КОНДУКТОМЕТРИЧЕСКИЙ МЕТОД КАК ИНСТРУМЕНТ МОНИТОРИНГА КИНЕТИКИ И УСТАНОВЛЕНИЯ МЕХАНИЗМА ОКИСЛЕНИЯ РЕЗОРЦИНА ПЕРСУЛЬФАТОМ КАЛИЯ
Аннотация
Описаны особенности применения кондуктометрического метода в установлении кинетики реакции окисления резорцина персульфатом калия, которая исследована в интервале температур 55 – 75 °С и представляет потенциальный интерес для процессов водоочистки. Установлено, что реакция подчиняется кинетическому уравнению первого порядка и характеризуется энергией активации 89 ± 2 кДж∙моль–1 и энтропией активации –74 ± 3 Дж∙моль–1∙К–1. Предэкспоненциальный множитель составил 2,5∙109 с–1, что позволяет отнести данную реакцию к категории медленных. Первый порядок реакции и отрицательное значение энтропии активации объяснены промежуточным образованием комплексов между резорцином и персульфат-анионом, возможность существования которых подтверждена квантово-химическими расчетами. Показано, что первый порядок будет наблюдаться в том случае, если скорость образования комплекса между реагентами превышает скорость его распада с образованием продуктов реакции. По данным квантово-химических расчетов, образующиеся комплексы были стабилизированы как образованием водородных связей, так и переносом заряда. Так рассчитанные энергии Гиббса стабилизации комплексов по сравнению с исходными реагентами составили -9,62 и –56,79 кДж/моль при сближении резорцина с персульфат-анионом и персульфатом калия соответственно, что указывает на возможность их самопроизвольного образования. Установлен различный механизм процессов окисления фенола и резорцина персульфатом калия: окислителем фенола являются радикалы, образующиеся при гомолитическом распаде пероксидной группы персульфат-аниона, а окисление резорцина происходит через образование промежуточных комплексов. Этот процесс характеризуется значительно меньшей энергией активации, недостаточной для гомолитического распада персульфат-аниона.
Для цитирования:
Гороховская Э.А., Солдатова А.В., Гривин А.В., Щербаков В.В. Кондуктометрический метод как инструмент мониторинга кинетики и установления механизма окисления резорцина персульфатом калия. Изв. вузов. Химия и хим. технология. 2026. Т. 69. Вып. 5. С. 54-64. DOI: 10.6060/ivkkt.20266905.6887.
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