The History of Gas Analysis in Electrochemistry

Electrochemistry is concerned with the range of oxidation-reduction (redox) reactions that cause electrons to transfer between the molecules of reactants. It is the study of the relationship between electricity and an identifiable chemical change, which was first observed in 1780. The chemical aspect of this relationship was largely ignored until Michael Faraday established the fundamental laws of electrolysis, laying the groundwork for modern voltaic technology. Yet the chemical aspect of many redox reactions remains ambiguous, particularly with respect to the specific interfacial behavior between electrodes and electrolytes. Gas analysis was subsequently considered unimportant in the technology’s early days.

DEMS Cell mass spectrometer

Early Electrochemistry Gas Analysis

In-situ dissolved gas and off-gas analysis at the electrode surface aims to provide a better understanding of the reactions that occur in a galvanic cell or half-cell structure. However, conventional techniques have proven incapable of combining electrochemical methods with an analytical technique sensitive enough to offer mass resolved determination of gaseous and volatile electrochemical reactants, intermediates, and products in real time. This is because the gas species generated at the interface are usually extremely small.

Mass spectrometry was first highlighted as an essential tool for electrochemical gas analysis by Bruckenstein and Gadde in 1971. They explored the use of a porous electrode for real-time determination of volatile electrode reaction products using an electron impact ionizer. This electrode contacted the electrolytic solution on one side and the high-vacuum chamber of a mass spectrometer on the other, facilitating the rapid identification of products generated in a typical electrochemical reaction.

Onset of Differential Electrochemical Mass Spectrometry

Differential electrochemical mass spectrometry (DEMS) is a sophisticated tool that was engineered to improve upon this pioneering method. This technique expanded on the early designs of Bruckenstein and Gadde with improved vacuum capacities to enhance sampling rates. It offers superior, quantitative insights into cell chemistry by integrating a mass spectrometer with a nanoporous gas diffusion electrode, enabling the acquisition of mass ion currents proportional to the electrode’s faradaic current.

Numerous advances have been made in the field of DEMS gas analysis in recent years, elevating the technique from a semblance of existing membrane inlet mass spectrometry (MIMS) to a powerhouse tool in its own right.

DEMS Gas Analysis with Hiden Analytical

Hiden Analytical offers a proprietary DEMS gas analysis system that enables direct analysis of gaseous and volatile products from electrochemical reactions.

The Hiden DEMS systems are offered with a wide range of DEMS cell types and inlets to accommodate a wide application range including CO2 reduction studies, Li-ion / Li air battery studies, gas solubility analysis, and gas diffusion rate analysis.

The DEMS systems have a standard mass range of 200 atomic mass units (amu) with a Faraday/Electron Multiplier detector to assist in the analysis of the potential dependence of electrochemical reactions in a typical half-cell structure.

If you would like to learn more about our HPR-40 DEMS gas analysis system, read our previous blog post: What is Differential Electrochemical Mass Spectrometry?

Otherwise, contact us directly with any more questions.

[Source: https://pubs.acs.org/doi/abs/10.1021/ja00732a049]

Gas Analysers for Fuel Cell Research

Electrochemical fuel cells are envisaged as a potential successor technology to combustion engines in the automotive sector. Although studies have considered numerous gaseous elements as the fuel source for electrochemical stacks, hydrogen (H2) remains the primary element of interest in automotive engineering. Gas analysers have proven instrumental in demonstrating the advantages and drawbacks of hydrogen fuel cell technology, and continue to provide accurate, quantitative insights for ongoing research and development (R&D).

Fuel Cell Research

The focus on hydrogen in fuel cell research is primarily due to the element’s high energy yield and relatively clean nature. Scientific and mainstream media have increasingly extolled the drawbacks of petroleum-based fuels in recent decades, yet the lack of a cost-effective, high energy alternative has complicated efforts to replace combustion technology with a more sustainable solution.

In this blog post, Hiden Analytical explores the importance of gas analysers in R&D of hydrogen fuel cells.

