Why are the tin(IV) halides more volatile than the \(\operatorname{tin}(\mathrm{II})\) halides?

Tin(IV) and tin(II) halides differ in their oxidation states. In tin(IV) halides, the tin atom is in +4 oxidation state (it has lost four electrons), while in tin(II) halides, the tin atom is in +2 oxidation state (it has lost two electrons). Tin(IV) halides can be represented as SnX4, where Sn is the tin atom and X is the halogen atom (fluorine, chlorine, bromine, or iodine). Tin(II) halides can be written as SnX2.

Tin is found in Group 14 of the Periodic Table, and its electronic configuration is [Kr] 5s^2 4d^10 5p^2. When tin loses two electrons and forms a tin(II) ion, its electron configuration becomes [Kr] 5s^0 4d^10 5p^0, which is more stable because it has a completely filled d-orbital. On the other hand, when tin loses four electrons and forms tin(IV) ion, the electron configuration is [Kr] 4d^10, which is less stable due to vacant 5s and 5p orbitals.

The stability of a tin-halogen bond depends on the strength of the ionic interaction between Sn and X atoms. In general, the bond strength decreases as the difference in the electronegativity of the two bonded atoms decreases. In the case of tin(II) halides, the oxidation state of tin (+2) forms a stronger bond with halides due to the smaller size of the tin(II) ion compared to the tin(IV) ion. A stronger bond between the tin and the halide results in lower volatility.

Tin(IV) halides have a lower bond strength as compared to tin(II) halides due to the larger size of the tin(IV) ion and the higher charge density. The weaker bond between the tin(IV) ion and the halide ion makes tin(IV) halides more susceptible to breaking apart, which results in higher volatility. Additionally, the free 5s and 5p orbitals in the electronic configuration of the tin(IV) ion also contribute to the weaker bond strength and increased volatility of tin(IV) halides. In conclusion, tin(IV) halides are more volatile than tin(II) halides mainly due to the weaker bond strength between the tin(IV) ion and halide ions resulting from the larger size and higher charge density of the tin(IV) ion, as well as the unstable electron configuration of the tin(IV) ion.