UNIT

4 THE d AND F-BLOCK ELEMENTS

OVERVIEW OF THE CHAPTER
ELEMENTS
THE TRANSITION ELEMENTS (d-BLOCK) GENERAL PROPERTIES OF TRANSITION
elements of groups 3-12 in the long forn of the Periodic 1. Metallic Character : AIl transition elements are metals,
The ductile. They have
Tableare
called transition elements. They lie in between s except mercur All are hard malleable and
p-block elements in the longform of the Periodic Table. and metallic bonding
and hcp. tcc or bcc structures. Covalent
elements are also called d-block elements, since they metals. The presence
both exist in the atoms of transition
These These metals
incomplete 3d, 4d, Sd and 6d subshells. Their general of unfilled d-orbitals favours covalent bonding
have nsl-2 where n
electronic configuration is (n - 1) d'- are good conductors of heat and electricity.
outermostshell. 2. Atomic and onic Radii : Generally the atomic
radii of
isthe
Periodic Table, there are four transition series of the atomic
Inthe d-block elements decrease with increase in the
follows :
elementsgiven as number from left to right in the period. This is due to the fact
1 First transition series or 3d series consisting of attract the
that an increase in the nuclear charge tends to
10 elements of the 4th period corresponding to electron cloud inwards. The atomic radii for the elements
filling of 3d orbitals. another. This
trom Cr to Cu are however very close to one
2 Second transition series or 4d series consists of electron to
10 elements of the 5th period corresponding to is due to the fact that simultaneous addition of
outer
filling of 4d orbitals. 3d-level exercise the reverse effect by screening the
4s-electrons fromn the inwards pu!l! of the nucleus. As a result
2 Third transition series or 5d series consists of
10 elements of the 6th period equivalent to filling of these two opposing effects, the atomic radii do not differ
of 5d orbitals. much on moving from Cr to Cu. At the end of the period, there
4 Fourth transition series or 6d series, filling of 6d iS a slight increase in the atomic radii. it is due to increased
sub-level, starting with actinium (Atomic number electron-electron repulsions on addition of electron in the
= 89) followed by elements with atomic number same orbitals with respect to increased attractive force due
104 onwards.
In the transition elements, the valence electrons are present
to nuclear charge. This causes the expansion of the
cloud and the atomic radius increases.
oVERVIEW
electron

in the outermost shell as well as d-orbitals of penultimate The atomic radii increase down the group but the atomic
transition
shell. radii of the elements of the second and third
metals are almost same due to lanthanide contraction.
Definition
The ionic radii of M and M ions follow the same trends
OF
Thus, a transition element may be defined as the element
whose atom in ground state or ion in one of the most common as their atomic radii. The ionic radii decrease
with increase THE
Thus, the ionic size of M ions are
oxidation states has incomplete d-subshell, i.e., 1-9 electrons in the oxidation state.
inthe d-subshell. Exceptions are zinc, cadmium and mercury smaller than those GHAPTER
ofM"ions. The ionic radii of the transition
smaller than those of the representative elements
which have completely filled d-subshell in their atomic state metals are
or common oxidation state. in the same period.

87
 CIoss NI! Yb
DO%
VATSAL ISC CHEMIS TR) HANDBO Table 4.1ioh.

Ho

Tb

ELEMENTS
3

OF
TABLE
PERIODIC

OVERVIEWoFTHE
CHAPTER
Configuration

why they have high enthalpies of atomization ie,

3. Melting and Boiling Points : The transition metals have required to break the metal lattice to get free
very high melting and boiling points. The melting points of strength of the metallic bond depends upon the atoms),
numbe3
transition metals increase to maximum and then decrease (half-filled d-orbitals).
unpaired d-electrons
as theatomic number increases. Manganese and technetium number of unpaired electrons(half-filled orbitals),
Greater
is
have abnormally low melting points. is the metallic bonding. So that
these
elements have tg ,strore
Strong metallic bonds between the atoms of these elements and boiling polnts. 1ne melting points der
nointe Thate Melting
dre responsible for high melting and boiline
 89
THE d AND BLOCKELEMENTS
ar middle (Cr) hecause of
increasing pairing of enthalpies of Sd elements are higher as
ungsten(W) has the
.block elements highest melting point electronsthe The tirst innization
among 4d-eernents due to the weak
Compared to those of 3d and
shielding of nucleus hy felectrons in 5d-elements So that

) Conceptual Questinn influence nf greater offective nuclear charge increases.