Demonstrating the Need for Fuel Cells

Ambient and process gas analysers have increasingly underlined the dangers of vehicular fossil fuel emissions and ambient air pollution. The Environmental Protection Agency (EPA) estimates that as much as 27% of greenhouse emissions in the US are attributable to vehicles on the road. These emissions contribute to the generation of hazardous ground-level ozone (O3), which can cause respiratory distress in humans and animals and is extremely damaging to natural ecosystems. It is also one of the primary contributors to summertime smog in urban environments.

It is difficult to quantify the human health impacts of vehicle emissions, but recent research suggests that as many as 385,000 people died in 2015 alone as a direct result of air pollution from vehicle emissions[1]. Gas analysers have been essential in demonstrating the environmental and human health burden of volatile organic compounds (VOCs) emitted by vehicle exhausts. Quantitatively demonstrating the dangers of vehicle emissions has catalysed interest in new, immature technologies such as hydrogen fuel cells.

Outlining Hydrogen Fuel Cells

Although there are numerous contending fuel cell architectures, they all operate on a similar electrochemical process. The energy potential of a stored fuel source is extracted via catalytic oxidation in a clean and silent process. They consist of an electrolyte, an anode, and a cathode which ionises hydrogen atoms to generate a direct current (DC) that is conditioned into an alternating current (AC). Immediate benefits of this architecture include long service lives if the cell stack is continually replenished with a source of hydrogen and an appropriate oxidant.

However, gas analysers are required to perform quality control of these individual elements to guarantee the efficiency of the electrochemical process. It is also important to monitor and characterise the emissions generated by fuel cells using hydrogen compounds rather than pure hydrogen as an energy source. Although abundant on earth, hydrogen is not readily available. Natural gas and methanol are envisaged as potential solutions to this issue, but both will generate pollutants that must be characterised to legitimise the green credentials of the technology.

Gas Analysers from Hiden Analytical

Hiden Analytical supplies an extensive range of gas analysers suitable for R&D and process control of hydrogen fuel cells, to support new levels of efficiency from electrochemical alternatives to petroleum-based fuels.

Our QIC Series gas analysers can reliably analyse reaction mixtures and product composition to detect impurities in hydrogen supplies and optimise the efficiency of fuel cell devices. It boasts a detection range from the parts per billion (ppb) level up to 100% concentration, providing outstanding resolution for quantifying gases in various compounds. The QIC Series gas analysers also feature a mass range of 200 amu for detecting ammonia (NH3), hydrogen, and methane in gas streams.

The QIC series gas analysis systems include special sampling options developed  for analysis of gas/vapour sample streams typical in fuel cell R&D, including high concentrations of light gases, hydrogen, water vapour, corrosive, flammable and explosive mixtures.

If you would like more information about our gas analysers for fuel cell research, please do not hesitate to contact us directly.

[Source: Science X]

The DLS Series: Three Instruments for Fusion Research

Physicists have been actively pursuing fusion energy since the early 20th Century. Low energy deuterium-deuterium (D2-D2) reactions were achieved using particle acceleration almost ten years before the Manhattan Project yielded the world’s first atomic weaponry, but fusion research only began in earnest at the closing of World War 2. Physicists have experienced numerous significant breakthroughs over the years, but still struggle to reconcile many of the inherent challenges of nuclear fusion. Cautious estimates suggest that fusion research will not yield a commercially-viable reactor for another fifty years.

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Still, the theoretical energy yields from achieving fusion on earth – notwithstanding the countless benefits associated with eliminating harmful emissions – continue to justify the time and cost expended on fusion research to date. This is underlined by the emergence of novel instruments capable of supplying more robust and quantitative measurements from existing fusion research equipment, such as tokamak devices.

In this blog post, we will explore three of the devices supplied by Hiden Analytical that are advancing the field of fusion research.

Fusion Research with DLS Series Mass Spectrometers

DLS Series quadrupole mass spectrometers are engineered for ultra-sensitive fusion fuel gas analysis. These systems are equipped with a threshold ionization mass spectrometry (TIMS) mode which can reliably distinguish between elements of similar atomic mass by controlling the energy of the electrons emitted within the ionisation source and generating distinct fingerprints for the species of interest. This has proven remarkably beneficial for fusion research as the integral isotopes deuterium and helium (4He) represent near-identical atomic mass values. They are separated by a mere 0.0254 amu, which complicates fuel purity validation using conventional mass spectrometry tools.

