Search results for: hydrogen batteries

Authors: Samira Rostom, Robert Symonds, Robin W. Hughes

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Hydrogen is considered as one of the most important clean and renewable energy carriers for a sustainable energy future. However, its efficient and cost-effective purification remains challenging. This paper presents the potential of using metal–organic frameworks (MOFs) in combination with pressure swing adsorption (PSA) technology for syngas based H2 purification. PSA process analysis is done considering high pressure and elevated temperature process conditions, it reduces the demand for off-gas recycle to the fuel reactor and simultaneously permits higher desorption pressure, thereby reducing the parasitic load on the hydrogen compressor. The elevated pressure and temperature adsorption we present here is beneficial to minimizing overall process heating and cooling demand compared to existing processes. Here, we report the comparative performance of zeolite-5A, Cu-BTC, and the mix of zeolite-5A/Cu-BTC for H2 purification from syngas typical of those exiting water-gas-shift reactors. The MOFs were synthesized hydrothermally and then mixed systematically at different weight ratios to find the optimum composition based on the adsorption performance. The formation of different compounds were characterized by XRD, N2 adsorption and desorption, SEM, FT-IR, TG, and water vapor adsorption technologies. Single-component adsorption isotherms of CO2, CO, CH4, N2, and H2 over single materials and composites were measured at elevated pressures and different temperatures to determine their equilibrium adsorption capacity. The examination of the stability and regeneration performance of metal–organic frameworks was carried out using a gravimetric system at temperature ranges of 25-150℃ for a pressure range of 0-30 bar. The studies of adsorption/desorption on the MOFs showed selective adsorption of CO2, CH4, CO, and N2 over H2. Overall, the findings of this study suggest that the Ni-MOF-74/Cu-BTC composites are promising candidates for industrial H2 purification processes.

Keywords: MOF, H2 purification, high T, PSA

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Authors: Anna Vanderbruggen, Kai Bachmann, Martin Rudolph, Rodrigo Serna

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Recycling of lithium-ion batteries has attracted a lot of attention in recent years and focuses primarily on valuable metals such as cobalt, nickel, and lithium. Despite the growth in graphite consumption and the fact that it is classified as a critical raw material in the European Union, USA, and Australia, there is little work focusing on graphite recycling. Thus, graphite is usually considered waste in recycling treatments, where graphite particles are concentrated in the “black mass”, a fine fraction below 1mm, which also contains the foils and the active cathode particles such as LiCoO2 or LiNiMnCoO2. To characterize the material, various analytical methods are applied, including X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Atomic Absorption Spectrometry (AAS), and SEM-based automated mineralogy. The latter consists of the combination of a scanning electron microscopy (SEM) image analysis and energy-dispersive X-ray spectroscopy (EDS). It is a powerful and well-known method for primary material characterization; however, it has not yet been applied to secondary material such as black mass, which is a challenging material to analyze due to fine alloy particles and to the lack of an existing dedicated database. The aim of this research is to characterize the black mass depending on the metals recycling process in order to understand the liberation mechanisms of the active particles from the foils and their effect on the graphite particle surfaces and to understand their impact on the subsequent graphite flotation. Three industrial processes were taken into account: purely mechanical, pyrolysis-mechanical, and mechanical-hydrometallurgy. In summary, this article explores various and common challenges for graphite and secondary material characterization.

Keywords: automated mineralogy, characterization, graphite, lithium ion battery, recycling

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Authors: Jung-Hwan Oh, Rajesh Kumar, Il-Kwon Oh

