[Cu(Me_6[14]4,11-dieneN_4]^(2+)-丙酮酸-溴酸钠-硫酸体系的新型振荡化学反应  

Study on the New Oscillating Reactions in the[Cu(Me 64,11-dieneN 4)] 2+ -Pyruvic acid-NaBrO 3-H 2SO 4 System

作　　者：张悠金[1] 赵亮[2] 张飚 谢复新[2] 赵祥大[2] 倪诗圣[2] 

机构地区：[1]合肥经济技术学院加工工艺系 [2]安徽大学化学系

出　　处：《Chinese Journal of Chemical Physics》1997年第1期78-83,共6页化学物理学报（英文）

基　　金：国家自然科学基金;南京大学配位化学国家重点实验室开放基金

摘　　要：报道一种以５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四－４，１１－二烯酮（ＩＩ）配合物为催化剂、丙酮酸为有机底物、溴酸钠作氧化剂、硫酸为介质的振荡化学反应新体系，描述了该体系的振荡特性，得到了振荡范围，详细研究了各物种的初始浓度、温度等对振荡行为的影响。通过研究还原性物质（维生素Ｃ和葡萄糖）、自由基抑制剂（丙烯酰胺、丙烯腈和Ｈ２Ｏ２）、Ａｇ＋、Ｈｇ２＋和ＣＣｌ４等对振荡的影响。In this paper new oscillating chemical reactions with the participation of pyruvic acid, an important intermediate in the glycolysis,as organic substrate and hexamethyltetraazamacrocycliccopper(II) complex as catalyst in acidic bromate media are reported. Here the macrocyc licligand is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene.The typical oscillation curve is shown in Fig.1.The colour of the solution changes periodically because of the oxidation-reduction 2+ (orange)-e+e 3+ (yellow).The concentration oscillations of this system are damped rapidly due to the consumption of the catalyst.We also got the domain of the existence of oscillations in the coordinates of NaBrO 3 and pyruvic acid concentrations (Fig.2) fixing the initial concentrations of 2+ and H 2SO 4 as 1.6×10 -3 and 1.0mol/L respectively.The effects of the initial concentration of pyruvic acid, 2+ ,H 2SO 4 and NaBrO 3 on the oscillation period(t p),the induction time(t in),the amplitude of oscillation (〖WTBX]A) and the oscillation times (I) are shown in Fig. 3～Fig. 6 respectively. Increasing reaction temperature will shorten the oscillation life, oscillation periods and induction time. The effects of reaction temperature on the oscillation periods are illustrated in Fig.7. The apparent activation energy of the oscillations is 53.21kJ/mol. We also studied the effects of Ag +,Hg 2+ ,CCl 4,Vc,glucose,acetonitrile,acrylamide and H 2O 2 on the oscillations. The mechanism of the oscillations is also discussed briefly. The pyruvic acid is brominated and oxidized in the oscillations as well as malonic acid.

关 键 词：丙酮酸 四氮杂大环 铜配合物 振荡化学反应 

分 类 号：Q5[生物学—生物化学]