Canada

In this paper CFD techniques were applied to the simulations of hydrogen release from a 400-bar tank to ambient through a Pressure Relieve Device (PRD) 6 mm (¼”) opening. The numerical simulations using the TOPAZ software developed by Sandia National Laboratory addressed the changes of pressure density and flow rate variations at the leak orifice during release while the PHOENICS software package predicted extents of various hydrogen concentration envelopes as well as the velocities of gas mixture for the dispersion in the domain. The Abel-Noble equation of state (AN-EOS) was incorporated into the CFD model implemented through the TOPAZ and PHOENICS software to accurately predict the real gas properties for hydrogen release and dispersion under high pressures. The numerical results were compared with those obtained from using the ideal gas law and it was found that the ideal gas law overestimates the hydrogen mass release rates by up to 35% during the first 25 seconds of release. Based on the findings the authors recommend that a real gas equation of state be used for CFD predictions of high-pressure PRD releases.

This study outlines an approach to identifying the difficulties associated with the bench-marking of alkaline single cells under real electrolyzer conditions. A challenging task in the testing and comparison of different catalysts is obtaining reliable and meaningful benchmarks for these conditions. Negative effects on reproducibility were observed due to the reduction in conditioning time. On the anode side a stable passivation layer of NiO can be formed by annealing of the Ni foams which is even stable during long-term operation. Electrical contact resistance and impedance measurements showed that most of the contact resistance derived from the annealed Ni foam. Additionally analysis of various overvoltages indicated that most of the total overvoltage comes from the anode and cathode activation overpotential. Different morphologies of the substrate material exhibited an influence on the performance of the alkaline single cell based on an increase in the ohmic resistance.

A buoyant round vertical hydrogen jet is investigated using Large Eddy Simulations at low Mach number (M = 0.3). The influence of the transient concentration fields on the extent of the gas envelope with concentrations within the flammability limits is analyzed and their structure are characterized. The transient flammable region has a complex structure that extends up to 30% beyond the time-averaged flammable volume with high concentration pockets that persist sufficiently long for potential ignition. Safety envelopes devised on the basis of simplified time-averaged simulations would need to include a correction factor that accounts for transient incursions of high flammability concentrations.

Widespread uptake of battery electric plug-in hybrid and hydrogen fuel-cell vehicles (collectively zero-emissions vehicles or ZEVs) could help many regions achieve deep greenhouse gas mitigation goals. Using the case of Canada this study investigates the extent to which increasing ZEV charging and refuelling availability may boost ZEV sales relative to other ZEV-supportive policies. We adapt a version of the Respondent-based Preferences and Constraints (REPAC) model using 2017 survey data from 1884 Canadian new vehicle-buyers to simulate the sales impacts of increasing electric vehicle charging access at home work public destinations and on highways as well as increasing hydrogen refuelling station access. REPAC is built from a stated preference choice model and represents constraints in supply and consumer awareness as well as dynamics in ZEV policy out to 2030. Results suggest that new ZEV market share from 2020 to 2030 does not substantially benefit from increased infrastructure. Even when electric charging and hydrogen refuelling access are simulated to reach “universally” available levels by 2030 ZEV sales do not rise by more than 1.5 percentage points above the baseline trajectory. On the other hand REPAC simulates ZEV market share rising as high as 30% by 2030 with strong ZEV-supportive policies even without the addition of charging or refuelling infrastructure. These findings stem from low consumer valuation of infrastructure found in the stated preference model. Results suggest that achieving ambitious ZEV sale targets requires a comprehensive suite of policies beyond a focus on charging and refuelling infrastructure.

