Industrial Electrochemical: a New Teaching Approach
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Electrolytic Cells
CHEMISTRY LEVEL 4C (CHM415115) ELECTROLYTIC CELLS THEORY SUMMARY & REVISION QUESTIONS (CRITERION 5) ©JAK DENNY Tasmanian TCE Chemistry Revision Guides by Jak Denny are licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. INDEX: PAGES • INTRODUCTORY THEORY 3 • COMPARING ENERGY CONVERSIONS 4 • APPLICATIONS OF ELECTROLYSIS 4 • ELECTROPLATING 5 • COMPARING CELLS 6 • THE ELECTROCHEMICAL SERIES 7 • PREDICTING ELECTROLYSIS PRODUCTS 8-9 • ELECTROLYSIS PREDICTION FLOWCHART 1 0 • ELECTROLYSIS PREDICTION EXAMPLES 11 • ELECTROLYSIS PREDICTION QUESTIONS 12 • INDUSTRIAL ELECTROLYTIC PROCESSES 13 • IMPORTANT ELECTRICAL THEORY 14 • FARADAY’S ELECTROLYSIS LAWS 15 • QUANTITATIVE ELECTROLYSIS 16 • CELLS IN SERIES 17 • ELECTROLYSIS QUESTIONS 18-20 • ELECTROLYSIS TEST QUESTIONS 21-22 • TEST ANSWERS 23 2 ©JAK CHEMISTRY LEVEL 4C (CHM415115) ELECTROLYTIC CELLS (CRITERION 5) INTRODUCTION: In our recent investigation of electrochemical cells, we encountered spontaneous redox reactions that release electrical energy such as takes place in the familiar situations of “batteries”. When a car battery is ‘flat’ and needs to be recharged, a power supply (‘battery charger’) is connected to the flat battery and chemical changes take place and it is subsequently able to operate again as a power supply. The ‘recharging’ process is non-spontaneous and requires an input of energy to occur. When a cell is such that an energy input is required to make a non-spontaneous redox reaction take place, we describe the cell as an ELECTROLYTIC CELL. The redox process occurring in an ELECTROLYTIC CELL is referred to as ELECTROLYSIS. For example, consider the spontaneous redox reaction associated with an electrochemical (fuel) cell; i.e. 2H2(g) + O2(g) → 2H2O(l) + ELECTRICAL ENERGY This chemical reaction RELEASES energy which can be used to power an electric motor, to drive a machine, appliance or car. -
How Do We Learn Electrochemistry? by Jeffrey W
redcat_ad_IF_Sp2012_1.pdf 1 4/11/2012 1:36:17 PM research • news • events • resources | search • explore • connect • share • discover How Do We Learn Electrochemistry? by Jeffrey W. Fergus he importance of electrochemistry is undeniable—we on education. The fall 2006 issue was devoted to education literally cannot live without electrochemistry for proper and included articles discussing general needs for education in Tcell function and transmission of signals through the electrochemistry as well as some examples of approaches, and nervous system. Electrochemistry is also vital in a wide range even specific laboratory activities, to enhance electrochemical of important technological applications. For example, batteries education. More recently, in the summer 2010 issue, the ECS are important not only in storing energy for mobile devices Industrial Electrochemistry and Electrochemical Engineering and vehicles, but also for load leveling to enable the use of Division provided an additional evaluation of needs and some renewable energy conversion technologies. Electrochemistry activities for introducing electrochemistry into courses. The is involved in the production of materials by electrorefining current issue complements those earlier issues and provides or electrodeposition as well as the destruction of materials by insights on the status and needs in electrochemical education. TM corrosion. In spite of its ubiquity there are very few formal The first article provides a general backdrop on the state educational degree programs in electrochemistry. of higher education. Marye Ann Fox discusses the financial If electrochemistry is ubiquitous, but formal educational challenges being faced by academic institutions and how these programs are rare, how do the scientists and engineers working on challenges have an impact on the design and implementation of electrochemical products and processes learn the electrochemistry educational programs. -
Electrochemical Real-Time Mass Spectrometry: a Novel Tool for Time-Resolved Characterization of the Products of Electrochemical Reactions
