Coadsorption of Para-toluene Sulfamide and 1.4-Butynediol at Mercury Electrode

用电毛细曲线、微分电容曲线、Ｓｔｕａｒｔ模型和自洽场分子轨道法（ＣＮＤＯ／２）研究对甲苯磺酰胺和１．４－丁炔二醇在汞电极上的共吸附特性。此共吸附本质上是一种物理吸附。在其最大的吸附电位附近，二者分别以侧卧与平卧方式吸附于汞表面，并在共吸附层中表现出静电斥力作用。当两者的浓度相等时，１．４－丁炔二醇的吸附占优势。The coadsorption characteristics of para-toluene sulfamide and 1,4-butynediol atmercury electrode have been studied by means of electrocapillary curve,differential capacity curve,Stuart model and the SCFMO method(CNDO/2).The coadsorption is a physical adsorption occuringnaturally. Lateral and flat orientations in the two adsorbates close to their maximum adsorptionpotential were considered respectively.Unlike attractive interactions of their own,there was arepulsive interaction at their coadsorption layer.A preferred adsorption of 1,4-butynediol occurredWhen they were at the same volume concentration.作者联系地址：湖南大学化学化工系Author's Address: Depart. Chem.Chem.Eng.Hunan Univ.,Changsha 41008

Study on Electrochemical Methods of Controlled Convolution ——A simple electron transfer reaction followed by a homogeneous catalytic reaction(Ⅰ)

采用控制卷积量的电化学实验方法，对伴有后续均相催化反应的电极过程进行了处理，得到恒半积分法、半积分扫描法和半微分扫描法的理论曲线，并对亚铁氰化钾——抗坏血酸体系进行了实验验证，获得后续均相催化反应的动力学速率常数，与文献值吻合．A simple electron transfer reaction followed by a homogeneous catalytic reaction is studied in this paper by three kinds of controlled convolution electrochemical experimental methods, which are the constant semi integral (CSI), linear semi integral sweep (LSIS) and linear semi differential sweep (LSDS). According to the three methods, the following equations can be obtained: CSI: πmΨ iI 1(τ)-1=ξe θ LSIS: π2bI 2(τ)-1=ξe θ LSDS: 3π8dI 3(τ)-1=ξe θ Where mΨ i=m i/nFAD 1/2 oC * o, b=D 1/2 ov/nFAk 02 C * o, d=cD 3/2 o/nFAk 04 C * o, m i, v and c are constant value of semi integral, sweep rate of semi integral and sweep rate of semi differential, respectively. With these equations, the theoretical curves of the above three methods can be computed. Experiments of the ferrocyanide ascorbic acid catalytic system have confirmed that kinetic rate constant in catalytic reaction is in good agreement with the previously reported values.作者联系地址：湖南师范大学化学系,湖南大学化学化工系Author's Address: Dept. of Chem., Hunan Normal Univ., Changsha 410081 Chem. Engiv. and Chem. Dept., Hunan Univ., Changsha 41008

An ESR Study of Free Radicals in Electroreduction Process of Allyl Alcohol

烯丙醇电还原自由基中间产物的ＥＳＲ研究张敬东，旷亚非，黄树坤，谢乃贤（湖南大学化学化工系，长沙４１００８２）汪风珍，陈德文（中南工业大学测试中心，长沙４１００８３）（中国科学院化学研究所，北京１０００８０）Ｈｏｒａｎｙｉ［１］、陈剑［２］等人对酸性水...Electrochemical-ESR technique with spin trap phenyl-t-butyl nitrone(PBN)was used to study the intermediates of electroreduction of allyl alcohol at platinized platinum electrode in acidic alcohol-aqua solution. Hydrogen and allyl group and(or)propyl group radicals were identified by a hyperfine spectrum of the radical adducts,and that provided a direct evidence for the presence of these radicals in the electroreduction of allyl alcohol.作者联系地址：湖南大学化学化工系，中南工业大学测试中心，中国科学院化学研究所，长沙水利电力学院化学系Author's Address: Dept.of Chem.and Chem. Eng.,Hunan University,Changsha 410082Wang FengzhenCentre Laboratory,Centre South University of Technology,Changsha 410083Chen DewenInst.of Chem.,Academia Sinica,Beijinq,10008