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Exercises · 11.27

Q.In some of the reactions thallium resembles aluminium, whereas in others it resembles with group I metals. Support this statement by giving some evidences.

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Thallium sits at the bottom of Group 13, so it shows both authentic Group 13 (+3) chemistry resembling aluminium and, because of a strong inert pair effect, Group 1-like (+1) chemistry resembling the alkali metals.

  1. Resemblance to aluminium (Group 13, +3 state). As a genuine member of Group 13, thallium can exist in the +3 oxidation state, paralleling aluminium's chemistry:

    • Tl2_2O3_3 shows a broadly similar pattern to Al2_2O3_3's Group 13 oxide behaviour.
    • TlCl3_3, like AlCl3_3, exists and shows covalent character.
    • Tl3+^{3+} forms complex ions in solution in a manner comparable to Al3+^{3+}.
  2. Resemblance to Group 1 (alkali) metals (+1 state). Down Group 13, the inert pair effect (the reluctance of the ns2ns^2 electron pair to participate in bonding) becomes progressively stronger, and for thallium it is strong enough that the +1 oxidation state is actually more stable than +3 — the reverse of aluminium, for which +3 is essentially the only important state. This makes Tl+^+ chemistry dominant, and Tl+^+ behaves very much like an alkali metal cation:

    • TlOH is a strong base, freely soluble in water — like NaOH or KOH — quite unlike the weak, essentially insoluble amphoteric Al(OH)3_3.
    • Tl2_2CO3_3 is soluble in water, again paralleling alkali metal carbonates (e.g. Na2_2CO3_3), whereas a stable aluminium carbonate does not even exist under normal conditions (Al3+^{3+} is too small/highly charged to stabilise the carbonate ion).
    • Tl+^+ salts in general show ionic, alkali-metal-like solubility and lattice behaviour rather than the more covalent character typical of Al3+^{3+} compounds. …

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