Zitieren Sie bitte immer diesen URN: urn:nbn:de:kobv:b43-483361
Understanding the unexpected effect of frequency on the kinetics of a covalent reaction under ball-milling conditions
- We here explore how ball-mill-grinding frequency affects the kinetics of a disulfide exchange reaction. Our kinetic data show that the reaction progress is similar at all the frequencies studied (15–30 Hz), including a significant induction time before the nucleation and growth process starts. This indicates that to start the reaction an initial energy accumulation is necessary. Other than mixing, the energy supplied by the mechanical treatment has two effects: (i) reducing the crystal size and (ii) creating defects in the structure. The crystal-breaking process is likely to be dominant at first becoming less important later in the process when the energy supplied is stored at the molecular level as local crystal defects. This accumulation is taken here to be the rate-determining step. We suggest that the local defects accumulate preferentially at or near the crystal surface. Since the total area increases exponentially when the crystal size is reduced by the crystal-breaking process,We here explore how ball-mill-grinding frequency affects the kinetics of a disulfide exchange reaction. Our kinetic data show that the reaction progress is similar at all the frequencies studied (15–30 Hz), including a significant induction time before the nucleation and growth process starts. This indicates that to start the reaction an initial energy accumulation is necessary. Other than mixing, the energy supplied by the mechanical treatment has two effects: (i) reducing the crystal size and (ii) creating defects in the structure. The crystal-breaking process is likely to be dominant at first becoming less important later in the process when the energy supplied is stored at the molecular level as local crystal defects. This accumulation is taken here to be the rate-determining step. We suggest that the local defects accumulate preferentially at or near the crystal surface. Since the total area increases exponentially when the crystal size is reduced by the crystal-breaking process, this can further explain the exponential dependence of the onset time on the milling frequency.…
Autor*innen: | A. Belenguer, Adam MichalchukORCiD, G Lampronti, J Sanders |
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Dokumenttyp: | Zeitschriftenartikel |
Veröffentlichungsform: | Verlagsliteratur |
Sprache: | Englisch |
Titel des übergeordneten Werkes (Englisch): | Beilstein journal of organic chemistry |
Jahr der Erstveröffentlichung: | 2019 |
Organisationseinheit der BAM: | 6 Materialchemie |
6 Materialchemie / 6.3 Strukturanalytik | |
Veröffentlichende Institution: | Bundesanstalt für Materialforschung und -prüfung (BAM) |
Verlag: | Beilstein-Institut zur Förderung der Chemischen Wissenschaften |
Verlagsort: | Frankfurt, M. |
Jahrgang/Band: | 15 |
Erste Seite: | 1226 |
Letzte Seite: | 1235 |
DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten |
Freie Schlagwörter: | Diffraction; Kinetics; Mechanochemistry |
Themenfelder/Aktivitätsfelder der BAM: | Material |
DOI: | 10.3762/bjoc.15.120 |
URN: | urn:nbn:de:kobv:b43-483361 |
ISSN: | 2195-951X |
Verfügbarkeit des Dokuments: | Datei für die Öffentlichkeit verfügbar ("Open Access") |
Lizenz (Deutsch): | Creative Commons - CC BY - Namensnennung 4.0 International |
Datum der Freischaltung: | 27.06.2019 |
Referierte Publikation: | Ja |
Datum der Eintragung als referierte Publikation: | 27.06.2019 |
Schriftenreihen ohne Nummerierung: | Wissenschaftliche Artikel der BAM |