{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1363670319582895104.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/chem.200900334"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.200900334"}},{"identifier":{"@type":"URI","@value":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.200900334"}}],"dc:title":[{"@value":"Directly Relating Gas‐Phase Cluster Measurements to Solution‐Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p><jats:bold>Hydrated ion nanocalorimetry</jats:bold> is used to measure reduction energies and H atom affinities of gaseous hydrated ions by determining the energy deposited into these nanodrops from the number of water molecules lost upon reduction by thermally generated electrons (see figure).<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" mimetype=\"image/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic/mcontent.gif\"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text></jats:p><jats:p>Solution‐phase, half‐cell potentials are measured relative to other half‐cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline‐earth or transition‐metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H<jats:sub>2</jats:sub>O)<jats:sub>24</jats:sub><jats:sup>2+</jats:sup>(g)+e<jats:sup>−</jats:sup>(g)→M(H<jats:sub>2</jats:sub>O)<jats:sub>24</jats:sub><jats:sup>+</jats:sup>(g) and 2) M(H<jats:sub>2</jats:sub>O)<jats:sub>24</jats:sub><jats:sup>2+</jats:sup>(g)+e<jats:sup>−</jats:sup>(g)→MOH(H<jats:sub>2</jats:sub>O)<jats:sub>23</jats:sub><jats:sup>+</jats:sup>(g)+H(g) and the hydrogen atom affinities of MOH(H<jats:sub>2</jats:sub>O)<jats:sub>23</jats:sub><jats:sup>+</jats:sup>(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e<jats:sup>−</jats:sup>(g) (standard deviation of 0.02 V) and a real proton solvation free energy of −265 kcal mol<jats:sup>−1</jats:sup> are obtained. With this method, the absolute SHE potential can be obtained from a one‐electron reduction of nanodrops containing divalent ions that are not observed to undergo one‐electron reduction in aqueous solution.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1383670319582895104","@type":"Researcher","foaf:name":[{"@value":"William A. Donald"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670319582895106","@type":"Researcher","foaf:name":[{"@value":"Ryan D. Leib"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670319582895107","@type":"Researcher","foaf:name":[{"@value":"Jeremy T. O'Brien"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670319582895105","@type":"Researcher","foaf:name":[{"@value":"Evan R. Williams"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"09476539"},{"@type":"EISSN","@value":"15213765"}],"prism:publicationName":[{"@value":"Chemistry – A European Journal"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2009-05-29","prism:volume":"15","prism:number":"24","prism:startingPage":"5926","prism:endingPage":"5934"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.200900334"},{"@id":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.200900334"}],"createdAt":"2009-05-13","modifiedAt":"2025-10-12","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360004230162788352","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Consistent scheme for computing standard hydrogen electrode and redox potentials"}]},{"@id":"https://cir.nii.ac.jp/crid/1360004233180934016","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"A Density Functional Theory Based Protocol to Compute the Redox Potential of Transition Metal Complex with the Correction of Pseudo-Counterion: General Theory and Applications"}]},{"@id":"https://cir.nii.ac.jp/crid/1360005516629589888","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Minimizing energy demand and environmental impact for sustainable NH3 and H2O2 production—A perspective on contributions from thermal, electro-, and photo-catalysis"}]},{"@id":"https://cir.nii.ac.jp/crid/1360009142830859520","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Ab Initio Evaluation of the Redox Potential of Cytochrome c"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285707061502976","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Quantum chemical approach for condensed-phase thermochemistry (III): Accurate evaluation of proton hydration energy and standard hydrogen electrode potential"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285707245926784","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Determination of the real potential of chloride ion in water by using a voltaic cell with a dropping carbon fluid electrode"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708212978560","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Accurate Standard Hydrogen Electrode Potential and Applications to the Redox Potentials of Vitamin C and NAD/NADH"}]},{"@id":"https://cir.nii.ac.jp/crid/1360298754848548992","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Electrolyzed–Reduced Water: Review I. 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