LiCl-KCl-LaCl3熔盐体系中La3+的反应动力学机理

    Kinetic Mechanism of La3+ Reaction in LiCl-KCl-LaCl3 Molten Salt System

    • 摘要: 在LiCl-KCl共晶盐中,研究了在不同温度下La3+的反应动力学机理。首先,在723~873 K范围内,利用循环伏安法(CV)测得La3+的扩散系数D为3.06×10-5~6.08×10-5 cm2/s,并根据Arrhenius方程计算了La3+在电解质中的扩散活化能ED=34.51 kJ/mol。随后,利用电化学阻抗谱技术(EIS)研究了La3+在电极上的动力学参数并测得交换电流密度i0为0.48~1.39 A/cm2、反应速率常数k0=2.04×10-4~5.90×10-4 cm/s及反应活化能Ea=35.04 kJ/mol。通过Nyquist图和拟合的等效电路图研究La3+在W电极上的反应动力学机理,发现在LiCl-KCl共晶盐中La3+的电化学反应速率不仅受扩散控制还受电荷转移控制,且与温度成正相关。

       

      Abstract: In this paper, the reaction kinetic mechanism of La3+ was studied in the LiCl-KCl eutectic salt at various temperatures. First, the diffusion coefficient of La3+(D) measured by cyclic voltammetry(CV) increases from 3.06×10-5 cm2/s to 6.08×10-5 cm2/s with the temperature ranging from 723 K to 873 K, and the activation energy of La3+ diffusion(ED) in the molten salts is 34.51 kJ/mol calculated by the Arrhenius equation. Subsequently, the kinetic parameters of La3+ on the W electrode were studied by the electrochemical impedance spectroscopy(EIS). In the temperature range of 723-873 K, the exchange current density(i0) is measured to be 0.48-1.39 A/cm2, and the reaction rate constant(k0) is determined as 2.04×10-4-5.90×10-4 cm/s. Moreover, the corresponding reaction activation energy(Ea) is found to be 35.04 kJ/mol. The Nyquist plots and the fitted circuit diagrams explored the reaction kinetic mechanism of La3+ on a W electrode. It was illustrated that the electrochemical reduction rate of La3+ in the LiCl-KCl eutectic salt is controlled by diffusion and charge transfer, and it is positively correlated with temperature.

       

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