Modeling Hot Wire Electrochemistry. Coupled Heat and Mass Transport at a Directly and Continuously Heated Wire

Beckmann, A.; Coles, Barry A.; Compton, Richard G.; Gründler, Peter; Marken, Frank; Neudeck, Andreas

doi:10.1021/jp992736s

Cited by 48 publications

(44 citation statements)

References 16 publications

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“…The latter even plays a dominant role. So, there exists a transition of mass transport at the electrode surface from linear diffusion at lower temperature to mixed cylindrical diffusion and convection at high temperature, which is in agreement with our previous work [28].…”

Section: Resultssupporting

confidence: 92%

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Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Wang

Gründler

2003

Electroanalysis

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Mercaptoundecanoic acid (MUA) and glutathione (GSH) self-assembled monolayers were prepared on gold-wire microelectrode. Cyclic voltammetry was used to investigate the influence of temperature on electrochemical behaviors of Fe(CN) 6 3À/4À and Ru(NH 3 ) 6 3/2 at these SAMs modified electrodes in aqueous solution. It is found that temperature shows great influence on electron transfer (ET) and mass transport (MT) for the two SAMs modified electrodes and the influence of temperature depends on the charge properties of the redox couples and terminal groups of SAMs and the structure of the monolayer on gold surface. The temperature can greatly increase MT rate of Fe(CN) 6 3À/4À at both MUA and GSH modified electrodes. However, the increased MT rate doesn×t have any effect on the CV×s for Fe(CN) 6 3À/4À /MUA system. For Ru(NH 3 ) 6 3/2 , temperature can greatly improve the electrochemical reaction in both MUA and GSH modified electrodes, which is ascribed to temperature-induced diffusion and convection and the electrostatic interaction between Ru(NH 3 ) 6 3/2 and negatively charged carboxyl groups on the electrode surface.

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Section: Resultssupporting

confidence: 92%

“…A single electrode was constructed. A heated electrode consists of two single electrodes and symmetric arrangement [28]. The total geometric area was ca.…”

Section: Construction Of a Heated Gold Wire Electrodementioning

confidence: 99%

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Wang

Gründler

2003

Electroanalysis

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“…The two characteristic features associated with the increase of the temperature at the electrode±solution interface in a nonisothermal cell [19] are (i) the increase in current due to the higher diffusivity and faster mass transport and (ii) the shift of the equilibrium potential of the redox system predominantly due to the reaction entropy associated with the redox process [20]. A correction accounting for the Soret effect [21] is assumed to remain insigni®cant. For a solution of 4 mM Fe(CN) 6 4À in aqueous 1 M KCl both the change in diffusivity [22] and the shift of the equilibrium potential, dEydT À1X53 mV K À1 [18], are well known.…”

Section: àmentioning

confidence: 99%

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

et al. 2000

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In situ microwave activation of electrochemical processes in a novel electrochemical cell, in which intense microwave radiation is focused locally into the region at the electrode surface±solution interface, is shown to allow high-temperature voltammetry experiments at 100 mm Pt disk electrodes. Factors such as the cell geometry and the deposition of a thin ®lm of mercury are shown to in¯uence the microwave effect. The detection of trace metals or impurities by anodic stripping voltammetry is a routinely applied procedure with applications especially in rapid online monitoring, in remote place analysis, or for extremely dilute samples. For cadmium detection by anodic stripping voltammetry microwave radiation is demonstrated to strongly affect the accumulation process but not the stripping process. Calibration of the effects induced by microwave radiation on the experimentally observed voltammetric data, based on the equilibrium potentials for the FeCN 4Àa3À 6 and the RuNH 3 3a2 6 redox systems, demonstrates that the data obtained are consistent with a thermally enhanced process. The temperature achievable at the electrode±solution interface before boiling and cavitation occurs, is shown to be strongly dependent on the type of electrode material and surface morphology. At a mercury ®lm electrode deposited on platinum temperatures in excess of 150C can be applied in voltammetric experiments in a constant heating mode.

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“…A study into the temperature profiles for both the continuous heating and TPV techniques has been reported [32,37,39]. These were modeled at a continuously heated wire using a finite element simulation package (FIDAP, version 8.52 Fluent Europe Ltd., Sheffield, UK, http:// www.fluent.com) [32].…”

Section: Non-isothermal Heating Methods: Ac Heating Of Wiresmentioning

confidence: 99%

“…These were modeled at a continuously heated wire using a finite element simulation package (FIDAP, version 8.52 Fluent Europe Ltd., Sheffield, UK, http:// www.fluent.com) [32]. The results obtained showed that the temperature profile expands into the solution much faster and further than any concentration profile generated electrochemically.…”

Section: Non-isothermal Heating Methods: Ac Heating Of Wiresmentioning

confidence: 99%

High‐Temperature Electrochemistry: A Review

et al. 2004

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High-temperature electrochemistry remains a relatively unexplored field of research, although in recent years significant developments have been made. This report details the main experimental methods and approaches to heating an electrochemical system under both isothermal and non-isothermal conditions and gives an insight into the experimental and electroanalytical results obtainable under such conditions. It has been shown that the promotion of mass transport at high-temperatures, through diffusion or convection, often results in increased current signals. This increase benefits electroanalytical measurements by lowering detection limits. High temperatures also usefully enhance the sensitivity of systems with sluggish kinetics.

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Modeling Hot Wire Electrochemistry. Coupled Heat and Mass Transport at a Directly and Continuously Heated Wire

Cited by 48 publications

References 16 publications

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

High‐Temperature Electrochemistry: A Review

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