甲苯胺蓝氧化二乙基硫脲可能机理的gc -质谱动力学研究

M. Qadri, F. Uddin, R. Azmat
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引用次数: 1

摘要

本文采用气相色谱-质谱-分光光度法研究了二乙基硫脲在酸性和碱性介质中对甲苯胺蓝(氯化托溴铵)的漂白作用。采用气相色谱-质谱分析验证染料的脱色效果,在反应混合物中是否也会发生由无色染料形成或降解引起的染料脱色。染料氧化还原反应过程对TB表现为一级动力学,DETU表现为一级动力学,对h表现为一级动力学。DETU存在下的脱色增强证明还原剂在氧化还原反应中起关键作用。与酸性介质相比,碱性介质中离子的脱色速度较慢,这表明介质的pH值对DETU的氧化有重要影响。研究了染料在不同温度下的漂白反应。在pH为1.0,温度为25C时,反应级数为二级,速率常数为15.81 mol.L s,速率定律为-d/dt [TBH] = k2 [TB + H][DETU]。对TB-DETU反应的不同反应能参数进行了评价,包括活化能(Ea = 60.786 kJmol -1(碱性介质)、1.669kJmol(酸性介质))、活化焓(∆H≠= -58.267 kJmol -1(碱性介质)、-12.6kJ mol -1(酸性介质))、活化熵(∆S = -131.525JmolK(碱性介质)、-243 JmolK(酸性介质))、活化自由能(∆G = 98.119kJmol(碱性介质)、-86.55kJmol(酸性介质))。在此基础上提出了染料漂白过程中离子相互作用的机理和氧化机理。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
GC-Mass Spectrokinetics Study of Probable Mechanism of the Oxidation of Diethylthiourea with Toluidine Blue
Thecurrent study describes the interactive role of diethylthiourea on the bleaching of toluidine blue (tolonium chloride) (TB) in acidic and basic media using the GC Mass Chromatography and Spectrophotometric technique. GC-Mass Spectrophotometric analysis was carried out to verify the decoloration of dye whether the bleaching of dye owed to leuco dye formation or degradation may also occur in the reaction mixture. The dye redox reaction process followed first order kinetics with respect to TB, DETU showed first order mechanism, first order kinetics with respect to H. Enhanced decoloration in the presence of DETU proved that reductant‘s role is pivotal in the redox reaction. Slow decoloration in basic medium with ions was seen compared to acidic media, suggesting that pH of the medium is significant in the oxidation of DETU. The bleaching reaction of dye was investigated at different temperatures. At pH of 1.0 and 25C, the order of reaction is found to be second having rate constant value of 15.81 mol.L s,and rate law is suggested to be -d/dt [TBH ] = k2 [TB + H][DETU].Different reaction energy parameters were evaluated for a TB-DETU reaction, including the energy of activation (Ea = 60.786 kJmol -1 (basic medium), 1.669kJmol (acidic medium)), enthalpy of activation (∆H ≠ = -58.267 kJ mol -1 (basic medium), -12.6kJ mol -1 (acidic medium)), entropy of activation (∆S = -131.525JmolK(basic medium),-243 JmolK(acidic medium)),and free energy of activation (∆G = 98.119kJmol (basic medium) and -86.55kJmol (acidic medium). A mechanism of interaction of involved ions in dye bleaching and a mechanism of oxidation based on the above findings is proposed.
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