LANTHANOIDES & ACTINOIDES

Lanthanide series

58 59 60 61 62 63 64 65 66 67 68 69 70 71 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Actinide series 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

1.Why Actinide contraction is greater than Lanthanide contraction?

Ans; its due to poor shielding effect 5f electrons than that of 4f electrons Additional information; LANTHNIDE CONTRACTION:

) Lanthanide contraction : The regular decrease in the size of lanthanide ions from to is known as lanthanide contraction. It is due to greater effect of the increased nuclear charge than that of the screening effect.

Consequences of lanthanide contraction

(a) It results in slight variation in their chemical properties which helps in their separation by ion exchange (b) Each element beyond lanthanum has same atomic radius as that of the element lying above it in the group (e.g. Zr 145 pm, Hf 144 pm); Nb 134 pm, Ta 134 pm ; Mo 129 pm, W 130 pm). (c) Tendency to form stable complexes from La3+ to Lu3+ increases as the size decreases in that order. (d) There is a slight increase in electronegativity of the trivalent ions from La to Lu. (e) Since the radius of Yb3+ ion (86 pm) is comparable to the heavier lanthanides Tb, Dy, Ho and Er, therefore they occur together in natural minerals.

2. The La (OH)3 is more basic& Lu (OH)3 is least basic. why?

Ans; The covalent character of hydroxides of lanthanides increases as the size decreases from La3+ to Lu3+ . However basic strength decreases. La (OH)3Thus is most basic whereas Lu

(OH)3 is least basic. Similarly, the basicity of oxides also decreases in the order from La3+ to Lu3+.

3. which is act as a oxidising agent.....? 1) . Sm2+, 2) Eu2+, 3)Yb2+ 4) Ce4+

Ans;

) Ce4+

REASON;
2

Sm +, Eu , Yb2+ lose electron to become +3 and hence are good reducing agents, Ce4+, Pr4+, Tb4+ in aqueous solution gain electron to become + 3 and hence are good oxidizing agents. Note:There is a large gap in energy of 4 f and 5 d subshells and thus the number of oxidation states is limited.
2+

4. which lanthanide ions are having different magnetic properties compared to that of other lanthanide ions? 1) Eu2+, Yb2+ 2) Ce4+, Pr4+ 3) Sm3+, Eu3+ 4) Pr4+, Tb4+
Ans: 3

Reason: genrally the lanthanide ion having spin-orbitcoupling value(LS) is zero.But in this case of Sm3+, Eu3+
Additonal information;
the spin orbit coupling value is not zero or L o.

Eu3+ Sm3+ the ground state J value is 5/2

the ground state J value is should be zero

All lanthanide ions with the exception of Lu3+, Yb3+ and Ce 4+ are paramagnetic because they contain unpaired electrons in the 4 f orbitals. These elements differ from the transition elements in that their magnetic moments do not obey the simple spin only formula eff= n(n+2) B.M. where n is equal to the number of unpaired electrons. In transition elements, the orbital contribution of the electron towards magnetic moment is usually quenched by interaction with electric fields of the environment but in case of lanthanides the 4f-orbitals lie too deep in the atom for such quenching to occur. Therefore, magnetic moments of lanthanides are calculated by taking into consideration spin as well as orbital contributions and a more complex formula eff= 4S ( S+1 ) + L (L+1 ) B.M. Which involves the orbital quantum number L and spin quantum number S. Spin magnetic moment; The spin motion of electron around its own axis produces magnetic moment is called spin magnetic moment(s)

Orbital magnetic moment; The orbital motion of electron around its nucleus produces magnetic moment is called orbital magnetic moment(L) Spin-Orbit coupling; In an atom the magnetic effects of L & S may interact or couple, giving a new quantum number J is called spin orbit coupling(L-S)

