Adam Luke C., Gordon Gilbert
Department of Chemistry, Miami University, Oxford, Ohio 45056.
Inorg Chem. 1999 Mar 22;38(6):1299-1304. doi: 10.1021/ic980020q.
The effects of pH, hypochlorite and chloride ion concentration, temperature, and ionic strength on the kinetics and mechanism of decomposition of concentrated hypochlorite ion and the formation of chlorate ion and oxygen in the pH 9-14 region has been investigated. In the absence of catalytic levels of transition-metal ions, the rate of chlorate ion formation is 8.7 times faster than the rate of oxygen formation for the concentration range of 0.7-3.0 M hypochlorite ion with various levels of chloride ion in 0.001-1.0 M OH(-) at 15-55 degrees C. Under these same conditions, the equation that describes the effect of temperature and ionic strength on the decomposition of OCl(-) is the following: log k(2) = 0.149&mgr; + log[2.083 x 10(10)T exp(-1.018 x 10(5)/RT) exp(-56.5/R)] where k(2) has units of M(-)(1) sec(-)(1) and &mgr; is between 1 and 6 molar. Numerical simulation of the decomposition of OCl(-) was carried out while taking into account the effect of each of the above experimental variables. Evidence is presented suggesting chloride ion catalyzed decomposition of hypochlorite ion in the pH 9-10 region that is in addition to the contribution of chloride ion to the ionic strength.
研究了pH值、次氯酸盐和氯离子浓度、温度以及离子强度对pH 9 - 14范围内浓次氯酸根离子分解动力学和机理以及氯酸根离子和氧气形成的影响。在不存在催化水平的过渡金属离子的情况下，对于0.7 - 3.0 M次氯酸根离子浓度范围，在0.001 - 1.0 M OH⁻中、15 - 55℃下含有不同水平氯离子时，氯酸根离子形成速率比氧气形成速率快8.7倍。在这些相同条件下，描述温度和离子强度对OCl⁻分解影响的方程如下：log k₂ = 0.149μ + log[2.083×10¹⁰T exp(-1.018×10⁵/RT) exp(-56.5/R)]，其中k₂的单位为M⁻¹ sec⁻¹，μ在1至6摩尔之间。在考虑上述每个实验变量影响的同时，对OCl⁻分解进行了数值模拟。有证据表明，在pH 9 - 10范围内，除了氯离子对离子强度的贡献外，氯离子还催化次氯酸根离子的分解。