Hydrogen is seen as the future automobile energy storage media due to its inherent cleanliness upon oxidation and its ready utilization in fuel cell applications. Its physical storage in light weight low volume systems is a key technical requirement. In searching for ever higher gravimetric and volumetric density hydrogen storage materials and systems it is inevitable that higher energy density materials will be studied and used. To make safe and commercially acceptable systems it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate risk mitigation strategies to handle unforeseen accidental events. To evaluate these materials and systems an IPHE sanctioned program was initiated in 2006 partnering laboratories from Europe North America and Japan. The objective of this international program is to understanding the physical risks involved in synthesis handling and utilization of solid state hydrogen storage materials and to develop methods to mitigate these risks. This understanding will support ultimate acceptance of commercially high density hydrogen storage system designs. An overview of the approaches to be taken to achieve this objective will be given. Initial experimental results will be presented on environmental exposure of NaAlH4 a candidate high density hydrogen storage compound. The tests to be shown are based on United Nations recommendations for the transport of hazardous materials and include air and water exposure of the hydride at three hydrogen charge levels in various physical configurations. Additional tests developed by the American Society for Testing and Materials were used to quantify the dust cloud ignition characteristics of this material which may result from accidental high energy impacts and system breach. Results of these tests are shown along with necessary risk mitigation techniques used in the synthesis and fabrication of a prototype hydrogen storage system.

The effect of surfaces on the extent of high pressure horizontal unignited jets of hydrogen and methane is studied using CFD numerical simulations performed with FLACS Hydrogen. Results for constant flow rate through a 6.35 mm PRD from 100 barg and 700 barg storage units are presented for horizontal hydrogen and methane jets. To quantify the effect of a horizontal surface on the jet the jet exit is positioned at various heights above the ground ranging from 0.1 m to 10 m. Free jet simulations are performed for comparison purposes.

Computational fluid dynamics (CFD) is used to numerically solve the sudden release of hydrogen from a high pressure tank (up to 70MPa) into air. High pressure tanks increase the risk of failure of the joints and pipes connected to the tank which results in release of Hydrogen. The supersonic flow caused by high pressure ratio of reservoir to ambient generates a strong Mach disk. A three dimensional in-house code is developed to simulate the flow. High pressure Hydrogen requires a real gas law because it deviates from ideal gas law. Firstly Beattie-Bridgeman and Abel-Noble real gas equation of states are applied to simulate the release of hydrogen in hydrogen. Then Abel-Noble is implied to simulate the release of hydrogen in air. Beattie-Bridgeman has stability problems in the case of hydrogen in air. A transport equation is used to solve the concentration of Hydrogen-air mixture. The code is second order accurate in space and first order in time and uses a modified Van Leer limiter. The fast release of Hydrogen from a small rupture needs a very small mesh therefore parallel computation is applied to overcome memory problems and to decrease the solution time. The high pressure ratio of the reservoir to ambient causes a very fast release which is accurately modelled by the code and all the shocks and Mach disk happening are observed in the results. The results show that the difference between real gas and ideal gas models cannot be ignored.

Experiments with a hydrogen jet were performed at two different pressures 96 psig (6.6 bars) and 237 psig (16.3 bars). The hydrogen leak was generated at two different hole sizes 1/16 inch (1.6 mm) and 1/32 inch (0.79 mm). The flammable shape of the plume was characterised by numerous measurements of the hydrogen concentration inside of the jet. The effect of the nearby horizontal surface on the shape of the plume was measured and compared with results of CFD numerical simulations. The paper will present results and an interpretation on the nature of the plume shape.

Computational Fluid Dynamics (CFD) is applied to investigate the near exit jet behavior of high pressure hydrogen release into quiescent ambient air through different types of orifices. The size and geometry of the release hole can affect the possibility of auto-ignition. Therefore the effect of release geometry on the behavior and development of hydrogen jet issuing from non-axisymmetric (elliptical) and expanding orifices is investigated and compared with their equivalent circular orifices. A three-dimensional in-house code is developed using the MPI library for parallel computing to simulate the flow based on an inviscid approximation. Convection dominates viscous effects in strongly underexpanded supersonic jets in the vicinity of release exit justifying the use of the Euler equations. The transport (advection) equation is applied to calculate the concentration of hydrogen-air mixture. The Abel-Nobel equation of state is used because high pressure hydrogen flow deviates from the ideal gas assumption. This work effort is conducted to fulfill two objectives. First two types of circular and elliptic orifices with the same cross sectional area are simulated and the flow behavior of each case is studied and compared during the initial stage of release. Second the comparative study between expanding circular exit and its fixed counterpart is carried out. This evaluation is conducted for different sizes of nozzle with different aspect ratios.