5. Oxidation States The transition elements exhibit
Why do transition elements have hrgh variable oxidation states The untque property is due to
points?
melting and boiling
the fact that the energy levels of 3d, 4d and 5d-orbitals are
very close to those of 4s, 5s and 6s orbitals respectively and
QAnswer therefore in addition to ns lectrons, variable number of
E Due to presence of unpaired (n- 1)d-electrons are also lost to exhibit various oxidation
electron in their atoms
transition elements in general have stronger interatomic states
interaction and hence stronger bending between atoms
This bonding is very strong. As a result in Following important puints are observed regarding the
boiling points and hence enthalpies of high melting and variable oxidation states
atomisation.
. lonization Enthalpies or Energies : The first () The most common oxidation state offirst transition
enthalpies of transition elements lie in between the
ionization series metals /s 2 except scandium (+ 3) due to
values loss of two ns electrons.
and p-block elements. Due to two opposing force i.e., (1) Mostly ionic bonds are formed in + 2 and + 3
shielding effect and increasing nuclear charge, there is slow oxidation states. Covalent bonds are formed in
ncrease in the ionization
potentials on moving in period. compounds of higher oxidation states because of
Therefore, the values for the first four 3d-block elements sharing of d-electrons
(Sc,Ti, and Cr) differ only slightly from one another. (ii) The elements showing maximum oxidation states
Cmilarly, the values for Fe, Co, Ni and Cu are fairly close to are present in or near the middle of the series. For
one another: The value for Zn, Cd, Hg is considerably higher examples, Mn shows the oxidation states from + 2
dueto extraastability of 3d" level which is completely to+7. Its highest oxidation state is +7. Th highest
(Fig.4.1)
filled. oxidation state i.e., + &is shown by osmium (0s) or
ruthenium (Ru).
900
(iv) The various oxidation states of transition elements
Au
is due to incompletely filled d-orbitals and there is
a difference of unity in their successive oxidation
(kJ
E4
nol) states.
800
W Pd (v) In group 6 elements, the higher oxidation states
Hf Re are more stable. For example, Mo[VI) and (VI)
CO are more stable than Cr[V). Thus, Cr(VI) in the
Mn,
.Cu form of dichromate in acidic medium is a strong
Ru Ni
700 Rh oxidizing agent whereas Mo0 and WOz are not.
Ag
Ti (vi) The nature of solvent also affects the stability of
an element in a particular oxidation state. For
example, Cu" is unstable in water, but Cu* is stable
Transition Elements
in water. Again Fe is unstable in aerated water.
The stability of Cu* (aq) rather than Cu" (aq) is
Fig. 4.1. lonization enthalpies of transition metals The igure
ustrates that the first ionization enthalpies of 5d metals are higher due to the much more negative Ahvd H of Cu(aq)
than those of 3d and 4d metals than Cu which move than compensates for the
second ionization enthalpy of Cu.
In general, second and third ionization enthalpies increase
along a period but there are few exceptions. For example, (vii) The relative stabilities of a particular element in
different oxidation states can also be known trom
there is a fall in second ionization enthalpy from Cr to Mn
and from Cu to Zn as they acquire stable configuration after
their standard electrode potential values.
For example:
the removal of first electron.
Cu (aq) + le Cu(s), E° =0.52V
The third ionization enthalpy of Mn is high because third
electron has to be removed from the stable half-filled Cu (aq) + 2e ’ Cu(s), E° = 0.34V