The DLS Series is comprised of three distinct quadrupole mass spectrometers with unique fusion research capabilities.

  • DLS-1: provides real-time quantitation of multiple gas species in complex mixtures with a mass range of 1 – 200 amu, and a sensitivity of D2 in helium of 100 parts per million (ppm).
  • DLS-10: offers ultra-high resolution with a mass range of 1 – 10 amu with mass separation of 0.006 amu, and a sensitivity of D2 in helium and helium in D2 to 10 ppm.
  • DLS-20: provides innovative dual-zone switching to enable both ultra-high resolution mass spectrometry and quantitative analysis of light gaseous species and helium isotopes for unmatched fusion research capabilities, with sensitivity to 1 ppm.

These units are individually suited for fusion research applications with the capacity to eliminate existing uncertainties that have complicated fusion experiments for decades. It is now possible to quantitatively measure and validate fuel purity using a combination of mass spectrometry and TIMS software analysis. The DLS-10 and DLS-20 mass spectrometers include the added advantage of operation of the quadrupole in the stability zone H, for ultra-high resolution with peak widths to 0.003 amu.

This represents significant potential for enhancing the accuracy and repeatability of fusion research experiments. The promise of the DLS Series’ unparalleled accuracy is particularly exciting for analysing various D2 cycles in tokamak reactors, which are widely considered the most viable fuel sources for achieving sustainable fusion on earth.

Fusion Research with Hiden Analytical

Hiden Analytical is a world leader in the development of novel mass spectrometers for advanced research applications. Our instruments are already demonstrating their outstanding potential in fusion research and fuel validation for the next generation of energy technologies. If you would like any more information about our dedication to fusion research, explore some of our other resources below:

Otherwise, contact us directly with any questions.

Quadrupole Systems for Fusion Research

Humanity’s energy supply comprises a mix of renewables, nuclear fission, and fossil fuel sources – a mixture that provides sufficient amounts of electricity for current consumption. However, the earth’s population is on an upward trajectory and is expected to increase by as much as three billion over the next thirty years. Associated increases in living standards, economic growth, and technological innovation is expected to raise the world’s energy demands by as much as three times their current value.

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Fusion research is perceived as one of the leading long-term solutions to the world’s increasing energy demands. This is the process of compressing hydrogen (H2) to form helium (He). The nuclei of multiple hydrogen atoms are fused into a single helium atom, and the resultant mass loss is expelled as energy. Fusion is the reaction process that powers stars, and it has long been revered as the theoretical golden standard for a non-carbon, renewable energy source.

Problems with fusion power generation have included the enormous energy deficit that fusion research experiments tend to exhibit, but measurement improvements for decades old technology is supporting a global push towards achievable fusion power.

Using Quadrupole Systems for Fusion Research

Among the most developed systems for fusion research is the tokamak device, designed in Soviet Russia in the 1950s. It magnetically confines extremely hot plasma in a vacuum vessel using magnetic coils to produce a field that extends in both vertical and horizontal planes. This enables the device to shape plasma, which is fed using an array of components and heating methods.

The cutting-edge nature and extreme parameters of fusion research create some of the most demanding research conditions on earth. Accurate vacuum analysis must be determined to assess the complicated interactions of hydrogen isotopes within the torus chamber. Residual gas analysis (RGA) has conventionally been applied to monitor fusion fuel purity from tokamak facilities, but the atomic masses of elements involved are often too similar for monitoring with conventional mass spectrometry equipment. Deuterium (D2) and helium-4 (4He), for example, occupy the same atomic mass, and both are isotopes associated with fusion reactions of hydrogen atoms. This presents significant problems for fuel purity validation in fusion research applications.

