Professional Documents
Culture Documents
Lanthanoides & Actinoides: 1.why Actinide Contraction Is Greater Than Lanthanide Contraction?
Lanthanoides & Actinoides: 1.why Actinide Contraction Is Greater Than Lanthanide Contraction?
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
) 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.
(OH)3 is least basic. Similarly, the basicity of oxides also decreases in the order
from La3+ to Lu3+.
) Ce4+
REASON;
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
2+
Reason: genrally the lanthanide ion having spin-orbitcoupling value(LS) is zero.But in this case of Sm3+, Eu3+
o.
Additonal information;
the ground state J value is should be zero
Eu3+
Sm3+ the ground state J value is 5/2
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?
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
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