassium di chromate in acidic medium are as follows :
(i) It liberates 12 from Kl.
, ~ 2Cr2o7 + 7H 2S0 4 + 6KI 4K 2S0 4 + Cri(S0 4 h + 7H 20 + 31 2
or, Cr2o~- + 61 + 14H+ ·2Cr 3+ · + 31 2 . + 7H 20
(ii) It oxidises ferrous salts to ferric salts.
~ so 4 + K2Cr20 7 + 7H 2S0 4 3Fe 2(S0 4 h + K2S0 4 + Cr2(S0 4 h + 7H 20
or, 6Fe 2+ + Cr2o~- + 14H+ 6Fe 3+ + 2Cr 3+ + 7H 0
2

h,
298 VATSAL ISC Handbook of Chell!·
, 1st~ ~
(iii) It o~i~ s hydrogen sulphide to sulphur.
'7 3HzS + KzCrzO7 + 4HzSO4 K2SO4 + Cr.z(S04h + 3S + 7H20
or, 3HzS . + CrzO~- + SH+ 2Cr3+ + 3S + 7HzO

Uses
Itisusedin: .
2
1. the volumetric analysis as primary standard for the estimation °.f Fe +and 1- in redox reacti
0
- ~a2CrzO7 _i~ no!_ m;ed.in .volumetric.analysis as it is deliquescent .in nature. ~
~ eing and calico printing. - - •· · ·- · ·
~the pr~paration of cl!!"ome alum-(K 2so 4 . Cr2(SO 4h ·24HzO) and 0th er compounds like Kc~
' \ 2 I
CrCl 3, CrO 3 etc. ,..
4. photography and hardening gelatin film and in breath analyzer.

Structure of Dichrontate Ion I

In Cr 20~- ion, the two Cr-O bonds which share an oxygen atom at the common vertex of bll
tetrahedra units are longer than the other six equivalent Cr-0 bonds.
2-
0 O 0
" ~ ~C/
I \
~Cr r--0
o
0 0
Fig. 8.3. Structure bf Cr2o~- ion in Which two tetrahedra sharing one oxygen ato mat one corner
0

STUDY OF THE INNER TRANSITION (f-BLOCK) ELEME.NTS

The elements in which the last electron enters the /-orbital of the atoms are called/-block elemen~
They are also called as inner transition elements. They consist of two series called Ianthanoids ana
actinoids: Their general electronic configuration is (n - 2)/1-14 (n - 1) JJ-1 ns2.
· 1. Lanthanoids : The elements in which the last electron enters one of the 4f-orbitals are call~
lantha~oids or lanthanides or lanthanons. There are fourteen elements in this series from cerium
Ce (Z = 58) to lutetium, Lu (Z = 71). They are also called as rare earth elements.
2. Actinoids : The elements in which the last electron enters into one of the Sf-orbitals are call~
actinides or actinons or actinoids. They include 14 elements starting from thorium, Th (Z == gO) w
lawrencium, Lr (Z = 103). ·

General Characteristics of The L~thanoids

1. Electronic Configuration : The lanthanoids have electronic configuration with 6s2 filled a;:
gradual filling of 4/-orbitals but due to similar energies of 4/ and. Sd-orbitals; the order of fi!Jing
4f-orbitals are quite irregular. For example, La has electronic configuration [Xe] 4.fsd1•6~ but nic
is successive filling of electrons in the 4/ subs hell onwards in succeeding 14 elements. The eiectfO
 r~e dand f-Block Elements
. 299
J2
ration of cerium (Z = 58) is 4 5do 2 7
c<>f and that of gadolinium (z _ l . Gs /h~ electronic conHguration of europium (Z = 63) is 4 /
,a 65 ·c configuration of ytterbi:n64(Z is 4/ 5d 652 due to extra stability of half-filled orbitals. The
I ctron1 == 70) is 4/4 6 2 H dl 6 2 -
ee · Atomic and Ionic Radii : In th . s and that oflutetium (Z = 71) is 4/ 5 s ·
2,. adii from one element to e 1anthano1d
h
seri h ·
es, t ere ls regular decrease in the atomic as we
11
is 1
·onic.r• radii is very small ; e anot
l er with increasing atomic number, but the decrease in atomic .
ind 1on1c d periods. . . ., on Y 10 pm an d 18 pm respectively with respect to elements of the
groups an
'fhUS, the regular or steady decrease in th . .
, d thanoid contract· e atomic and tonic radii with increasing atomic number
is calle Ian ion.
Table 8.2 Atomic and Ionic Rad"n (p m) of- Lanth anum an d Lan th an01'ds