Fusion Research Equipment from Hiden Analytical

For tokamak fusion research Hiden Analytical have developed special RGA quadrupole mass spectrometer systems, including the DLS range quadrupole mass spectrometers for research and the HAL 101X RGA for monitoring, diagnostics and analysis applications at the tokamak.

The DLS-1 instrument includes a threshold ionisation mass spectrometry (TIMS) mode that separates Deuterium (D2) and helium-4 (4He). TIMS mode provides for control of the energy of the electrons emitted within the ionisation source, resulting in each species having a unique fingerprint that can be determined by DLS-1 – including deuterium and helium-4. The DLS-1 is a real-time quantitative RGA with a mass range of 1-200 amu and a 0.5 eV electron energy resolution over the range of 4 to 150 eV.

The DLS-20 system includes a 20 mm pole diameter quadrupole analyser that operates in both the zone 1 and the zone H stability regions. This provides both ultra-high mass resolution up to 20 amu using zone H, with a mass separation as small as 0.006 amu, and using zone 1, ultra-high sensitivity analysis over the mass range to 200 amu.

The HAL101X RGA is designed for critical monitoring, diagnostics, and analysis in tokamak operation, and includes new transformer coupled RF technology. The transformer coupled technology enables the analyser to be separated from the RGA electronics, the RF and interface units by extended distances of up to 80 m enabling RGA operation in both the standard RGA and TIMS modes in the harsh radiation environment of the tokamak.

Hiden Analytical are leading suppliers of quadrupole mass spectrometry equipment, with over 35 years’ experience in designing and manufacturing mass analysis instrumentation for an enormous range of applications.

Few of the sectors that we have provided for exhibit as much potential to change the world as fusion research, which researchers believe will begin supplementing global power grids in coming decades. Our quadrupole systems for fusion research are on the leading edge of energy analysis, with innovative benefits over conventional equipment.

If you would like any more information about our quadrupole systems for fusion research, please do not hesitate to contact us.

Southeast Asia Catalysis Conference (SACC 2017)

From 22 – 23 May our Agents in Singapore, Accord, attended and exhibited at the Southeast Asia Catalysis Conference (SACC 2017) on behalf of Hiden Analytical. There were discussions regarding the advances and challenges in the fields of homogeneous, heterogeneous, bio, photo and computational catalysis.

Invited speakers were top catalysis experts including Shell Professor Lynn GLADDEN (University of Cambridge), Dr Gary CASTY (ExxonMobil Research & Engineering), Prof Michael CLAEYS (Catalysis Institute & DST-NRF Centre of Excellence in Catalysis – University of Cape Town, South Africa), Prof Erik HEERES (University of Groningen, Netherlands) and many others from Southeast Asia countries.

Southeast Asia Catalysis Conference
The Hiden Analytical Stand at Southeast Asia Catalysis Conference (SACC 2017) on 22 – 23 May

 

Molecular Beam Mass Spectrometer Monitors Reactive Ions at Ambient Pressure

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HPR-60 MBMS

The Hiden HPR-60 mass spectrometer is a research tool conceived specifically for direct analysis of ions, radicals and neutral species in reactive processes and is of special interest to researchers studying plasma and flame chemistry, reaction kinetics, gas-phase intermediate species. The system typically operates in pressure regimes from 10E-3 mbar to 5 bar, and mass spectrometer options provide for measurement of neutrals, positive ions, negative ions and ion energies with choice of mass range up to 5000 amu. A new option is targeted specifically to isotopic measurement of light gases, with the ability to quantify trace deuterium in helium, for example, down to just 10 part per million.

The system samples direct from the reaction zone using a sequence of up to three pressure reduction stages to provide a sampling range from 10E-3 mbar to 100 mbar for the two-stage system and to 5 bar with the third stage. Intermediate aligned beam skimmers within each stage form a supersonic molecular beam for direct, near collision-free  transfer of sampled species direct to the UHV-operating mass spectrometer. The potential of each skimmer stage is independently biased to optimise ion extraction, beam focussing and ion transmission.

