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本文讨论配位吸附准可逆波测定标准电极反应速率常数(kα)和转移系数(α)的理论与方法, 实验结果证实, 方法简便, 结果正确。 相似文献
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本文推导了受扩散和前行化学反应控制的示差脉冲极谱电流方程,并用实验进行了验证。根据该方程测得的动力学参数与文献报道值相符合。 相似文献
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Dong-shanZhou Xiao-liangWang BoChe LiangLi Jin-luChen GiXue 《高分子科学》2005,(2):159-163
Entropic contribution to the interaction parameter xeff in the model incompressible polymer/oligomer system is calculated by the lattice cluster theory (LCT). It is found that in the oligomer solvent, there exists a wide concentration range that the non-combinatorial “entropic interaction” term xeff φ1φ2 perceptibly counteracts the mean field combinary entropy ΔSMF. With the increase of the solvent size, both xeff and the ratio xefc φ1φ2/ΔSMF first reach their maximum and finally become trivially to zero. It is worth noting that no any demixing was found in the current calculation. This makes the controversial idea “entropically driven demixing” even elusive. However, we propose that further work on compressible polymer solution with structured monomer will witness the demixing owning to an increased configurational correlation. 相似文献
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在278.15~318.15K(间隔10K)下, 测定了无液接电池Pt,H~2(g,p)│HCl(m~E)│AgCl-AgPt,H~2(g,p)│HCl(m~E),GL(m~N)│AgCl-Ag的电动势, 其中GL为丙三醇, m~E=0.005~0.1mol·kg^-^1,m~N=0.4~1.0mol·kg^-^1。实验数据用来计算HCl-GL-H~2O体系的盐效应常数k~s及HCl-GL在水中的相互作用的热力学参数f~E~N(g~E~N,s~E~N,h~E~N和C~p~,~E~N)。结果k~s>0,g~E~N>0, s~E~N>0, C~p~,~E~N<0。在353K时k~s有最小值0.0076kg·mol^-^1。f~H~C~l~-~G~L的数值比f~H~C~l~-~P~G(PG是1,2-丙二醇)小。应用结构相互作用模型和基团加合性原理分析讨论了这些参数的符号及其随温度变化的规律。 相似文献
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本文介绍了过渡态理论对双键取代物顺反异构化过程的处理方法. 计算了1,2-二叔丁基-1,2-二(2,4,6-三甲苯基)二硅烯、1,2-二[二(三甲硅基)]-氨基-1,2-二(2,4,6-三甲苯基)二硅烯和1,2-二甲基-1,2-二苯基二硅烯等化合物的顺反异构化的活化熵变和相应过程的Arrhenius A因子. 前两个化合物的计算结果与West的实验值符合得很好. 后一个化合物, 尚未见到动力学实验结果的报道. 本文指出了这类化合物构型熵贡献的重要性. 相似文献
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The stability constants of complexes of N-phenylthiourea with bismuth (III) in 1M perchloric acid have been studied spectrophotemetrically by the method of corresponding solutions. The enthalpy change ΔH5^0 is obtained from the temperature coefficient data. The Gibbs free energy changes ΔG5^0 and the entropy changes ΔS5^0 are calculated from known formulas respectively. The experimental results are discussed. The successive accumulative stability constants and thermodynamic parameters ΔH5^0, ΔG5^0, ΔS5^0 are listed in Table 6 of the Chinese Text. 相似文献
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