Hydration and ion pair formation in common aqueous La(III) salt solutions: a Raman scattering and DFT study

Raman spectra of aqueous lanthanum perchlorate, triflate (trifluorosulfonate), chloride and nitrate solutions were measured over a broad concentration (0.121–3.050 mol Lˉ¹) range at room temperature (23 °C). A very weak mode at 343 cmˉ¹ with a full width at half height at 49 cmˉ¹ in the isotropic spectrum suggests that the nona-aqua La(III) ion is thermodynamically stable in dilute perchlorate solutions (∼0.2 mol Lˉ¹) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The La³⁺ nona-hydrate was also detected in a 1.2 mol Lˉ¹ La(CF₃SO₃)₃(aq). In lanthanum chloride solutions chloro-complex formation was detected over the measured concentration range from 0.5–3.050 mol Lˉ¹. The chloro-complexes in LaCl₃(aq) are fairly weak and disappear with dilution. At a concentration <0.1 mol Lˉ¹ almost all complexes disappeared. In LaCl₃ solutions, with additional HCl, a series of chloro-complexes of the type [La(OH₂)₉₋nCln]⁺³⁻ⁿ (n = 1–3) were formed. The La(NO₃)₃(aq) spectra were compared with a spectrum of a 0.409 mol Lˉ¹ NaNO₃(aq) and it was concluded that in La(NO₃)₃(aq) over the concentration range from 0.121–1.844 mol Lˉ¹, nitrato-complexes, [La(OH₂)₉₋n-(NO₃)n]⁺³⁻ⁿ (n = 1, 2) were formed. These nitrato-complexes are quite weak and disappear with dilution