The integrated molecular beam chopper enables automated sequential acquisition of foreground/background data to provide refined measurement of neutrals composition with real-time display of the net acquired signal. Vacuum system operation is automated and systems are fully over-pressure protected. A custom-engineering service is available for design of any required system-to-process interface.

For full details of this and of other Hiden Analytical products contact Hiden Analytical at info@hiden.co.uk or visit the main website by clicking here.

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229th ECS Meeting Review

229thecs-logo-256x144pxHiden Analytical exhibited at the recent 229th Electrochemical Society (ECS) Meeting in San Diego,  California. Peter & Gerard were on the Hiden Booth No. 309. Every ECS meeting is a forum for sharing the latest scientific and technical developments in electrochemistry and solid state science and technology. Scientists, engineers and industry leaders come from around the world to attend the technical symposia, poster sessions, professional development workshops, networking opportunities and social events offered at our meetings.

What was showcased on the Hiden Booth?

Hiden Gas Analysers at 229th ECS Meeting

Research and development facilities around the world have chosen Hiden’s QGA and HPR-20 atmospheric pressure gas analysis systems to facilitate high sensitivity, fast response studies of process gases, reaction products and breakthrough gases In catalyst characterization, materials screening, fuel cell development and biogas studies – to name just a few of the many applications our systems have addressed over the last 3 decades. On display at the forthcoming 229th ECS Meeting will be our QGA quantitative gas analysis system, for direct real time analysis, quantification and control of gas related processes ranging in pressure from 100 mbar to 50 bar. Please drop by our Booth No. 309 in San Diego, CA, May 29-June 2, 2016, and we will be pleased to learn more about your requirements and have the opportunity to guide you in the choice of gas analysis system.

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QGA 

The bench-top mass spectrometer systems are coupled to the user process by the integral robust, flexible, quartz-lined heated capillary with sample consumption rates as low as 1 mL/min and response times as low as 150 milliseconds. Process interface options enable analyses through the very broad pressure regime and are suited to diverse application areas including top-gas analysis, measurement of dissolved species, multi-stream monitoring of gas feed and process exhaust lines (up to 80 individual gas streams), process/thermal reaction studies, respiratory analysis.

System operation, calibration, data acquisition and display are fully automated, with full manual control selectable when required. Integral I/O’s permit import of external data, such as temperature, for integration with the mass spectral display, and output of process detail for process control functions

Mass spectrometers for electrochemistry with Hiden’s unique DEMS cells  for monitoring of electrochemical reactions at 229th ECS Meeting

The HPR-40 DSA mass spectrometer system was introduced specifically for measurement of gases and vapours in aqueous media. Product development is application driven, with introduction of new media interface styles an on-going process to address novel user requirements and encompassing measurement in areas such as fermentation processing, photosynthesis, electrochemical reaction studies, water quality and soil condition assessment, plant root performance, analysis of enzyme kinetics.compilation350px

Cuvette on Stirrer, DEMS Cell, Membrane Inlet Probe, Kinetic Enzyme Probe, Dissolved Species Inlet

A fine membrane separates the aqueous media from the mass spectrometer sample intake, the membrane providing a very significant enrichment in gaseous throughput relative to that of water vapour. Interface types include insertion probes for direct immersion in the liquid media, flow-through patterns, cuvette styles for photo-sensitive biofuel studies, DEMS cells for monitoring of electrochemical reactions. The media interface flexibility is of significant interest for multiple application users in university and research laboratories, and all systems are equipped with automated inlet isolation to protect the system from overpressure in the event of membrane malfunction.

How was the show?

PITTCON is a more general application trade show that catered to laboratory equipment and instrumentation. For Hiden this meant that the show allowed for us to raise our company profile in disciplines that were not traditionally familiar with mass spectrometry and potentially branch out into other fields and newer applications. The size of the show was a great benefit as the number of attendees meant that different people stopped by the booth from day to day and that the people that stopped by the booth were largely different from those that stopped by last year. At the same time the general appeal of the show limited the number of people at the show that had an application that could use our products to a fraction of the total attendees.

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The Hiden stand at 229th ECS Meeting 2016

230th ECS Meeting October 2016!

