{"title":"长石中的氢缺陷:碱支撑的苯胺脱氢","authors":"Harald Behrens","doi":"10.1007/s00269-023-01242-9","DOIUrl":null,"url":null,"abstract":"<div><p>In the first two papers of this series [Behrens, Phys Chem Minerals 48:8, 2021a; Behrens, Phys Chem Minerals 48:27, 2021b], incorporation of hydrogen in the feldspar structure, partitioning of hydrogen between feldspars and gases/fluids and self-diffusion of hydrogen in feldspars have been discussed, with particular focus on sanidine. Here, the results of reactions between sanidine containing strongly bonded hydrogen defects and (Na,K)Cl are presented. Experiments were performed at ambient pressure at temperatures of 605–1000 °C, and hydrogen profiles were measured by IR microspectroscopy. Profiles can be interpreted by an incomplete dehydrogenation at the crystal surface or a strong concentration dependence of hydrogen diffusivity. Both are consistent with hydrogen located on interstitial sites and difficult to substitute by the larger alkali ions. Chemical diffusivities of hydrogen derived from fitting of the profiles or Boltzmann–Matano analysis are similar to self-diffusivities determined by D/H exchange experiments. Activation energies are also comparable. Comparison to sodium and potassium diffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363: 79–84, 2015; Hergemöller et al. in Phys Chem Minerals 44:345–351, 2017) supports a mechanism of proton diffusion charge-compensated by Na<sup>+</sup> diffusion for hydrogen removal in the sanidines under dry conditions.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2023-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-023-01242-9.pdf","citationCount":"0","resultStr":"{\"title\":\"Hydrogen defects in feldspars: alkali-supported dehydrogenation of sanidine\",\"authors\":\"Harald Behrens\",\"doi\":\"10.1007/s00269-023-01242-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In the first two papers of this series [Behrens, Phys Chem Minerals 48:8, 2021a; Behrens, Phys Chem Minerals 48:27, 2021b], incorporation of hydrogen in the feldspar structure, partitioning of hydrogen between feldspars and gases/fluids and self-diffusion of hydrogen in feldspars have been discussed, with particular focus on sanidine. Here, the results of reactions between sanidine containing strongly bonded hydrogen defects and (Na,K)Cl are presented. Experiments were performed at ambient pressure at temperatures of 605–1000 °C, and hydrogen profiles were measured by IR microspectroscopy. Profiles can be interpreted by an incomplete dehydrogenation at the crystal surface or a strong concentration dependence of hydrogen diffusivity. Both are consistent with hydrogen located on interstitial sites and difficult to substitute by the larger alkali ions. Chemical diffusivities of hydrogen derived from fitting of the profiles or Boltzmann–Matano analysis are similar to self-diffusivities determined by D/H exchange experiments. Activation energies are also comparable. Comparison to sodium and potassium diffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363: 79–84, 2015; Hergemöller et al. in Phys Chem Minerals 44:345–351, 2017) supports a mechanism of proton diffusion charge-compensated by Na<sup>+</sup> diffusion for hydrogen removal in the sanidines under dry conditions.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2023-06-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-023-01242-9.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/s00269-023-01242-9\",\"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/s00269-023-01242-9","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
在本系列的前两篇论文中[Behrens,物理化学矿物48:8,2021a;Behrens,物理化学矿物48:27,2021 [b],讨论了氢在长石结构中的掺入,氢在长石与气体/流体之间的分配以及氢在长石中的自扩散,特别是氢在长石中的自扩散。本文介绍了含强键氢缺陷的苯胺与(Na,K)Cl的反应结果。实验在605-1000°C的环境压力下进行,并通过红外显微光谱测量氢谱。剖面可以通过晶体表面的不完全脱氢或氢扩散率的浓度依赖性来解释。两者都与位于间隙位置的氢相一致,难以被较大的碱离子取代。由玻尔兹曼-马塔诺分析得到的氢的化学扩散系数与由D/H交换实验确定的自扩散系数相似。活化能也是可以比较的。(Wilangowski et al.,缺陷扩散论坛363:79-84,2015;Hergemöller等人在物理化学矿物44:35 5 - 351,2017)支持质子扩散机制,由Na+扩散补偿,以在干燥条件下去除氢。
Hydrogen defects in feldspars: alkali-supported dehydrogenation of sanidine
In the first two papers of this series [Behrens, Phys Chem Minerals 48:8, 2021a; Behrens, Phys Chem Minerals 48:27, 2021b], incorporation of hydrogen in the feldspar structure, partitioning of hydrogen between feldspars and gases/fluids and self-diffusion of hydrogen in feldspars have been discussed, with particular focus on sanidine. Here, the results of reactions between sanidine containing strongly bonded hydrogen defects and (Na,K)Cl are presented. Experiments were performed at ambient pressure at temperatures of 605–1000 °C, and hydrogen profiles were measured by IR microspectroscopy. Profiles can be interpreted by an incomplete dehydrogenation at the crystal surface or a strong concentration dependence of hydrogen diffusivity. Both are consistent with hydrogen located on interstitial sites and difficult to substitute by the larger alkali ions. Chemical diffusivities of hydrogen derived from fitting of the profiles or Boltzmann–Matano analysis are similar to self-diffusivities determined by D/H exchange experiments. Activation energies are also comparable. Comparison to sodium and potassium diffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363: 79–84, 2015; Hergemöller et al. in Phys Chem Minerals 44:345–351, 2017) supports a mechanism of proton diffusion charge-compensated by Na+ diffusion for hydrogen removal in the sanidines under dry conditions.
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)