Иваново, Ивановская область, Россия
Ярославский государственный технический университет (Кафедра «Технология строительного производства»., Профессор)
Ярославль, Ярославская область, Россия
УДК 544.653.2/.3 Электрохимическое окисление-восстановление. Ред-окс процесс
УДК 544.332 Теплота (энтальпия) химических процессов. Изменение энтальпии в химической реакции (^ДH). Аддитивность теплот реакций. Закон Гесса *
The paper presents the analysis on chemical, thermal and electrochemical stability of some aromatic macroheterocycles (MHC) of porphyrin (H2P) class as well as their benzo- and aza-analogues, establishes electronic and structural factors determining the rate of pigment destruction in the presence of oxidant. The values of redox potentials of porphyrin-, tetraaz-, tetrabenzo-porphyrin- and phthalocyanine-type MHCs correlate with the temperatures at which their thermo-oxidative degradation starts and the decomposition rates in oxidizing media. The combined benzo- and azamer substitution in H2P molecules leads to their destabilisation with respect to oxidants, the situation depending strongly on the nature of the oxidant (H2O2, S2O82- and NO3-), the solvent (H2SO4, HOAc) as well as the nature of the metal in the molecule. The polymer state or spatial distortion of the MHC has a significant influence on the resistance to oxidising agents. The reaction mechanisms of oxidation of label-free porphyrins and phthalocyanines by hydrogen peroxide are shown to be identical. In both cases, the reaction centres of MHCs are N H bonds, either in the meso-position (H2Ps) or in the coordination cavity of the H2N4 molecule (H2P), and the pigments are cleaved to colourless products.
tetrapyrrolemacroheterocyclic compounds; porphyrins; phthalocyanines; oxidative degradation, redox potentials
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