Natural convection in electrochemical systems

<p>This thesis is concerned with modelling natural convective flows and specifically with their role in electrochemistry. The studies described here demonstrate that many electroanalytical techniques are prone to non-negligible natural convective effects, thus making the standard assumption fo...

Full description

Bibliographic Details
Main Author: Novev, Y
Other Authors: Compton, R
Format: Thesis
Language:English
Published: 2018
Subjects:
_version_ 1797090872660066304
author Novev, Y
author2 Compton, R
author_facet Compton, R
Novev, Y
author_sort Novev, Y
collection OXFORD
description <p>This thesis is concerned with modelling natural convective flows and specifically with their role in electrochemistry. The studies described here demonstrate that many electroanalytical techniques are prone to non-negligible natural convective effects, thus making the standard assumption for purely diffusional mass transport inapplicable. The chosen approach focusses on investigating idealized systems and establishing orders of magnitude for the quantities of interest. The complexity of the observed natural convective flows and their strong dependence on factors such as container geometry serve as compelling arguments for rigorously excluding natural convection in experimental measurements.</p> <p>The text is structured as follows. Chapter 1 introduces the theoretical framework used in the rest of the text and gives an outline of the electrochemical techniques to which the results in later chapters apply. Chapter 2 surveys the literature on natural convection in electrochemistry and emphasizes recent developments. Chapter 3 studies the natural convection induced by the intrinsic heat of an electrochemical reaction, specifically its effect on mass transport in chronoamperometry and cyclic voltammetry. Chapters 4-6 deal exclusively with coupled heat and momentum transport. Chapter 4 considers the thermal convective flows that arise in an idealized cell for scanning electrochemical microscopy (SECM) and the surrounding air under conditions of imperfect thermostating. Chapter 5 is dedicated to thermal convection in an SECM cell that is being thermostated from below through a solid substrate. This chapter demonstrates the influence of the spatial distribution of substrate thermal conductivity on the observed flows and highlights this effect by using a simpler model of the SECM cell than Chapter 4. Chapter 6 investigates the thermal convection in a novel thermostated cell for electrochemical measurements. Chapter 7 contains the main conclusions from the studies described in the thesis. Appendices A, B and C provide additional data for Chapters 3, 5 and 6, respectively.</p>
first_indexed 2024-03-07T03:24:57Z
format Thesis
id oxford-uuid:b8badcfd-e376-4ff6-b2da-b8f821871777
institution University of Oxford
language English
last_indexed 2024-03-07T03:24:57Z
publishDate 2018
record_format dspace
spelling oxford-uuid:b8badcfd-e376-4ff6-b2da-b8f8218717772022-03-27T04:57:52ZNatural convection in electrochemical systemsThesishttp://purl.org/coar/resource_type/c_db06uuid:b8badcfd-e376-4ff6-b2da-b8f821871777ElectrochemistryPhysical chemistryEnglishORA Deposit2018Novev, YCompton, R<p>This thesis is concerned with modelling natural convective flows and specifically with their role in electrochemistry. The studies described here demonstrate that many electroanalytical techniques are prone to non-negligible natural convective effects, thus making the standard assumption for purely diffusional mass transport inapplicable. The chosen approach focusses on investigating idealized systems and establishing orders of magnitude for the quantities of interest. The complexity of the observed natural convective flows and their strong dependence on factors such as container geometry serve as compelling arguments for rigorously excluding natural convection in experimental measurements.</p> <p>The text is structured as follows. Chapter 1 introduces the theoretical framework used in the rest of the text and gives an outline of the electrochemical techniques to which the results in later chapters apply. Chapter 2 surveys the literature on natural convection in electrochemistry and emphasizes recent developments. Chapter 3 studies the natural convection induced by the intrinsic heat of an electrochemical reaction, specifically its effect on mass transport in chronoamperometry and cyclic voltammetry. Chapters 4-6 deal exclusively with coupled heat and momentum transport. Chapter 4 considers the thermal convective flows that arise in an idealized cell for scanning electrochemical microscopy (SECM) and the surrounding air under conditions of imperfect thermostating. Chapter 5 is dedicated to thermal convection in an SECM cell that is being thermostated from below through a solid substrate. This chapter demonstrates the influence of the spatial distribution of substrate thermal conductivity on the observed flows and highlights this effect by using a simpler model of the SECM cell than Chapter 4. Chapter 6 investigates the thermal convection in a novel thermostated cell for electrochemical measurements. Chapter 7 contains the main conclusions from the studies described in the thesis. Appendices A, B and C provide additional data for Chapters 3, 5 and 6, respectively.</p>
spellingShingle Electrochemistry
Physical chemistry
Novev, Y
Natural convection in electrochemical systems
title Natural convection in electrochemical systems
title_full Natural convection in electrochemical systems
title_fullStr Natural convection in electrochemical systems
title_full_unstemmed Natural convection in electrochemical systems
title_short Natural convection in electrochemical systems
title_sort natural convection in electrochemical systems
topic Electrochemistry
Physical chemistry
work_keys_str_mv AT novevy naturalconvectioninelectrochemicalsystems