5. why Ln3+ ion will not form a stable complexes with the following ligands? 1)CO 2)c2H4 3)No But stable water ilgand(H2O)?
Reason; The 4f orbitals are deeply buried in the lanthanoids& lanthanides form no complex with pi-bonding ilgands such as No,co etc,..... Addional: the f orbitals bond order is less than one compare to that of s, p, d.this due to rising the coordination number of s, p, d, orbitals. 6.what do u mean by MISCH METALS? Alloy of Lanthanides are called MISCH Metals(Ce 50%,La 40%,7% Fe ,3% other metals) it is pyrophoric& used lighter fints

7. In periodic table the Transition metals shos least sharp band than Lanthanide metals why? Ans yes.its
REASON; the f orbitals are deeply inside,they are largely from environmental factors such as forming complexes(which affects the outer electrons) . Ce3+, Yb3+ gives strong absorption in the uv region. Now the question arises why Ce4+ gives colour solution even though in the absence of 4f electrons?

Yes it gives colour due to charge transfer from ligand to metal .Higher the oxidation state or ligand has reducing properties& the strong colour of ce4+ solution arises from charge transfer rather than f-f orbitals.

8.The ligand field stabilisation energy in Transition

metals are higer than that of lanthanide metals. Why?

Explanation; yes its. This is due to f orbital are interact less effectively with the ligand Additional; Since the 4f-electrons are deeply buried inside the atom, there are no CFE. Hence this orbital motion of the magnetic moment is not quenched by ligand

9. d-orbital metal carbonyl cluster containing Metal-Metal bond. But lanthanide alkoxide cluster do not .why? Explanation; yes its. In lanthanide the f orbital the bond involvement is least, the metal containing higher oxidation state 10.Zr/Hf having same size due to.................... Reason. Lantanide contraction Assertion; poor shielding effect
a) Both Reason and Assetion are correct. b) Both Reason and Assertion are wrong. c) Reason is correct but Assertion is wrong. d) Reason is wrong but Assertion is correct. Ans; a)

11. In Ion Exchange method which lanthanide ion is 1st eluted from the colum? why?
Ans;Heavier the ion is 1St eluted in the column in Iron Exchange metod. So La3+ is 1st eluted than Lu3+ Uses of lanthanide Lanthanide & its salts are used in lab, bcause 1.steel mixed with La,Pr,Nd in the manufacture of flame yhrowing tanks 2.Ce-Mg alloys are used for the manufacture of light powders 3.Nd oxide dissolved in Se oxochloride serves as a powerful liquid Laser

11.Uranium exhibits several oxidation states because a) It is an inner transition element b) its atomic number is high c) 5f orbitals participate in bonding d) it forms strong bond with oxygen reasons:
- The 5f orbitals are not that much buried in the atom and hence not that much shielded from the external environement. The energy gap between 5f, 6d and 7s orbitals is very small (near degenerate) and hence all the electrons in them can participate in bonding. NOTE;now seen by the chemistry of later actinides resemble that of lanthanides due to poor shielding effect of 5f orbitals Actinide contraction: (1)There is a regular decrease in ionic radii with increase in atomic number from Th to Lr. This is called actinide contraction analogous to the lanthanide contraction. It is caused due to imperfect shielding of one 5f electron by another in the same

shell. This results in increase in the effective nuclear charge which causes contraction in size of the electron cloud. (ii) Colour of the ions: Ions of actinides are generally coloured which is due to f f transitions. It depends upon the number of electrons in 5 f orbitals. (3) Magnetic properties: Like lanthanides, actinide elements are strongly paramagnetic. The magnetic moments are lesser than the theoretically predicted values. This is due to the fact that 5f electrons of actinides are less effectively shielded which results in quenching of orbital contribution. (iv) Complex formation: Actinides have a greater tendency to form complexes because of higher nuclear charge and smaller size of their atoms. They form complexes even with pbonding ligands such as alkyl phosphines, thioethers etc, besides EDTA, -diketones, oxine etc. The degree of complex formation decreases in the order. M4+> MO2+2 > M3 > MO+2 Where M is element of actinide series. There is a high concentration of charge on the metal atom inMO2+2 which imparts to it relatively high tendency towards complex formation