In the current study a Large Eddy Simulation strategy is applied to model the dispersion of compressible turbulent hydrogen jets issuing from realistic pipe geometries. The work is novel as it explores the effect of jet densities and Reynolds numbers on vertical buoyant jets as they emerge from the outer wall of a pipe through a round orifice perpendicular to the mean flow within the pipe. An efficient Godunov solver is used and coupled with Adaptive Mesh Refinement to provide high resolution solutions only in areas of interest. The numerical results are validated against physical experiments of air and helium which allows a degree of confidence in analysing the data obtained for hydrogen releases. The results show that the jets investigated are always asymmetric. Thus significant discrepancies exist when applying conventional round jet assumptions to determine statistical properties associated with gas leaks from pipelines.

Hydrogen has the potential to be used by many countries as part of decarbonising the future energy system. Hydrogen can be used as a fuel ‘vector’ to store and transport energy produced in low-carbon ways. This could be particularly important in applications such as heating and transport where other solutions for low and zero carbon emission are difficult. To enable the safe uptake of hydrogen technologies it is important to develop the international scientific evidence base on the potential risks to safety and how to control them effectively. The International Association for Hydrogen Safety (known as IA HySAFE) is leading global efforts to ensure this. HSE hosted the 2018 IA HySAFE Biennial Research Priorities Workshop. A panel of international experts presented during nine key topic sessions: (1) Industrial and National Programmes; (2) Applications; (3) Storage; (4) Accident Physics – Gas Phase; (5) Accident Physics – Liquid/ Cryogenic Behaviour; (6) Materials; (7) Mitigation Sensors Hazard Prevention and Risk Reduction; (8) Integrated Tools for Hazard and Risk Assessment; (9) General Aspects of Safety.<br/>This report gives an overview of each topic made by the session chairperson. It also gives further analysis of the totality of the evidence presented. The workshop outputs are shaping international activities on hydrogen safety. They are helping key stakeholders to identify gaps in knowledge and expertise and to understand and plan for potential safety challenges associated with the global expansion of hydrogen in the energy system.

Hydrogen mixed natural gas for combustion can improve combustion characteristics and reduce carbon emission which has important engineering application value. A casing swirl burner model is adopted to numerically simulate and research the natural gas hydrogen mixing technology for combustion in gas boilers in this paper. Under the condition of conventional air atmosphere and constant air excess coefficient the six working conditions for hydrogen mixing proportion into natural gas are designed to explore the combustion characteristics and the laws of pollution emissions. The temperature distributions composition and emission of combustion flue gas under various working conditions are analyzed and compared. Further investigation is also conducted for the variation laws of NOx and soot generation. The results show that when the boiler heating power is constant hydrogen mixing will increase the combustion temperature accelerate the combustion rate reduce flue gas and CO2 emission increase the generation of water vapor and inhibit the generation of NOx and soot. Under the premise of meeting the fuel interchangeability it is concluded that the optimal hydrogen mixing volume fraction of gas boilers is 24.7%.

The rapid evolution of information related to hydrogen safety is multidimensional ranging from developing codes and standards to CFD simulations and experimental studies of hydrogen releases to a variety of risk assessment approaches. This information needs to be transformed into system design risk decision-making and first responder tools for use by hydrogen community stakeholders. The Canadian Transportation Fuel Cell Alliance (CTFCA) has developed HySTARtm an interactive Hydrogen Safety Training And Risk System. The HySTARtm user interacts with a Web-based 3-D graphical user interface to input hydrogen system configurations. The system includes a Codes and Standards Expert System that identifies the applicable codes and standards in a number of national jurisdictions that apply to the facility and its components. A Siting Compliance and Planning Expert System assesses compliance with clearance distance requirements in these jurisdictions. Incorporating the results of other CTFCA projects HySTARtm identifies stand-out hydrogen release scenarios and their corresponding release condition that serves as input to built-in consequence and risk assessment programs that output a variety of risk assessment metrics. The latter include on- and off-site individual risk probability of loss of life and expected number of fatalities. These results are displayed on the graphical user interface used to set up the facility. These content and graphical tools are also used to educate regulatory approval and permitting officials and build a first-responder training guide.

