酸性水溶液中磷酸盐离子对氯化钋染料的降解作用:动力学方法

P. Umoru, Mohammad Lawal, O. A. Babatunde, Yusuf Sahabi
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摘要

在 301 K、I= 1.0 M、[TC+]= 1.5 × 10-5 M、[H+]= 1.0×10-3 M 和 ʎmax 600 nm 的条件下,使用分光光度法分析研究了磷酸离子 (PO43-) 在酸性水溶液中降解氯化碘铵 (TC+) 染料的情况。为了确定反应物的效力和速率,采用了酸性水介质。在没有中间络合物/游离原子形成的情况下,反应生成物为苯基亚砜、苯胺和 HPO32-,两种反应物的摩尔比为 1:1。在反应中发现氯化碘铵的反应性是一阶的,而磷酸离子的反应性是一阶的,因此总体上是二阶反应。随着盐酸浓度的升高,反应过程加快。反应时间随着离子强度浓度的增加而缩短,加入的 Ca2+ 和 Cl- 对反应起正催化作用。通过绘制 1/ko 与 PO43- 浓度的关系曲线,可以得出一条穿过原点的直线。光谱分析显示,600 纳米的 λmax 没有明显偏移。此外,温度升高会加速反应过程。反应的自由能变化为负值 G(-3.13-1.12 KJ/mol),这表明反应是自发的,反应物的自由能大于生成物的自由能。活化焓 H 为正值,表明反应是内热的,并遵循关联路径,而活化熵 S 也为负值(-7.45-1.10 KJ/mol),表明反应的无序程度较低。由于在反应过程中添加了离子催化作用且不存在自由原子,该反应被认为是一种外球体机理。
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Degradation of Tolonium Chloride Dye by Phosphate Ion in Aqueous Acidic Solution: Kinetic Approach
The degradation of tolonium chloride (TC+) dye by phosphate ion (PO43-) in an aqueous acidic solution was studied using spectrophotometric analysis at 301 K, I= 1.0 M, [TC+]= 1.5 × 10-5 M, [H+]= 1.0×10-3 M, and ʎmax 600 nm. To determine the potency and rate of the reactant species, an aqueous acidic medium was employed. The reaction's direction and tendency were predicted using a thermodynamic analysis at an interval of 5.0 K and a temperature range of 301-321 K. Without the presence of intermediate complex/free atoms formation, a reaction that produced phenyl sulphoxide, phenylamine, and HPO32- as products of the reaction was obtained with a molar ratio of 1:1 for both reactants. First-order tolonium chloride reactivity was found in the reaction and first-order for the phosphate ion, resulting in a second-order reaction overall. The reaction process accelerated as the concentration of hydrochloric acid rose. The response time decreased with an increase in ionic strength concentration and added Ca2+ and Cl- did catalyze the reaction positively. A straight line that went through the origin was produced by plotting 1/ko vs PO43- concentration. The spectroscopic analysis showed no discernible shift from λmax of 600 nm. Additionally, an increase in temperature accelerated the reaction process. The reaction has a negative free energy change, G (-3.13–1.12 KJ/mol) which indicates that it is spontaneous and that the reactants have more free energy than that of the products. While the enthalpy of activation, H is positive and indicates that the reaction was endothermic and followed an associative path, the entropy of activation, S, is also negative (-7.45–1.10 KJ/mol), indicating that the reaction is less disordered. Due to the added ions catalysis and absence of free atoms during the course of the reaction, an outer-sphere mechanism was suggested for the reaction.
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