α-FeOOH (goethite)-ScOOH 固溶体的热力学

IF 1.2 4区 地球科学 Q4 MATERIALS SCIENCE, MULTIDISCIPLINARY
Juraj Majzlan
{"title":"α-FeOOH (goethite)-ScOOH 固溶体的热力学","authors":"Juraj Majzlan","doi":"10.1007/s00269-024-01298-1","DOIUrl":null,"url":null,"abstract":"<div><p>Scandium (Sc) is a rare element that finds uses in modern technologies. Thermodynamic properties of Sc phases could help in the development of innovative technologies to extract Sc from mining waste. In this work, we investigated the FeOOH–ScOOH solid solution with the goethite structure. The end members and five intermediate compositions were synthesized and characterized. The lattice parameters show that the solid solution is non-ideal, with complex behavior induced by the Fe–Sc substitution. The excess unit-cell volume deviates negatively for the Sc-rich region, and positively for the Fe-rich region from the ideal behavior (Vegard’s law). Enthalpies of dissolution were determined by acid-solution calorimetry in 5 mol<span>\\(\\cdot \\hbox {dm}^{-3}\\)</span> HCl at <i>T</i> = 343.15 K. Enthalpies of mixing (<span>\\(\\Delta _{mix}H\\)</span>), calculated from the experimental data, are small and positive. The available data allow for fitting the data as <span>\\(\\Delta _{mix}H = W x (1-x)\\)</span>, with the mixing parameter <span>\\(W = 15.2\\pm\\)</span>1.0 kJ<span>\\(\\cdot \\hbox {mol}^{-1}\\)</span>. Using <span>\\(\\Delta _fG^o\\)</span> of ScOOH from earlier literature, we calculated a Lippmann diagram that shows that Sc should strongly partition into the aqueous phase upon goethite precipitation. The field observations from lateritic profiles show that Sc is primarily harbored by goethite <i>via</i> adsorption. It seems that under weathering conditions, thermodynamically driven partitioning of <span>\\(\\hbox {Sc}^{3+}\\)</span> into the aqueous phases and its subsequent adsorption onto goethite surfaces controls the mobility of Sc in the weathering profiles.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":"51 4","pages":""},"PeriodicalIF":1.2000,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-024-01298-1.pdf","citationCount":"0","resultStr":"{\"title\":\"Thermodynamics of the α-FeOOH (goethite)-ScOOH solid solution\",\"authors\":\"Juraj Majzlan\",\"doi\":\"10.1007/s00269-024-01298-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Scandium (Sc) is a rare element that finds uses in modern technologies. Thermodynamic properties of Sc phases could help in the development of innovative technologies to extract Sc from mining waste. In this work, we investigated the FeOOH–ScOOH solid solution with the goethite structure. The end members and five intermediate compositions were synthesized and characterized. The lattice parameters show that the solid solution is non-ideal, with complex behavior induced by the Fe–Sc substitution. The excess unit-cell volume deviates negatively for the Sc-rich region, and positively for the Fe-rich region from the ideal behavior (Vegard’s law). Enthalpies of dissolution were determined by acid-solution calorimetry in 5 mol<span>\\\\(\\\\cdot \\\\hbox {dm}^{-3}\\\\)</span> HCl at <i>T</i> = 343.15 K. Enthalpies of mixing (<span>\\\\(\\\\Delta _{mix}H\\\\)</span>), calculated from the experimental data, are small and positive. The available data allow for fitting the data as <span>\\\\(\\\\Delta _{mix}H = W x (1-x)\\\\)</span>, with the mixing parameter <span>\\\\(W = 15.2\\\\pm\\\\)</span>1.0 kJ<span>\\\\(\\\\cdot \\\\hbox {mol}^{-1}\\\\)</span>. Using <span>\\\\(\\\\Delta _fG^o\\\\)</span> of ScOOH from earlier literature, we calculated a Lippmann diagram that shows that Sc should strongly partition into the aqueous phase upon goethite precipitation. The field observations from lateritic profiles show that Sc is primarily harbored by goethite <i>via</i> adsorption. It seems that under weathering conditions, thermodynamically driven partitioning of <span>\\\\(\\\\hbox {Sc}^{3+}\\\\)</span> into the aqueous phases and its subsequent adsorption onto goethite surfaces controls the mobility of Sc in the weathering profiles.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":\"51 4\",\"pages\":\"\"},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2024-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-024-01298-1.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physics and Chemistry of Minerals\",\"FirstCategoryId\":\"89\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00269-024-01298-1\",\"RegionNum\":4,\"RegionCategory\":\"地球科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-024-01298-1","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

