硫化合物中硫K-Beta谱研究  

SKp Spectra Applied to Chemical State Analysis

作　　者：吉昂[1] 刘红超[1] 陶光仪[1] 王庆广[2] 马光祖[3] 

机构地区：[1]中国科学院上海硅酸盐研究所,上海200050 [2]中国科学院生态环境研究中心 [3]中国国家地质实验测试中心

出　　处：《分析化学》1995年第10期1113-1116,共4页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金资助

摘　　要：作者应用加了限制垂直发散准直器的Philips PW1404型X-射线荧光分析仪测定了多种含硫化合物中SK_β谱及其卫星线,谱获取后以统计实验最优化方法处理,获得SK_β和SK_(β＇)谱峰值.结果表明硫酸盐中SK_β和SK_(β＇)谱峰值能量差与分子轨道理论DV-Xα方法计算结果相一致.可应用SK_β和SK_β—SK_(β＇)能量差判别化合物中硫的价态及硫与相邻原子结合的类型.作者还根据二苯基硫巴腙的SK_β谱讨论了它的结构.SKβ spectra at modified PW1404 and RIGAKU 3070 were Fisted. From the figures , it could easily be seen that SKβ spectra showed considerable variation in their structure. SKβ spectra of sulphur oxy-anions could be distinguished from other by its characteristic SKβ' peaks. Pure S gave broadened Kβ spectrum which may contain two or more peaks. SKβ spectrum from NH2CSNH2 has two peaks varied in intensity, while only one peak appeared in SKβ spectrum of FeS.Chemical shift (AE), energy position of a peak shifting to that of a standard substance, is very important factor in state analysis. So chemical shifts of Kβ and Kβ' peaks were given, in order to discriminate the states of sulphur oxy-anions whose SKβ spectra were similar. Energy differences(SE) between SKβand SKβ' were also calculated. From these values, it could be found that SE reduced with the decreasing of Kβchemical shifts, increased with decreasing Kβ' chemical shifts; with the exception of sulphonate salicylic, which maybe caused by the strange electron distribution of aromatic ring neighbouring with sulphur.In SQl- cluster, S3/,character enters the sulphate 4i3 and 3t2 molecular orbitals. The energy difference between the two levels calculated by DV-X. cluster calculations was 13. i eV, by SCF-Xct was 13. 6 eV and that got by soft XES 14. 7 eV, which shows a very good agreement with our experimental result; 14. 4 eV. Other SKo spectra could also be understood in terms of MO theory. The structure of diphenyl thiocarbasone was also proposed.

关 键 词：X-射线荧光光谱 硫化合物 二苯基硫巴腙 

分 类 号：O613.51[理学—无机化学] O657.34[理学—化学]