Studies On Anion-Selective Electrodes With Ferrocene And Schiff Base Metallic Complexes As Neutral Carriers

The analytical method of ion-selective electrode is direct and nondestructive, it has simple structure, simple handled, wide potentiometric response range, highly sensitive, it can rapidly determine sample continuously, so it has been applied in most departments of industry and agriculture and science technology. Design, synthsis and application of highly selective and sensitive neutral carriers are main research subjects in the ion-selective electrode studies. Recently, study on ion-selective electrodes with anti-Hofmeister selectivity pattern is an important and interesting project in the fields of electrochemistry and electroanalytical chemistry. This thesis focuses on seeking design and synthsis of novel metallic complex and basic studies on solvent polymeric membrane(SPM) anion-selective electrodes containing the novel metallic complex. The electrodes can be applied to practice sample analysis.Part I of this thesis deals with design of neutral carrier for solvent polymeric membrane thiocyanate electrode with high selectivity.1. Bis-[(3-ferrocenyl)-(2-crotonic acid)] metallic complex of copper(II), cobalt(II) and riickel(II) were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these ferrocene derivatives as neutral carrier, and found that the electrode based on bis-[(3-ferrocenyl)-(2-crotonic acid)] copper(II) complex [Cu(II)-BFCA] as neutral carrier demonstrates high selectivity towards thiocyanate ion and anti-Hofmeister selectivity sequence in following order: SCN-'> I^-> C1O₄^-> Sal^-> Br^-> NO₃^-> Cl^-NO₂^- > SO₃^- > SO₄²-. The response mechanism is discussed in view of the UVspectroscopy and the A.C. impedance technique. The electrode was successfully applied to the determination of thiocyanate ion in actual sample.2. Dimethylaminobenzaldehyde-(o-aminobenzoic acid) metallic complexes of Cu(II), Ni(II), Co(II) and Zn(II) were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these metallic complexes as neutral carrier, and found that the electrode based on dimethylaminobenzaldehyde-(o-aminobenzoic acid) copper(II) complex [Cu(II)-DMABABA] as neutral carrier demonstrates high selectivity towards thiocyanate ion and anti-Hofmeister selectivity sequence in following order: SCN > r > Sal" > C1O4" > NO2" > Br > Cl" > NO3 > SO32 > SO42 > H2PO4^. The response mechanism is discussed in view of the UV spectroscopy and the A.C. impedance technique. The electrode was successfully applied to the determination of thiocyanate ion in actual sample.Part II of this thesis deals with design of neutral carrier for solvent polymeric membrane iodide electrode with high selectivity.1. yV,./V-bis-(acetylferrocene)-ethylenediamine metallic complexes of Hg(II), Cu(II) and Zn(II) were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these metallic complexes as neutral carrier, and found that the electrode based on 7V,A^-bis-(acetylferrocene)-ethylenediamine mercury(II) complex [Hg(II)-BAFEDA] as neutral carrier demonstrates high selectivity towards iodide ion and anti-Hofmeister selectivity sequence in following order: I" > Br > SCN > C1O4" > NO2" > Cl" > SO32 > NO3" > SO42". The response mechanism is discussed in view of the UV spectroscopy technique. The electrode was successfully applied to the determination of iodide ion in actual sample.2. #,A^-bis-(dimethylaminobenzaldehyde)-glycine metallic complexes of Co(II), Ni(II) and Cu(II) were synthesized. We firstly study the potentiometric response characteristics of the anion-selective PVC membrane electrode based on these...