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Physical Properties of f-block is considered one the most difficult concept.
Properties of Actinoids is considered one of the most asked concept.
24 Questions around this concept.
In context of the lanthanoids, which of the following statement is not correct ?
The outer electronic configuration of Gd (Atomic No : 64) is
Arrange and in increasing order of their ionic radii.
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The radius of (Atomic number of La = 57) is 1.06 . Which one of the following given values will be closest to the radius of (Atomic number of Lu = 71)?
The actinoids exhibit more number of oxidation states in general than the lanthanoids. This is because
Cerium (Z = 58) is an important member of the lanthanoids. Which of the following statements about cerium is incorrect?
Larger number of oxidation states are exhibited by the actinoids than those by the lanthanoids, the main reason being
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Gadolinium belongs to the 4f series. Its atomic number is 64. Which of the following is the correct electronic configuration of gadolinium?
The reason for the greater range of oxidation states in actinoids is attributed to:
Electronic Configurations
It may be noted that atoms of these elements have electronic configuration with 6s2 common but with variable occupancy of 4f level. However, the electronic configurations of all the tripositive ions (the most stable oxidation state of all the lanthanoids) are of the form 4fn (n = 1 to 14 with increasing atomic number).
Atomic and Ionic Sizes
The overall decrease in atomic and ionic radii from lanthanum to lutetium (the lanthanoid contraction) is a unique feature in the chemistry of the lanthanoids. It has far reaching consequences in the chemistry of the third transition series of the elements. The decrease in atomic radii (derived from the structures of metals) is not quite regular as it is regular in M3+ ions. This contraction is, of course, similar to that observed in an ordinary transition series and is attributed to the same cause, the imperfect shielding of one electron by another in the same sub-shell. However, the shielding of one 4f electron by another is less than one d electron by another with the increase in nuclear charge along the series. There is fairly regular decrease in the sizes with increasing atomic number.
Oxidation States
In the lanthanoids, La(II) and Ln(III) compounds are predominant species. However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained. This irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty, half-filled or filled f subshell. Thus, the formation of CeIV is favoured by its noble gas configuration, but it is a strong oxidant reverting to the common +3 state. The Eo value for Ce4+/ Ce3+ is + 1.74 V which suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent. Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is formed by losing the two s electrons and its f7 configuration accounts for the formation of this ion. However, Eu2+ is a strong reducing agent changing to the common +3 state. Similarly Yb2+ which has f14 configuration is a reductant. TbIV has half-filled f-orbitals and is an oxidant. The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation states.
General Characteristics
All the lanthanides are metals. They are soft, malleable and ductile in nature. They are not good conductors of heat and electricity. They are highly dense metals and their densities are in the range of 6.77 to 9.74 gcm-3. The densities and atomic volumes, in general, increase with increase in atomic number. But a regular trend is not observed. They have fairly high melting points. However, no definite trend is observed.
Colour
Many of the lanthanide ions are coloured in solid-state as well as in solution. The colour is due to partially filled f-orbitals which allow f-f transitions. M3+ ions having 4f0, 4f7 or 4f14 configurations are colourless.
Magnetic Properties
Ions having unpaired electrons are paramagnetic while those having all the orbitals paired are diamagnetic. The lanthanide ions(M3+) except La3+(4f0) and Lu3+(4f14) are paramagnetic since they contain 1,2,....7 unpaired electrons.
The actinoids include the fourteen elements from Th to Lr. The actinoids are radioactive elements and the earlier members have relatively long half-lives, the latter ones have half-life values ranging from a day to 3 minutes for lawrencium (Z =103). The latter members could be prepared only in nanogram quantities. These facts render their study more difficult.
Electronic Configurations
All the actinoids are believed to have the electronic configuration of 7s2 and variable occupancy of the 5f and 6d subshells. The fourteen electrons are formally added to 5f, though not in thorium (Z = 90) but from Pa onwards the 5f orbitals are complete at element 103. The irregularities in the electronic configurations of the actinoids, like those in the lanthanoids are related to the stabilities of the f0, f7 and f14 occupancies of the 5f orbitals. Thus, the configurations of Am and Cm are [Rn]5f77s2 and [Rn]5f76d17s2. Although the 5f orbitals resemble the 4f orbitals in their angular part of the wave-function, they are not as buried as 4f orbitals and hence 5f electrons can participate in bonding to a far greater extent.
Ionic Sizes
The general trend in lanthanoids is observable in the actinoids as well. There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as the actinoid contraction (like lanthanoid contraction). The contraction is, however, greater from element to element in this series resulting from poor shielding by 5f electrons.
Oxidation States
The actinoids show in general +3 oxidation state. The elements, in the first half of the series frequently exhibit higher oxidation states. For example, the maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and Np but decreases in succeeding elements. The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state. However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states among the actinoids is so uneven and so different for the former and later elements, it is unsatisfactory to review their chemistry in terms of oxidation states.
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