Специфические взаимодействия оксоанионов хрома (VI) с анионообменными мембранами и их влияние на поведение мембран в растворах бихромата калия
Аннотация
В растворах NaCl (pH 5.7) и K2Cr2O7 (pH 4.0) определены толщина, обменная емкость, влагосодержание, объёмные доли гелевой фазы, концентрационные зависимости удельной электропроводности и диффузионной проницаемости анионообменных мембран PFAEM, AEM Type 1, изготовленных методом заполнения пор инертной подложки ионообменным материалом, и мембраны МА-41П, изготовленной методом горячего прессования размолотой ионообменной смолы и пудры полиэтилена низкого давления. Поведение исследуемых мембран в растворах NaCl аналогично поведению таких же и подобных им мембран, полученному в независимых экспериментальных исследованиях, и находится в хорошем согласии с прогнозируемым известной микрогетерогенной моделью. Вблизи точки изоэлектропроводности их удельная электропроводность растет в ряду PFAEM<<МА-41П<AEM Type 1 с увеличением обменной емкости. В более концентрированных растворах она контролируется объемной долей электронейтрального раствора, находящегося в их порах. Интегральные коэффициенты диффузионной проницаемости мембран снижаются с ростом их обменной емкости и с разбавлением внешнего раствора благодаря усилению доннановского исключения коионов. Наличие крупных протяженных макропор на границе ионообменный материал/армирующие волокна коммерческих мембран, во многом определяют их высокую диффузионную проницаемость.
Показано, что в исследованном интервале концентраций раствора K2Cr2O7 электропроводность всех мембран снижается на 1-2 порядка по сравнению с растворами NaCl вследствие специфических взаимодействий оксоанионов Cr (VI) c фиксированными группами мембран. Интегральные коэффициенты диффузионной проницаемости мембран уменьшаются с увеличением концентрации K2Cr2O7 в растворе благодаря его обогащению анионами полихроматов. Транспортные характеристики МА-41П быстро (в течение 2-5 часов) деградируют из-за окисления хроматами ароматической полимерной матрицы и их хемосорбции фиксированными группами. Порозаполненные мембраны, основу которых составляет сополимер винилиденфторида и гексафторпропилена (PFAEM) или полиакриламид (AEM Type 1), являются более стабильными в хроматсодержащих растворах. Фиксированные группы (CH3)N+(C8H17)3 мембраны PFAEM устойчиво функционируют в растворах K2Cr2O7, в отличие от фиксированных групп –N+(CH3)3 мембран AEM Type 1 и МА-41П.
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Литература
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