{"title":"用氯化钙证明水溶液的性质。温度对解离程度和结合水数量的影响","authors":"Andreas A. Zavitsas*, ","doi":"10.1021/acs.jced.4c0030210.1021/acs.jced.4c00302","DOIUrl":null,"url":null,"abstract":"<p >Water solutions of CaCl<sub>2</sub> are important in many fields beside chemistry, such as biology, botany, enhanced petroleum recovery, construction, CO<sub>2</sub> capture, etc. The hydrodesmic (water-binding) number of CaCl<sub>2</sub> decreases from 12 waters strongly bound by 1 mol of CaCl<sub>2</sub> at 0 °C to only 6 waters at 250 °C. The extent of dissociation decreases from 2.55 to 1.78. Bound waters are not available as solvents for any additional solute. This changes the effective molality, which is linearly related to decreases in vapor pressure up to the point of 50% bound water. The diminution of the dielectric constant of water with increasing temperature causes increases in ion pairing and diminishes the number of unpaired ions present rather than their water-binding affinity. From 0 to 250 °C, a plot of hydrodesmic numbers versus extents of dissociation is linear. Understanding what causes these changes enables the calculation of solution properties at any temperature from 0 to 250 °C.</p>","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":"69 11","pages":"3669–3677 3669–3677"},"PeriodicalIF":2.0000,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Properties of Aqueous Solutions as Demonstrated by Calcium Chloride. The Effect of Temperature on the Extent of Dissociation and on the Number of Bound Waters\",\"authors\":\"Andreas A. Zavitsas*, \",\"doi\":\"10.1021/acs.jced.4c0030210.1021/acs.jced.4c00302\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Water solutions of CaCl<sub>2</sub> are important in many fields beside chemistry, such as biology, botany, enhanced petroleum recovery, construction, CO<sub>2</sub> capture, etc. The hydrodesmic (water-binding) number of CaCl<sub>2</sub> decreases from 12 waters strongly bound by 1 mol of CaCl<sub>2</sub> at 0 °C to only 6 waters at 250 °C. The extent of dissociation decreases from 2.55 to 1.78. Bound waters are not available as solvents for any additional solute. This changes the effective molality, which is linearly related to decreases in vapor pressure up to the point of 50% bound water. The diminution of the dielectric constant of water with increasing temperature causes increases in ion pairing and diminishes the number of unpaired ions present rather than their water-binding affinity. From 0 to 250 °C, a plot of hydrodesmic numbers versus extents of dissociation is linear. Understanding what causes these changes enables the calculation of solution properties at any temperature from 0 to 250 °C.</p>\",\"PeriodicalId\":42,\"journal\":{\"name\":\"Journal of Chemical & Engineering Data\",\"volume\":\"69 11\",\"pages\":\"3669–3677 3669–3677\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2024-09-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical & Engineering Data\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jced.4c00302\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical & Engineering Data","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jced.4c00302","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
除化学外,CaCl2 的水溶液在许多领域都很重要,如生物学、植物学、提高石油采收率、建筑、二氧化碳捕获等。在 0 °C 时,1 摩尔 CaCl2 与 12 个水分子强烈结合,而在 250 °C 时,仅与 6 个水分子结合。解离程度从 2.55 降至 1.78。结合水不能作为任何额外溶质的溶剂。这就改变了有效摩尔数,而有效摩尔数与蒸气压的降低呈线性关系,直至 50%的结合水。水的介电常数随温度升高而减小,导致离子配对增加,减少了未配对离子的数量,而不是其与水的结合亲和力。从 0 到 250 °C,水配对离子数与解离程度的关系图呈线性。了解了这些变化的原因,就可以计算出 0 至 250 °C 任何温度下的溶液特性。
Properties of Aqueous Solutions as Demonstrated by Calcium Chloride. The Effect of Temperature on the Extent of Dissociation and on the Number of Bound Waters
Water solutions of CaCl2 are important in many fields beside chemistry, such as biology, botany, enhanced petroleum recovery, construction, CO2 capture, etc. The hydrodesmic (water-binding) number of CaCl2 decreases from 12 waters strongly bound by 1 mol of CaCl2 at 0 °C to only 6 waters at 250 °C. The extent of dissociation decreases from 2.55 to 1.78. Bound waters are not available as solvents for any additional solute. This changes the effective molality, which is linearly related to decreases in vapor pressure up to the point of 50% bound water. The diminution of the dielectric constant of water with increasing temperature causes increases in ion pairing and diminishes the number of unpaired ions present rather than their water-binding affinity. From 0 to 250 °C, a plot of hydrodesmic numbers versus extents of dissociation is linear. Understanding what causes these changes enables the calculation of solution properties at any temperature from 0 to 250 °C.
期刊介绍:
The Journal of Chemical & Engineering Data is a monthly journal devoted to the publication of data obtained from both experiment and computation, which are viewed as complementary. It is the only American Chemical Society journal primarily concerned with articles containing data on the phase behavior and the physical, thermodynamic, and transport properties of well-defined materials, including complex mixtures of known compositions. While environmental and biological samples are of interest, their compositions must be known and reproducible. As a result, adsorption on natural product materials does not generally fit within the scope of Journal of Chemical & Engineering Data.