Kinetics and reactivity correlation in diol oxidation by tetramethyl-ethylenediammonium dichromate across acetic acid–water mole fractions

Kinetics and reactivity correlation in diol oxidation by tetramethyl-ethylenediammonium dichromate across acetic acid–water mole fractions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Kinetics and reactivity correlation in diol oxidation by tetramethyl-ethylenediammonium dichromate across acetic acid–water mole fractions Dinesh panday This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9087208/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The present investigation focuses on the oxidation kinetics of four vicinal diols, four non-vicinal diols, and one monoether by tetramethyl-ethylenediammonium dichromate (TMEDADC) in water–acetic acid mixtures of different molar ratios. All the selected diols resulted in the formation of corresponding hydroxyaldehyde as a main product of the oxidation. The reaction follows first-order kinetics with respect to TMEDADC and shows a fractional order (between 1 and 2) in diol concentration. Oxidation of [1,1,2,2- 2 H 4 ] ethane diol exhibits a noticeable primary kinetic isotope effect ( k H / k D = 5.58 at 298 K). A strong linear correlation is observed between the rate constants for vicinal diols and the Taft polar substituent constants (Σσ*), and the negative polar reaction constant (ρ* = − 2.19 at 298 K) indicates the development of an electron-deficient center in the rate-determining step. A plausible process involving the pre-equilibrium generation of chromate ester has been postulated. Diols tetramethyl-ethylenediammonium dichromate kinetics oxidation correlation solvent polarity mechanism Full Text Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9087208","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":607755785,"identity":"c8c6e5e9-5001-4c87-a48a-bec12bf8a36c","order_by":0,"name":"Dinesh panday","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA40lEQVRIiWNgGAWjYDCCA0DMw8Agx8/eAGQZWBCvxViyB8QykCBeS+KGGQkgLhFa+G43P3vwpuYw4wbJ51c3/CiQYOBv707Aq0XyzjFzwznHDjObS+eU3ewBOkzizNkNeLUY3Egwk+ZhO8xmOTsn7QYPUIuBRC4hLenfpHn+HeYxuHkm7eYf4rTkmEnzth2WMLjBfuw2UbZI3jlTJjm3L91AsieH7baMgQQPQb/w3W7fJvHmm3V9P/vxZzff/LGR42/vxa8FGhHNQMxjAGLx4FeO0FIHxOwPCKseBaNgFIyCEQkAM/dMYEur1XoAAAAASUVORK5CYII=","orcid":"","institution":"Mohanlal Sukhadia University","correspondingAuthor":true,"prefix":"","firstName":"Dinesh","middleName":"","lastName":"panday","suffix":""}],"badges":[],"createdAt":"2026-03-10 19:08:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9087208/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9087208/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108456506,"identity":"6b830cbb-f015-47f9-971b-d74933609882","added_by":"auto","created_at":"2026-05-04 21:54:05","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":709512,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript..pdf","url":"https://assets-eu.researchsquare.com/files/rs-9087208/v1_covered_e6e06415-db2e-4089-a973-fd8d4c3f369d.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Kinetics and reactivity correlation in diol oxidation by tetramethyl-ethylenediammonium dichromate across acetic acid–water mole fractions","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Diols, tetramethyl-ethylenediammonium dichromate, kinetics, oxidation, correlation, solvent polarity, mechanism","lastPublishedDoi":"10.21203/rs.3.rs-9087208/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9087208/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe present investigation focuses on the oxidation kinetics of four vicinal diols, four non-vicinal diols, and one monoether by tetramethyl-ethylenediammonium dichromate (TMEDADC) in water\u0026ndash;acetic acid mixtures of different molar ratios. All the selected diols resulted in the formation of corresponding hydroxyaldehyde as a main product of the oxidation. The reaction follows first-order kinetics with respect to TMEDADC and shows a fractional order (between 1 and 2) in diol concentration. Oxidation of [1,1,2,2- \u003csup\u003e2\u003c/sup\u003eH\u003csub\u003e4\u003c/sub\u003e] ethane diol exhibits a noticeable primary kinetic isotope effect (\u003cem\u003ek\u003c/em\u003e\u003csub\u003eH\u003c/sub\u003e/\u003cem\u003ek\u003c/em\u003e\u003csub\u003eD\u003c/sub\u003e = 5.58 at 298 K). A strong linear correlation is observed between the rate constants for vicinal diols and the Taft polar substituent constants (Σσ*), and the negative polar reaction constant (ρ* = \u0026minus;\u0026thinsp;2.19 at 298 K) indicates the development of an electron-deficient center in the rate-determining step. A plausible process involving the pre-equilibrium generation of chromate ester has been postulated.\u003c/p\u003e","manuscriptTitle":"Kinetics and reactivity correlation in diol oxidation by tetramethyl-ethylenediammonium dichromate across acetic acid–water mole fractions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-18 23:06:19","doi":"10.21203/rs.3.rs-9087208/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b6f2a796-0329-4a8a-b427-d40d308af12d","owner":[],"postedDate":"March 18th, 2026","published":true,"recentEditorialEvents":[{"type":"decision","content":"Rejected","date":"2026-05-04T21:37:17+00:00","index":"","fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-05-11T08:11:02+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-18 23:06:19","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9087208","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9087208","identity":"rs-9087208","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}