{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/140088"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/140088","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Kinetic and Thermodynamic Aspects of Voltage as a Driving Force for Ammonia Activation","abstract":"Renewable energy sources, such as solar and wind, have become increasingly prevalent and helped drive progress toward decarbonization of electricity. The commodity chemical industry is a large consumer of energy and a major contributor to global greenhouse gas emissions, and electrification of the industry using renewable sources is a possible step toward reducing the carbon footprint of chemicals. In this thesis, I first propose a paradigm where electrochemical systems enable bond-formation steps in the chemical industry, leveraging voltage as an alternative driving force to enable operation at mild temperatures and pressures. I then aim to answer the question “If I can apply mechanical energy (pressure), thermal energy (temperature), or electrical energy (voltage) to a chemical reaction, which should I use?” In particular, I present a universal expression for the equilibrium constant of a chemical reaction as a function of thermodynamic driving forces, and demonstrate how this universal equation and facile visualization of chemical reactions enables quick and informed justification for electrochemical versus thermochemical energy sources. I then focus on the particular case of electrochemical utilization of ammonia, a ubiquitous nitrogen precursor throughout the chemical industry. First, I look at an electrochemical analogue to reductive amination, where a carbonyl group is converted to an amine. Specifically, I demonstrate the electrochemical reductive amination reaction of benzaldehyde and ammonia and investigate its kinetics. I find that the reaction proceeds via an inner-sphere route at heterogeneous metal surfaces, in contrast to most previous work on outer-sphere electrochemical reductive amination systems. I then investigate the kinetics of activating ammonia by breaking the nitrogen-hydrogen bond oxidatively, and I find that the reaction proceeds through an outer-sphere, radical pathway. Last, I propose an energy storage paradigm that leverages ammonium formate, a combination of ammonia and formic acid, to store renewable electricity. I discuss the advantages of this fuel and demonstrate how voltage can aid in the release of energy from this fuel. Overall, in this thesis I start with the broad question of why and when to choose electrochemistry over traditional thermochemical routes in the chemical industry, and I then focus in on how electrochemistry can aid in the utilization of ammonia for both synthesis reactions as well as energy storage purposes.","abstract_html":"Renewable energy sources, such as solar and wind, have become increasingly prevalent and helped drive progress toward decarbonization of electricity. The commodity chemical industry is a large consumer of energy and a major contributor to global greenhouse gas emissions, and electrification of the industry using renewable sources is a possible step toward reducing the carbon footprint of chemicals. In this thesis, I first propose a paradigm where electrochemical systems enable bond-formation steps in the chemical industry, leveraging voltage as an alternative driving force to enable operation at mild temperatures and pressures. I then aim to answer the question “If I can apply mechanical energy (pressure), thermal energy (temperature), or electrical energy (voltage) to a chemical reaction, which should I use?” In particular, I present a universal expression for the equilibrium constant of a chemical reaction as a function of thermodynamic driving forces, and demonstrate how this universal equation and facile visualization of chemical reactions enables quick and informed justification for electrochemical versus thermochemical energy sources. I then focus on the particular case of electrochemical utilization of ammonia, a ubiquitous nitrogen precursor throughout the chemical industry. First, I look at an electrochemical analogue to reductive amination, where a carbonyl group is converted to an amine. Specifically, I demonstrate the electrochemical reductive amination reaction of benzaldehyde and ammonia and investigate its kinetics. I find that the reaction proceeds via an inner-sphere route at heterogeneous metal surfaces, in contrast to most previous work on outer-sphere electrochemical reductive amination systems. I then investigate the kinetics of activating ammonia by breaking the nitrogen-hydrogen bond oxidatively, and I find that the reaction proceeds through an outer-sphere, radical pathway. Last, I propose an energy storage paradigm that leverages ammonium formate, a combination of ammonia and formic acid, to store renewable electricity. I discuss the advantages of this fuel and demonstrate how voltage can aid in the release of energy from this fuel. Overall, in this thesis I start with the broad question of why and when to choose electrochemistry over traditional thermochemical routes in the chemical industry, and I then focus in on how electrochemistry can aid in the utilization of ammonia for both synthesis reactions as well as energy storage purposes.","abstract_has_math":false,"creators":["Schiffer, Zachary J"],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemical