{"title":"氢键溶剂中Ni2+络合动力学:丙二酸镍在水-甘油溶液中","authors":"Warren Hirsch , Sergio Petrucci","doi":"10.1016/0378-4487(82)80028-9","DOIUrl":null,"url":null,"abstract":"<div><p>The kinetics of complexation at 25°C of nickel malonate in water-glycerine mixtures has been studied by the pressure-jump relaxation technique. For the water-glycerine mixtures, the ratio k<sub>f</sub>/K<sub>F</sub>, (namely the ratio between the forward rate constant k<sub>f</sub> and the pre-equilibration constant for the bimolecular diffusion step K<sub>F</sub>), shows a decrease within a factor of two from pure water to 49% glycerine in water. This decrease, if significant, is at variance with the apparently random scatter of the same data for water-fructose mixtures. In order to decide whether these changes in k<sub>f</sub>/K<sub>F</sub> reflect solvation of nickel ion, or modification of the chelation mechanism, the complexation of Ni(NCS)<sub>2</sub> at 10°C in the same solvent of composition 49% glycerine has been studied. It is proposed that the changes in k<sub>f</sub>/K<sub>F</sub>, may be caused by the changes in the K<sub>F</sub> with solvent composition, namely with changes in the ion-pair distance rather than with changes in the reaction mechanism. This is reflected in the constancy of the k<sub>f</sub>'s with solvent composition.</p></div>","PeriodicalId":100049,"journal":{"name":"Advances in Molecular Relaxation and Interaction Processes","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1982-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0378-4487(82)80028-9","citationCount":"0","resultStr":"{\"title\":\"Kinetics of complexation of Ni2+ in hydrogen bonded solvents: nickel malonate in water-glycerine solutions\",\"authors\":\"Warren Hirsch , Sergio Petrucci\",\"doi\":\"10.1016/0378-4487(82)80028-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The kinetics of complexation at 25°C of nickel malonate in water-glycerine mixtures has been studied by the pressure-jump relaxation technique. For the water-glycerine mixtures, the ratio k<sub>f</sub>/K<sub>F</sub>, (namely the ratio between the forward rate constant k<sub>f</sub> and the pre-equilibration constant for the bimolecular diffusion step K<sub>F</sub>), shows a decrease within a factor of two from pure water to 49% glycerine in water. This decrease, if significant, is at variance with the apparently random scatter of the same data for water-fructose mixtures. In order to decide whether these changes in k<sub>f</sub>/K<sub>F</sub> reflect solvation of nickel ion, or modification of the chelation mechanism, the complexation of Ni(NCS)<sub>2</sub> at 10°C in the same solvent of composition 49% glycerine has been studied. It is proposed that the changes in k<sub>f</sub>/K<sub>F</sub>, may be caused by the changes in the K<sub>F</sub> with solvent composition, namely with changes in the ion-pair distance rather than with changes in the reaction mechanism. This is reflected in the constancy of the k<sub>f</sub>'s with solvent composition.</p></div>\",\"PeriodicalId\":100049,\"journal\":{\"name\":\"Advances in Molecular Relaxation and Interaction Processes\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1982-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/0378-4487(82)80028-9\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advances in Molecular Relaxation and Interaction Processes\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/0378448782800289\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advances in Molecular Relaxation and Interaction Processes","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0378448782800289","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Kinetics of complexation of Ni2+ in hydrogen bonded solvents: nickel malonate in water-glycerine solutions
The kinetics of complexation at 25°C of nickel malonate in water-glycerine mixtures has been studied by the pressure-jump relaxation technique. For the water-glycerine mixtures, the ratio kf/KF, (namely the ratio between the forward rate constant kf and the pre-equilibration constant for the bimolecular diffusion step KF), shows a decrease within a factor of two from pure water to 49% glycerine in water. This decrease, if significant, is at variance with the apparently random scatter of the same data for water-fructose mixtures. In order to decide whether these changes in kf/KF reflect solvation of nickel ion, or modification of the chelation mechanism, the complexation of Ni(NCS)2 at 10°C in the same solvent of composition 49% glycerine has been studied. It is proposed that the changes in kf/KF, may be caused by the changes in the KF with solvent composition, namely with changes in the ion-pair distance rather than with changes in the reaction mechanism. This is reflected in the constancy of the kf's with solvent composition.
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