INFLUENCE OF CATION ADSORPTION ON THE KINETICS OF ELECTRODE PROCESSES
INFLUENCE OF CATION ADSORPTION ON THE KINETICS OF ELECTRODE PROCESSES
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DOI：
10.1039/tf9595500156
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发表时间：
1959-01-01
影响因子：
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通讯作者：
FRUMKIN, AN
中科院分区：
文献类型：
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作者：
FRUMKIN, AN
讨论了阳离子吸附对阳离子的电还原和形成速度以及对阴离子电还原的影响。所观察到的效应与41-电位的变化有关，但在有阳离子参与的反应中，可以使用+L-电位的平均值，而在阴离子电还原中，必须考虑41-电位与反应阴离子与其邻阳离子之间的距离的依赖关系。具有扁平构型的PtC42-阴离子的电还原对阳离子的敏感性远小于S2082-和Fe(CN)-阴离子的电还原。在Cs+离子存在的情况下，反应速率和微分容量的测量表明Cs+离子具有一定的特定吸附能力。如果阳离子和阴离子都是表面活性的，吸附对反应速率的影响在一定的电势下仍然是增强的。Herasymenko和Slendyk 1观察到溶液中阳离子的存在影响了汞上的氢过电压，并随着阳离子浓度的增加而增加。他们发现，阳离子的有效性随着电荷的增加而增加，一价阳离子的有效性顺序为Lif<；Na+<；K+<；Rb+。在La3+和Th4+的存在下，过电压升高最大。作者试图将这些现象与双电层内的电势分布联系起来。设c是反应粒子的体积浓度，n是它们的电荷，$1是反应粒子电荷中心所在的表层点上的电势。反应粒子的表面浓度与cexp成正比(-1nF/RT)；从电极表面到反应粒子的电子转移速度，即电流密度i等于
The influence of cation adsorption on the rate of the electroreduction and formation of cations as well as on the electroreduction of anions is discussed. The effects observed are correlated with changes of the 41-potentia1, but whereas in reactions with the participation of cations average values of the+ l-potential can be used, in the anion electroreduction the dependence oL the 41-potential on the distance between the reacting anion and the cation which is its next neighbour must be taken into account. The electroreduction of the PtC42-anion which has a flat configuration shows a much smaller sensitivity towards cations than the electroreduction of the S2082-and Fe (CN) $-anions. Measurements of reaction rates and differential capacities in the presence of Cs+ ons indicate a certain specific adsorbability of the Cs+ ion. If both the cation and the anion are surface-active, that effect of the adsorption on reaction rates which prevails at a definite potential is still enhanced.Herasymenko and Slendyk 1 observed that the presence of cations in solution influences the hydrogen overvoltage on mercury, which rises with the increase of the cation concentration. They found that the effectiveness of the cations increases with increasing charge and for univalent cations in the order Lif< Na+< K+< Rb+. The largest rise of the overvoltage was observed in the presence of La3+ and Th4+. The author made an attempt2 to correlate these phenomena with the distribution of the potential within the electric double layer. Let c be the bulk concentration of the reacting particles, n their charge and $1 the potential at the point of the surface layer where the centre of the charge of the reacting particle is situated. The surface concentration of the reacting particle is proportional to c exp (-$1 nF/RT); and the velocity of the electron transfer from the electrode surface to the reacting particle, ie the current density i, is equal to