The challenges and approaches of the safety and risk management for the hydrogen production with nuclear-based thermochemical water splitting have been far from sufficiently reported as the thermochemical technology is still at a fledgling stage and the linkage of a nuclear reactor with a hydrogen production plant is unprecedented. This paper focuses on the safety issues arising from the interactions between the nuclear heat source and thermochemical hydrogen production cycle as well between the proximate individual processes in the cycle. As steam is utilized in most thermochemical cycles for the water splitting reaction and heat must be transferred from the nuclear source to hydrogen production plant this paper particularly analyzes and quantifies the heat hazard for the scenarios of start-up and shutdown of the hydrogen production plant. Potential safety impacts on the nuclear reactor are discussed. It is concluded that one of the main challenges of safety and risk management is efficient rejection of heat in a shutdown accident. Several options for the measures to be taken are suggested. Copper-chlorine and sulphur-iodine thermochemical cycles are taken as two representative examples for the hazard analysis. It is expected that these newly reported challenges and approaches could help build the future safety and risk management codes and standards for the infrastructure of the thermochemical hydrogen production.

In order to facilitate the application of hydrogen energy and ensure its safety the compressed hydrogen storage tank on board needs to be full of hydrogen gas within 3 minutes. Therefore to meet this requirement the effects of refueling parameters on the filling time need to be investigated urgently. For the purpose of solving this issue a novel analytical solution of filling time is obtained from a lumped parameter model in this paper. According to the equation of state for real gas and dimensionless numbers Nu and Re the function relationships between the filling time and the refueling parameters are presented. These parameters include initial temperature initial pressure inflow temperature final temperature and final pressure. These equations are used to fit the reference data the results of fitting show good agreement. Then the values of fitting parameters are further utilized so as to verify the validity of these formulas. We believe this study can contribute to control the hydrogen filling time and ensure the safety during fast filling process.

Metal fuels as recyclable carriers of clean energy are promising alternatives to fossil fuels in a future low-carbon economy. Fossil fuels are a convenient and widely-available source of stored solar energy that have enabled our modern society; however fossil-fuel production cannot perpetually keep up with increasing energy demand while carbon dioxide emissions from fossil-fuel combustion cause climate change. Low-carbon energy carriers with high energy density are needed to replace the multiple indispensable roles of fossil fuels including for electrical and thermal power generation for powering transportation fleets and for global energy trade. Metals have high energy densities and metals are therefore fuels within many batteries energetic materials and propellants. Metal fuels can be burned with air or reacted with water to release their chemical energy at a range of power-generation scales. The metal-oxide combustion products are solids that can be captured and then be recycled using zero-carbon electrolysis processes powered by clean energy enabling metals to be used as recyclable zero-carbon solar fuels or electrofuels. A key technological barrier to the increased use of metal fuels is the current lack of clean and efficient combustor/reactor/engine technologies to convert the chemical energy in metal fuels into motive or electrical power (energy). This paper overviews the concept of low-carbon metal fuels and summarizes the current state of our knowledge regarding the reaction of metal fuels with water to produce hot hydrogen on demand and the combustion of metal fuels with air in laminar and turbulent flames. Many important questions regarding metal-fuel combustion processes remain unanswered as do questions concerning the energy-cycle efficiency and life-cycle environmental impacts and economics of metals as recyclable fuels. Metal fuels can be an important technology option within a future low-carbon society and deserve focused attention to address these open questions.

