I learned that $\ce{Hg2Cl2}$ is almost insoluble to hot water and $\ce{NH3}$ water in my textbook, but $\ce{HgCl2}$ dissolves well in water.
I wanted to know the reason and searched for it. It's written on some website that thanks to low shielding effect of f-orbitals and the fact that Hg has full f-orbitals, Hg has a high effective nuclear charge. And this makes it possible for the $\ce{Hg+}$ ion to form covalent metal–metal bonds. I searched further and found some information that bond between $\ce{[Hg-Hg]^2+}$ and $\ce{Cl-}$ is more ionic than the bond between $\ce{Hg^2+}$ and $\ce{Cl-}$, according to Fajans' rules.
I thought if the $\ce{[Hg-Hg]^2+}$ and $\ce{Cl-}$ bond is more ionic than the bond between $\ce{Hg^2+}$ and $\ce{Cl-}$, then $\ce{Hg2Cl2}$ would be more likely to dissolve in water because water is a polar solvent. Why is this not the case? Is the $\ce{HgCl2}$ covalent bond so weak that it will dissociate in water? Why?
I came across the theory of negative and positive hydration [1]. Does anyone think this theory could explain the difference of solubility of these two salts?
Reference
- Rodnikova, M. N. Negative Hydration of Ions. Russian Journal of Electrochemistry 2003, 39 (2), 192–197. DOI: 10.1023/A:1022317227140.