Electrochemical engineering

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Electrochemical engineering is the branch of chemical engineering dealing with the technological applications of electrochemical phenomena, such as electrosynthesis of chemicals, electrowinning and refining of metals, flow batteries and fuel cells, surface modification by electrodeposition, electrochemical separations and corrosion.

Contents

According to the IUPAC, the term electrochemical engineering is reserved for electricity-intensive processes for industrial or energy storage applications and should not be confused with applied electrochemistry, which comprises small batteries, amperometric sensors, microfluidic devices, microelectrodes, solid-state devices, voltammetry at disc electrodes, etc.

More than 6% of the electricity is consumed by large-scale electrochemical operations in the US. [1]

Scope

This diagram shows the relationship between electrochemical engineering and other disciplines. Electrochemical engineering (corrected).jpg
This diagram shows the relationship between electrochemical engineering and other disciplines.

Electrochemical engineering combines the study of heterogeneous charge transfer at electrode/electrolyte interphases with the development of practical materials and processes. Fundamental considerations include electrode materials and the kinetics of redox species. The development of the technology involves the study of the electrochemical reactors, their potential and current distribution, mass transport conditions, hydrodynamics, geometry and components as well as the quantification of its overall performance in terms of reaction yield, conversion efficiency, and energy efficiency. Industrial developments require further reactor and process design, fabrication methods, testing, and product development.

Electrochemical engineering considers current distribution, fluid flow, mass transfer, and the kinetics of the electro reactions to design efficient electrochemical reactors. [2]

Most electrochemical operations are performed in filter-press reactors with parallel plate electrodes or, less often, in stirred tanks with rotating cylinder electrodes. Fuel cell and flow battery stacks are types of filter-press reactors. Most of them are continuous operations.

History

Cell room of a chlor-alkali plant ca. 1920 Cell room of a chlorine-caustic soda plant.JPG
Cell room of a chlor-alkali plant ca. 1920

This branch of engineering emerged gradually from chemical engineering as electrical power sources became available in the mid-19th century. Michael Faraday described his laws of electrolysis in 1833, relating for the first time the amount of electrical charge and converted mass. In 1886 Charles Martin Hall developed a cheap electrochemical process for extracting aluminium from its ore in molten salts, constituting the first true large-scale electrochemical industry. Later, Hamilton Castner improved the process aluminium manufacturing and devised the electrolysis of brine in large mercury cells for the production of chlorine and caustic soda, effectively founding the chlor-alkali industry with Karl Kellner in 1892. The next year, Paul L. Hulin patented filter-press type electrochemical cells in France. Charles Frederick Burgess developed the electrolytic refining of iron ca. 1904 and later ran a successful battery company. Burgess published one of the first texts on the field in 1920. Industrial electrochemistry followed an empirical approach during the first three decades of the 20th century. [3]

After the Second World War, interest focused on the fundaments of electrochemical reactions. Among other developments, the potentiostat (1937) enabled such studies. A critical advance was provided by the work of Carl Wagner and Veniamin Levich in 1962, who linked the hydrodynamics of a flowing electrolyte towards a rotating disc electrode with the mass transport control of the electrochemical reaction through a rigorous mathematical treatment. The same year, Wagner described "The Scope of Electrochemical Engineering" for the first time as a separate discipline from a physicochemical perspective. [4] During the 60s and 70s Charles W. Tobias, who is regarded as the "father of electrochemical engineering" by the Electrochemical Society, was concerned with ionic transport by diffusion, migration, and convection, exact solutions of potential and current distribution problems, conductance in heterogeneous media, quantitative description of processes in porous electrodes. Also in the 60s, John Newman pioneered the study of many of the physicochemical laws that govern electrochemical systems, demonstrating how complex electrochemical processes could be analysed mathematically to correctly formulate and solve problems associated with batteries, fuel cells, electrolyzer, and related technologies. In Switzerland, Norbert Ibl contributed to experimental and theoretical studies of mass transfer and potential distribution in electrolyses, especially at porous electrodes. Fumio Hine carried out equivalent developments in Japan. In addition, several individuals, including Kuhn, Kreysa, Rousar, Fleischmann, Alkire, Coeuret, Pletcher, and Walsh established many other training centers and, with their colleagues, developed important experimental and theoretical methods of study. Currently, the main tasks of electrochemical engineering consist of the development of efficient, safe, and sustainable technologies for the production of chemicals, metal recovery, remediation, and decontamination technologies as well as the design of fuel cells, flow batteries, and industrial electrochemical reactors.

