Determination of solubilities of uranium complexes in supercritical CO2 by on-line laser-induced fluorescence
Determination of solubilities of uranium complexes in supercritical CO2 by on-line laser-induced fluorescence
复制标题
在线激光诱导荧光测定铀配合物在超临界 CO2 中的溶解度
DOI：
10.1021/ac0003450
复制
发表时间：
2000
影响因子：
7.4
通讯作者：
Wai
中科院分区：
文献类型：
--
作者：
Addleman;Carrott;Wai
报道了一种利用激光诱导荧光测量超临界二氧化碳溶解度的新方法。人们发现这种选择性技术能够以高灵敏度（10(-9) M）快速进行多点溶解度测量。其灵敏度使得可以在低压（80-130 atm）（通常低于其他方法的范围）下对少量分析物进行测量。使用此方法研究了四种铀酰络合物：UO2(TTA)2.H20、UO2(TTA)2.TBP、UO2(TTA)2.TOPO 和 UO2(NO3)2.2TBP（其中 TTA = 噻吩酰三氟丙酮，TBP = 磷酸三丁酯，TOPO = 三辛基氧化膦）。与之前通过紫外-可见光谱获得的溶解度数据进行比较，表明这些技术之间具有良好的一致性。我们已经证明，Chrastil 溶解度方程在较低的 ScF 密度下同样有效，因此，在高压下确定的溶解度值可以外推到低压区域，对于固体材料反之亦然。
A new approach to the measurement of solubilities in supercritical CO2 is reported, utilizing laser-induced fluorescence. This selective technique was found to be capable of rapid multipoint solubility measurements with high sensitivity (10(-9) M). The sensitivity enables measurements to be performed with small amounts of analytes and at low pressure, 80-130 atm, typically below the range of other methods. Four uranyl complexes were investigated using this method, UO2(TTA)2.H20, UO2(TTA)2.TBP, UO2(TTA)2.TOPO, and UO2(NO3)2.2TBP (where TTA = thenoyltrifluoroacetone, TBP = tributyl phosphate, and TOPO = trioctyl phosphine oxide). Comparison with solubility data previously obtained with UV-visible spectroscopy shows good agreement between the techniques. We have shown that the Chrastil solubility equation is equally valid at lower ScF densities, and consequently, solubility values determined at high pressures can be extrapolated to the low-pressure regions and vice versa for solid materials.