钪(Sc)是一种稀有元素,可用于现代技术。钪相的热力学性质有助于开发从采矿废料中提取钪的创新技术。在这项工作中,我们研究了具有网闪石结构的 FeOOH-ScOOH 固溶体。我们合成并表征了最终成分和五种中间成分。晶格参数表明,该固溶体是非理想的,Fe-Sc置换引起了复杂的行为。与理想行为(维加定律)相比,富含钪区域的过剩单胞体积呈负偏离,富含铁区域的过剩单胞体积呈正偏离。根据实验数据计算出的混合焓(\(\Delta _{mix}H\))很小且为正值。根据现有数据,可以拟合数据为(\Δ _{mix}H=W x (1-x)),混合参数为(W = 15.2\pm\)1.0 kJ\(\cdot \hbox {mol}^{-1})。利用早期文献中 ScOOH 的 \(\Delta _fG^o\),我们计算出了一个 Lippmann 图,该图显示,Sc 应在网纹石沉淀后强烈地分出到水相中。从红土剖面的实地观测结果表明,Sc 主要是通过吸附作用被网纹石吸附的。看来,在风化条件下,热力学驱动的(\hbox {Sc}^{3+}\)向水相的分配及其随后在鹅绿泥石表面的吸附控制了Sc在风化剖面中的流动性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Thermodynamics of the α-FeOOH (goethite)-ScOOH solid solution

Scandium (Sc) is a rare element that finds uses in modern technologies. Thermodynamic properties of Sc phases could help in the development of innovative technologies to extract Sc from mining waste. In this work, we investigated the FeOOH–ScOOH solid solution with the goethite structure. The end members and five intermediate compositions were synthesized and characterized. The lattice parameters show that the solid solution is non-ideal, with complex behavior induced by the Fe–Sc substitution. The excess unit-cell volume deviates negatively for the Sc-rich region, and positively for the Fe-rich region from the ideal behavior (Vegard’s law). Enthalpies of dissolution were determined by acid-solution calorimetry in 5 mol\(\cdot \hbox {dm}^{-3}\) HCl at T = 343.15 K. Enthalpies of mixing (\(\Delta _{mix}H\)), calculated from the experimental data, are small and positive. The available data allow for fitting the data as \(\Delta _{mix}H = W x (1-x)\), with the mixing parameter \(W = 15.2\pm\)1.0 kJ\(\cdot \hbox {mol}^{-1}\). Using \(\Delta _fG^o\) of ScOOH from earlier literature, we calculated a Lippmann diagram that shows that Sc should strongly partition into the aqueous phase upon goethite precipitation. The field observations from lateritic profiles show that Sc is primarily harbored by goethite via adsorption. It seems that under weathering conditions, thermodynamically driven partitioning of \(\hbox {Sc}^{3+}\) into the aqueous phases and its subsequent adsorption onto goethite surfaces controls the mobility of Sc in the weathering profiles.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Physics and Chemistry of Minerals
Physics and Chemistry of Minerals 地学-材料科学:综合
CiteScore
2.90
自引率
14.30%
发文量
43
审稿时长
3 months
期刊介绍: Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are: -Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.) -General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.) -Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.) -Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.) -Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems -Electron microscopy in support of physical and chemical studies -Computational methods in the study of the structure and properties of minerals -Mineral surfaces (experimental methods, structure and properties)
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信