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C H A P T E R 10 Lanthanoids and Actinoids

Syllabus
Recovery. Periodic properties, spectra and magnetic properties.

CHAPTER ANALYSIS
Topic GATE GATE GATE GATE GATE GATE GATE GATE GATE GATE GATE
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
Recovery 1
Periodic Properties 1 1
Spectra and magnetic
1 1 1
properties

QUESTIONS

1. The strongest reducing ion of the following is (a) [Ce(NO3 )6 ]2− (b) [La(acac)3 ( H 2 O) 2 ]
(a) U 3+ (b) Am3+
3+
(c) [Ce(acac) 4 ] (d) [Eu(acac)3 ( Phen )]
(c) Cm (d) Cf 3+
(GATE 2005: 2 Marks)
(GATE 2001: 1 Mark)
5. The reaction between Pr6O11 and dilute HCl leads to the
2. The ligand field bands of lanthanide complexes are gen- formation of
erally sharper than those of transition metal complexes
because (a) a colored solution.
(b) only a black precipitate PrO2.
(a) transitions are allowed for lanthanide complexes.
(c) a black precipitate of PrO2 and soluble PrCl3.
(b) intensity of the bands are higher for lanthanide
complexes. (d) only soluble PrCl3.
(c) f-orbitals have higher energy than d-orbitals. (GATE 2006: 2 Marks)
(d) f-orbitals, compared to d-orbitals, interact less 6. The difference in the measured and calculated magnetic
effectively with ligands. moment (based on spin-orbit coupling) is observed for
(GATE 2003: 1 Mark) (a) Pm3+ (b) Eu3+
3. Ligand field stabilization energies are smaller for (c) Dy3+ (d) Lu3+
­lanthanides compared to transition metals in the same (GATE 2007: 1 Mark)
­oxidation state because
7. The separation of trivalent lanthanide ions, Lu3+, Yb3+,
(a) size of lanthanide ions is larger. Dy3+ Eu3+ can be effectively done by a cation exchange
(b) f-orbitals interact less effectively with ligands. resin using ammonium o-hydroxy isobutyrate as the
(c) size of lanthanide ions is smaller. ­eluent. The order in which the ions will be separated is
(d) lanthanides favor oxygen donor ligands. (a) Lu3+, Yb3+ Dy3+, Eu3+
(GATE 2005: 2 Marks) (b) Eu3+, Dy3+, Yb3+, Lu3+
4. The lanthanide complex (acac = acetylacetonate; phen = (c) Dy3+, Yb3+, Eu3+, Lu3+
1, 10-phennathroline) that do not have square antipris- (d) Yb3+, Dy3+, Lu3+, Eu3+
matic structure is (GATE 2007: 2 Marks)

Ch wise GATE_CHEM_Ch10.indd 201 12/14/2020 2:29:47 PM

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202 GATE chemistry Chapter-wise Solved Papers

8. The correct electronic configuration and spin only mag- (a) greater than 6 and sharp.
netic moment of Gd3+ (At. no. = 64) are (b) 6 and broad.
(a) [Xe]4f 7 and 7.9 BM (c) less than 6 and sharp.
(b) [Xe]4f 7 and 8.9 BM (d) greater than 6 and broad.
(c) [Xe]4f 65d1 and 7.9 BM (GATE 2018: 2 Marks)
(d) [Rn]5f 7 and 7.9 BM
12. In a uranium recovery process, an aqueous solution of
(GATE 2013: 2 Marks) uranyl ion is evaporated, dried in air at 400°C and sub-
9. The calculated and observed magnetic moments differ sequently reduced with hydrogen at 700°C to obtain a
considerably for an aqua complex of a lanthanide(III) uranium compound (X). The oxidation state of uranium
ion as a result of low lying states of high J. The ion, in X is _______.
among the following, is (Given: Atomic number of U = 92)
(a) Ce3+ (b) Pr3+ (GATE 2020: 1 Mark)
(c) Eu3+ (d) Yb3+ 13. The experimental magnetic moment (3.4 BM) of a
(GATE 2016: 2 Marks) hydrated salt of Eu3+ at 27°C is significantly different
10. The lanthanide ion that exhibits color in aqueous solu- from the calculated value. The difference is due to
tion is (Given: Atomic number of Eu = 63)
(a) La(III) (b) Eu(III) (a) population of electrons at higher J-level(s) via
(c) Gd(III) (d) Lu(III) thermal excitation.
(GATE 2017: 1 Mark) (b) strong ligand field splitting of f-orbitals.
(c) strong spin-orbit coupling.
11. Generally, the coordination number and the nature of the
(d) pairing of electrons in f-orbitals.
electronic absorption band ( f → f transition) of lantha-
nide(III) ion in their complexes are, respectively, (GATE 2020: 2 Marks)

Answer KeyS

1. (a) 2. (d) 3. (b) 4. (a) 5. (a) 6. (b) 7. (a) 8. (a) 9. (c) 10. (b)
11. (a) 12. (4) 13. (a)