--- .
E).eIIlent La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

A,toJJllC 187 183 182 181 181 180 199 180 178 177 176 175 174 173 172

-
Radii (Ln)
Jonie 106 103 101 99 91 90 89 88 97 86
98 96 95 94 92
Radii (Ln3)
-Gause of Lanthano1d Contraction ·
,~ ~v~ on the e;iod from left to right, the nuclear charge increases with atomic number
wiJ!!1.ddiriao of djfferentia mg electron in the inner 4f..orbit:a: . . 4 s h
o~from the tJ!1..dear chgrge imp~rfec~ or poorly due to diffused shapes of the /-orbitals. This causes
.re?11lar - the size of lanthanoids. The sum of the su~ essive contractions gives the total
lanth noid contraction in atomic radius from Ce to Lu is about 15 pm. However, in case of tripositive
ions, the trend is very regular.
Consequences of Lanthanoid Contraction
to lanthanoid contraction, the elements of second and third transition s · s resemble
"~ mor.e than the e~ements of first an second transition series. '
l,Y.fhe chemic;l properties of lanthanoids are quite similar due to very small difference in
. . --::; _,. ,
~atomic radii s~ that it is very difficult to separate the elemen~ in pure state.
~ Due-to lanthanoid contraction, tn,er~j~_decrea~e in siz~~nd th~!r..£.wil~nt character betwe5n
lcrn,thanide ion and OH- ions increases and basic str~ngth of the hydroxides decreases from
La3+ to Lu 3+. Thus, La OH is most basic ~ ~Hh is .thtleast basic. ._
3. Oxidation .States : Lant anQjgs_fxhibit_,.a,.common oxidation state of +3. In addition to this,
some of the elements also exhibit +2 and +4 oxidation states. For example, Ce and Tb attain / and
t7 configuration respectively when they show +4 oxidation state. Eu and Yb exhibit4
J7 configuration
respectively when they show +4 oxidation state. Eu and Yb exhibit J7 and /1 configuration in +2
3 4
oxidation state. Exceptional examples are Sm 2 (4f), Tm +(4/1 ), Pr4+ (4/1), oy4+ ( /.), Nd4+ (4/2)
2
.
300 VATSAL ISC Handbook of Ch .
. .
Table 8.3 Electronic cotiflgurutloh of lanthanum and lanthanolds
4
(General symbol - Ln) with their oxidation states (General E.C. "" [Xe]4r l - l 5d0-I 6s2)
-
Name of the At. Oxidation E.C. Outside IXeJ
Symbol Electronic
Element No. - Cort
(Ln)
(Z)
Configuration States LnZ+ Ln3+ I"-
Lanthanum La 57 [Xe] sd16s2 +3 sd1 4f -~
Cerium Ce 58 [Xe] 4f st 6s2 +3,+4 4f 4/1
4f
Praseodymium Pr 59 [Xe] 4/ st 6s2 +3,+4 4/3 4/2 4/1
Neodymium Nd 60 [Xe] 4/ st 6s2 + 2,+ 3 ,+4 4t 4/ 4f
Promethium• Pm 61 [Xe] 4f st 6s
2 +3 4/5 4/
Samarium Sm 2 +2,+ 3 4/' 4/
62 [Xe] 4/ st 6s
Europium Eu 63 [Xe] 4/7 st 6s2 · +2,+ 3 4/ 4/'

Gadolinium Gd 64 [Xe] 4/7 sd1 6s2 +3 4t7sd1 4/7

Terbium
Dysprosium
Holmium
Tb
Dy
Ho
65
66
67
[Xe] 4/9 sf 6s2
[Xe] 4/1° st 6s2
[Xe] 4/11
st 6s2 +3
+3,+4
+3,+4
4f. -
4/
·4J10
11
4/
4/
4[1Q .
~,
4/
....
. ·• - 11-
Erbium·-"~·· ·· Er 68 [Xe] 4/1 2 "St ·6s2. -. +3 .. -- .. - .. -4J12 · 4/
-~ --- -
riiu11iim-- .. ,·,.·; tm" ... -:,..- -69. ...
.[Xe]' 4/1 3 Sa° 6;2··-
....
+2,+ 3 i,j13 4/2 · ·
·- ..... .. -- . - -- ·---· -
Ytterbium Yb 70 [: 1r 14 st 6s2 + 2,+3 4/14 4/13