The history of electrochemical engineering has been summarised by Wendt, [5] Lapicque, [6] and Stankovic. [7]

Applications

Electrochemical engineering is applied in industrial water electrolysis, electrolysis, electrosynthesis, electroplating, fuel cells, flow batteries, [8] decontamination of industrial effluents, electrorefining, electrowinning, etc. The primary example of an electrolysis-based process is the Chloralkali process for caustic soda and chlorine production. Other inorganic chemicals produced by electrolysis include:

Conventions

The established performance criteria, definitions, and nomenclature for electrochemical engineering can be found in Kreysa et al. [9] and an IUPAC report. [10]

Awards

See also

Related Research Articles

<span class="mw-page-title-main">Electrochemistry</span> Branch of chemistry

Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference and identifiable chemical change. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.

<span class="mw-page-title-main">Electrochemical cell</span> Electro-chemical device

An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells that generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

<span class="mw-page-title-main">Galvanic cell</span> Electrochemical device

A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous oxidation–reduction reactions. A common apparatus generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.

<span class="mw-page-title-main">Electrolytic cell</span> Cell that uses electrical energy to drive a non-spontaneous redox reaction

An electrolytic cell is an electrochemical cell that utilizes an external source of electrical energy to force a chemical reaction that would otherwise not occur. The external energy source is a voltage applied between the cell's two electrodes; an anode and a cathode, which are immersed in an electrolyte solution. This is in contrast to a galvanic cell, which itself is a source of electrical energy and the foundation of a battery. The net reaction taking place in a galvanic cell is a spontaneous reaction, i.e., the Gibbs free energy remains -ve, while the net reaction taking place in an electrolytic cell is the reverse of this spontaneous reaction, i.e., the Gibbs free energy is +ve.

The chloralkali process is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide, which are commodity chemicals required by industry. Thirty five million tons of chlorine were prepared by this process in 1987. The chlorine and sodium hydroxide produced in this process are widely used in the chemical industry.

A regenerative fuel cell or reverse fuel cell (RFC) is a fuel cell run in reverse mode, which consumes electricity and chemical B to produce chemical A. By definition, the process of any fuel cell could be reversed. However, a given device is usually optimized for operating in one mode and may not be built in such a way that it can be operated backwards. Standard fuel cells operated backwards generally do not make very efficient systems unless they are purpose-built to do so as with high-pressure electrolysers, regenerative fuel cells, solid-oxide electrolyser cells and unitized regenerative fuel cells.

<span class="mw-page-title-main">Flow battery</span> Type of electrochemical cell

A flow battery, or redox flow battery, is a type of electrochemical cell where chemical energy is provided by two chemical components dissolved in liquids that are pumped through the system on separate sides of a membrane. Ion transfer inside the cell occurs through the membrane while both liquids circulate in their own respective space. Cell voltage is chemically determined by the Nernst equation and ranges, in practical applications, from 1.0 to 2.43 volts. The energy capacity is a function of the electrolyte volume and the power is a function of the surface area of the electrodes.

<span class="mw-page-title-main">Electrolysis of water</span> Electricity-induced chemical reaction

Electrolysis of water is using electricity to split water into oxygen and hydrogen gas by electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, but must be kept apart from the oxygen as the mixture would be extremely explosive. Separately pressurised into convenient 'tanks' or 'gas bottles', hydrogen can be used for oxyhydrogen welding and other applications, as the hydrogen / oxygen flame can reach approximately 2,800°C.

