The theoretical study of hypoiodous and iodous acid isomers, which can be written in the common form HIO n (n ) 1,2), is presented. For this purpose, several basis sets and several computational methods are tested. The best fitting with the values known in the literature is achieved using density functional theory at the level of Gill96 exchange and Perdew-Wang91 correlation functional (G96PW91) method, with Lanl2DZ basis set augmented with p and d diffuse and polarization functions for oxygen, relativistic effective core potential of Hay and Wadt combined with Lanl2DZ basis set augmented with diffuse (s and p) and polarization (d and f) functions for iodine, and 6-311++G(3df,3pd) basis set for hydrogen. Using this method for the calculation of bond lengths, vibrations, and energies, the mentioned species are analyzed. The justification of the calculated values is performed by thermochemical calculations of enthalpy of formation of mentioned species. We found that between hypoiodous acid isomers HOI is more stable then HIO, and that between iodous acid isomers HOIO is the most stable isomer. Therefore, they are the most probable ones in the reactions where they take part. All calculations are performed for the species in the gaseous phase. As far as we know, these calculations give the first such information for iodous acid isomers and HIO.

The mechanisms of the carboxylations of lithium, potassium, rubidium, and cesium phenoxides are investigated by means of the DFT method with the LANL2DZ basis set. It is shown that the reactions of all alkali metal phenoxides with carbon dioxide occur via very similar reaction mechanisms. The reactions can proceed in the ortho and para positions. The exception is lithium phenoxide which yields only salicylic acid in the Kolbe-Schmitt reaction. It is found that the yield of the para substituted product increases with increasing the ionic radius of the alkali metal used. An explanation for this experimental and theoretical observation is proposed.

The influence of heavy water on the Bray−Liebhafsky (BL) oscillating reaction was investigated for varying amounts of D2O, at three different temperatures. Evolution of the system was monitored potentiometrically. Simultaneous recordings of gaseous oxygen over the reaction solution were also performed. In separate experiments the iodine concentration was monitored spectrophotometrically. Replacement of H2O by D2O progressively intensifies the reactions of oxidation of the iodine species, compared to the reactions of their reduction. As a result there is a critical ratio of D2O/H2O, after which the dynamics of the system is considerably altered. The same effect is observed at all temperatures, but it is more pronounced at lower temperatures. Two possible explanations for the progressively intensified oxidation are discussed:  the reverse isotope effect and the selective energy transfer. It is established that the oxidation and reduction of the iodine species in the BL reaction do not proceed through the same intermediates. The important role of bulk water in surmounting the high activation energy threshold of the oxidation branch is revealed in the experiments.