Wednesday, January 18, 2017

inorganic chemistry - Thermal stability of alkali metal hydrides and carbonates


Why is it that thermal stability of alkali metal hydrides decreases down the group, but for carbonates, it increases?


I used Fajan's rule to check for ionic character but somehow this is only applicable for carbonates.



Answer



Down the group, atoms of the alkali metals increase in both atomic and ionic radii, due to the addition of electron shells. This results in the charge density of their corresponding cations decreasing down the group. Thus, as we go down the group, the cations become "softer".


Now, note that the hydride ion is "hard", having high negative charge density. While the carbonate ion is "soft", having a lower negative charge density.


Applying the "hard-soft acid base" (HSAB) principle, we would expect the "hard" ions to form more stable compounds with each other and the "soft" ions to form more stable compounds with each other.


Since the heavier alkali metal ions are softer, we would expect them to form more stable compounds with carbonate. As for the harder lighter metal ions, we would expect them to form more stable compounds with hydrides.


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