This is an alphabetical list of articles pertaining specifically to chemical engineering.

In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically-determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.

In electrochemistry, electrosynthesis is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reactions, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well.

In electrochemistry, Faraday efficiency describes the efficiency with which charge (electrons) is transferred in a system facilitating an electrochemical reaction. The word "Faraday" in this term has two interrelated aspects: first, the historic unit for charge is the faraday (F), but has since been replaced by the coulomb (C); and secondly, the related Faraday's constant correlates charge with moles of matter and electrons. This phenomenon was originally understood through Michael Faraday's work and expressed in his laws of electrolysis.

Gas diffusion electrodes (GDE) are electrodes with a conjunction of a solid, liquid and gaseous interface, and an electrical conducting catalyst supporting an electrochemical reaction between the liquid and the gaseous phase.

In electrochemistry, polarization is a collective term for certain mechanical side-effects by which isolating barriers develop at the interface between electrode and electrolyte. These side-effects influence the reaction mechanisms, as well as the chemical kinetics of corrosion and metal deposition. In a reaction, the attacking reagents can displace the bonding electrons. This electronic displacement in turn may be due to certain effects, some of which are permanent, and the others are temporary. Those effects which are permanently operating in the molecule are known as polarization effects, and those effects which are brought into play by attacking reagent are known as polarisability effects.

A Bioelectrochemical reactor is a type of bioreactor where bioelectrochemical processes are used to degrade/produce organic materials using microorganisms. This bioreactor has two compartments: The anode, where the oxidation reaction takes place; And the cathode, where the reduction occurs. At these sites, electrons are passed to and from microbes to power reduction of protons, breakdown of organic waste, or other desired processes. They are used in microbial electrosynthesis, environmental remediation, and electrochemical energy conversion. Examples of bioelectrochemical reactors include microbial electrolysis cells, microbial fuel cells, enzymatic biofuel cells, electrolysis cells, microbial electrosynthesis cells, and biobatteries.

<span class="mw-page-title-main">Zinc–cerium battery</span>

Zinc–cerium batteries are a type of redox flow battery first developed by Plurion Inc. (UK) during the 2000s. In this rechargeable battery, both negative zinc and positive cerium electrolytes are circulated though an electrochemical flow reactor during the operation and stored in two separated reservoirs. Negative and positive electrolyte compartments in the electrochemical reactor are separated by a cation-exchange membrane, usually Nafion (DuPont). The Ce(III)/Ce(IV) and Zn(II)/Zn redox reactions take place at the positive and negative electrodes, respectively. Since zinc is electroplated during charge at the negative electrode this system is classified as a hybrid flow battery. Unlike in zinc–bromine and zinc–chlorine redox flow batteries, no condensation device is needed to dissolve halogen gases. The reagents used in the zinc-cerium system are considerably less expensive than those used in the vanadium flow battery.

Sonoelectrochemistry is the application of ultrasound in electrochemistry. Like sonochemistry, sonoelectrochemistry was discovered in the early 20th century. The effects of power ultrasound on electrochemical systems and important electrochemical parameters were originally demonstrated by Moriguchi and then by Schmid and Ehert when the researchers investigated the influence of ultrasound on concentration polarisation, metal passivation and the production of electrolytic gases in aqueous solutions. In the late 1950s, Kolb and Nyborg showed that the electrochemical solution hydrodynamics in an electrochemical cell was greatly increased in the presence of ultrasound and described this phenomenon as acoustic streaming. In 1959, Penn et al. demonstrated that sonication had a great effect on the electrode surface activity and electroanalyte species concentration profile throughout the solution. In the early 1960s, the electrochemist Allen J. Bard showed in controlled potential coulometry experiments that ultrasound significantly enhances mass transport of electrochemical species from the bulk solution to the electroactive surface. In the range of ultrasonic frequencies [20 kHz – 2 MHz], ultrasound has been applied to many electrochemical systems, processes and areas of electrochemistry both in academia and industry, as this technology offers several benefits over traditional technologies. The advantages are as follows: significant thinning of the diffusion layer thickness (δ) at the electrode surface; increase in electrodeposit/electroplating thickness; increase in electrochemical rates, yields and efficiencies; increase in electrodeposit porosity and hardness; increase in gas removal from electrochemical solutions; increase in electrode cleanliness and hence electrode surface activation; lowering in electrode overpotentials ; and suppression in electrode fouling.

