Abstract
The electron-transfer reaction between the erythrosin dianion triplet, 3Er2-, and Mo(CN)84- was studied by laser-induced optoacoustic spectroscopy in the presence of various cations (Li+, Na+, K+, and Cs+, all at 4.4 × 10-2 M analytical concentration). The buffer was in each case the corresponding H3BO3/B(OH)4-,M+ (pH 9.18 at 20 °C). The enthalpy level of the triplet 3Er2- is ΔH1 = 180 ± 10 kJ mol-1 independent of the cation. The structural volume change for 3Er2- formation is ΔV1 = ca. 2 mL mol-1, attributed to intrinsic changes upon its formation. The formation of the redox products Er3- + Mo(CN)83- also leads to an expansion, ΔV2, between 12 mL mol-1 for Li+ and 8 mL mol-1 for Cs+, which linearly correlates with the heat released during the radical formation step. The correlation is interpreted in terms of an enthalpy−entropy compensation effect, due to the strong influence of the cations on the H-bond water network, also reflected in the correlation between ΔV2 and the literature values for the abilit...
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