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确定以1.5N H_2SO_4-1.2%NH_4Cl-0.0012M(CH_2)_6N_4-0.003%N_2H_4·H_2SO_(4)为连续测定超微量铂、铑的催化极谱体系。铂、铑在此体系中同时分别产生峰电位103V和-1.27 V(对S.C.E.)的催化氢波。利用此两催化波可检出0.01 Ppb铂和0.0025 ppb铑在确定条件下,铂的浓度在0.05～1.0ppb范围内,铑的浓度在0.0025～0.10)ppb范围内的相应催化电流与它们的浓度间有良好的线性关系。铂、铑比为200∶1及1∶10时的测定互不干扰。研究产生铑催化波的机理,证明此波是体系中六次甲基四胺水解产物甲醛与[RhCl_6]~(3-)形成的配阴离子[Rh(CH_2O)_2Cl_4]~-催化氢离子放电的结果。证明铂催化波属催化氢波,其生成机理是:六次甲基四胺水解中间产物CH_2=NH或最终产物甲醛与硫酸肼反应生成的(CH_2-X)_2与[PtCl_6]~2-构成配阴离子[Pt(CH_2=N)_2Cl_5]~-催化氢离子放电的结果,并提出具有CH_2-N基的物质可使铂产生高灵敏度的催化波。由于硫酸肼能与催化体系中水解产物甲醛作用,既形成能产生铂催化波的(CH_2=N)_2,又能控制体系中甲醛量而有利于活性配合物[Rh(CH_2O)_2Cl_4]~-的形成,从而保持铑、铂催化波的稳定性。
The catalytic system for the determination of trace platinum and rhodium with 1.5N H_2SO_4-1.2% NH_4Cl-0.0012M (CH_2) _6N_4-0.003% N_2H_4 · H_2SO_ (4) was determined. Platinum and rhodium also generate catalytic hydrogen waves with peak potentials of 103V and -1.27 V (for S.C.E.) at the same time in this system. Using these two catalytic waves, 0.01 Ppb platinum and 0.0025 ppb rhodium can be detected. The corresponding catalytic currents in the range of 0.05 to 1.0 ppb for platinum and 0.0036 to 0.10 ppb for rhodium under certain conditions are proportional to their concentrations Have a good linear relationship between. Platinum, rhodium ratio of 200: 1 and 1:10 when the determination of non-interference. The mechanism of producing rhodium catalyzed wave was studied, and it was proved that this wave was the anion of [Rh (CH_2O) _2Cl_4] ~ -catalyzed hydrogen formed by formaldehyde and [6-methyltetraamine hydrolysates formaldehyde and [RhCl_6] ~ (3-) result. It is proved that platinum catalyzed wave belongs to catalytic hydrogen wave and its formation mechanism is: (CH_2-X) _2 and [PtCl_6] ~ 2- formed by the reaction of hexamethylenetetramine hydrolysis intermediate CH_2 = NH or the final product formaldehyde and hydrazine sulfate With the anion [Pt (CH_2 = N) _2Cl_5] ~ - catalytic hydrogen ion discharge results, and the proposed CH_2-N-based material can produce high sensitivity platinum catalytic wave. Hydrazine sulfate can react with formaldehyde, a hydrolysable product in the catalytic system, to form (CH_2 = N) _2, which can generate platinum catalytic wave, and to control the amount of formaldehyde in the system, which is in favor of the active complexes [Rh (CH_2O) _2Cl_4] The formation of rhodium, platinum thus catalyze the stability of the wave.