The study on temper embrittlement and hydrogen embrittlement of a test block from a 3Cr1Mo1/4V hydrogenation reactor after ten years of service was carried out by small punch test (SPT) at different temperatures. The SPT fracture energy Esp (derived from integrating the load-displacement curve) divided by the maximum load (Fm) of SPT was used to fit the Esp/Fm versus-temperature curve to determine the energy transition temperature (Tsp) which corresponded to the ductile-brittle transition temperature of the Charpy impact test. The results indicated that the ratio of Esp/Fm could better represent the energy of transition in SPT compared with Esp. The ductile-to-brittle transition temperature of the four different types of materials was measured using the hydrogen charging test by SPT. These four types of materials included the base metal and the weld metal in the as-received state and the base metal and the weld metal in the de-embrittled state. The results showed that there was a degree of temper embrittlement in the base metal and the weld metal after ten years of service at 390 °C. The specimens became slightly more brittle but this was not obvious after hydrogen charging. Because the toughness of the material of the hydrogenation reactor was very good the flat samples of SPT could not characterize the energy transition temperature within the liquid nitrogen temperature. Additionally there was no synergetic effect of temper embrittlement and hydrogen embrittlement found in 3Cr1Mo1/4V steel.

The potential benefits are examined of the “Power-to-Gas” (P2G) scheme to utilize excess wind power capacity by generating hydrogen (or potentially methane) for use in the natural gas distribution grid. A parametric analysis is used to determine the feasibility and size of systems producing hydrogen that would be injected into the natural gas grid. Specifically wind farms located in southwestern Ontario Canada are considered. Infrastructure requirements wind farm size pipeline capacity geographical dispersion hydrogen production rate capital and operating costs are used as performance measures. The model takes into account the potential production rate of hydrogen and the rate that it can be injected into the local gas grid. “Straw man” systems are examined centered on a wind farm size of 100 MW integrating a 16-MW capacity electrolysis system typically producing 4700 kg of hydrogen per day.

Unintended releases can occur during the production storage transportation and filling of liquid hydrogen which may cause devastating consequences. In the present work liquid hydrogen leak is modeled in ANSYS Fluent with the numerical model validated using the liquid hydrogen spill test data. A three-layer artificial neural network (ANN) model is built in which the wind speed ground temperature leakage time and leakage rate are taken as the inputs the horizontal diffusion distance and vertical diffusion distance of combustible gas as the outputs of the ANN. The representative sample data derived from the detailed calculation results of the numerical model are selected via the orthogonal experiment method to train and verify the back propagation (BP) neural network. Comparing the calculation results of the formula fitting with the sample data the results show that the established ANN model can quickly and accurately predict the horizontal and vertical diffusion distance of flammable vapor cloud relatively. The influences of four parameters on the horizontal hazard distance as well as vertical hazard height are predicted and analyzed in the case of continuous overflow of liquid hydrogen using the ANN model.

Recent modeling efforts of non-equilibrium effects in detonations have suggested that hydrogen-based detonations may be affected by vibrational non-equilibrium of the hydrogen and oxygen molecules effects which could explain discrepancies of cell sizes measured experimentally and calculated without relaxation effects. The present study addresses the role of vibrational relaxation in 2H2/O2 detonations by considering two-bath gases argon and helium. These two gases have the same thermodynamic and kinetic effects when relaxation is neglected. However due to the bath gases differences in molecular weight and reduced mass differences which affect the molecular collisions relaxation rates can be changed by approximately 50-70%. Experiments were performed in a narrow channel in mixtures of 2H2/O2/7Ar and 2H2/O2/7He to evaluate the role of the bath gas on detonation cellular structures. The experiments showed differences in velocity deficits and cell sizes for experimental conditions keeping the induction zone length constant in each of the mixtures. These differences were negligible in sensitive mixtures but increased with the increase in velocity deficits while the cell sizes approaching the channel dimensions. Near the limits differences of cell size in two mixtures approached a factor of 2. These differences were however reconciled by accounting for the viscous losses to the tube walls evaluated using a modified version of Mirels' laminar boundary layer theory and generalized Chapman-Jouguet theory for eigenvalue detonations. The experiments suggest that there is an influence of relaxation effects on the cellular structure of detonations which is more sensitive to wall boundary conditions. However the previous works showed that the impact of vibrational non-equilibrium in a mixture of H2/Air is more visible due to the effects of N2 in the air slowest to relax. Previous discrepancies suggested to be indicative of relaxation effects should be reevaluated by the inclusion of wall loss effects.