Electrochemical real-time mass spectrometry: A novel tool for time-resolved characterization of the products of electrochemical reactions Elektrochemische Realzeit-Massenspektrometrie: Eine neuartige Methode zur zeitaufgelösten Charakterisierung der Produkte elektrochemischer Reaktionen Der Technischen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr.-Ingenieur vorgelegt von Peyman Khanipour Mehrin aus Shiraz, Iran Als Dissertation genehmigt von der Technischen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 17.11.2020 Vorsitzender des Promotionsorgans: Prof. Dr.-Ing. habil. Andreas Paul Fröba Gutachter: Prof. Dr. Karl J.J. Mayrhofer Prof. Dr. Frank-Michael Matysik I Acknowledgements This study is done in the electrosynthesis team of the electrocatalysis unit at Helmholtz- Institut Erlangen-Nürnberg (HI ERN) with the financial support of Forschungszentrum Jülich. I would like to express my deep gratitude to Prof. Dr. Karl J. J. Mayrhofer for accepting me as a Ph.D. student and also for all his encouragement, supports, and freedoms during my study. I’m grateful to Prof. Dr. Frank-Michael Matysik for kindly accepting to act as a second reviewer and also for the time he has invested in reading this thesis. This piece of work is enabled by collaboration with scientists from different expertise. I would like to express my appreciation to Dr. Sandra Haschke from FAU for providing shape-controlled high surface area platinum electrodes which I used for performing oxidation of primary alcohols and also the characterization of the provided material SEM, EDX, and XRD. Mr. Mario Löffler from HI ERN for obtaining the XPS data and his remarkable knowledge with the interpretation of the spectra on copper-based electrodes for the CO 2 electroreduction reaction. -
Electrochemical Cells
Electrochemical cells = electronic conductor If two different + surrounding electrolytes are used: electrolyte electrode compartment Galvanic cell: electrochemical cell in which electricity is produced as a result of a spontaneous reaction (e.g., batteries, fuel cells, electric fish!) Electrolytic cell: electrochemical cell in which a non-spontaneous reaction is driven by an external source of current Nils Walter: Chem 260 Reactions at electrodes: Half-reactions Redox reactions: Reactions in which electrons are transferred from one species to another +II -II 00+IV -II → E.g., CuS(s) + O2(g) Cu(s) + SO2(g) reduced oxidized Any redox reactions can be expressed as the difference between two reduction half-reactions in which e- are taken up Reduction of Cu2+: Cu2+(aq) + 2e- → Cu(s) Reduction of Zn2+: Zn2+(aq) + 2e- → Zn(s) Difference: Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq) - + - → 2+ More complex: MnO4 (aq) + 8H + 5e Mn (aq) + 4H2O(l) Half-reactions are only a formal way of writing a redox reaction Nils Walter: Chem 260 Carrying the concept further Reduction of Cu2+: Cu2+(aq) + 2e- → Cu(s) In general: redox couple Ox/Red, half-reaction Ox + νe- → Red Any reaction can be expressed in redox half-reactions: + - → 2 H (aq) + 2e H2(g, pf) + - → 2 H (aq) + 2e H2(g, pi) → Expansion of gas: H2(g, pi) H2(g, pf) AgCl(s) + e- → Ag(s) + Cl-(aq) Ag+(aq) + e- → Ag(s) Dissolution of a sparingly soluble salt: AgCl(s) → Ag+(aq) + Cl-(aq) − 1 1 Reaction quotients: Q = a − ≈ [Cl ] Q = ≈ Cl + a + [Ag ] Ag Nils Walter: Chem 260 Reactions at electrodes Galvanic cell: -
Gas-Phase Electrochemistry: Measuring Absolute Potentials and Investigating Ion and Electron Hydration*
Pure Appl. Chem., Vol. 83, No. 12, pp. 2129–2151, 2011. doi:10.1351/PAC-CON-11-08-15 © 2011 IUPAC, Publication date (Web): 7 October 2011 Gas-phase electrochemistry: Measuring absolute potentials and investigating ion and electron hydration* William A. Donald1,‡ and Evan R. Williams2 1School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria, Australia; 2Department of Chemistry, University of California, Berkeley, CA, USA Abstract: In solution, half-cell potentials and ion solvation energies (or enthalpies) are meas- ured relative to other values, thus establishing ladders of thermochemical values that are ref- erenced to the potential of the standard hydrogen electrode (SHE) and the proton hydration energy (or enthalpy), respectively, which are both arbitrarily assigned a value of 0. In this focused review article, we describe three routes for obtaining absolute solution-phase half- cell potentials using ion nanocalorimetry, in which the energy resulting from electron capture (EC) by large hydrated ions in the gas phase are obtained from the number of water mole- cules lost from the reduced precursor cluster, which was developed by the Williams group at the University of California, Berkeley. Recent ion nanocalorimetry methods for investigating ion and electron hydration and for obtaining the absolute hydration enthalpy of the electron are discussed. From these methods, an absolute electrochemical scale and ion solvation scale can be established from experimental measurements without any models. Keywords: absolute potentials; clusters; electrochemistry; electron capture dissociation; elec- tron transfer; gaseous state; hydrated ions; hydration; ion nanocalorimetry; solvation; thermo chemistry. -