3d-orbital. The third ionization enthalpies for Cu, Ni and Zn Thus, Cu is reduced more easily. Hence, it is less
are very high. stable than Cut
 THE d AND (-BLOCK ELEMENTS 91
3K,Mn04 +2C0,
In neutral medium, the equivalent mass of KMnO4
2KMn0, + Mn0, +2K,CO, isone-third of its molecular mass i.e., 52.67.
2K,MnO4 +Cl, ’ 2KMn0, + It oxidises hydrogen sulphide to sulphur.
2KCI
2K,MnO4 + H,0+ 0, ’ 2KMnO0, + 2KMnO, +3H,S ’ 2KOH + 2MnO, + 2H,0 + 3S
Potassium
2KOH + O2
manganate thus formed (I0) In highly alkaline solution : In strongly alkaline
disproportionation in the
neutral or acidic undergoes solution, manganate ions are further reduced to
permanganate if allowed to stand for medium to give MnO2
some time.
3Mn0 4H* 2KMnO, + 2KOH 2K,MnO, + H,0 +
Manganate ion 2MnO4 + MnO, +2H,0
Permanganate ion [K,MnO, + H,0 Mnz + 2KOH + O]x 2
li) Electrolytic Oxidation : It is the preferred method.
The Therefore, the complete reaction is
alkaline potassium
electrolysed between iron manganate
electrodes.
solution is 2KMnO4 + H,0 2MnO, + 2KOH + 3(0]
K,MnO4 2K* In alkaline medium, the equivalent weight of
Mn0 +
KMnO4 is same as that of neutral medium i.e.,
H,0 H* + OH 52.67.
At anode: Mno Mn0, + e It oxidises potassium iodide to potassium iodate.
(Green) 2KMnO4 + KI + H,0 ’ 2Mn0, + 2KOH + KI0,
(Purple)
Atcathode: Ht + e
H (iii) In acidic mediumn: In the presence of dilute
2H ’ H, sulphuric acid, it behaves as strong oxidizing
agent.
At the end of the reaction, the solution is filtered and 2KMn04 +3H,SO
evaporated under controlled ’ K,SO4 + 2MnSO4 +3Hz0+SU
potassium permanganate.
conditions to get the crystals of
The equivalent mass of KMnO in acidic medium is
3, Laboratory Preparation one-fifth of its molecular mass, i.e., 31.6.
2Mn* +
24
S,0 +8H,0’ 2Mn0, +10S0 Some oxidising properties of KMnO, in acidic medium
Peroxodi are as follows:
sulphate ion
(a) It oxidises oxalicacid to carbon dioxide.
+ 16H" V2KMn0, +3H,S0, +5H,C,04- ’ K,SO 4
+2MnSO +8H,0+ 10CO2
PROPERTIES b) It oxidises potassium iodide to iodine.
2KMnO, +8H,S0, + 10K! 6K,S04 +2MnSO4
1. Potassium permanganate is dark violet crystalline solid
having metallic lusture. Its melting point is 523 K. It is fairly + 8H,0 +5l,
soluble in water to form purple coloured solution. The deep Vc) Itoxidises ferrous sulphate to ferric sulphate.
purple colour of KMn04 is not due to d-d transition but due 2KMn04 +8H,S04 + 10FeSO4 K,S0, +2MnSO4
to charge transfer (from 0 to Mn) reducing the oxidation + SFe,(S0,), +8H,0
state of Mn from +7 to +6 momentarily.
3. Action of conc. HzSO4 : With cold and conc. H,SO4. it USES
gives Mn0, which on warming decomposes to MnO,. 1. It is often used in volumetric analysis for the
2KMnO4 + 2H,S04 Mn,0, + 2KHSO, + H,0 estimation of ferrous salts, oxalates, iodides
and hydrogen peroxide. It is standardised first
2Mn,0, 4Mn0, 302 with standard solution of oxalic acid as it does
With warm and conc. H,S04, it gives oxygen. not exist in pure state. Volumetric titrations are
carried out with KMnO4 in the presence of dilute
4KMn0, +6H,S04 2K,SO4+ 4MnSO,+ 6H,0 +50, HzS0, but not with HCl and HNO3 as the oxygen
3. Oxidising Property : It is a powerful oxidizing agent in produced from KMnO4 and HCI is used to oxidise
HCIto chlorine but in case of HNO3, it behaves as
neutral, alkaline or acidic solution. oxidizing agent.
(i) In neutral or faintly alkaline solution :
2. It is used for the detection of presence of
2KMnO4 +H,0 2KOH +2MnO, +30 unsaturation in the organic compound in the form
of Baeyer's reagent (alkaline KMnO4).
 mong the

