Raman and infrared spectra of aqueous CdSO4 and (NH4)2SO4 solutions have been recorded over a broad concentration (0. 040 to 3. 51 mol/kg) and temperature range (‐10 to 109°C). Whereas the v1SO2‐4 band profile is symmetrical in (NH4)2SO4 solutions, in CdSO4 solutions a shoulder appears on the high frequency side at 989 cm−1, which increases in intensity with increasing concentration and temperature. The relative molar scattering coefficient of the v1SO42−v band is the same for all forms of sulfate in (NH4)2SO4 and CdSO4 solutions and is independent of temperature up to 109°C. The high frequency shoulder is attributed to the formation of a 1:1 inner‐sphere complex [Cd2+(OH2)5OSO32− The v3SO42− antisymmetric stretching mode, normally forbidden in the isotropic scattering, contains a contribution in concentrated CdSO4 solutions. The bending modes, v2SO42− and v4SO42−, also forbidden in the isotropic scattering, show contributions at 472 and 640 cm−1, well apart from the frequencies normally observed in the anisotropic spectrum in (NH4)2SO4 solution. A polarized band at 240 cm−1 has been assigned to the Cd2+‐OSO32− ligand vibration. Further spectroscopic evidence for contact ion pair formation at 25°C is provided by i.r. spectroscopy. Higher associates or anionic complexes are not required to interpret the spectroscopic data, but it has been established that at room temperature the favourable complex is an outer‐sphere complex whereas above 109°C the inner‐sphere complex is becoming the favourable one (inner‐sphere complex formation is entropically driven). The Raman spectroscopic results confirm the stepwise reaction mechanism of sulfato‐complex formation in aqueous CdSO4 solution.
The degree of association has been measured as a function of concentration and temperature. At concentrations above 1.0 mol · kg−1 the concentration quotient, QA equal to QU, has a relatively high and constant value of 0.14±0.02. The thermodynamic association constant, enthalpy and entropy for the outer‐sphere/inner‐sphere complex formation have been estimated to be: KII = 3.3±0.3, ΔH° =(6.2±0.2) kJ · mol−1 and ΔS° = (33±1)J · K−1 · mol−1.