{"title":"对“水溶液中Sn(IV)物种的热力学数据:争议和错误的问题”的评论","authors":"Dhanpat Rai","doi":"10.1007/s10953-023-01323-x","DOIUrl":null,"url":null,"abstract":"<div><p>May and Filella (J Solution Chem 52:754–761, 2023) concluded that they had verified the data in Gamsjäger et al. (Chemical thermodynamics of tin OECD, Nuclear Energy Agency Data Bank, Leoben, 2012). However, they used exactly the same primary data and not surprisingly came up with essentially the same values. They (1) provided no new data; (2) did not comment on/re-evaluate the existing experimental data (e.g., Sn–Cl complexes) that determine the accuracy of the <i>E</i><sup>0</sup> value for the (Sn<sup>4+</sup>/Sn<sup>2+</sup>) couple, but instead relied on a calculated value that is precise but of questionable accuracy; (3) disregarded extensive cassiterite (SnO<sub>2</sub>(cass)) solubility data that is critical to (a) ascertaining the accuracy of the <i>E</i><sup>0</sup> value based on <span>\\({\\mathrm{Sn}(\\mathrm{Cl})}_{y}^{4-\\mathrm{y}}\\)</span> complexes presented in Gamsjäger et al. (2012) and May and Filella (2023), (b) determining the solubility product of SnO<sub>2</sub>(cass), and (c) determining reliable overall <i>K</i><sup>0</sup> values for SnO<sub>2</sub>(s) solubility reactions involving <span>\\({\\mathrm{Sn}(\\mathrm{OH})}_{n}^{4-n}\\)</span> instead of Sn<sup>4+</sup>; and (4) in no way help resolve the many orders of magnitude differences in reported <i>K</i><sup>0</sup> values for various Sn(IV)–OH system reactions. These issues were extensively addressed in Rai (J Solution Chem.51:1169–1186, 2022) and are briefly discussed herein, and they help to determine that, contrary to May and Filella’s (2023) conclusions, the Sn(IV)–OH system thermodynamic constants presented in Rai (2022) are indeed reliable.</p></div>","PeriodicalId":666,"journal":{"name":"Journal of Solution Chemistry","volume":"52 12","pages":"1386 - 1393"},"PeriodicalIF":1.4000,"publicationDate":"2023-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10953-023-01323-x.pdf","citationCount":"0","resultStr":"{\"title\":\"Comment on “Thermodynamic Data for Sn(IV) Species in Aqueous Solution: Matter of Controversy and Error”\",\"authors\":\"Dhanpat Rai\",\"doi\":\"10.1007/s10953-023-01323-x\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>May and Filella (J Solution Chem 52:754–761, 2023) concluded that they had verified the data in Gamsjäger et al. (Chemical thermodynamics of tin OECD, Nuclear Energy Agency Data Bank, Leoben, 2012). However, they used exactly the same primary data and not surprisingly came up with essentially the same values. They (1) provided no new data; (2) did not comment on/re-evaluate the existing experimental data (e.g., Sn–Cl complexes) that determine the accuracy of the <i>E</i><sup>0</sup> value for the (Sn<sup>4+</sup>/Sn<sup>2+</sup>) couple, but instead relied on a calculated value that is precise but of questionable accuracy; (3) disregarded extensive cassiterite (SnO<sub>2</sub>(cass)) solubility data that is critical to (a) ascertaining the accuracy of the <i>E</i><sup>0</sup> value based on <span>\\\\({\\\\mathrm{Sn}(\\\\mathrm{Cl})}_{y}^{4-\\\\mathrm{y}}\\\\)</span> complexes presented in Gamsjäger et al. (2012) and May and Filella (2023), (b) determining the solubility product of SnO<sub>2</sub>(cass), and (c) determining reliable overall <i>K</i><sup>0</sup> values for SnO<sub>2</sub>(s) solubility reactions involving <span>\\\\({\\\\mathrm{Sn}(\\\\mathrm{OH})}_{n}^{4-n}\\\\)</span> instead of Sn<sup>4+</sup>; and (4) in no way help resolve the many orders of magnitude differences in reported <i>K</i><sup>0</sup> values for various Sn(IV)–OH system reactions. These issues were extensively addressed in Rai (J Solution Chem.51:1169–1186, 2022) and are briefly discussed herein, and they help to determine that, contrary to May and Filella’s (2023) conclusions, the Sn(IV)–OH system thermodynamic constants presented in Rai (2022) are indeed reliable.