90
VATSAL ISC CHEMISTRY HANDBOOK C
Class NII
highly
distributed
cachotherDue
tosimilarin size, the atoms of one
metal. Th me

with
(vii) The compounds of metals
example,ferrous
alloy.
higher Oxidation states. -
for
corrosion nah,
paradeicin t

lower ox0dation states decreases. Toccontor

eenentsare lhela.It
magnetic
Is dueto
orbitals
The
whicihare at
of
Cdpableo-bonding For hy
the the(n- 1)
clectronsin termsof magnetiC
moment.
magieuc char
compound has ligands
character in addition to the the oxidation eypressed
example, in Ni(CO), and Fe(C0)s
state ofnickel andiron is zero, compounds is
in

calculatedfromspinoniy
numberof
torrmula';
unpaired
and electrons
MagnetiC Thon
6. Coloured lons : Most of the transition metal
either in solid form orin solution form, are
where
10.
n
coloured unlike magnetons.
is
CatalyticProperties:The catalytic activity of tran
compoundsis due to BM.HL
electronsfoldfrom
o-owrbinitgaltshe. Tereaay
the compounds of s and p-block elements. their
elementsand presence of vacant (n - 1)
Energy (i) The atomscanaccept
Absorption
these Sa
of form intermediate
light of
certain
wavelength
atoms and
providelowenergy
path for

Certain metal compounds

change
the
provide low croemactpoiuonn.ds
d-d transition

metalsis due
(ii) reaction by
forthe Vandanium
example :
of
changes its oxidationenesrtaates
duurinogxidaoxitiondat,
The colour of the compounds of the transition (V,0;) to +4 (V,04)
to the presence of incomplete d-subshell. When the anions from +5
their
or ligands approach near the transition metal ions,crystal So,toS03
d-orbitals split into different energy levels, known
field splitting. In case of transition metal ions, the
as
electrons V,04 + S0,
can be easily promoted from lower energy level to
higher
2V,0,
+ 02 2V,05
energy level within the same d-subshell by absorbing
POTASSIUM PERMANGANATE (KMNOJ
nght of a particular wavelength in the region of visible ligntd
They appear coloured due to emission of the remaindeT
coloured light. The observed colour of asubstance is
complenmentary colour of the colour which is absorbed Dy PREPARATION
the substance. The coBour of the transition metal complex is extracted from the
dependent on the energy difference of the twvo d-levels. Ins It is prepared or
involvestwo steps:
pyolu mineral
in turn depends on the nature of the ligand and the type ol (MnO,). It
salts look blue due to 1. Conversion of Mn0, into Potassium Manganate
the complex formed. For example, Cu
the absorption of the red wavelength. Anhydrous cobalt () (K,Mn04)
compounds absorb red light and appear blue. powdered pyrolusite ore is fused with
The transition metal ions taving completely filled d-orbitals
The finely p
epresence of air or any oxidizing agent likeKOHKN
(3410 4gl0 or 5d") such as Zn*, Hg,Ag ions are K,CO inthe
colourless as the excitation of electron or electrons is not + 0, Heat, 2K,Mn04+ 2H,0
possible within d-orbitals. 2Mn0, + 4KOH Potassium
The colour may also arise by charge transter. For example, in manganate

MnO4, an electron is momentarily transferred from oxygen

to the metal and oxygen changes from 0 to 0 and Mn
7
Mn0, +2KOH +KNO, KzMnO4 + KNO, +Ha
to Mn+ Manganate to Potossium
Complexes : The transition elements have 2. Oxidation of Potossium
7. Formation of Permangongte
bVERVEY
the tendency to form the coordination compounds due to :
The oxidation process can be carried out either
by chei
() small size of metal ions;
(i) _high nuclear charge; process or by electrolytic method.
() Chemical Oxidation : The fused mass
(i) availability of vacant d-orbitals to accept lone pairs and conve
of electrons from the ligands. extracting with water is filtered
8. Alloy Formation : Alloys are homogeneous solid solutions into potassium permanganate by bubbling C
of two or more metals in which one metal are randomly Cl, or ozonised oxygen through the solution.
 ELEMENTS 93
THE d AND -BLOCK
4photogaphy and hardening gelatin Blm and in hreath electron
analyzer 1. Lanthanoids : The clements in which the last
or
enters one of the 4forbitals are called lanthanoids
STRUCTURE OF DICHROMATE IiON Ianthanies or lanthanons. There are fourteen elements in
InCr,03 ion, the two Cr 0 bonds which
share an oxygen this series from cerium, Ce (7 58)to lutetium, Lu (271).
atom at the common vertex of two tetrahedra units are They are also called as rare earth elements.
than the
longer other six equivalent Cr0bonds (Fig. 4.3). Z. Actinoids: The elements in which the last electron enters
into one of the 5forbitals are called actinides or actinons or
actinojds, They incdude 14 elements starting from thorium,
179

