INFLUENCE OF pH UPON THE PHOTOLYSIS OF THE URANYL OXALATE ACTINOMETER SYSTEM.
INFLUENCE OF pH UPON THE PHOTOLYSIS OF THE URANYL OXALATE ACTINOMETER SYSTEM.
复制标题
pH 对草酸铀酰光解计系统光解作用的影响。
DOI：
10.1021/j100704a009
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发表时间：
1970
期刊：
影响因子：
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通讯作者：
F. A. Middleton
中科院分区：
文献类型：
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作者：
L. J. Heidt;G. Tregay;F. A. Middleton
在254nm光下，研究了pH值对草酸铀酰光度计系统消耗草酸盐和产生二氧化碳、一氧化碳和铀离子的相对量子产率的影响。铀酰离子温度为0.01 F，草酸盐温度为0.06 F，初始pH为0-6。大约12%的草酸被分解。发现草酸消耗的量子产率与pH值在1和5之间无关，但在此范围之外会减少。发现在任何pH值下的反应都消耗酸。在pH为0到5的情况下，每摩尔草酸所消耗的各种形式的二氧化碳（co2, H2CO3, HCO3"， co32和碳酸铀酰络合物）的摩尔数几乎是相等的。消耗每摩尔草酸产生的一氧化碳的摩尔数总是小于1；在pH 1 ~ 2之间，随着pH的增加，它们突然下降，在pH 3以上可以忽略不计。产生的铀离子与消耗的草酸盐的摩尔比从pH 1.5 ~ 4时的约0.03缓慢增加到pH 6时的约0.08。讨论了反应的机理。
A study has been made at 25 of the influence of pH upon the relative quantum yields for the consumption of oxalate and the production of carbon dioxide, carbon monoxide, and uranous ion by light of 254 nm absorbed by the uranyl oxalate actinometer system. The uranyl ion was at 0.01 F, the oxalate at 0.06 F, and initial pH was at 0-6. About 12% of the oxalate was decomposed. The quantum yields for theconsumption of oxalate were found to be independent of the pH between 1 and 5 but to decrease outside this range. The reaction at all values of pH was found to consume acid. The moles of carbon dioxide produced in all forms (C02, H2CO3, HCO3", CO32-and the uranyl carbonatecomplexes) per mole of oxalate consumed very nearly equalled unity at pH 0 to 5. The moles of carbon monoxide produced per mole of oxalateconsumed were always less than unity; they decreased with increase in pH abruptly between pH 1 and 2, and became negligible above pH 3. The mole ratio of uranous ion produced to oxalate consumed increased slowly from about 0.03 between pH 1.5 and 4 to about 0.08 at pH 6. The mechanisms of the reactions are discussed.