Radiolytic degradation of 4-hydroxybenzoate in aerated and deoxygenated aqueous solutions

Guadalupe Albarrán, E. Mendoza
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Abstract

The radiolytic degradation of 4-hydroxybenzoate (4-HBA–) in aerated, oxygen-free and N2O-saturated aqueous solutions at concentrations of 0.10 and 0.25 mmol/dm3 were gamma irradiated at different doses in a source of Co-60. The results show that ·OH adds predominantly to the third position of the aromatic ring, and elimination of the acid group leads to the degradation of 4-HBA–. With an N2O-saturated 0.10 mmol/dm3 4-HBA– solution, total degradation occurred at 1.6 kGy, and with a 0.25 mmol/dm3 solution, total degradation occurred at 3.5 kGy. In the aerated and oxygen-free 0.25 mmol/dm3 4-HBA– solutions, the behavior was similar, degradation occurring at a dose of 13.1 kGy. At the concentration of 0.10 mmol/dm3, total degradation occurred at 7.0 kGy, with small amounts of radiolytic products and byproducts. We propose a mechanism for the degradation of 4-HBA– caused by water radicals produced in the three environments, leading to formation of the identified stable products. Oxidation was followed by chemical oxygen demand (COD), which decreased as the 4-HBA− concentration increased. The kinetics showed a pseudo-first-order behavior. The rate constant of degradation was similar for the solutions with and without oxygen.
4-hydroxybenzoate 在通气和脱氧水溶液中的放射性降解
在通气、无氧和 N2O 饱和的水溶液中,浓度分别为 0.10 和 0.25 mmol/dm3 的 4-羟基苯甲酸(4-HBA-)在 Co-60 源中受到不同剂量的伽马射线辐照后发生了放射性降解。结果表明,-OH 主要添加到芳香环的第三个位置,酸基的消除导致 4-HBA- 的降解。在 N2O 饱和的 0.10 mmol/dm3 4-HBA- 溶液中,1.6 kGy 时发生完全降解;在 0.25 mmol/dm3 溶液中,3.5 kGy 时发生完全降解。在通气和无氧的 0.25 mmol/dm3 4-HBA- 溶液中,情况类似,降解发生在 13.1 kGy 剂量时。在浓度为 0.10 mmol/dm3 的溶液中,7.0 kGy 时出现完全降解,并产生少量的放射性产物和副产品。我们提出了 4-HBA- 在三种环境中产生的水自由基导致降解的机制,从而形成了已确定的稳定产物。化学需氧量(COD)随 4-HBA- 浓度的增加而降低,氧化作用也随之发生。动力学表现为伪一阶行为。有氧和无氧溶液的降解速率常数相似。
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