RU2014135077A

RU2014135077A - METHOD FOR POTENTIOMETRIC DETERMINATION OF PEROXYL RADICAL GENERATION SPEED

Info

Publication number: RU2014135077A
Application number: RU2014135077A
Authority: RU
Inventors: Алла Владимировна Иванова; Елена Леонидовна Герасимова; Елена Ринатовна Газизуллина; Анатолий Иванович Матерн
Priority date: 2014-08-26
Filing date: 2014-08-26
Publication date: 2016-03-20

Abstract

1. Способ определения скорости генерирования пероксильных радикалов, включающий генерацию пероксильных радикалов на модели термического разложения азоинициатора с помощью изменения концентрации акцептора свободных радикалов, отличающийся тем, что в качестве акцептора свободных радикалов используют восстановленную форму реагента и регистрируют значение окислительно-восстановительного потенциала во времени, затем рассчитывают концентрацию восстановленной формы реагента [MeL] по формуле:C([MeL]) - концентрация восстановленной формы реагента в каждый момент времени, М.C([MeL]) - начальная концентрация восстановленной формы реагента, М;е] - потенциал, измеренный через промежуток времени t=t, В;Е- потенциал, измеренный через промежуток времени t=ht, В;h-отношение tк t,а скорость реакции генерирования пероксильных радикалов рассчитывают по формуле:W=-d{C([MeL])}/dt,где W- скорость генерирования радикалов, М·с.d{C([MeL])} - изменение концентрации восстановленной формы реагента, М.dt - промежуток времени, за который изменилась концентрация восстановленной формы реагента, с.2. Способ по п. 1, отличающийся тем, что в качестве восстановленной формы реагента используют [Fe(II)-EDTA], [Fe(Phen)], К[Fe(CN)], К[Mn(CN)], K[Mo(CN)], [Fe(SCN)], тетраэтиламмония гексацианоферрат (II), тетраэтиламмония тетрахлороферрат (II), Fe(II)-TPTZ.1. A method for determining the rate of generation of peroxyl radicals, including the generation of peroxyl radicals on the model of thermal decomposition of the azo initiator by changing the concentration of the free radical acceptor, characterized in that the reduced form of the reagent is used as the acceptor of free radicals and the value of the redox potential is recorded over time, then calculate the concentration of the reduced form of the reagent [MeL] according to the formula: C ([MeL]) is the concentration of the reduced form of the reagent enta at each moment of time, M. C ([MeL]) - initial concentration of the reduced form of the reagent, M; e] - potential measured after a period of time t = t, B; E - potential measured after a period of time t = ht, B; h-ratio tк t, and the reaction rate for generating peroxyl radicals is calculated by the formula: W = -d {C ([MeL])} / dt, where W is the radical generation rate, M · s.d {C ([MeL ])} - change in the concentration of the reduced form of the reagent, M. dt - the period of time for which the concentration of the restored form of the reagent has changed, p.2. The method according to claim 1, characterized in that [Fe (II) -EDTA], [Fe (Phen)], K [Fe (CN)], K [Mn (CN)], K [ Mo (CN)], [Fe (SCN)], tetraethylammonium hexacyanoferrate (II), tetraethylammonium tetrachloroferrate (II), Fe (II) -TPTZ.

Claims

1. A method for determining the rate of generation of peroxyl radicals, including the generation of peroxyl radicals on the model of thermal decomposition of the azo initiator by changing the concentration of the free radical acceptor, characterized in that the reduced form of the reagent is used as the acceptor of free radicals and the value of the redox potential is recorded over time, then calculate the concentration of the reduced form of the reagent [Me ^Red L] according to the formula:

C ([Me ^Red L]) is the concentration of the reduced form of the reagent at each point in time, M.

C ⁰ ([Me ^Red L]) is the initial concentration of the reduced form of the reagent, M;

e] is the potential measured after a period of time t ₁ = t, V;

E ₁ is the potential measured after a period of time t ₂ = ht, V;

h is the ratio of t ₁ to t ₂ ,

and the reaction rate of generation of peroxyl radicals is calculated by the formula:

W _i = -d {C ([Me ^Red L])} / dt,

where W _i - the rate of generation of radicals, M · s ^-1 .

d {C ([Me ^Red L])} - change in the concentration of the reduced form of the reagent, M.

dt is the period of time during which the concentration of the reduced form of the reagent has changed, s.

2. The method according to p. 1, characterized in that as the reduced form of the reagent use [Fe (II) -EDTA], [Fe (Phen) ₃ ] ²⁺ , K ₄ [Fe (CN) ₆ ], K ₄ [ Mn (CN) ₆ ], K ₄ [Mo (CN) ₈ ], [Fe (SCN) ₂ ], tetraethylammonium hexacyanoferrate (II), tetraethylammonium tetrachloroferrate (II), Fe (II) -TPTZ.