【摘要】 <正> 线性变势吸附伏安法是一种简便的痕量分析方法。本文讨论了此方法中不可逆过程的峰电流方程式,并对其作了验证。仪器与试剂 83-2.5型多阶自动新极谱仪（各档灵敏度已校正）,LZ₃-100型函数记录仪,Metrohm E410型悬汞电极,所用试剂同文献[1]。实验方法在含0.1mol/dm³NH₃/NH₄Cl,1×10^-4mol/dm³丁二肟,pH=9.2的Co（Ⅱ）溶液中用氮气除氧并搅拌。由于配合物的稳定常数很大(β=10¹⁷),可以认为Co（Ⅱ）A₂的浓度等于Co（Ⅱ）的浓度。由于电势负于-1.20V时Co（Ⅱ）A₂在电极上不吸附,因此先将电极置于-1.5V,一当从悬汞电极中旋出新的汞滴,立即将电势恒定于-0.8V,富集一定时间,然后关闭搅拌器,30秒后,电势以100mV/s的速度向负方向扫描至-1.3V,同时更多还原

【Abstract】 The peak current equation for irreversible process on a spherical electrode in a stirred solution for linear sweep adsorption voltammetry, corresponding to the case of a strong adsorption, can be expressed as follows i_p=i_p（t_a）+i_p（t_r）=K’vD²/³r_o²v^-1/⁶ω^1/2t_aC^*+i_p（t_r） where i_p（t_a） is the peak current for the preconcentration time（t_a） in a stirred solution; i_p（t_r） is the peak current for the rest period, t_r,v is the scan rate; D is the diffusion coefficient; r_o is the radius of the spherical electrode; ω is the angular velocity of the solution; v is the kinematic viscosity, C^* is the bulk concentration of the, depolarizer; K’ is a constant. The equation has been verified experimentally for system of Co（Ⅱ）-dimethylglyoxime in NH₃/NH₄Cl.更多还原