3 PRACTICAL APPLICATION BATTERIES and ELECTROLYSIS Dr
ELECTROCHEMISTRY – 3 PRACTICAL APPLICATION BATTERIES AND ELECTROLYSIS Dr. Sapna Gupta ELECTROCHEMICAL CELLS An electrochemical cell is a system consisting of electrodes that dip into an electrolyte and in which a chemical reaction either uses or generates an electric current. A voltaic or galvanic cell is an electrochemical cell in which a spontaneous reaction generates an electric current. An electrolytic cell is an electrochemical cell in which an electric current drives an otherwise nonspontaneous reaction. Dr. Sapna Gupta/Electrochemistry - Applications 2 GALVANIC CELLS • Galvanic cell - the experimental apparatus for generating electricity through the use of a spontaneous reaction • Electrodes • Anode (oxidation) • Cathode (reduction) • Half-cell - combination of container, electrode and solution • Salt bridge - conducting medium through which the cations and anions can move from one half-cell to the other. • Ion migration • Cations – migrate toward the cathode • Anions – migrate toward the anode • Cell potential (Ecell) – difference in electrical potential between the anode and cathode • Concentration dependent • Temperature dependent • Determined by nature of reactants Dr. Sapna Gupta/Electrochemistry - Applications 3 BATTERIES • A battery is a galvanic cell, or a series of cells connected that can be used to deliver a self-contained source of direct electric current. • Dry Cells and Alkaline Batteries • no fluid components • Zn container in contact with MnO2 and an electrolyte Dr. Sapna Gupta/Electrochemistry - Applications 4 ALKALINE CELL • Common watch batteries − − Anode: Zn(s) + 2OH (aq) Zn(OH)2(s) + 2e − − Cathode: 2MnO2(s) + H2O(l) + 2e Mn2O3(s) + 2OH (aq) This cell performs better under current drain and in cold weather. It isn’t truly “dry” but rather uses an aqueous paste. -
Electrostatics of Two Suspended Spheres (Eletrost´Atica De Duas Esferas Suspensas)
Revista Brasileira de Ensino de F´ısica, v. 34, n. 3, 3308 (2012) www.sbfisica.org.br Electrostatics of two suspended spheres (Eletrost´atica de duas esferas suspensas) Fernando Fuzinatto Dall'Agnol1, Victor P. Mammana and Daniel den Engelsen Centro de Tecnologia da Informa¸c~aoRenato Archer, Campinas, SP, Brasil Recebido em 25/2/2011; Aceito em 6/2/2012; Publicado em 21/11/2012 Although the working principle of a traditional electroscope with thin metal deflection foils is simple, one needs numerical methods to calculate its foil's deflection. If the electroscope is made of hanging spheres instead of foils, then it is possible to obtain an analytical solution. Since the separation of the charged spheres is of the order of their radius the spheres cannot be described as point charges. We apply the method of image charges to find the electrostatic force between the spheres and then we relate the voltage applied to their separation. We also discuss the similarity with the sphere-plane electrostatic problem. This approach can be used as an analytical solution for practical problems in the field of electrodynamics and its complexity is compatible with undergraduate courses. Keywords: electroscope, electrometer, method of image, image charge, electrostatic, sphere-sphere. Apesar da simplicidade do princ´ıpiode funcionamento do eletrosc´opiotradicional feito de folhas met´alicas finas, ´enecess´ariom´etodos num´ericospara calcular a deflex˜aodas folhas. Se o eletrosc´opiofor feito de esferas penduradas ao inv´esde folhas, ent~ao´eposs´ıvel obter uma solu¸c~aoanal´ıtica. Como a deflex˜aodas esferas car- regadas ´eda ordem dos seus raios, as esferas n~aopodem ser descritas como cargas pontuais. -
Electrochemistry Cell Model
