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

我们研究了磷酸盐、高氯酸盐、汞、硫代酸盐离子选择电极，并将其应用于常规分析。在本报告中，我们测定了含有1,4,7,10,13,16-六athiacyclocadecane （HTCO）的增塑型PVC膜的离子选择电极的潜在Tl ^+选择性。研制了以1,4,7-三硫烷（TTCN）为载体的膜塑锡选择电极和以中性载体（HTCO和1,10-二氮杂-4,7,13,16-四硫十八烷（ATCO））为载体的银选择电极。膜基质的作用，例如；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-硝基辛基辛基醚（NPOE））在电极上的离子加成性[亲脂盐，四（对氯苯）硼酸钾（KTpcClPB）]的用量及选择性。制备的膜电极性能好，响应最佳：铊电极：HTCO: 2.0w/w%…More, PVC: 28.0w/w%, DOP: 68w/w%, KTpClPB: 2.0w/w%；锡电极：TTCN: 3.0w/w%, PVC: 75/08w/w%, DOP: 21.17w/w%, KTpClPB: 0.75w/w%；银电极：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%。分别用混合溶液法、单溶液法和连续变分法测定了上述电极的选择性。例如，连续变分法的结果如下：选择性的递减顺序为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^+（铊电极）；Bi ^ < 3 + > > Ca ^ < 2 + > > Pb ^ < 2 + >,锌^ < 2 + > >铁^ < 3 + > >公司^ < 2 + > >铜^ < 2 + > > Na ^ +(锡(II)电极);Hg ^ < 2 + >, Mg ^ < 2 + > >倪^ < 2 + > >锌^ < 2 + > > Ca ^ < 2 + >, Mn ^ < 2 + > >公司^ < 2 + > > Ce ^ < 3 + > >铁^ < 3 + > > Cr ^ < 3 + >(银电极(I)与HTCO);Hg ^ < 2 + > > Mg ^ < 2 + > >倪^ < 2 + > > Mn ^ < 2 + >,锌^ < 2 + > > Ca ^ < 2 + > >公司^ < 2 + > > Cr ^ < 3 + >, Ce ^ < 3 + > >铁^ < 3 + >(与ATCO银电极(I))。研究发现，高电荷干扰离子对电极的性能没有影响，而软金属离子对电极的性能有影响。为了研究中性载体膜电极上离子交换和络合机理，讨论了阻抗谱。利用两个半圆的cole-cole图分析了膜的体电阻、双层电容、电荷传递的电流密度、膜内扩散系数和Warburg系数。建立了电化学选择性与交换电流密度比之间的关系。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