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Porous graphene has extensive potential applications in variety of fields such as hydrogen storage, CO oxidation, gas separation, supercapacitors, fuel cells, nanoelectronics, oil adsorption, and so on. However, the generation of some carbon atoms vacancies for precise small holes have been not extensively studied to prevent the agglomerates of graphene sheets and to obtain porous graphene with high surface area. Recently, many research efforts have been presented to develop physical and chemical synthetic approaches for porous graphene. But physical method has very high cost of manufacture and chemical method consumes so many hours for porous graphene. Herein, we propose a porous graphene contained holes with atomic scale precision by embedding metal nano-particles through microwave irradiation for hydrogen storage and CO oxidation multi- functionalities. This proposed synthetic method is appropriate for fast and convenient production of three dimensional nanostructures, which have nanoholes on the graphene surface in consequence of microwave irradiation. The metal nanoparticles are dispersed quickly on the graphene surface and generated uniform nanoholes on the graphene nanosheets. The morphological and structural characterization of the porous graphene were examined by scanning electron microscopy (SEM), transmission scanning electron microscopy (TEM) and RAMAN spectroscopy, respectively. The metal nanoparticle-embedded porous graphene exhibits a microporous volume of 2.586cm3g-1 with an average pore radius of 0.75 nm. HR-TEM analysis was carried out to further characterize the microstructures. By investigating the RAMAN spectra, we can understand the structural changes of graphene. The results of this work demonstrate a possibility to produce a new class of porous graphene. Furthermore, the newly acquired knowledge for the diffusion into graphene can provide useful guidance for the development of the growth of nanostructure.

Keywords: CO oxidation, hydrogen storage, nanocomposites, porous graphene

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Authors: Rafael Alvarenga, Hubert Herbaux, Laurent Linguet

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The uncertainty concerning the power production of intermittent renewable energy is one of the main barriers to the integration of such assets into the power grid. Efforts have thus been made to develop methods to quantify this uncertainty, allowing producers to ensure more reliable and profitable engagements related to their future power delivery. Even though a diversity of probabilistic approaches was proposed in the literature giving promising results, the added value of adopting such methods for scheduling intermittent power plants is still unclear. In this study, the profits obtained by a decision-making model used to optimally schedule an existing PV power plant connected to batteries are compared when the model is fed with deterministic and probabilistic forecasts generated with two of the most recent methods proposed in the literature. Moreover, deterministic forecasts with different accuracy levels were used in the experiments, testing the utility and the capability of probabilistic methods of modeling the progressively increasing uncertainty. Even though probabilistic approaches are unquestionably developed in the recent literature, the results obtained through a study case show that deterministic forecasts still provide the best performance if accurate, ensuring a gain of 14% on final profits compared to the average performance of probabilistic models conditioned to the same forecasts. When the accuracy of deterministic forecasts progressively decreases, probabilistic approaches start to become competitive options until they completely outperform deterministic forecasts when these are very inaccurate, generating 73% more profits in the case considered compared to the deterministic approach.

Keywords: PV power forecasting, uncertainty quantification, optimal scheduling, power systems

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Authors: Eun-Joong Kim, Sankarprasad Bhuniya, Hyunseung Lee, Hyun Min Kim, Chaejoon Cheong, Su-khendu Maiti, Kwan Soo Hong, Jong Seung Kim

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Metastatic cancers have historically been difficult to treat. However, metastatic tumors have been found to have high levels of reactive oxygen species such as hydrogen peroxide (H2O2), supporting the hypothesis that a prodrug could be activated by intracellular H2O2 and lead to a potential anti-metastatic therapy. In this study, prodrug 7 was designed to be activated by H2O2-mediated boronate oxidation, resulting in activation of the fluorophore for detection and release of the therapeutic agent, SN-38. Drug release from prodrug 7 was investigated by monitoring fluorescence after addition of H2O2 to the cancer cells. Prodrug 7 activated by H2O2 selectively inhibited tumor cell growth. Furthermore, intratracheally administered prodrug 7 showed effective anti-tumor activity in a mouse model of metastatic lung disease. Thus, this H2O2-responsive prodrug has therapeutic potential as a novel treatment for metastatic cancer via cellular imaging with fluorescence as well as selective release of the anti-cancer drug, SN-38.

