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Properties of lithium under hydrothermal conditions revealed by in situ Raman spectroscopic characterization of Li2O-SO3-H2O (D2O) systems at temperatures up to 420 degrees C
Wang, Xiaolin1,2; Wang, Xiaoyu1; Chou, I-Ming3; Hu, Wenxuan1,2; Wan, Ye1; Li, Zhen4; Xiaolin Wang,Wenxuan Hu
2017-02-20
Source PublicationCHEMICAL GEOLOGY
Volume451Issue:2017Pages:104-115
AbstractLithium (Li) is an important component of hydrothermal fluids, especially submarine hydrothermal fluids. Investigation of the species and ion complexation of Li+ at elevated temperature and pressure can improve our knowledge on the behavior of Li under hydrothermal conditions. In this study, in situ optical and Raman spectroscopic experiments were conducted on the Li2SO4-H2SO4-H2O system and its D2O analogue at temperatures <= 420 degrees C. An unexpected liquid-liquid phase separation (immiscibility) was observed at temperatures above 336.5 degrees C; the aqueous phase was separated into a sulfate-rich heavy liquid phase and a sulfate-poor light liquid phase at vapor-saturation pressures. The liquid-liquid phase separation temperature decreased as the Li2SO4 concentration increased in dilute solutions (<= 1.25 m), increased as the Li2SO4 concentration increased in concentrated solutions (>1.25 m), and exhibited a lower critical solution temperature (LCST) at similar to 336.5 degrees C. The presence of excess H2SO4 (or D2SO4) increased the liquid-liquid phase separation temperature at a constant Li2SO4 concentration. Liquid-liquid phase separation is common in organic-bearing solutions, and LCST is considered to be a macro scale property of polymer solutions, indicating complicated ion pairing between Li+ and SO42- at high temperature. In situ Raman spectra of the v(1)(SO42-) band indicated the presence of "free" SO42-, LiSO4-, possible Li2SO4 and other poly-ion associations. The Li+-SO42- association increased with increasing temperature at a constant Li2SO4 concentration. These results indicate that Li+ can form contact ion pairs with ligands despite its strong hydration tendency.
SubtypeReview
KeywordRaman Spectroscopy Liquid-liquid Immiscibility Li++ Speciation Mineral Crystallization Hydrothermal Fluids
WOS HeadingsScience & Technology ; Physical Sciences
DOI10.1016/j.chemgeo.2017.01.013
Indexed BySCI
Language英语
WOS KeywordJUAN-DE-FUCA ; LIQUID-LIQUID IMMISCIBILITY ; ALKALI SULFATE-SOLUTIONS ; AQUEOUS ZNSO4 SOLUTIONS ; UPPER OCEANIC-CRUST ; ION-PAIR FORMATION ; EAST PACIFIC RISE ; NORTH FIJI BASIN ; VENT FLUIDS ; DIELECTRIC-SPECTROSCOPY
WOS SubjectGeochemistry & Geophysics
WOS IDWOS:000394916900010
Citation statistics
Cited Times:5[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Version出版稿
Identifierhttp://ir.idsse.ac.cn/handle/183446/1695
Collection深海科学研究部_深海极端环境模拟研究实验室
Corresponding AuthorXiaolin Wang,Wenxuan Hu
Affiliation1.Nanjing Univ, Sch Earth Sci & Engn, State Key Lab Mineral Deposits Res, Nanjing 210023, Jiangsu, Peoples R China
2.Nanjing Univ, Inst Energy Sci, Nanjing 210023, Jiangsu, Peoples R China
3.Chinese Acad Sci, Inst Deep Sea Sci & Engn, Lab Expt Study Under Deep Sea Extreme Condit, Sanya 572000, Hainan, Peoples R China
4.Curtin Univ, Inst Geosci Res, Dept Appl Geol, GPOB U1987, Perth, WA 6845, Australia
Recommended Citation
GB/T 7714
Wang, Xiaolin,Wang, Xiaoyu,Chou, I-Ming,et al. Properties of lithium under hydrothermal conditions revealed by in situ Raman spectroscopic characterization of Li2O-SO3-H2O (D2O) systems at temperatures up to 420 degrees C[J]. CHEMICAL GEOLOGY,2017,451(2017):104-115.
APA Wang, Xiaolin.,Wang, Xiaoyu.,Chou, I-Ming.,Hu, Wenxuan.,Wan, Ye.,...&Xiaolin Wang,Wenxuan Hu.(2017).Properties of lithium under hydrothermal conditions revealed by in situ Raman spectroscopic characterization of Li2O-SO3-H2O (D2O) systems at temperatures up to 420 degrees C.CHEMICAL GEOLOGY,451(2017),104-115.
MLA Wang, Xiaolin,et al."Properties of lithium under hydrothermal conditions revealed by in situ Raman spectroscopic characterization of Li2O-SO3-H2O (D2O) systems at temperatures up to 420 degrees C".CHEMICAL GEOLOGY 451.2017(2017):104-115.
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