A new spinelized Ni catalyst (Ni-UGSO) using Ni(NO₃)₂·6H₂O as the Ni precursor was prepared according to a less material intensive protocol. The support of this catalyst is a negative-value mining residue UpGraded Slag Oxide (UGSO) produced from a TiO2 slag production unit. Applied to dry reforming of methane (DRM) at atmospheric pressure T = 810 °C space velocity of 3400 mL/(h·g) and molar CO₂/CH₄ = 1.2 Ni-UGSO gives a stable over 168 h time-on-stream methane conversion of 92%. In this DRM reaction optimization study: (1) the best performance is obtained with the 10–13 wt% Ni load; (2) the Ni-UGSO catalysts obtained from two different batches of UGSO demonstrated equivalent performances despite their slight differences in composition; (3) the sulfur-poisoning resistance study shows that at up to 5.5 ppm no Ni-UGSO deactivation is observed. In steam reforming of methane (SRM) Ni-UGSO was tested at 900 °C and a molar ratio of H₂O/CH₄ = 1.7. In this experimental range CH4 conversion rapidly reached 98% and remained stable over 168 h time-on-stream (TOS). The same stability is observed for H₂ and CO yields at around 92% and 91% respectively while H₂/CO was close to 3. In mixed (dry and steam) methane reforming using a ratio of H₂O/CH₄ = 0.15 and CO2/CH4 = 0.97 for 74 h and three reaction temperature levels (828 °C 847 °C and 896 °C) CH₄ conversion remains stable; 80% at 828 °C (26 h) 85% at 847 °C (24 h) and 95% at 896 °C (24 h). All gaseous streams have been analyzed by gas chromatography. Both fresh and used catalysts are analyzed by scanning electron microscopy-electron dispersive X-ray spectroscopy (SEM-EDXS) X-ray diffraction (XRD) and thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) and BET Specific surface. In the reducing environment of reforming such catalytic activity is mainly attributed to (a) alloys such as FeNi FeNi3 and Fe3Ni2 (reduction of NiFe2O4 FeNiAlO4) and (b) to the solid solution NiO-MgO. The latter is characterized by a molecular distribution of the catalytically active Ni phase while offering an environment that prevents C deposition due to its alkalinity.

Currently hydrogen production is based on the reforming process leading to the emission of pollutants; therefore a substitute production method is imminently required. Water electrolysis is an ideal alternative for large-scale hydrogen production as it does not produce any carbon-based pollutant byproducts. The production of green hydrogen from water electrolysis using intermittent sources (e.g. solar and eolic sources) would facilitate clean energy storage. However the electrocatalysts currently required for water electrolysis are noble metals making this potential option expensive and inaccessible for industrial applications. Therefore there is a need to develop electrocatalysts based on earth-abundant and low-cost metals. Nickel-based electrocatalysts are a fitting alternative because they are economically accessible. Extensive research has focused on developing nickel-based electrocatalysts for hydrogen and oxygen evolution. Theoretical and experimental work have addressed the elucidation of these electrochemical processes and the role of heteroatoms structure and morphology. Even though some works tend to be contradictory they have lit up the path for the development of efficient nickel-based electrocatalysts. For these reasons a review of recent progress is presented herein.

When hydrogen flows through a small finite length constant exit area nozzle the viscous effects create a fluid throat which acts as a converging-diverging nozzle and lead to Mach number greater than one at the exit if the jet is under-expanded. This phenomenon influences the mass flow rate and the dispersion cloud size. In this study the boundary layer effect on the unsteady hydrogen sonic jet flow through a 1 mm diameter pipe from a high pressure reservoir (up to 70 MPa) is studied using computational fluid dynamics with a large eddy simulation turbulence model. This viscous flow simulation is compared with a non-viscous simulation to demonstrate that the velocity is supersonic at the exit of a small exit nozzle and that the mass flow is reduced.

