Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.
","abstract_html":"<p>Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH<sub>3</sub>)<sub>6</sub><sup>3+</sup> in the aqueous phase could be reduced to Ru(NH<sub>3</sub>)<sub>6</sub><sup>2+</sup>. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH<sub>3</sub>)<sub>6</sub><sup>2+</sup> could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH<sub>3</sub>)<sub>6</sub><sup>3+</sup> by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E<sub>1/2</sub> comparing the reaction undertaken in the recessed cavity and the bulk solution.</p>","abstract_has_math":false,"creators":["Agyekum, Isaac"],"institution":null,"degree_name":"MS (Master of Science)","degree_level":"Thesis - unrestricted","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T07:00:00Z","date_published":"2011-05-07T07:00:00Z","updated_at":"2026-07-24T02:20:14Z","subjects":["Charge Transfer (CT)","Nanometer sized Electrode","Electron Transfer (ET)","Ion Transfer (IT)","Interface Between Two Immiscible Electrolyte Solut","Chemistry","Physical Chemistry","Physical Sciences and Mathematics"],"languages":[],"rights":["Copyright by the authors."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://dc.etsu.edu/etd/1316","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Agyekum, Isaac"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["1990-01-01T08:00:00Z"]},{"key":"dc:date.issued","label":"Date","values":["2011-05-07T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis - unrestricted"]},{"key":"thesis:degree_name","label":"Degree Name","values":["MS (Master of Science)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Charge Transfer (CT)","Nanometer sized Electrode","Electron Transfer (ET)","Ion Transfer (IT)","Interface Between Two Immiscible Electrolyte Solut","Chemistry","Physical Chemistry","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Copyright by the authors."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://dc.etsu.edu/context/etd/article/2507/viewcontent/AgyekumI010411f.pdf","https://dc.etsu.edu/etd/1316"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.
"]},{"key":"dc:title","label":"Title","values":["Electrochemical Studies of Reactions in Small Volumes Less Than 1 Femto Litres."]}]}],"canonical_facts":{"dc:creator":["Agyekum, Isaac"],"dc:date.available":["1990-01-01T08:00:00Z"],"dc:date.issued":["2011-05-07T07:00:00Z"],"dc:description.abstract":["Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.
"],"dc:identifier":["https://dc.etsu.edu/context/etd/article/2507/viewcontent/AgyekumI010411f.pdf","https://dc.etsu.edu/etd/1316"],"dc:rights":["Copyright by the authors."],"dc:subject":["Charge Transfer (CT)","Nanometer sized Electrode","Electron Transfer (ET)","Ion Transfer (IT)","Interface Between Two Immiscible Electrolyte Solut","Chemistry","Physical Chemistry","Physical Sciences and Mathematics"],"dc:title":["Electrochemical Studies of Reactions in Small Volumes Less Than 1 Femto Litres."],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis - unrestricted"],"thesis:degree_name":["MS (Master of Science)"]},"updated_at":"2026-07-24T02:20:14Z"}