126 Th(Z 90) to lawrencium, I.r (Z - 103).

163pm c Cr
GENERAL CHARACTERISTICS OF THE LANTHANOIDS
1. Electronic Configuration: The lanthanoids have electronic
Fig. 4.3. Structuro of Cr,0, Ion in which two configuration with 6s filled and gradual filling of 4f-orbitals
totrahedra shanng ono Oxygen atom at one corner but due to similar energies of 4f and 5d-orbitals, the order
of filling of the 4f-orbitals are quite irregular. For example,
Conceptual Question La has electronic configuration [Xel 4fsd 6s but there
g What is the oxidising action of potassium dichromate? is successive filling of electrons in the 4f subshell onwards
in succeeding 14 elements. The electronic configuration of
cerium (Z - 58) is 4f sd 6s'. The electronic configuration
Answer
of europium (Z = 63) is 4f sd 6s and that of gadolinium
ta Potassium dichromate acts as a strong oxidising agents
in acidic medium because it exists as dichromate ion in (Z = 64) is 4f Sd' 6s due to extra stability of half-filled
acidic medium. It has a negative charge of 2. Therefore, it orbitals. The electronic configuration of ytterbium(Z= 70)
readily taked up electrons and oxidises other compounds.
In alkaline medium, it exists as potassium chromate instead is 4fl 6sand that of lutetium (Z = 71)is 4f Sd' 6s.
of potassium dichromate. 2. Atomic and lonic Radii : In the lanthanoid series, there
is regular decrease in the atomic as well as ionic radii from
STUDY 0F THE INNER TRANSITION (f-BLOCK) one element to another with increasing atomic number, but
ELEMENTS the decreaseinatomic and ionic radii is very small i.e., only
The elements in which the last electron enters the -orbital 10 pm and 18 pm respectively with respect to elements of
ofthe atoms are called fblock elements. They are also called the groups and periods.
as inner transition elements. They consist of two series Thus, the regular or steady decrease in the atomic and ionic
called lanthanoids and actinoids. Their general electronic radii with increasing atomic number is called lanthanoid
configuration is (n -2)f(n-1) -ns contraction.
Table 4.2 Atomic and lonic Radii (pm) of Lanthanum and Lanthanoids
Element La Ce Pr Nd Pm Sm Eu Lu
Gd Tb Dy Ho Er Tm Yb
Atomic
187 183 182 181 181 180 199 180 173 172
Radii (Ln) 178 177 176 175 174

Ionic
106 103 101 99 98 96 95 86
Radii (Ln) 94 92 91 90 89 88 97

Cause of Lanthanoid Contraction contraction in atomic radius from Ce to Lu is about 15 pm.

As we move along the period from left to right, the nuclear However, in case of tripositive ions, the trend is very regular.
charge increases with atomic number with addition of Consequences of Lanthanoid Contraction
differentiating electron in the inner 4f-orbital. However,
the 4f electrons shield each other from the nuclear charge I . Due to lanthanoid contraction, the elements of
second and third transition series resemble each
imperfectly or poorly due to diffused shapes of the forbitals. other much more than the elements of first and
This causes regular contraction in the size oflanthanoids. The
second transition series.
sum of the successive contractions gives the total lanthanoid
 stale ot Ct hom
HANDRWA Class NM
VATSAL ISC HEMISTRY 2AthnofMeat:
IK.Cr0,

4.
purihing watet Alkalies
Rs also us tor hlehing Actino
3. rot chromate
STRUCTURE OF PERMANGANATE IUN
arahbindisaonamd ehangesback
(\ellow)
to
Manganese
hene four
in n,
ogen atotsundergoes
tetrabatalh avnf hd1ngil
K,Cr,0,poassiun
Buton
Imangaese (Fig 4.2) (Orange)
dhomate ion (Cr;0;)
cquililbriunn at and
the
Thus eNzst n changing
g the pH
pH =
of the: 4.chtroma
i0;)
Thes
intenvmertibleby
2Cro
Yellow
solution
Orangensi
solution, chromate ions
alkaline
diichromateions are present.
are preSent w
Thus,in
soution.
Fig. 2 Stutu ENHANCE
adic YOURKNOWLEDGE
Demanganate chromiumin chromate and
of
POTASSIUM DICHROMATE (K,Cr,07
EXTRACTION FROM CHROMITE ORE
The
oxidationstate
dichromate
4. Oxidising Properties : It is apowerful oxidizing ag
the preseneofdilutesulphuriccacid (acidic medium
H,S0’K,SO,
It is prepared from chrom1te one (FeCr;04 or Fe0-Cr;0;) or
terrochrome or chrome iron. t involves following
1. Conversion of Chromite Ore to Sodium
steps: iThe K,C0,+
Chromate equialent mass
in acidic +Crz(S04 at4H0
medium is 294/6
powdered chromite ore is fused with sodium hydrONiae o Its oxidising properties
of the of
sodium carbonate in the presence of air.
4FeCr,0, - 16Na0H -70,
dichromate
Some in acidic medium are as follows:

liberatesI, from
KI. pota y
(Air) ()t
+6KI ’ 4K,S04 +
SNa,CrO4 - 2Fe,0, - 8H,0 K,Cr,0,+7H,S0,
Sodium chromate

4FeCr,04 - 8Na,c0, +70,

8Na,Cro, +2Fe,0, +8C0,
ferrous salts to ferric
(ii) It oxidises
7H,S04
+7H0+3,
salts.
2. Conversion of Sodium Chromate into Sodium Dichromate: 6FeS0, +K,Cr,0, + +Crz(S04)s +7H0
The solution containing sodium chromate is filtered and
treated with conc. sulphuric acid. (ii) Ittoxidises hydrogen sulphide to sulphur.
2Na-CrO, + H,S04 ’ Na,Cr,0, + Na,So4 + H,0
4H,S04 K,S04
3H,S +K,Cr0, + +Cr(S0,
+3S +7H0)
On cooling, sodium sulphate crystallizes out as
NazSO410H,0 and the remaining solution contains sodium
dichromate. acid.
3. Conversion of Sodium Dichromate into Potassium
Dichromate : Hot concentrated solution of sodium
(iv) It oxidises S0, to sulphuric
’ K,SO4 + Cry (S04) +38
dichromate is treated with calculated amount of KCl. K,Cr,0, +H,S0, +350,
OFT
EW Na,Cr,0, + 2KCI KzCr,0, + 2NaCI
USES
On cooling, K,Cr,0, as orange crystals crystallizes out as it It is used in:
is less soluble than sodium chloride. 1. the volumetric analysis as primary standardNa.. for :
estimation of Fe and I in redox reactions.
PROPERTIES is not used in volumetric analysis as it is deliquescer
1.It is an orange coloured crystals having melting point 669 nature.
K and ismoderately soluble in cold water but highly soluble 2. dyeing and calico printng.
In hot water. The orange colour of potassium dichromate 3. thepreparationofchromealum(KzSO4-Cr2(S04)24H
is not due to d-d transition but due to charge transfer ie. and other compounds like KzCrO4, CrCl3, CrOz etc.
momentary transfer of charge from 0-atom to metal atom
 THE d AND (-BLOCK
ELEMENTS 95
which consists of(lanthanoid metal (about 95%), iron (about 9. Complex Formation : Lanthanoid ions in spite of having
596) and traces of s. C. Ca, Al etc. It is used in magnesium high charge (+3) have small charge to size ratio (charge
based,alloy to produce bullets, shells etc.
Cerium forms about 30-50% of the density) due to their large size. Therefore, they have poor
alloys of lanthanoids tendency to form complexes. They form complexes mainiy
which are used for scavenging oxygen and sulphur from
other metals. Cerium-magnesium alloys are used in flash with chelating agents like EDTA, ethylene diamine etc.
lightpowders.
7. Chemical Reactivity : Thetfirst few members of this series THE ACTINOIDS
arequite reactive but this property decreases on increasing The actinoids are also f-block elements and are also called
atomicnumber. The chemical reactions of lanthanoids (Ln) as inner transition elements. They have been placed at
are summarised below the bottom of the Periodic Table. Their chemistry is very
Lng03
complicated as they show wide range of oxidation states and
are radioactive in nature.
LnzS3
GENERAL CHARACTERISTICS OF THE ACTINO!DS
Heated
with:
ung
Heated
wth LnN
1. Electronic Configuration : All actinoids have common
7s" configuration with variable occupancy of 5f and 6d
Acids subshells. The 14 electrons are being added into 5f-orbitals
Ht of the rest of the elements except thorium (2 = 90) and