Lutetium Lu 71 [Xe] 4f 5 sd16s2 +3 4/1 sd1

3 4/4
4;·Magnetic Behaviour : Lanthanoids show paramagnetic character in their cationic1orm exo
La3+ (f) and Lu 3+ (/14). In the case oflanthanoids, their magnetic moment is calculated byconJder
spin as well as orbital contribution. i.e., µ = ,J4s(s + 1) + L(L + 1) B.M. . .__
wheres is the spin quantum ~umber and L is orbital qi'.ia°i-itum number. .
_5.Colour : The lanth_anoids are. silvery white but many of the trivaient ions of the Ianthanoids,
c~loured in the solid as well as in sblution. The colour of lanthanoid ions is due to absorat?.on of vi~
region of the spectrum resultin![-ftransitio~s ~ecause they ha~: p~r~y filled orbitals.
It is interesting to npte that lanthanoid-toos with ukrlectrons have iibout the same colouraslhl
with.11! Q) {electrons, e.g., Pr3+ (
3
and Tm + ( 4f)
2
4?
) are green in colour. i
&. Alloy Formation : Lanthanoids find special use for the production of alloy steels for plate\
3 1

ipes. They are known as mischmetals. Awell known alloy is mischmetal which consists oflantb 3l
P · based
· (about 5%_) an d traces of S, C, Ca, Al etc. It is used in magnesium
metal (about 95%), iron
to produce bullets, shells etc. . . . goxyge ni
fl
Cerium forms about 30-50% of the aIIoys o ant ano1ds which are used for scavengt.n
h
sulphur from other metals. Cerium-magnesium alloys are used in flash light powders.
 iock Elements
da~d f-!3 al React·1v1·ty .• Th e f'1rst few rnernb 301
61111c . . ers of this .
1C~ ·ncreasing atomic number. The ch . series are quite reactive but this property
. on I ern1ca1 re ti . d
Jt,re.iseS ac 0 ns of lanthanoids (Ln) _are summarise
1l·

'S! ,s
~ti .s;
E~ ri. LnN

H2 .., Acids -eu' ,J..J>

_,~;/i(''
L (OH)
n 3 + H2
/ ii
:c LnX,

Ln3C, ln3C3 and LnC

2
bTty of Compounds · The fl ·d • ,
s. Solu I I th . • , uon es, oxides, hydroxides, carbonates, phosphates, ·chromates
doxalates of lan anmds are largely insoluble in water but the sulphate·s unlike the sulphates of
' u 2elements are so1ubl e m
· water. .
, p 'd Of 1 th 'd · ·
The hydroxi es an anm s are rnmc and basic in character. They are stronger bases than
M[OHh but wea~~r th_an Ca(OH)z. · . . .
g, Com.pl ex Formation : Lanthanoid ions in spite of having high charge (+3) have small charge-to size
ratio(charge density) due to their large size. Therefore, they have·poor tendency to form complexes.
They form complexes mainly with chelating agents like EDTA, ethylene diamine etc.

vfHE ACTtNOIDS
The a_ctinoids are also /-block elements and are also called as inner transition elements. They have
oeen placed at the bottom of the periodic table. Their chemistry is very complicated as they show wide
range of oxidation states and are radioactive in nature.

General Characteristics of the Actinoids .

