氨基酸-BrO_3^--Mn^(2+)-H_2SO_4-丙酮振荡体系的非线性动力学及热力学研究

Study on Nonlinear Kinetics and Thermodynamics of Oscillating Reaction of Amino Acid-BrO_3^--Mn^(2+)-H_2SO_4-Acetone System

通过所获得的4种氨基酸(丙氨酸Ala,甘氨酸Gly,丝氨酸Ser及酪氨酸Tyr)在氨基酸-KBrO-3-Mn2+-H2SO4-丙酮振荡体系的动力学参数(诱导期及周期的速率常数kin、kp及表观活化能Ein、Ep)及Oregonator模型和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,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。这与振荡反应从无序到有序的特征及不可逆过程热力学完全相符,从而圆满解释了实验现象。

With the help of the kinetic parameters such as the rate constant（kin,kp） and the apparent activation energy（Ein,Ep） of the oscillatory induction period and oscillation period of the oscillating reaction for four amino acids,alanine（Ala）,glycine（Gly）,serine（Ser） and tyrosine（Tyr）,in amino acid-BrO-3-Mn2＋-H2SO4-acetone system,the thermodynamic functions（ΔHin,ΔGin,ΔSin and ΔHp,ΔGp,ΔSp） of these oscillating system were obtained on the basis of the Oregonator model and the thermodynamics theory in irreversible process.The results indicated that the entropy ΔSin and ΔSp of these oscillating reaction were all negative.Thereby it was proved that the oscillating reaction was a noequilibrium system with dissipation structure in agreement with the character of the oscillating reaction from disorder to order in irreversible thermodynamics,which were satisfactory to explain the experimental phenomena.