Halogens
H o
w t a t e r

the filling continues after thorium till 5fis complete i.e., at

Z= 103 (1awrencium).
LnX3 There is also irregularity in those cases where the stability
Ln(OH)+ H2
off°.f' and fl4,configuration are involved. For example Am
LngC, LngC, and LnC2 has the configuration of (Rn] 5f 6d 7s and Cm has the
configuration of [Rn] 5f 6d'7s.
Salubility of Compounds : The fluorides, oxides, Berkelium (Bk, Z=97) shows the exceptional
hydroxides, carbonates, phosphates, chromates and
Oxalates of lanthanoids are largely insoluble in water but of[Rn] s/6d 752.
conthguration
.he sulphates unlike the sulphates of group 2 elements are 2. Oxidation States : Actinoids show various oxidation states
soluble in water. due to very small energy gap among 5f, 6d and 7s subshel.
The hydroxides of lanthanoids are ionic and basic in The common oxidation state of actinoids is +3. Besides
character. They are stronger bases than Al(OH), but weaker this, they can also exhibit +4 oxidation state. The oxidation
than Ca(0H)2. state first increases up to the middle of the series and then

Table 4.4 Electronic configuration of actiniun and

decreases.
actinoids with their oxidation states
Name of the Symbol At. No. Electronic E.C. Outside [Rn] Core
Element (M) (Z) Configuration Oxidation States
Mt
Actinium Ac 89 [Rn] 6d' 75 +3
Thorium Th 90 [Rn] 6d 72 (+3), +4 Sd'
Protactinium Pa 91 [Rn] 4f 6d' 7 +3, +4, +5
Uranium 92
s
+3,+4, +5, +6
Neptunium Np 93 [Rn] 5f*6d +3,+4, +5, +6,+7
Plutonium Pu 94 [Rn] 5f° 6ds +3, +4, +5, +6, +7
Americium Am 95 [Rn) 5f' 6dz +3, (+4), +5, +6
Curium Cm 96 [Rn] 5f°67 +3, (+4) 5f?
Berkelium Bk 97 [Rn] 5 +3,+ 4
Californium Cf 98 (Rn] sfl6a +3
Einsteinium Es 99 [Rn] 5fl6 7s +3
Fermium Fm 100 [Rn] 5f 6d 7 +3
 and
+2
ClassXII exhibit the
94
VATSAL ISC CHEMISTRY HANDBOOK quite itsnoble
gasstate.
Thus, formation of Cef:
are
configurationbut it tends to change
+4oxidation \s to

value forlavwuNco
lanthanoids Oxidant T
2. The
chemical properties of
separatethe Stirong co
P
a that it
behavesas SUggests
radii so that it is very difficult to
elements in pure state.
3. Due to lanthanoid contraction,
and
decrease +1.74Vwhich
thereis between ic contguration
oxidise water
in size and their covalent

Lu. Thus, La(OH), is

the least basic.
character

most
La to
ndYb
exhibitj
Oxidation State. EU
decreasesfrom i s . . A in+2 oxidation state.
strength of the hydroxides basic butLu/OH); configuration
areSm(4/Tm2
and y