Engineering","school":null,"contributors":[],"advisors":["Manthiram, Karthish"],"committee_chairs":[],"committee_members":[],"year":2021,"date_issued":"2021-09","date_published":"2021-09","updated_at":"2026-07-22T22:22:20Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"rights_urls":["http://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/140088","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Manthiram, Karthish"]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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The commodity chemical industry is a large consumer of energy and a major contributor to global greenhouse gas emissions, and electrification of the industry using renewable sources is a possible step toward reducing the carbon footprint of chemicals. In this thesis, I first propose a paradigm where electrochemical systems enable bond-formation steps in the chemical industry, leveraging voltage as an alternative driving force to enable operation at mild temperatures and pressures. I then aim to answer the question “If I can apply mechanical energy (pressure), thermal energy (temperature), or electrical energy (voltage) to a chemical reaction, which should I use?” In particular, I present a universal expression for the equilibrium constant of a chemical reaction as a function of thermodynamic driving forces, and demonstrate how this universal equation and facile visualization of chemical reactions enables quick and informed justification for electrochemical versus thermochemical energy sources. I then focus on the particular case of electrochemical utilization of ammonia, a ubiquitous nitrogen precursor throughout the chemical industry. First, I look at an electrochemical analogue to reductive amination, where a carbonyl group is converted to an amine. Specifically, I demonstrate the electrochemical reductive amination reaction of benzaldehyde and ammonia and investigate its kinetics. I find that the reaction proceeds via an inner-sphere route at heterogeneous metal surfaces, in contrast to most previous work on outer-sphere electrochemical reductive amination systems. I then investigate the kinetics of activating ammonia by breaking the nitrogen-hydrogen bond oxidatively, and I find that the reaction proceeds through an outer-sphere, radical pathway. Last, I propose an energy storage paradigm that leverages ammonium formate, a combination of ammonia and formic acid, to store renewable electricity. I discuss the advantages of this fuel and demonstrate how voltage can aid in the release of energy from this fuel. Overall, in this thesis I start with the broad question of why and when to choose electrochemistry over traditional thermochemical routes in the chemical industry, and I then focus in on how electrochemistry can aid in the utilization of ammonia for both synthesis reactions as well as energy storage purposes."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Kinetic and Thermodynamic Aspects of Voltage as a Driving Force for Ammonia Activation"]}]}],"canonical_facts":{"dc:contributor.advisor":["Manthiram, Karthish"],"dc:contributor.department":["Massachusetts Institute of Technology. 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I then aim to answer the question “If I can apply mechanical energy (pressure), thermal energy (temperature), or electrical energy (voltage) to a chemical reaction, which should I use?” In particular, I present a universal expression for the equilibrium constant of a chemical reaction as a function of thermodynamic driving forces, and demonstrate how this universal equation and facile visualization of chemical reactions enables quick and informed justification for electrochemical versus thermochemical energy sources. I then focus on the particular case of electrochemical utilization of ammonia, a ubiquitous nitrogen precursor throughout the chemical industry. First, I look at an electrochemical analogue to reductive amination, where a carbonyl group is converted to an amine. Specifically, I demonstrate the electrochemical reductive amination reaction of benzaldehyde and ammonia and investigate its kinetics. I find that the reaction proceeds via an inner-sphere route at heterogeneous metal surfaces, in contrast to most previous work on outer-sphere electrochemical reductive amination systems. I then investigate the kinetics of activating ammonia by breaking the nitrogen-hydrogen bond oxidatively, and I find that the reaction proceeds through an outer-sphere, radical pathway. Last, I propose an energy storage paradigm that leverages ammonium formate, a combination of ammonia and formic acid, to store renewable electricity. I discuss the advantages of this fuel and demonstrate how voltage can aid in the release of energy from this fuel. Overall, in this thesis I start with the broad question of why and when to choose electrochemistry over traditional thermochemical routes in the chemical industry, and I then focus in on how electrochemistry can aid in the utilization of ammonia for both synthesis reactions as well as energy storage purposes."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/140088"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"dc:rights.uri":["http://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Kinetic and Thermodynamic Aspects of Voltage as a Driving Force for Ammonia Activation"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:22:20Z"}