Electrochemistry Cell Model Dennis Dees and Kevin Gallagher Chemical Sciences and Engineering Division May 9-13, 2011 Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting Washington, D.C. Project ID: ES031 This presentation does not contain any proprietary, confidential, or otherwise restricted information. Overview Timeline Barriers . Start: October 2008 . Development of a safe cost-effective PHEV . Finish: September 2014 battery with a 40 mile all electric range . ~43% Complete that meets or exceeds all performance goals – Interpreting complex cell electrochemical phenomena – Identification of cell degradation mechanisms Budget Partners (Collaborators) . Total project funding . Daniel Abraham, Argonne – 100% DOE . Sun-Ho Kang, Argonne . FY2010: $400K . Andrew Jansen, Argonne . FY2011: $400K . Wenquan Lu, Argonne . Kevin Gering, INL Vehicle Technologies Program 2 Objectives, Milestones, and Approach . The objective of this work is to correlate analytical diagnostic results with the electrochemical performance of advanced lithium-ion battery technologies for PHEV applications – Link experimental efforts through electrochemical modeling studies – Identify performance limitations and aging mechanisms . Milestones for this year: – Initiate development of AC impedance two phase model (completed) – Integrate SEI growth model into full cell model (completed) . Approach for electrochemical modeling activities is to build on earlier successful characterization and modeling studies in extending efforts to new PHEV technologies -
Physical and Analytical Electrochemistry: the Fundamental
Electrochemical Systems The simplest and traditional electrochemical process occurring at the boundary between an electronically conducting phase (the electrode) and an ionically conducting phase (the electrolyte solution), is the heterogeneous electro-transfer step between the electrode and the electroactive species of interest present in the solution. An example is the plating of nickel. Ni2+ + 2e- → Ni Physical and Analytical The interface is where the action occurs but connected to that central event are various processes that can Electrochemistry: occur in parallel or series. Figure 2 demonstrates a more complex interface; it represents a molecular scale snapshot The Fundamental Core of an interface that exists in a fuel cell with a solid polymer (capable of conducting H+) as an electrolyte. of Electrochemistry However, there is more to an electrochemical system than a single by Tom Zawodzinski, Shelley Minteer, interface. An entire circuit must be made and Gessie Brisard for measurable current to flow. This circuit consists of the electrochemical cell plus external wiring and circuitry The common event for all electrochemical processes is that (power sources, measuring devices, of electron transfer between chemical species; or between an etc). The cell consists of (at least) electrode and a chemical species situated in the vicinity of the two electrodes separated by (at least) one electrolyte solution. Figure 3 is electrode, usually a pure metal or an alloy. The location where a schematic of a simple circuit. Each the electron transfer reactions take place is of fundamental electrode has an interface with a importance in electrochemistry because it regulates the solution. Electrons flow in the external behavior of most electrochemical systems. -
Concepts and Tools for Mechanism and Selectivity Analysis in Synthetic Organic Electrochemistry
Concepts and tools for mechanism and selectivity analysis in synthetic organic electrochemistry Cyrille Costentina,1,2 and Jean-Michel Savéanta,1 aUniversité Paris Diderot, Sorbonne Paris Cité, Laboratoire d’Electrochimie Moléculaire, Unité Mixte de Recherche Université–CNRS 7591, 75205 Paris Cedex 13, France Contributed by Jean-Michel Savéant, April 2, 2019 (sent for review March 19, 2019; reviewed by Robert Francke and R. Daniel Little) As an accompaniment to the current renaissance of synthetic organic sufficient to record a current-potential response but small electrochemistry, the heterogeneous and space-dependent nature of enough to leave the substrates and cosubstrates (of the order of electrochemical reactions is analyzed in detail. The reactions that follow one part per million) almost untouched. Competition of the the initial electron transfer step and yield the products are intimately electrochemical/chemical events with diffusional transport under coupled with reactant transport. Depiction of the ensuing reactions precisely mastered conditions allows analysis of the kinetics profiles is the key to the