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Voltammetric determination of stability constants of lead complexes with diallyl disulfide, dimethyl disulfide, and diallyl sulfide

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Chinese Chemical Letters 2016年第1期27卷 71-76页

作者： Mohammad Ali Kamyabi Fatemeh Soleymani-Bonoti Saeed Zakavi Department of Chemistry University of Zanjan Department of Chemistry Institute for Advanced Studies in Basic Sciences

The complexation of Pb^（2＋）by diallyl disulfide（DADS）, dimethyl disulfide（DMDS） and diallyl sulfide（DAS）has been studied by differential pulse voltammetry. Stability constants,（log b）, of the 1：1（PbL） and 1：2（PbL_2） complexes, where L = ligand, were found to be in the range of ca. 3.8-4.2 and 9.4-10.2,respectively. Complex formation is accompanied with a significant decrease in the peak current and the shift of the Pb2＋/Pb half-wave potential to a higher one upon the addition of the sulfur containing ligands（L）. The formation of 1：1 and 1：2 complexes, i.e., PbL^（2＋）and PbL_2^（2＋）was observed in the case of the three ligands. The consecutive formation constants of labile lead complexes with DADS, DMDS, and DAS were determined at 298 K by the method of De Ford and Hume. Apparently due to the large size of the lead ion,steric hindrance caused by the greater steric bulk of DADS compared to that of DMDS have little or no effects on the formation constants, so that very similar values were obtained in the case of the two ligands. Also, the possible participation of C=C double bonds in coordination with the metal center in the case of DADS appears to compensate for the steric effects caused by the larger size of this ligand. In agreement with the Jorgensen principle of symbiosis, the second formation constants were found to be approximately six orders of magnitude greater than the first ones.

关键词： Garlic oil organic sulfur compounds Pb^(2+)-DADS,DMDS,and DAS complexes Stability constant

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Molecular characterization of sulfur compounds in some special sulfur-rich Chinese crude oils by FT-ICR MS

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Science China Earth Sciences 2014年第1期57卷 1158-1167页

作者： LU Hong SHI Quan MA QingLin SHI Yang LIU JinZhong SHENG GuoYing PENG PingAn State Key Laboratory of organic Geochemistry Guangzhou Institute of Geochemistry Chinese Academy of Sciences State Key Laboratory of Heavy Oil China Petroleum University Beijing Southern Petroleum Exploration and Development Ltd. (CNPC)

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions;thus,relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur *** this article,Fourier Transform Ion Cyclotron Resonance Mass Spectrometry(FT-ICR MS)with high resolution is employed to investigate the distribution of organic sulfur compounds(OSCs)in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type,carbon number,and double bond equivalent(DBE).A variety of miscellaneous atomic types with S1,S2,S3,OS,OS2,O2S,O2S2,NS,and NOS etc.(S1 means those OSCs with one sulfur atom in a molecule)were identified in OSCs in these oil *** levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene,dibenzothiophene *** with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian *** carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin,obviously,they possess different chemical diagenetic pathway of sulfur under various microbial reactions,leading to diverse distributional characteristics on biomarkers,OSCs,and even different hydrocarbon generation mechanism of immature crude oil.

关键词： ESI FT-ICR MS organic sulfur compounds sulfur-rich oil Jianghan Basin Jinxian Sag

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