The Castner Gold Medal on Industrial Electrochemistry is an biennial award given by the Electrochemical Technology Group of Society of Chemical Industry (SCI) to an authority on applied electrochemistry or electrochemical engineering connected to industrial research. The award is named in honor of Hamilton Castner, a pioneer in the field of industrial electrochemistry, who patented in 1892 the mercury cell for the chloralkali process. Castner was an early member of SCI.

Elod Lajos Gyenge is a professor of Chemical and Biological Engineering at the faculty of Applied Science in University of British Columbia in Vancouver, BC, Canada. He is also an associate member of the Clean Energy Research Center of UBC Vancouver campus. Elod Gyenge has been nominated for several teaching and research awards including Japanese Society for Promotion of Science (JSPS) Fellowship at Osaka University and the recipient of the distignshuied Elisabeth and Leslie Gould Endowed Professorship at UBC from 2007 to 2014. His research has been toward development of electrochemical systems such as fuel cells, batteries and electrosynthesis systems. He is also an appointed professor in the engineering school of Osaka University in Japan.

References

  1. Bebelis, S.; Bouzek, K.; Cornell, A.; Ferreira, M.G.S.; Kelsall, G.H.; Lapicque, F.; Ponce de León, C.; Rodrigo, M.A.; Walsh, F.C. (October 2013). "Highlights during the development of electrochemical engineering". Chemical Engineering Research and Design. 91 (10): 1998–2020. doi:10.1016/j.cherd.2013.08.029.
  2. Newman, John (1968). "Engineering design of electrochemical systems". Industrial & Engineering Chemistry. 60 (4): 12–27. doi:10.1021/ie50700a005.
  3. "List of Electrochemistry Books Published Before 1950". The Electrochemical Society.
  4. Wagner, C. (1962). "The scope of electrochemical engineering". Advances in Electrochemistry and Electrochemical Engineering. 2: 1–14.
  5. Wendt, H.; Kreysa, G. (1999). "The Scope and History of Electrochemical Engineering". Electrochemical Engineering. pp. 1–7. doi:10.1007/978-3-662-03851-2_1. ISBN   978-3-642-08406-5.
  6. Lapicque, F. (2004). "Electrochemical Engineering: An Overview of its Contributions and Promising Features". Chemical Engineering Research and Design. 82 (12): 1571–1574. doi:10.1205/cerd.82.12.1571.58046.
  7. Stankovic, V. (2012). "Electrochemical Engineering - its appearance, evolution, and present status. Approaching an anniversary". Journal of Electrochemical Science and Engineering. 2: 1–14. doi: 10.5599/jese.2012.0011 .
  8. Arenas, L.F.; Ponce de León, C.; Walsh, F.C. (June 2017). "Engineering aspects of the design, construction and performance of modular redox flow batteries for energy storage" (PDF). Journal of Energy Storage. 11: 119–153. doi:10.1016/j.est.2017.02.007.
  9. Kreysa, G. (1985). "Performance criteria and terminology in electrochemical engineering". Journal of Applied Electrochemistry. 15 (2): 175–179. doi:10.1007/BF00620931. S2CID   106022706.
  10. Gritzner, G.; Kreysa, G. "Nomenclature, symbols and definitions in electrochemical engineering". Pure and Applied Chemistry. 65 (5): 1009–1020. doi: 10.1351/pac199365051009 .

Bibliography