Pr
r(4f).esExcpecetpvteioynal
Dy"
vhe
a
n oxidation
3.Oxidation States:L
state of +3. In
Lanthanoids exhibit acommono
Some of the
elements also (4/)etc. andllanthanoids
lanthanum (Ne4r-11,
addition to this,
confiurationof (GeneralE.C =
Table 4.3 Elcctroriuc oxdaionstates E.C. Outside [Xe<
(General symbol =Jn) with
their
Oxidation
Ln2+ Ln3+
Core
Name of the At. Electronic States Ln
Symbo! No. Coniguration 4f0
Element (Ln)
(Z) +3
4 4f
Lanthanum La S7 -3. - 4
4f3 4f²
Cerium Ce 58 +3,+ 4
4f
[Xej4f°s6s 4f 4f
Praseodymium 59 4f
+2,+3,+4
Pr
4f5 4f
Neodymium Nd 60
-3
Promethium Pm 61 [Xej 4 5 6s' 4 4f5
+2.+3
Samarium Sm 62 [Xej4°5 6' 4f 4f6
-2,-3
Europium Eu 63
4f'sa' 4f?
+3
Gadolinium Gd 64 [Xej 4fsd' 6s
-3,-4
Terbium 4f
Tb 65
+3, +4
4f
Dysprosium 66
[Xej 4f°sds 4flo
Dy
Holmium Ho 67 [Xe] 4fl sis? +3
4fl2 4fl1
(Xej 4l? s 6s?
-3
Erbium Er 68
+2.+3
Thulium Tm 69 4fl4
+2,+3
Ytterbium Yb 70
4flsa' 4fl4
+3
Lutetium Lu 71
solution. The colour of lanthanoid ions ist
as well as in
4. Magnetic Behaviour : Lanthanoids show paramagnetic spectrum resultine !
character in their cationic form except La () and Lu* to absorption of visible region oI the filled orbitals
because they have partly
fl). In the case of lanthanoids, their magnetic moment is transitions to note that lanthanoid ions with nf-eletm
caiculated by considering spin as well as orbitalcontribution. It is interesting
1.e., u = 4s(s + 1) + L(L + 1) B.M. have about the same colour as those with (14n)felectre
quantum e.g. Pr (4f) and Tm (4f) are green in colour.
where s is the spin quantum number andLis orbital 6. Alloy Formation : Lanthanoids find special use for s
number.
and pipes. They z
Colour : The lanthanoids are silverv white but many of production of alloy steels for plates
known alloy is mischme
5. known as mischmetals. A well
the trivalent ions of the lanthanoids are coloured in the solid
 TSAL ISC
Mendelevium CHEMISTRY
Mu
HANDBOOKClass
+3 Sf13
Nobeliun NO
I01
[Rn) 5f 67s
+3
5f14
Lawrencium Lr
102
I03 [Rnj 5fl 6d' 7s
+3
are generally coloured. The cations having
ENHANCE YOUR KNOWLEDGE
Oxidation states given orhalf-filled
electrons are colourless. This
elements ararime
in 1.F
3. brackets are less stable.
lonic Radii and Actinoid transition
actinoid 2. L
Due to actinoid Radioactivity : Allthe
contraction like lanthanoid Contractionthe: atomic
contraction, and ionic 5.
They have halF lives ranging from few days to f 3. T
radii of these : They are
4. F
metals regularly across the series. Chemical Behaviour highly
contractiondecrease
The actinoid 6.

hydrochloricreadtn
water,
poor shielding effect of 5/
is due to with boiling
electrons.
4. Colour :
They react
attacked by alkalies. a
These
Differences in metals
They show Lanthanoids and Actinoids
are silvery white but their cations

differences in some ofof their characteristics

as foilows:
characferistus of LaRth1d
d acunods
Table 4.5 Differeri Cs in
S. No. Actinoids FIL

1 Lanthanoids Besides +3 oxcidation state, they show higher oxidation 1

Besides +3 oxidation state, they show +2 and * +6, +7 also.
oxidation states only in few cases.
2 are coloured.
Most of their ions are Most of their ions
3. colourless.
They have less tendency greater tendency towards complex formation.
towards complex They have
formation.
4 more basic.
Lanthanoid compounds are less basic. Actinoid comnpounds are
and Uo*,
Form oxOcations e.g., Uo.Puo
5 Do not form
6. oxOcations. They are radioactive.
EXcept promethium, they are
7.
Their magnetic properties non-radioactive.
can be explained Their magnetic properties
cannot be explained
easily, as they
easily. complex.
Inner Transition Elements
Iabie 4.6 Differences in Transition and
S. No.
Transition Elements Inner Transition Elements
1
These elements have partially filled d-orbitals ie., these These elements have partially filled
elements have last two incompletely filled outermost shell. last three incompletely filled outermost shell ie, ta f-orbitals
2
Elements placed between group 3 to 12 in middle of the Elements placed in two separate rows at the
modern Periodic Table. modern Periodic Table.
USES OF ACTINOIDS
1. Uses of Thorium: It is used in MNEMONICS
atomic reactors, treatment
of cancer and their salts are used in
gas mantles.
making incandescent Concept: Uses of Some Actinoids
2. Uses of Uranium : It is used as Mnemonics : Programmable Unijunction Transistor (pUT
nuclear fuel. Its salts are Interpretation :
used in glass, textile and ceramic industry and in
3. Uses of Plutonium : It is used as a medicines. P: Plutonium :" In nuclear reactors
fuel for atomic reactors " For nuclear bombs
as well as for making atomic
bombs. U:Uranium: As nuclear fuel
" In glass, textile and ceramic industry
" In medicines
T:Thorium : In atomic reactors
" In the treatment of cancer
" In making incandescent gas mantles