DEVELOPEMENT OF ION-SELECTIVE ELECTRODE WITH MACROCUYCIC COMPOUNDS AND THE ANALYTICAL APPLICATION

本文研究了磷酸根、高氯酸根、汞根、硫氰酸根离子选择电极及其在常规分析中的应用，并测定了含1，4，7，10，13，16-六硫杂环十八烷（HTCO）的增塑PVC膜离子选择电极对Tl ^+的电位选择性。研制了以1，4，7-三硫杂壬烷（TTCN）为载体的增塑膜锡选择电极和以HTCO和1，10-二氮杂-4，7，13，16-四硫杂十八烷（ATCO）为载体的银选择电极。离子加成量[（亲脂性盐，四（对氯苯基）硼酸钾详细研究了不同增塑剂（邻苯二甲酸二辛酯（DOP）、癸二酸二辛酯（DOS）、2-硝基苯辛基醚（NPOE））对膜电极的影响及其选择性，制得性能良好、响应最佳的膜电极如下：铊（I）电极：HTCO：2.0w/w % 关于我们 、PVC：28.0w/w %，DOP：68w/w %，KTpClPB：2.0w/w %;锡（II）电极：TTCN：3.0w/w %，PVC：75/08w/w %，DOP：21.17w/w %，KTpClPB：0.75w/w %;银（I）电极：HTCO：1.52w/w %，PVC：22.94w/w %，DOP：74.71w/w %，KTpClPB：用混合溶液法、单溶液法和连续变化法测定了上述电极的选择性。以连续变化法为例，其结果为：选择性从高到低依次为Fe ^<3 +>> Co ^<2 +>，Ni ^<2 +>，Cr ^<3 +>> Mn ^<2 +>，Cd ^<2 +>，Mg ^<2 +> Ba ^<2 +>，Zn ^<2 +>，Pb ^<2 +>> NH ^4 ^+，K ^+，Na ^+> Li ^+（铊（I）电极）：Bi ^<3 +>> Ca ^<2 +>> Pb ^<2 +>，Zn ^<2 +>> Fe ^<3 +>> Co ^<2 +> Cu ^<2 +>> Na ^+（锡（II）电极）; Hg ^2+、Mg ^2 +> Ni ^2 +> Zn ^2 +> Ca ^2+、Mn ^2 +> Co ^2 +> Ce ^3 +> Fe ^3 +> Cr ^3 +>（具有HTCO的银（I）电极）; Hg ^2 +> Mg ^2 +> Ni ^2 +> Mn ^2 +> Zn ^2 +> Ca ^2 +> Co ^2 +> Cr ^3+，Ce ^<3 +>> Fe ^<3 +>（含ATCO的银（I）电极），发现高电荷干扰离子对这些电极的电化学性能无影响，而软金属离子对电极的电化学性能有影响。为了研究中性载体膜电极中的离子交换和络合机理，对阻抗谱进行了讨论。通过对两个半圆的Cole-Cole图的分析，计算了膜的体电阻、双电层电容、电荷转移电流密度、膜内扩散系数和瓦尔堡系数。建立了电位选择性与交换电流密度比的关系。少

We have been studied phosphate-, perchlorate-, mercury-, thiocianate-ions-selec-tive electrode and their electrode were applied to the routin analysis.In this report, we have determined potentically Tl ^+ selectivivity of the ion selective electrode with plasticized PVC membrane containing 1,4,7,10,13,16-hexathiacyclooctadecane (HTCO). Membrane plasticized tin-selective electrode with 1,4,7-trithianonane (TTCN) and silver-selecctive electrode with neutral carriers (HTCO and 1,10-diaza-4,7,13,16-tetrathiaoctadecane (ATCO)) were developed.The effect of the membrane matrix, eg. amount of ionic additivity [(lipophilic salt , potassium tetrakis (p-chlorophenyl) borate (KTpcClPB)] and different plasticizer (dioctyl phtalate, DOP ; dioctyl sebacate, DOS ; 2-nitrophenyl octhylether (NPOE) on these electrodes and the selectivities have been investigated in detail.The produced membrane electrodes with good performanece and optimum response are as follows : Thallium (I) electrode : HTCO : 2.0w/w% … More , PVC : 28.0w/w%, DOP : 68w/w%, KTpClPB : 2.0w/w% ; Tin (II) electrode : TTCN : 3.0w/w%, PVC : 75/08w/w%, DOP : 21.17w/w%, KTpClPB : 0.75w/w% ; Silver (I) electrode : HTCO : 1.52w/w%, PVC : 22.94w/w%, DOP : 74.71w/w%, KTpClPB : 0.823w/w% ; ATCO : 1.67w/w%, PVC : 22/85w/w%, DOP : 74.53w/w%, KTpClPB : 0.943w/w%.Selectivities of above described electrodes were determined the mixed-solution, the sigle-solution and the continuous-variation methods. For example, the results of the continuous-variation method are as follows : The decreasing order of selectivities are Fe^<3+>>Co^<2+>, Ni^<2+>, Cr^<3+>>Mn^<2+>, Cd^<2+>, Mg^<2+>>Ba^<2+>, Zn^<2+>, Pb^<2+>>NH_4^+, K^+, Na^+>Li^+ (thallium(I)electrode) ; Bi^<3+>>Ca^<2+>>Pb^<2+>, Zn^<2+>>Fe^<3+>>Co^<2+>>Cu^<2+>>Na^+ (tin(II) electrode) ; Hg^<2+>, Mg^<2+>>Ni^<2+>>Zn^<2+>>Ca^<2+>, Mn^<2+>>Co^<2+>>Ce^<3+>>Fe^<3+>>Cr^<3+> (silver(I) electrode with HTCO) ; Hg^<2+>>Mg^<2+>>Ni^<2+>>Mn^<2+>, Zn^<2+>>Ca^<2+>>Co^<2+>>Cr^<3+>, Ce^<3+>>Fe^<3+> (silver(I) electrode with ATCO).It is found that the interference ion with high electric charge does not affected on peformance of these electrode, while soft metal ions do. To investigate the ion exchange and complexation mechanism in membrane electrode with neutral carriers the impedace spectra was discussed. Bulk resistance of the membrane, the double layr capacitances, electric current dencity of charge transfer, diffusion coefficients in the membrane and Warburg coefficient were evaluated by the analysis of the cole-cole plot with two half circle. The relationship between the potentiometrically selectivity and exchange current dencity ratio was consisted. Less