Electrochemical oxidation of some p-substituted phenols (p-nitrophenol, p-hydroxybenzaldehyde, phenol, p-cresol, and p-methoxyphenol) with electron-donating and -withdrawing substituents was studied to reveal the relationship between the structure and the electrochemical reactivity of p-substituted phenols using a boron-doped diamond electrode by voltammetry and bulk electrolysis. Voltammetric study shows that the oxidation peak potentials of p-substituted phenols become more positive with an increase of Hammett's constants, that is, the direct electrochemical oxidation of p-substituted phenol with an electron-withdrawing group is more difficult than that of p-substituted phenol with an electron-donating group. However,the p-substituted phenols with electron-withdrawing groups are degraded faster than those with electron-donating groups in bulk electrolysis, which is opposite to the result obtained on the Pt electrode. These results indicate that the p-substituted phenols are mainly degraded by indirect electrochemical oxidation with hydroxyl radicals on a boron-doped diamond electrode. Under the attack of hydroxyl radicals, the release of p-substituted groups from the aromatic ring is the rate-limiting step. Since electron-withdrawing groups are easy to be released, the p-substituted phenols with these groups are degraded faster than those with electron-donating groups. Therefore, the degradation rates of the p-substituted phenols rise with an increase of Hammett's constants.

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Colloidal particles of environmental concern often have nonspherical shapes. However, theories and models such as the classical filtration theory have been developed based on the behavior of spherical particles. This study examined the effect of particle shape on colloid retention (e.g., attachment and straining) and release in saturated porous media. Two‐ and three‐step transport experiments were conducted in water‐saturated glass bead columns using colloids dispersed in deionized water and an electrolyte solution. The particles used in the experiments were carboxylate‐modified latex colloids of spherical (500 nm diam.) and rod (aspect ratio, 7.0) shapes. The rod‐like particles were prepared by stretching the spherical particles. Analysis of the colloid breakthrough curves indicates that particle shape affected transport behavior, but retention did not increase with increasing aspect ratio. Retention of the spherical particles occurred mainly in the secondary energy minimum, whereas retention of rod‐like particles occurred in primary and secondary energy minima. There was less straining of rod‐like particles compared with spherical ones, indicating that the minor axis was the critical dimension controlling the process. Release of spherical particles on elution was instantaneous, whereas release of rod‐like particles was rate limited, giving rise to long tails, implying an orientation effect for rod‐like colloids. The results suggest that the differences in electrostatic properties and shape contributed to the observed different retention and release behaviors of the two colloids.