Electroanalytical Chemistry and Interfacial Eleclrocj3emlstry Elsevier Sequom S-a , Lausanne -printed Iii the Netherlands the Chromium Content of the Solutions Was Determined Spectrophotometrically after Oxidation to Croz-in Alkaline Medium. the Thiocyanate Content Was Determined by Destruction of t
Electroanalytical Chemistry and Interfacial Eleclrocj3emlstry Elsevier Sequom S-a , Lausanne -printed Iii the Netherlands the Chromium Content of the Solutions Was Determined Spectrophotometrically after Oxidation to Croz-in Alkaline Medium. the Thiocyanate Content Was Determined by Destruction of t
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电分析化学和界面电学Elsevier Sequom S-a，洛桑印刷Iii 荷兰在Croz-in 碱性介质氧化后通过分光光度法测定溶液的铬含量。
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D. Zuccari
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作者：
G. R. Varallo;B. Jardim;P. Alexandre;H. Fukumasu;D. Zuccari
515高氯酸钠和高氯酸钠-硫氰酸盐体系中顺式和反式二异硫氰酸铬（~）离子的极谱还原在Yamaoka杂志的一篇最近的论文中，描述了在酸性高氯酸盐水溶液中，在汞表面不吸附SCN-离子的情况下，六水合和一、二异硫氰酸铬（II 1）络合离子的极谱还原。本文研究了某些铬（Ⅱ）配合物在含游离碘和碘的水溶液中的极谱和循环伏安行为。结果使还原电位更负，还原波更可逆.本文给出了反式和顺式-[Cr（NCS），-W ~（2+）]~* 络离子的计算结果。实验大多数实验细节已在其他地方描述2。根据Hougen等人3制备和分离络合离子。在电解液中NaSCN连续取代NaClO 4对异硫氰酸铬（II 1）络合物的极谱还原有两个影响：使还原波向更负的电位移动和增加δ值，这意味着还原变得更可逆。这可以解释如下：从表1中我们看到，在电解质中用NaSCN代替NaClO 4导致Ep，a比Ep，a向更负电位的更大偏移。这意味着电解质中SCN-离子的存在（因此在汞表面）促进了铬（I1）离子的氧化，正如Barclay等人4所发现和解释的那样。铬的再氧化
515 Polarographic reduction ofcis-and trans-diisothiocyanatochromium(~) ions ia acid sohtion of sodium perchlorate and sodium perchlorate-thiocyaate Tntroduction In a recent paper in this journal Yamaoka' describes the polarographic reduction of hexaaquo-and mono-and diisothiocyanatochromium(II1) complex ions in aqueous acidic perchlorate solution at the mercury surface free from adsorbed SCN-ions. We studied the polarographic and cyclic voltammetric behaviour of some chromium(II1) complexes in aqueous solutions containing free l&and. The results for to more negative potentials and makes the reduction wave more reversible. In this communication the results are given for the trans-and cis-[Cr(NCS),-W2%J* complex ions. Experimental Most experimental details have been described elsewhere2. The complex ions were prepared and separated according to Hougen et aL3. The successive replacement of NaC104 by NaSCN in the electrolyte has two effects on the polarographic reduction of the isothiocyanatochromium(II1) complexes : it shifts the reduction waves to more negative potentials and increases the 8 value, which means that the reduction becomes more reversible. This may be explained as follows : from Table 1 we see that the replacement of NaC104 by NaSCN in the electrolyte causes a much greater shift to more negative potentials of Ep,a than of E,,,. This means that the presence of SCN-ions in the elec-trolyte (and thus at the mercury surface) facilitates the oxidation of chromium(I1) ions, as was also found and explained by Barclay et aL4. The reoxidation of chro