Keywords: hydrogen peroxide, prodrug, metastatic tumors, fluorescence

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Authors: Hammam Aljabri, Hong G. Im

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Hydrogen is a promising future fuel to support the transition of the energy sector toward carbon neutrality. The direct utilization of H2 in Internal Combustion Engines (ICEs) is possible, and this technology faces mainly two challenges; high NOx emissions and severe knocking at mid to high loads. In this study, we numerically investigated the potential of H2 combustion in a truck-size engine operated in SI mode. To mitigate the knocking nature of H2 combustion, we have focused on studying the effects of three primary parameters; the compression ratio (CR), the air-fuel ratio, and the spark time. The baseline case was set using a CR of 16.5 and an equivalence ratio of 0.35. In simulations, the auto-ignition tendency was evaluated based on the maximum pressure rise rate and the local pressure fluctuations at the monitoring points set along the wall of the combustion chamber. To mitigate the auto-ignition tendency while enabling a wider range of engine operation, the effect of lowering the compression ratio was assessed. The results indicate that by lowering the compression ratio from 16.5:1 to 12.5:1, an indicated thermal efficiency of 47.5% can be achieved. Aiming to restrain the auto-ignition while maintaining good efficiency, a reduction in the equivalence ratio was examined under different compression ratios. The result indicates that higher compression ratios will require lower equivalence ratios, and due to practical limitations, a lower equivalence ratio of 0.25 was set as the limit. Using a compression ratio of 13.5 combined with an equivalence ratio of 0.3 resulted in an indicated thermal efficiency of 48.6%, that is, at a fixed spark time. It is found that under such lean conditions, the incomplete combustion losses and exhaust losses were high. Thus, advancing the spark time was assessed as a possible solution. The results demonstrated the advantages of advancing the spark time, where an indicated thermal efficiency exceeding 50% was achieved using a compression ratio of 14.5:1 and an equivalence ratio of 0.25.

Keywords: hydrogen, combustion, engine knock, SI engine

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Authors: Ali Mashayekh, Mahdiye Khorasani, Thomas weyh

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The demand for battery electric vehicles (BEV) is steadily increasing, and it can be assumed that electric mobility will dominate the market for individual transportation in the future. Regarding BEVs, the focus of state-of-the-art research and development is on vehicle batteries since their properties primarily determine vehicles' characteristic parameters, such as price, driving range, charging time, and lifetime. State-of-the-art battery packs consist of invariable configurations of battery cells, connected in series and parallel. A promising alternative is battery systems based on multilevel inverters, which can alter the configuration of the battery cells during operation via semiconductor switches. The main benefit of such topologies is that a three-phase AC voltage can be directly generated from the battery pack, and no separate power inverters are required. Therefore, modular battery systems based on different multilevel inverter topologies and reconfigurable battery systems are currently under investigation. Another advantage of the multilevel concept is that the possibility to reconfigure the battery pack allows battery cells with different states of charge (SoC) to be connected in parallel, and thus low-loss balancing can take place between such cells. In contrast, in conventional battery systems, parallel connected (hard-wired) battery cells are discharged via bleeder resistors to keep the individual SoCs of the parallel battery strands balanced, ultimately reducing the vehicle range. Different multilevel inverter topologies and reconfigurable batteries have been described in the available literature that makes the before-mentioned advantages possible. However, what has not yet been described is how an intelligent operating algorithm needs to look like to keep the SoCs of the individual battery strands of a modular battery system with integrated power electronics balanced. Therefore, this paper suggests an SoC balancing approach for Battery Modular Multilevel Management (BM3) converter systems, which can be similarly used for reconfigurable battery systems or other multilevel inverter topologies with parallel connectivity. The here suggested approach attempts to simultaneously utilize all converter modules (bypassing individual modules should be avoided) because the parallel connection of adjacent modules reduces the phase-strand's battery impedance. Furthermore, the presented approach tries to reduce the number of switching events when changing the switching state combination. Thereby, the ohmic battery losses and switching losses are kept as low as possible. Since no power is dissipated in any designated bleeder resistors and no designated active balancing circuitry is required, the suggested approach can be categorized as a proactive balancing approach. To verify the algorithm's validity, simulations are used.