mechanism and selectivity parameters. within extended time windows (from minutes to submicroseconds). Analysis is eased by the steady state resulting from coupling of However, for irreversible processes, these approaches are blind on diffusion with convection forced by solution stirring or circulation. reaction bifurcations occurring beyond the kinetically determining Homogeneous molecular catalysis of organic electrochemical reactions step, which are precisely those governing the selectivity of the re- of the redox or chemical type may be treated in the same manner. The same benchmarking procedures recently developed for the activation action. This is not the case of preparative-scale electrolysis accom- of small molecules in the context of modern energy challenges lead to panied by identification and quantitation of products. -
Four Channel Liquid Chromatography/Electrochemistry
Four Channel Liquid Chromatography/Electrochemistry Bruce Peary Solomon, Ph.D. The new epsilon family of electrochemical detectors from BAS can Hong Long, Ph.D. Yongxin Zhu, Ph.D. control up to four working electrodes simultaneously. There are several Chandrani Gunaratna, Ph.D. advantages to using multiple detector electrodes. By using four different Lou Coury, Ph.D.* applied potentials with electrodes placed in a parallel arrangement, a Bioanalytical Systems, Inc. hydrodynamic voltammogram can be generated quickly through Corporate R&D Laboratories 2701 Kent Avenue acquisition of four data points for every analyte injection. This speeds West Lafayette, IN method development time. In addition, co-eluting compounds in complex 47906-1382 mixtures can be resolved on the basis of their observed half-wave * corresponding author potentials by using the same arrangement of electrodes, also in parallel. This article presents a few examples of four-electrode experiments performed with epsilon detectors in the BAS R&D labs during the past few months, using both radial-flow and cross-flow thin-layer configurations. The epsilon Platform the past fifteen years, our contract These instruments are fully network- research division, BAS Analytics, able and will be upgradable over the BAS developed and introduced the has provided analytical data of the Internet. New techniques and fea- first commercial electrochemical de- highest quality to the world’s leading tures may initially be ordered àla tector for liquid chromatography pharmaceutical companies using carte, or added at any time when the over twenty-five years ago. With this state-of-the-art products from BAS, need arises. In the coming months, issue of Current Separations,BAS as well as other leading vendors. -
Electrolytic Production of Aluminium:� Fundamental
r , ELECTROLYTIC PRODUCTION OF ALUMINIUM:� FUNDAMENTAL AND APPLIED STUDIES ON THE EFFECT OF ANODE COMPOSITION ON TEE ANODE-ELECTROLYTE INTERFACIAL CONDITIONS. by :,:.!::_OSBORNE. B.Sc. (Hons.), (Tas.) being a Thesis submitted. in fulfilment of the require ments for the Degree of Master of Science UNIVERSITY OF TASMANIA HOBART'. (May 1968) DECLARATION OF ORIGINALITY All of the experimental w0rk in this thesis, except where directly ascribed to others, has been performed solely by the auth0r. No part 0f the text bas previoµsly been submitted f@r any other degree or diplGma in any University, nor dees it contain, to the best knowledge of the undersigned, any material which has been published by others, except where due reference bas been SQ made. SUMMARY This thesis deals with a study of the wettability of amorphous carbon, of the type empl©yed as anode material in the production of aluminium, by cryolite based solutions. The wettability of carbon has been improved by the addition of inorganic additives 0f the type used in cryolite electrolytes, such as aluminium oxide, calcium flanride and carbonate, and lithium flunride and carbonate. Particular improvements in carbon wettability are noted when the system is contained in an atmosphere of carbon dioxide - carbon monoxide, corresponding to practical production conditions. Furtheremore, when anodes prepared c0ntaining these additives are used in a laboratory aluminium cell, notable reductions in cell voltage are achieved at practical an0de current densities. The improved adhesion of the two phases has also been demonstrated by measurement of the current density and voltage con ditions required to llinduce anode effects in this cell •.