The use of high-fidelity simulation methods based on large-eddy simulation (LES) are proving useful for understanding and mitigating the safety hazards associated with hydrogen releases from nuclear power plants. However accurate modelling of turbulent premixed hydrogen flames via LES can require very high resolution to capture both the large-scale turbulence and its interaction with the flame fronts. Standard meshing strategies can result in impractically high computational costs especially for the thin fronts of hydrogen flames. For these reasons the use of a recently formulated integral length scale approximation (ILSA) subfilter-scale model in combination with an efficient anisotropic block-based adaptive mesh refinement (AMR) technique is proposed and examined herein for performing LES of turbulent premixed hydrogen flames. The anisotropic AMR method allows dynamic and solution-dependent resolution of flame fronts and the grid-independent properties of the ILSA model ensure that numerical errors associated with implicitly-filtered LES techniques in regions with varying resolution are avoided. The combined approach has the potential to allow formally converged LES solutions (direct numerical simulation results are typically reached in the limit of very fine meshes with standard subgrid models). The proposed LES methodology is applied to combustion simulations of lean premixed hydrogen-air mixtures within closed vessels: a problem relevant to hydrogen safety applications in nuclear facilities. A progress variable-based method with a multi-phenomena burning velocity model is used as the combustion model. The present simulation results are compared to the available experiment data for several previously studied THAI vessel cases and the capabilities of the proposed LES approach are assessed.

During the early phase of the transient process following a hydrogen leak into the atmosphere a contact surface appears separating air heated by the leading shock from hydrogen cooled by expansion. Locally the interface is approximately planar. Diffusion leads to a temperature decrease on the air side and an increase in the hydrogen-filled region and mass diffusion of hydrogen into air and of air into hydrogen potentially resulting in ignition. This process was analyzed by Li ˜nan and Crespo [1] for unity Lewis number and Li ˜nan and Williams [2] for Lewis number less than unity. We included in the analysis the effect of a slow expansion [3 4] leading to a slow drop in temperature which occurs in transient jets. Chemistry being very temperature-sensitive the reaction rate peaks close to the hot side of the interface where only a small fuel concentration present close to the warm air-rich side which depends crucially upon the fuel Lewis number. For Lewis number unity the fuel concentration due to diffusion is comparable to the rate of consumption by chemistry. If the Lewis number is less than unity diffusion brings in more fuel than temperature-controlled chemistry consumes. For a Lewis number greater than unity diffusion is not strong enough to bring in as much fuel as chemistry would burn; combustion is controlled by fuel diffusion. If the temperature drop due to expansion associated with the multidimensional jet does not lower significantly the reaction rate up to that point analysis shows that ignition in the jet takes place. For fuel Lewis number greater than unity chemistry does not lead to a defined explosion so that eventually expansion will affect the process; ignition does not take place [3 4]. In the current paper these results are extended to consider multistep chemical kinetics but for otherwise similar assumptions. High activation energy is no longer applicable. Instead results are obtained in the short time limit still as a perturbation superimposed to the self-similar solution to the chemically frozen diffusion solution. In that approximation the initiation step which consumes fuel and oxidant is taken to be slow compared with steps that consume one of the reactants and an intermediate species. The formulation leads to a two point boundary value problem for set of coupled rate equations plus an energy equation for perturbations. These equations are linear with variable co-effcients. The coupled problem is solved numerically using a split algorithm in which chemical reaction is solved for frozen diffusion while diffusion is solved for frozen chemistry. At each time step the still coupled linear problem is solved exactly by projecting onto the eigenmodes of the stiff matrix so that the solution is unaffected by stiffness. Since in the short time limit temperature is only affected at the perturbation level the matrix depends only on the similarity variable x t but it is otherwise time-independent. As a result determination of the eigenvalues and eigenvectors is only done once (using Maple) for the entire range of discretized values of the similarity variable. The diffusion problem consists of a set of independent equations for each species. Each of these is solved using orthogonal decomposition onto Hermite polynomials for the homogeneous part plus a particular solution proportional to time for the non-homogeneous (source) terms. That approach can be implemented for different kinetic schemes.