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

本文研究了磷酸盐、高氯酸盐、汞、硫代柠檬酸根离子选择电极及其在常规分析中的应用，测定了含有1，4，7，10，13，16-六硫代环十八烷(HTCo)的塑化聚氯乙烯膜离子选择电极对Tl~(2+)的潜在选择性。研制了1，4，7-三硫杂环己烷(TTCN)膜增塑锡选择电极和中性载体银选择电极(HTCo和1，10-二氮-4，7，13，16-四硫杂十八烷(ATCO))。详细研究了离子加和性[(亲脂盐，四(对氯苯基)硼酸钾(KTpcClPB)]和不同增塑剂(邻苯二甲酸二辛酯，DOP；癸二酸二辛酯，DOS；2-硝基苯基辛醚)在这些电极上的选择性。所制得的膜电极具有良好的性能和最佳的响应：Tl(I)电极：HTCo：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：0.823w/w%；ATCO：1.67w/w%，PVC：22/85w/w%，DOP：74.53w/w%，KTpClPB：0.943w/w%。例如，连续变化法的结果如下：选择性由大到小的顺序是：Fe^lt；3+>t；；Co^&lt；2+>t；，Ni^&lt；2+&gt；，Cr^&lt；3+&gt；；2+&gt；，Cd^&lt；2+&gt；，Mg^&lt；2+&gt；2+&gt；2+&gt；，Pb^&lt；2+&gt；Li^+(铊(I)电极)；Bi^&lt；3+&gt；&gt；Ca^&lt；2+&gt；&gt；Pb^&lt；2+&gt；，Zn^&lt；2+&gt；&gt；Fe^&lt；3+&gt；&gt；Co^&lt；2+&gt；&gt；Cu^&lt；2+&gt；&gt；Na^+(锡(II)电极)；Hg^&lt；2+；2+&gt；&gt；Ca^&lt；2+&gt；Mn^&lt；2+&gt；&gt；Co^&lt；2+&gt；&gt；Ce^&lt；3+&gt；&gt；Fe^&lt；3+&gt；&gt；Cr^&lt；3+&gt；(含高温钴的银(I)电极)；Hg^&lt；2+&gt；&gt；Mg^&lt；2+&gt；&gt；Ni^&lt；2+&gt；&gt；Mn^&lt；2+&gt；，锌；2+&gt；&gt；Ca^&lt；2+&gt；&gt；Co^&lt；2+&gt；&gt；Cr^&lt；3+&gt；，Ce^&lt；3+&gt；&gt；Fe^&lt；3+&gt；(含ATCO的银(I)电极)，发现高电荷干扰离子对电极性能没有影响，而软金属离子对电极性能有影响。为了研究中性载体膜电极的离子交换和络合机理，对阻抗谱进行了讨论。通过两个半圆的Cole-Cole图分析，估算了膜的体阻、双电层电容、电荷转移电流密度、膜内扩散系数和Warburg系数。建立了电极的电位选择性与交换电流密度比之间的关系。较少

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