Keywords: battery management system, BEV, battery modular multilevel management (BM3), SoC balancing

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Authors: Shajaratuldur Ismail, Nurlidia Mansor, Zakaria Man

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Thermoplastic starch (TPS) plasticized by 1-ethyl-3-methylimidazolium acetate [Emim][OAc] were obtained through gelatinization process. The gelatinization process occurred in the presence of water and [Emim][OAc] as plasticizer at high temperature (90˚C). The influence of [Emim][OAc] and water on the gelatinization and interactions with starch have been studied over a range of compositions. The homogenous mass was obtained for the samples containing 35, 40 and 43.5 % of water contents which showed that water plays important role in gelatinization process. Detailed IR spectroscopy analysis showed decrease in hydrogen bonding intensity and strong interaction between acetate anion in [Emim][OAc] and starch hydroxyl groups in the presence of [Emim][OAc]. Starch-[Emim][OAc]-water mixture at 10-3-8.7 presented homogenous mass, less hydrogen bonding intensity and strong interaction between acetate anion in [Emim][OAc] and starch hydroxyl groups.

Keywords: starch, ionic liquid, 1-ethyl-3-methylimidazolium acetate, plasticizer, gelatinization, IR spectroscopy

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Authors: Nelson S. Andres, Robert O. Aguilar, Mar O. Tapia, Meeko C. Masangcap, John Denver Catapang, Greg C. Mallari

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This study focuses on exploring the possibility of using solar PV as an alternative for generating electricity to electrify the AGT System installed in BPSU Main Campus instead of using the power grid. The output of this study gives BPSU the option to invest on solar PV system to pro-actively respond to one of UN’s Sustainable Development Goals of having reliable, sustainable and modern energy sources to reduce energy pollution and climate change impact in the long run. Thus, this study covers the technical as well as the financial studies, which BPSU can also be used to outsource funding from different government agencies. For this study, the electrical design and requirements of the on-going DOST AGT system project are carefully considered. In the proposed design, the AGT station has installed with a rechargeable battery system where the energy harnessed by the solar PV panels installed on the rooftop of the station/NCEA building shall be directed to. The solar energy is then directly supplied to the electric double-layer capacitors (EDLC's) batteries and thus transmitted to other types of equipment in need. When the AGT is not in use, the harnessed energy may be used by NCEA building, thus, lessening the energy consumption of the building from the grid. The use of solar PV system with EDLC is compared with the use of an electric grid for the purpose of electrifying the AGT or the NCEA building (when AGT is not in use). This is to figure how much solar energy are accumulated by the solar PV to accommodate the need for coaches’ motors, lighting, air-conditioning units, door sensor, panel display, etc. The proposed PV Solar design, as well as the data regarding the charging and discharging of batteries and the power consumption of all AGT components, are simulated for optimization, analysis and validation through the use of PVSyst software.

Keywords: AGT, Solar PV, railway, EDLC

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Authors: Ahmed A. Al-Harbi

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This paper presents a comparative study of effects of the repeated solid obstacles on the propagation of H2-Air premixed flames. Pressure, speed of the flame front as well as structure of reaction zones are studied for hydrogen. Two equivalence ratios are examined for different configurations of three baffle plates and two obstacles with a square cross-section having blockage ratios of either 0.24 or 0.5. Hydrogen fuel mixtures with two equivalence ratios of 0.7 and 0.8 are studied and this is limited by the excessive overpressures. The results show that the peak pressure and its rate of change can be increased by increasing the blockage ratio or by decreasing the space between successive baffles. As illustrated by the high speed images of LIF-OH, the degree of wrinkling and contortion in the flame front increase as the blockages increase. The images also show how the flame front relaminarises with increasing distances between obstacles, which accounts for the pressure decrease with increasing separation. It is also found that more than one obstacle is needed to achieve a turbulent flame structure with intense corrugations.

Keywords: premixed propagating flames, flame-obstacle interaction, turbulent premixed flames, overpressure, transient flames

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Authors: Aibek Kukpayev, Dhawal Shah

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Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.