1. Electronic Configuration: All actinoids have common 7s2 configuration with variable occupancy of
l/and 6d sub~hells. The 14 electrons are being added into Sf orbitals of the·rest of the elements ~xcept
iliorium (Z == 90) and the filling continues after thorium till 5/ is complete i.e., at Z = 103 (lawrencium).
/7
There is also irregularity in those cases where the stabiJity of / 0, and 4 configuration are J1
involved. For
1 example Am has the configuratjon of [Rn]
[Rnj st7 6d 7s2_
s/
6d 0 7s 2 and Cm has the configuration of
.
Berkelium (Bk, z= 97) shows-the exceptional configuration of [Rn]
2
6d0 7s 2. s/ ·
-Oxidation States : Actinoids show various oxidation states due to very small energy gap among
lf,Gd and 7s subshell. The common oxidation state of actinoids is +3. Besides this, they can also exhibit
ij'>idatton state. The oxidation state first increases up to the middle of the series and then decreases.
 302
VATSAL ISC Handbook of Che .
Table 8.4 Electronic configuration of actinium and actinoids with their OXidation st lllist~~
ates 1
Name of the Symbol At.No. Electronic
E.c. Outside
Element (M) (Z) Oxidation States Core l~I
Configuration
M3+
[Rn] 6d17s2
Actinium Ac 89 +3
[Rn] 6d2 7s2
Thorium Th 90 (+3), +4 Sd1
[Rn] 4f 6d17s2
Protactinium Pa 91 Sf I
Uranium
+3,+4; +5 st2 5{1 1
u .92 [Rn] sf 6d1 7s2 +3, +4, +5, +6 5/3
Neptunium
[Rn] sf 6d17s2 Sf I
Np 93 +3, +4, +S, +6, +7 st
Plutonium Pu 94 [Rn] s/' 6JJ 1s2 +3, +4, +S, +6, +7 5/5
Sf \
[Rn] st7 6JJ 7s2
Americium Am 95 +3, (+4), +S, +6
Sf I
Sf'
[Rn] s/9 6JJ 7s2 sr I
Curium Cm 96 +3, (+4) st7 Sf
Berkelium Bk 97 [Rn] st9 JJ 1s2 +3,+4 sf st7
Californium Cf 98 [Rn] s/1° 6JJ 7s2 +3 st9 sf
Einsteinium [Rn] s/1 26/J 7s2
'
Es s/10
Fermium Fm
99
100 [Rn] s/1 26JJ 1s2
+3
+3 5/11
sf
sfO
I
Mendelevium [Rn] 5/13 6d07s2 st12 sf1
Md 101 +3
Nobelium - No 102 [Rn] s/1 46Jl 7s2 +3 5/13 sf
Lawrencium Lr 103 [Rn] s/1 46d17s2 sf14
+3 s/l
Note : Oxidation states given in brackets are less stable .

. Ionic Radii and Actinoid Contraction : Due to actinoid contraction like lanthanoid contraction,~
. atomic and ionic radii of these metals decrease regularly across the series. The actinoid contraction,
due to;1oor shielding effect of 5/ electrons. · . .
v- Colour : These metals are silvery white but their cations are generally coloured. The catiom
, having no 5/ ele_~ons or half-fil~ed _electrons are colou:less._ This arise~ iti~n.
v-5. Radloact1v1ty : All the actin01d elements are rad1oact1ve. Thex have half lives rangmg from[el
days to few m ~ . .
6~Chemical Behaviour : They are highly reactive metals.They react with boiling water, hydrochlo~
acid but.not attacked by alkalies.

· , C#>arison of Lanthanoids and Actinoids

'(//' Similarities : As both lanthanoids and actinoids involve filling of /-orbitals, they show similariti~
in many respects as follows :
1. Both show mainly an oxidation state of +3.
\ '

2. Both are electropositive and very reaxttive.

3. Both exhibit magnetic and spectral properties. 'd
4. Actinoids exhibit actinoid contraction like lanthanoid contraction shown by lanthanoi s.
 and (-Block Elements 303
fhe d .
Differences : e show differences in some 0 f t helr characteristics as follows :
Table 8.5 Differences in characterisllcs of lcnthanolds and actlnolds

.Lanthanoids Actinoids
Besides . 2 and +4 Besides +3 oxidation state, they show higher
. . +3 oxidation state' they sh ow+
oxidation states only in few cases. oxidation states of +4, +5, +6, +7 also.
Most of their ions are colourless. Most of their ions are coloured.
2.
They have less tendency towards They have greater tendency towards complex
3. formation. complex formation.

