| 四氮杂大环配合物催化的甘氨酸振荡体系的非线性动力学及热力学研究 |
| Nonlinear Kinetic and Thermodynamics to Glycine Oscillating System Catalyzed by Tetraazamacrocyclic Nickel(Ⅱ) Complex |
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| 摘要: 以甘氨酸为振荡底物, 研究了四氮杂大环镍(Ⅱ)配合物[以NiL(ClO4)2表示](L为5，5，7，12，12，14-六甲基-1，4，8，11-四氮杂十四环-7，14-二烯)催化的氨基酸-KBrO3-H2SO4-丙酮体系的化学振荡反应。通过所获得的该振荡体系的振荡波形、振荡诱导期tin及振荡周期tp数据，估算了动力学参数(诱导期及周期的速率常数kin、kp，表观活化能Ein、Ep及指前因子Ain，Ap)，进而依据Oregonator模型及不可逆过程热力学理论，获得了该振荡体系的热力学函数(ΔHin，ΔGin，ΔSin及ΔHp，ΔGp，ΔSp)。结果表明，四氮杂大环配合物不仅能催化丙二酸等有机羧酸参与的化学振荡反应，也是以甘氨酸为底物的B-Z(Belousov-Zhabotinskii)振荡反应的催化剂。该振荡体系的诱导期和周期的熵变ΔSin和ΔSp均为负值，从而进一步证明化学振荡反应是具有耗散结构的非平衡态体系。 |
| 关键词: 化学振荡反应 甘氨酸 四氮杂大环镍(Ⅱ)配合物 动力学参数 热力学函数 |
| 基金项目: |
| Abstract: A chemical oscillating reaction of amino acid-KBrO3-H2SO4-acetone system was studied using glycine as organic substrate and catalyzed by tetraazamacrocyclic nickel(Ⅱ) complex([NiL(ClO4)2], where L is 5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetraazabutadecacyclo-7, 14-diene). With the help of the oscillatory induction period tin and oscillation period tp obtained by the oscillating wave and Arrhenius equation, the kinetic parameters(the rate constant(kin, kp)， the apparent activation energy(Ein, Ep) and pre-exponential constant(Ain，Ap)) of the above-mentioned oscillating reaction was estimated. And then based on the Oregonator Model and the theory of irreversible process thermodynamics, the thermodynamic functions (ΔHin，ΔGin，ΔSin and ΔHp，ΔGp，ΔSp) of the oscillating system were studied. The results indicate that tetraazamacrocyclic nickel(Ⅱ) complex can not only catalyze the chemical oscillating reaction using malonic acid as organic substrate but also is a catalyst for glycine system in the chemical oscillating reaction. The entropy ΔS(ΔSin and ΔSp) of this oscillating reaction are negative in agreement with irreversible thermodynamics. |
| Keywords: chemical oscillating reaction glycine tetraazamacrocyclic nickel(Ⅱ) complex kinetic parameters thermodynamic function |
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| 原春兰,李宗孝.四氮杂大环配合物催化的甘氨酸振荡体系的非线性动力学及热力学研究[J].无机化学学报,2010,26(7):1230-1234. |
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