Hints and Explanations

1. Concept: Periodic Properties is very small. Thus, the ligand field stabilization energy
(a) Actinides, like lanthanoids shows a common for lanthanides is smaller as compared to transition
oxidation state as An(III). The +3 oxidation state of ­elements in the same oxidation state.
actinides is most stable, while uranium can show +3 to 4. Concept: Complexes of Lanthanides
+6 oxidation states. Thus, the outermost six electrons of
(a) [Ce( NO3 )6 ]2− does not have square antiprismatic
U are available for bonding. The electronic configura-
structure. As NO3− is bidentate ligand, so it will form
tion of U( Z = 91) is [Rn](5 f 3 6 d 1 7 s 2 ).
cuboctahedron geometry around cerium ion.
Thus, U3+ can be oxidized to U4+ or U6+ and can act as
2−
strong reducing agent. O
O
O N O
2. Concept: Spectra and Magnetic Properties O N
O O
(d) Due to the diffused shape of the f- orbitals, the N
O
interaction of the f- orbital with the incoming ligands is O
O
Ce O
less effective than d-orbitals. N
O
N O O
O O O
3. Concept: Periodic Properties N

(b) The size of f-orbitals is large and more diffused O

in space due to which their interaction with the ligands Cuboctahedron geometry

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Chapter 10 • Lanthanoids and Actinoids 203

5. Concept: Properties of Lanthanide Oxides 9. Concept: Magnetic Properties

(a) The reaction involved is (c) For lanthanides and actinides magnetic properties
( III ) include both spin and orbit contributions. Magnetic
Pr6 O11 + dil.HCl → Pr O 2 + Cl 2 ↑ moment of a J-state is expressed by the Lande’ formula:
( Colored solution )

μ = g J J ( J + 1) μ B
6. Concept: Magnetic Properties
+3 +2 +1 0 −1 −2 −3 ⎡ 3 S ( S + 1) − L( L + 1) ⎤
(b) Pm 3+
= 4 f 5d 6 s
4 0 0
Σ l = 6.
 ⎢ where, g J = 2 + 2 J ( J + 1) ⎥
⎣ ⎦
Maximum orbital contribution.
+3 +2 +1 0 −1 −2 −3
(i) Sm3+ and Eu 3+ does not fit with observed magnetic
moment and calculated magnetic moment by Lande’
Eu 3+ = 4 f 6 5d 0 6 s 0 Σl = 3.
formula.
+3 +2 +1 0 −1 −2 −3
(ii) Magnetic moments of Sm3+ and Eu 3+ are altered
Dy 3+ = 4 f 9 5d 0 6 s 0 Σl = 5 from the Lande’ expression by temperature dependent
+3 +2 +1 0 −1 −2 −3 population of low-lying excited J-state.
Lu 3+ = 4 f 14 5d 0 6 s 0 Σl = 0
10. Concept: Color of Lanthanide ions
From the above, Pm3+ will have maximum difference (b) The electronic configuration of Eu(III) is
in measured and calculated magnetic moment, but due
to the calculation of magnetic moment for Eu3+ from
[Xe] 4 f 6 6 s0 .
Eu(III) has partially filled f-orbital, thus shows a pale
Landé expression is altered by temperature dependent
pink color in aqueous solution.
population of low lying excited J-state, hence, calculated
magnetic moment of Eu3+ is 0 while observed magnetic 11. Concept: Spectra
moment is ranging from 3.3 to 3.5, which shows a large
(a) Lanthanide(III) ions form complexes with coordi-
difference in observed and calculated magnetic moment.
nation number greater than 6, usually 8 and 9. The elec-
7. Concept: Recovery tronic absorption band (f – f transition) is more sharp as
compared to d – d transition.
(a) The size of hydrated ions increases down the
group, so the ions with larger size bound weakly with 12. Concept: Recovery of Actinides
resin and on washing out got eluted first.
(4) The uranyl ion, UO 2+ 2 is used for the recovery
Hydrated radius order of lanthanide follows the order: of uranium through reduction process. The reactions
Lu3+ > Yb3+ > Dy3+ > Eu3+. involved are as follows:
Thus, the tendency of ions to bound with resin also
follow the same trend. Lu3+ weakest and Eu3+ will be UO 22 + + H 2 O ⎯Δ⎯→[UO 2 ( H 2 O) 4 ]2 + ⎯Reduction
⎯⎯⎯
H2
→[UO( H 2 O)3 (OH)]+
( VI )
strongly bound with resin. Hence, order of elution will
be Lu3+ > Yb3+ > Dy3+ > Eu3+. UO 22 + + H 2 O ⎯Δ⎯ →[UO 2 ( H 2 O) 4 ]2 + ⎯Reduction
⎯⎯⎯
H2
→[UO( H 2 O)3 (OH)]+
( VI )
 Since, water is a neutral ligand, thus, oxidation state
8. Concept: Periodic Properties
of U in complex X is +4.
(a) The electronic configuration of Gd (Z = 64) is [Xe]
4f 7 5d1 6s2 and after loss of 3e−, it will form Gd3+ cat- 13. Concept: Magnetic Properties
ion which has electronic configuration [Xe] 4f 7 5d0 6s0. (a) For Eu3+ ion, the first excited J-state is sufficiently
Hence, the number of unpaired electrons is 7 or close to the ground state even second and third excited
states have very less energy gap, which are appreciably

populated at room temperature. So, due to population
We know in higher J-states the number of unpaired electrons
μspin = n( n + 2) BM increases and thus the experimental value of magnetic
Thus, spin only magnetic moment is moment differs from the calculated value of magnetic
moment.
( μ ) = 7(7 + 2) = 63 = 7.9 BM.

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