</p></div>\",\"PeriodicalId\":666,\"journal\":{\"name\":\"Journal of Solution Chemistry\",\"volume\":\"52 12\",\"pages\":\"1386 - 1393\"},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2023-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s10953-023-01323-x.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Solution Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10953-023-01323-x\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Solution Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10953-023-01323-x","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
May和Filella(《溶液化学杂志》52:754–7612023)得出结论,他们已经验证了Gamsjäger等人的数据。(锡的化学热力学,经合组织,核能机构数据库,Leoben,2012)。然而,他们使用了完全相同的主要数据,并得出了基本相同的值,这并不奇怪。他们(1)没有提供新的数据;(2) 没有对确定(Sn4+/Sn2+)对E0值准确性的现有实验数据(例如,Sn–Cl络合物)进行评论/重新评估,而是依赖于精确但准确性可疑的计算值;(3) 忽略了大量锡石(SnO2(cass))溶解度数据,这些数据对于(a)基于Gamsjäger等人(2012)和May and Filella(2023)中提出的\({\mathrm{Sn}(\mathrm{Cl})}_{y}^{4-\mathrm}})络合物确定E0值的准确性至关重要,(b)确定SnO2(cass)的溶解度积,和(c)确定涉及\({\mathrm{Sn}(\mathrm{OH})}_{n}^{4-n}\)而不是Sn4+的SnO2(s)溶解度反应的可靠的总K0值;和(4)决不能帮助解决各种Sn(IV)-OH体系反应的K0值的许多数量级差异。这些问题在Rai(J Solution Chem.51:1169–11862022)中得到了广泛的讨论,并在本文中进行了简要讨论,它们有助于确定,与May和Filella(2023)的结论相反,Rai(2022)中提出的Sn(IV)–OH系统热力学常数确实是可靠的。
Comment on “Thermodynamic Data for Sn(IV) Species in Aqueous Solution: Matter of Controversy and Error”
May and Filella (J Solution Chem 52:754–761, 2023) concluded that they had verified the data in Gamsjäger et al. (Chemical thermodynamics of tin OECD, Nuclear Energy Agency Data Bank, Leoben, 2012). However, they used exactly the same primary data and not surprisingly came up with essentially the same values. They (1) provided no new data; (2) did not comment on/re-evaluate the existing experimental data (e.g., Sn–Cl complexes) that determine the accuracy of the E0 value for the (Sn4+/Sn2+) couple, but instead relied on a calculated value that is precise but of questionable accuracy; (3) disregarded extensive cassiterite (SnO2(cass)) solubility data that is critical to (a) ascertaining the accuracy of the E0 value based on \({\mathrm{Sn}(\mathrm{Cl})}_{y}^{4-\mathrm{y}}\) complexes presented in Gamsjäger et al. (2012) and May and Filella (2023), (b) determining the solubility product of SnO2(cass), and (c) determining reliable overall K0 values for SnO2(s) solubility reactions involving \({\mathrm{Sn}(\mathrm{OH})}_{n}^{4-n}\) instead of Sn4+; and (4) in no way help resolve the many orders of magnitude differences in reported K0 values for various Sn(IV)–OH system reactions. These issues were extensively addressed in Rai (J Solution Chem.51:1169–1186, 2022) and are briefly discussed herein, and they help to determine that, contrary to May and Filella’s (2023) conclusions, the Sn(IV)–OH system thermodynamic constants presented in Rai (2022) are indeed reliable.
期刊介绍:
Journal of Solution Chemistry offers a forum for research on the physical chemistry of liquid solutions in such fields as physical chemistry, chemical physics, molecular biology, statistical mechanics, biochemistry, and biophysics. The emphasis is on papers in which the solvent plays a dominant rather than incidental role. Featured topics include experimental investigations of the dielectric, spectroscopic, thermodynamic, transport, or relaxation properties of both electrolytes and nonelectrolytes in liquid solutions.