We will see you all at 230th ECS Meeting, 2nd – 7th October, 2016. This meeting will be held in partnership with PRiME 2016.

PRiME 2016 offers a diverse blend of electrochemical and solid-state science and technology; and serves as one of the largest pacific rim forums for the discussion of our interdisciplinary research. Much of the research being discussed here supports efforts advancing the scientific discipline involved with the renewable energy, biomedical, water sanitation, communications, transportation, and infrastructure sectors.

This is the largest most significant research conference in the world. Held every four years, this international gathering is the joint effort of The Electrochemical Society (ECS), The Electrochemical Society of Japan (ECSJ), and The Korean Electrochemical Society (KECS), with the technical co-sponsorship of the Chinese Society of Electrochemistry, the Electrochemistry Division of the Royal Australian Chemical Institute, the Japan Society of Applied Physics, the Korean Physical Society Semiconductor Division, and the Semiconductor Physics Division of the Chinese Physics Society.

PRiME 2016 / 230th ECS Meeting

October 2 – 7, 2016
Honolulu, Hawaii

Visit conference website : 230th ECS Meeting / PRiME 2016

Find out more about our Forthcoming Conferences

251st American Chemical Society National Meeting & Exposition

Hiden are exhibiting at 251st American Chemical Society
National Meeting & Exposition, 13-17 March, to be held in San Diego, CA, USA. Visit Peter & Gerard on the Hiden Analytical Booth No. 1312.

ACS organizes two national meetings & expositions each year, and each one attracts an estimated 11,000 to 13,000 chemists, chemical engineers, academicians, graduate and undergraduate students, and other related professionals. During the meeting, scientists present new multidisciplinary research, hear the latest information in their areas of professional interest, and network with colleagues. Programming is planned by our 33 technical divisions that cover all scientific fields, secretariats that focus on multidisciplinary programming, and ACS committees. Each meeting will feature more than 7,000 presentations organized into technical symposia that highlight important research advances.

What’s being showcased on the Hiden Booth this year?

Hiden Gas Analysers at 251st ACS

Research and development facilities around the world have chosen Hiden’s QGA and HPR-20 atmospheric pressure gas analysis systems to facilitate high sensitivity, fast response studies of process gases, reaction products and breakthrough gases In catalyst characterization, materials screening, fuel cell development and biogas studies – to name just a few of the many applications our systems have addressed over the last 3 decades. On display at the forthcoming spring meeting of the ACS will be our QGA quantitative gas analysis system, for direct real time analysis, quantification and control of gas related processes ranging in pressure from 100 mbar to 50 bar. Please drop by our Booth No. 1312 in San Diego, CA, March 13-17, and we will be pleased to learn more about your requirements and have the opportunity to guide you in the choice of gas analysis system.

The bench-top mass spectrometer systems are coupled to the user process by the integral robust, flexible, quartz-lined heated capillary with sample consumption rates as low as 1 mL/min and response times as low as 150 milliseconds. Process interface options enable analyses through the very broad pressure regime and are suited to diverse application areas including top-gas analysis, measurement of dissolved species, multi-stream monitoring of gas feed and process exhaust lines (up to 80 individual gas streams), process/thermal reaction studies, respiratory analysis.

System operation, calibration, data acquisition and display are fully automated, with full manual control selectable when required. Integral I/O’s permit import of external data, such as temperature, for integration with the mass spectral display, and output of process detail for process control functions.

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Hiden QGA Atmospheric Gas Analyser

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Hiden Booth at Spring ACS, March 2014

Come and visit the Hiden Booth No. 1312 and speak to Peter and Gerard about our range of products. 

Visit conference website : 251st ACS

Find out more about our Forthcoming Conferences

HPR-30 Installation

Thomas Gaudy, Hiden’s French representative, completed the installation of a HPR-30 for Vacuum Monitoring in Semiconductor Processing.

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HPR-30 Installation for Vacuum Monitoring in Semiconductor Processing, France

Find out more about the HPR-30 residual gas analyser : HPR-30

Find out more about our representatives for France : Europe