Selected Topics in

Inorganic
the experimentalfact that Sm*ion has atendency to get oxidised to Sm ion and
462
ion in aqueous solution.
Cheris
reducedto Cet
Ce+ ion has a
tendency to get 2Sm+ + OH + H,
2Sm2* + 2H,0 (H = 0)
(RA) (H=+1)
Ce3+ + Fe+
Ce++Fe2+
(OA)
RA and Ce+t is agood OA n aqueous solution, Prt
Thus sm2+ is a good oxidising agents. and
powerful
Tbt* are even more Contraction
Lanthanide
Atomic and Ionic Radii: ions are given below
3. lt may be seen
Atomic radii ofLn
Thein
decrease steady
as and
atoms
that
of radii.
decrease
the value
ionic radii ofLn*
we move along lanthanide series, there is asteady

in atomic (Eu, has

inTable93.
abnormally high value) and ionic
l elements with increasing atomic number is called lanthanid
radü of lanthanide
contraction.
Table 9.3. Atomic and ionic radii (pm) of La., and lanthanides (Ceg toL)
Tb Dyol| Er
Lanthanides |La, Ce|Pr NdgoPm Smg| Eug Gg Tm
Atomic radii 187| 183|182 181 181 180 199 180 178177| 176|175 174 173|158
of Ln atoms
Lonic radii of 94 92 91 89 88 87 86 85
106| 103| 101| 99 98 96 95
Ln+ jons
Cause of Lanthanide Contraction
We know that as we proceed from one element to the next one in lanthani
series, the nuclear charge (i.e., atomic number) increases by +1 at each next
element. Thus as we move from Ce to Lu, the attraction between the nucleus and
the outermost shellelectron increases gradually at each step. It is also known that
as we move from Ce to Lu, the addition of extra electron takes place to 4forbitals
Since 4forbitals have very diffused shape, the electrons in these orbitals are not able
to shield (decrease) effectively the attraction of the nucleus for the electrons in the
outer-most shell as the atomic number of lanthanides increases. Thus it is only due
tothe gradual increase in the nuclear charge (i.e., increase in the attraction betwen
the nucleus and the outer-most shel electrons) that the sizeof the lanthanide atoms
and M3+ ions decreases gradually with atomic number. The above discussion snowsS
that it is due to the poor shielding effect of 4felectrons and gradual increase in the
nuclear charge that the lanthanide contraction takes place among lanthanides.
Consequences of Lanthanide Contraction
Lanthanide contraction plays an important role in determining the chemisuy
oflanthanides and heavier transition series elements. Some important consequen
of lanthanide contraction are
discussed below:
() The atomic radii of the
Mo-W etc. are almost the same. twoThis
elemnents
fact is in the pairs
adirect viz Zr ofH,
consequence Nh-Tà
lanthanide
contraction as explained below. The atomic (covalent) radii of
the elements o
 Chemistry of Lanthanides (4f-Block Elements)
483
2ndand 3rdtransition serios aro givon in Tablo
radius'of La (element of 3rd transition Herios)9,4.This
is
table shows that the atomic
groater than that of Y(element
of2ndtransition
radii
series) (La = 187 pm, Y=180 pm), On tho basis of this trend, the
atomic ofthe two elements prosent in cach of
etd. should be in the order Hf> Zr, Ta > Nb, W> Mo theetc,
pairs
butvizthe
Zr-Hf,
atomicNb-Ta,
radii ofMo-W
the
nelements present in cach pair given above has been
isevident from '1able 9.4. T'he similarity in atomic found to be almost the same
radii ofthe twoelements is due
Btnthanide contraction seen in lanthanides (Ce,, to Lu,) which lie between La.
n Hf Thus we can say that, due to lanthanide
wny element of Brd transition series following Lu, contraciion, the utomicradius of
is nearly the same as that of the
corresponding element lyingin the same group of 2nd
transition series.
Table 9.4. Atomic radii (pm) of transition series element
Groups 3 4 5 6 7 8 10 11 12
Elements of Ist Sco1 Ti0 Cr Mn Fe Co Ni
transition series 162 147 134 127 126 126 125 124
CugZn
124 138
Elements of 2nd Y Nb Mo Tc Ru Rh Pd AgCdg
transition series 180 160 146 139 136 134 134 137 144 154
Elements of 3rd La,*Hf72 Ta Re Os Ir Pt Au|Hg
transition series 187 158 146 139 137
135 136 138 144 157
*Lanthanide contraction
(i) Similarity in properties of the two elements in the pairs viz Zr-Hf,
Nb-Ta, Mo-W ete, We have said above that, due to lanthanide contraction, the
atomic size of the two elements present in the pairs viz Zr-Hf, Nb-Ta, Mo-W ete.
are almost the same. Due tosimilarity in their atomic size, the properties of the
twoelements in each of the above pairs are very similar.
(iüi) Difficulty in the separation of lanthanides. We know that the
properties of metal ions is determined by their size and charge. Now since, on
proceeding from Ce.,to Lu., the change in the size of Ln* ions is very small and
these ions have the same charge (= +3), chemical properties of lanthanides are
almost identical. Due to identical properties, the separation of lanthanides from
one another in the pure state is difficult.
elements of 2nd and
(iv) Comparison between the densities of the given in Table 9.5.
3rd transition series. The densities of d-block elements are belonging to the same
It may be seen from the table that the densities of
elements
The densities of the elements
sub-group increases on moving down the sub-group. corresponding