Lanthanoid compounds are less basic. Actinoid compounds are more basic.
4. 2
Do not form oxocations. Form oxocations e.g., uo~+, Pu0 2+and uo+.
s.
They are radioactive.
Except promethium, they are non-radioactive.
6.
· Their magnetic properties can be explained Their magnetic properties cannot be explained
7. easily, as they are more complex.
easily.

u~e, !JJ 1'ctinoids · •

V,Uses of Thorium : It is used in atomic reactors, treatment of cancer and their salts are used in
maki,wilCandescentgasmantles. · • .. . . - - - • ·•
if.Uses of Uranium : It is used as nuclear fuel: Its Salts are used in glass, textile and ceramic industry
ana in_fldicines. ,__.,-.---= - s . _ : . -
~~--
ij(.'Uses of Plutonium : It is used ~s a fuel for atomic.react~rs as well as for making atomic bombs.

1
A. Fill in the Blanks (1 mark) _
1. The general electronic configuration for transition elements is . . . . . . . . . and there are ........ .
transition series in the periodic table.
2. The atomic radii of the elements of second and ......... transition series are almost same due

to .......... .
3. The highest oxidation state i.e., + 8 is shown by ......... and .. .. .. . .. . .
4. The bonds formed by transition metals in lower oxidation states are .... ..... while those formed in
higher oxidation states are ......... .
5. Most of the transition metal ions are ........ . and ..... : ... in nature.
6.lfhe colour of transition metals ion is due to ......... electron in d-subshell and : ........ transition.
7. Due to presence of ... ...... electrons in ......... orbitals, the transition metals have magnetic

properties.
8. The basicity ofoxides and hydroxides oflanthanoids ......... with increase in atomic ......... due to

9. The common oxidation state of lanthanoids and actinoids is ......... .

10. There are ...... ;.. elements in lanthanoids and are commonly known as ......... metals.
304 VATSAL ISC Handb
, . . . . d. . .. Ook of Ch
11. In the actinoids series there 1s regular •••· · · · · · m atomic an mmc rad11 but this ch elllist,
ange . ),1
d ue to . . . . .. .. . . isv
12. Lanthanoids show paramagnetic character in their cationic form except ... _
. .... . and
13. Lanthanoids show paramagnetic character due to both •••• ••••. and . . . . . . . . . . •· ,.
14. All the actinoids except ......... and ......... have high densities. ·
15. Except ...... ... , all the lanthanoids are non-radioactive.
16. La, Gd. and ..... . ... exhibit only ...... _. .. oxidation state in lanthanoid series.
17. Lanthanoid ions with ......... electrons have about the same colour as those With
18. . ........ and ......... ions oflanthanoids are colourless. ... ······ eleq11
19. The basicity of hydroxides of lanthanoids ......... with ••••••••• in atomic number d
contraction. · · · · ue to Ian~
20. The deep purple colour of KMn0 4 is due to . . . . . . . . . . ·
In ......... and ......... medium,· the equivalent mass _o f KMn04 remains same.
21. · I
1
22. Potassium perm_a nganate ......... potassium iodide to . . . . . . . . . . . .
23. Alkaline potassium permangan·a te ·is use~ in the name of . . . . . . . . . reagent for the detecti
presence of ......... in the organic compounds. - ~1
24. Potassium dichromate on heating with cone. H2 S04 and NaCl, gives .. ....... coloured va
chromyl chloride which is used for the detectipn of .... : .... ions. POUn
25. The transition metals show ......... character because of the presen_ce of unpaired electro ,
Cu+ 1s
· . . . . . . . . . b ecause its · con ti1gurat1on
· e Iectromc · · IAr I 3d 10 .
1s . m
ns ,i
Answers
1. (n - -l)dt -10 ns t-2 , f;our 2. third, lanthanoid contraction
3 . . osmium, n.ith_enium 4. ionic, covalent
5. paramagnetic, coloured 6. unpaired, d - d
7. unpaired, d 8. decreases, number, lanthanoid contraction
9. +3 10. fourteen, rare earth
11. decrease, lanthanoid contraction 12. La 3 +, Lu 3 +
13. electron spin, orbital motion 14. thorium, a_m ercium
15. promethium 16. Lu, +3
17. nf, (14 - n)f 18. La 3 +, Lu 3 +
19. decreases, increase 20. charge transfer
21. neu~ral, alkaline 22. oxidises, iodine
23. Baeyer, unsaturation 24. orange red, chloride
25. paramagnetic, diamagnetic _