of 2nd transition series are only slightly higher than those of the
elements of 1st transition series while these values for the transition elements
almost double these values
from H£, to Hgo (elements of 3rd transition series)are series.)
(elements of 2nd transition
for the elements from Zr to Cdg respectively
double that of the value for Y,, (= 4.47).
not
NOte that the density of La,, (=6.17) is series element in the given sub-group, as
The variation ofdensities oftransition
follows on the basis of lanthanide contraction.
Uscussed above, can be explained as
contraction occurring in lanthanides, the atomic sizes
Because of lanthanide (i.e., elements from HE, to
3rd transition series coming after Lag
of the elements of
Consequently the packing of the atoms in their metallic
Hg) become very small.
that their
Thus the
densities become very high.
ystals become s0 much compact
 Selected Toplcs In
464 lnorganlc
densitie of the elements of 3rd transition
8ories bocomo
transition sorics.
almost doubln
tlhe densClheimtir
of the corresponding elomonts of 2nd
d-block elenenta
Table 9.5. Donsitios (g/omn)of (VIII
VB| VB VIB VII B
Group IIIB
Fe Co
Mn Ni
8,90 Cu8.96Za
Cr
Elements of lst Sco 6.10 7.19 7.43 7.86 8.90
transition series 3,01 4.51 | 77
To Ru Rh Pd
12.40 12.00 Ag ca
ND Mo
Elements of 2nd Y,39 8.40 10.21|11.50|12.20
transition series 4.47 6.49
Os Ir Pt
10.51| 8,85
Elements of 3rd | La,, Coa-Luy H Ta W Re
21.00|22.60 22.50 22.40
Au Hg
transition series6.17 |Lanthanides 13.10| 16.60 19.30 19.30|13.s
from
(u) Basic character of hydroxides, M(OH), decreases
decreases Due
Lu(0H),. tolanthanide
regularly
contraction, the size of +3 lanthanide ions (M3
with increase in atomic number. As a result of this decreasein
La(OH),t%
increases from
size, the covalent character between M ion and OH- ions
Lu(OH),. (Fajan's rules). Therefore, the basic character of the hydroxides decreno
most basic while Iu(0
La(OH),te
with increase in atomic number. Consequently, La(OH), is
is the least basic.
Hydroxides of lanthanides are stronger bases than AI(OH), but weaker than
Ca(OH),
(M* Ions)
4. Colour of Tripositive Lanthanide Ions
in the sola
Most of the trivalent cations of lanthanide elements are coloured
are colourless. (See Fig. 9.4)
as well as in aqueoussolution while only a few ions
It may beseen from Fig. 9.4 that the colour depends on the number of electrong
orbitals has the same colour
present in 4forbitals. The ion having n electrons in 4f example La (4) which
as the ion which has (14 - n)electrons in 4forbitals. For Lu ion (4f4) which has
and
has noelectron in its 4f orbitals (n = 0) is colourless
Similarly Pr ion (4f) which
(14-0)= 14 electrons in 4forbitals is also colourless.ion (4f2) which has (14 -2) =
has two electrons in its 4f orbitals (n = 2) and Tm+
(green). (See Fig. 9.3).
12 electrons in its 4f orbitals have the same colour
Origin of colour. Colour of lanthanide tripositive ions is due to f-ftransition
electronic spectra of the ions in their
The absorption bands in the visible region of range. This resultsin
compounds arise due tothe absorption of light in the visible
lower energy 4f-orbitals tothe
the transition of the electrons of the ions from the
colour which is complementar
higher energy 4f-orbitals. Thus lanthanide ions have
electronic transition, which takes
tothe colour of the absorbed light. This type of Evidently absorption banas
place due to absorption of light, is called f-ftransition.
electronic transition within 4forbitals.
seen in the electronic spectra arise due to
forbidden than d-d transitin
f-f transitions of lanthanides are more lanthanide ions are much less afiec
transition metal ions, because 4felectrons of
d-orbitals of transition metal 10s
by the ligand electrons than the electrons in followed: for
transitions
their comnplexes. Hence the selection rules are more strictly transition metalo
of
in the compounds of lanthanides than in the compounds
Chemistry of
Lanthanides (4f-Block Elements)
The
M0 very individual absorption bands of the 465
sharp. is of these bands are spectra of
the temperature Many
4f-orbitals are lowered. This is due tolinethelikefact andtripositive
become lanthanide
even ions
orbitals of the effectively shielded by the that the narrower
electrons
as
tripositive
The colourless ions lanthanideions. overlying electrons present in
present in
5s and 5p
knfrared region (Yb ion).absorb either in the
Ln4t jon which is stable in The Ln ions absorbultravioletin(Ce, Gds jons) or in the
ultraviolet regions. strongly
aqueous solution, is Cel+ the
ion. This ionultraviolet. The
absorbs in the only
blue
3+
La (4", n =0)
Ce (4f,n=1)
P4,n=2)
Pr

Na(4°,n3)
Pm 3+,(4f,n=4)
4

Sm"(4f°, n=5). Colourless

E(4,n=6) Pink
Pink
Colourless
G 4f,n=7)--- Pale yellow Green
colourless pink
Yellow

Tb(4f n=14-6 =8)

D,4f,
Dy n= 145 =9)
Ho(4n= 14 -4=10
E(4 ,n= 14-3= 11)
|Tm 4 ,n 14-2= 12)
,n=l4-1=13)
3+
Lu(44 ,n= 14-0= 14)
ions havingn electrons in 4forbitals is almost the same
g. 8.4 Colour of M3+ (14-n) electrons in 4forbitals.
as that of M+ ions having
heen