Keywords: deep eutectic solvents, desulfurization, molecular dynamics simulations, thiophenes

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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy

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Authors: Gabriel Wosiak, Jeyse da Silva, Sthefany S. Sena, Renato N. de Andrade, Ernesto Pereira

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The bubble formation during hydrogen production by electrolysis and several electrochemical processes is an inherent phenomenon and can impact the energy consumption of the processes. In this work, it was reported both experimental and computational results describe the effect of bubble displacement, which, under the cases investigated, leads to the formation of a convective flow in the solution. The process is self-sustained, and a solution vortex is formed, which modifies the bubble growth and covering at the electrode surface. Using the experimental data, we have built a model to simulate it, which, with high accuracy, describes the phenomena. Then, it simulated many different experimental conditions and evaluated the effects of the boundary conditions on the bubble surface covering the surface. We have observed a position-dependent bubble covering the surface, which has an effect on the water-splitting efficiency. It was shown that the bubble covering is not uniform at the electrode surface, and using statistical analysis; it was possible to evaluate the influence of the gas type (H2 and O2), current density, and the bubble size (and cross-effects) on the covering fraction and the asymmetric behavior over the electrode surface.

Keywords: water splitting, bubble, electrolysis, hydrogen production

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Authors: Ilze Pelece, Imants Ziemelis, Henriks Putans

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Traditionally the solar energy has been used in southern countries, but it has been used also in northern ones. Most popular kind of use of solar energy in Latvia is solar collector for water heating. Traditionally flat-plate solar collectors are used because of simplicity of manufacturing. However, some peculiarities in use of solar energy in northern countries must be taken into account. In northern countries, there is lower irradiance, but longer day and longer path of the sun during summer. Therefore traditional flat-plate solar collectors are not appropriate enough in northern countries, but new forms must be developed. There are two forms of solar collectors - cylindrical and semi-spherical – proposed in this work. Such collectors can be made both for water or air heating. Theoretical calculations and measurements of energy gain from those two collectors have been done. Results show that daily energy sum received by the semi-spherical collector from the sun at the middle of summer is 1.43 times more than that of the flat one, but for the cylindrical collector, it is 1.74 times more than that of the flat one or equal to that of the tracking to sun flat-plate collector. The resulting difference in energy gain from collector will be not so large because of the difference in heat loses. Heat can be decreased by switching off the water circulation pump when the sun is covered by clouds. For this purpose solar batteries, powered pump can be used instead of complicated and expensive automatics. Even more important than overall energy gain is the fact that semi-spherical and cylindrical collectors work all day (17 hours in the middle of summer at 57 northern latitudes), while flat-plate collector only about 11 hours. Yearly energy sum received by the collector from the sun is 1.5 and 1.9 times larger for the semi-spherical and cylindrical collector respectively as for the flat one. The cylindrical solar collector is easier to manufacture, but semi-spherical one is more aesthetical and durable against the impact of the wind. Although solar collectors for water and air heating are studied in this article, main ideas are applicable also for solar batteries.

Keywords: cylindric, semi-spherical, solar collector, solar energy, water heating

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Authors: Maria Alekxandra B. Sison, Reginald C. Mallare, Joseph Albert M. Mendoza

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Ammonia (NH₃) is the alternative carbon-free fuel of the future for its promising applications. Investigations on NH₃-fuel blends recommend using hydrogen (H₂) to increase the heating value of NH3, promote combustion performance, and improve NOx efflux mitigation. To further examine the effects of this concept, the study analyzed the combustion performance, in terms of turbulence, combustion efficiency (CE), and NOx emissions, of NH3/fuel with variations of combustor diameter ratio, H2 fuel mole fraction, and fuel mass flow rate (ṁ). The simulations were performed using Computational Fluid Dynamics (CFD) modeling to represent a non-premixed (NP) and partially premixed (PP) combustion under a two-dimensional ultra-low NOx Rich-Burn, Quick-Quench, Lean-Burn (RQL) combustor. Governed by the Detached Eddy Simulation model, it was found that the diameter ratio greatly affects the turbulence in PP and NP mode, whereas ṁ in PP should be prioritized when increasing CE. The NOx emission is minimal during PP combustion, but NP combustion suggested modifying ṁ to achieve higher CE and Reynolds number without sacrificing the NO generation from the reaction.

Keywords: combustion efficiency, turbulence, dual-stage combustor, NOx emission

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Authors: Javier Carroquino, Nieves García-Casarejos, Pilar Gargallo, F. Javier García-Ramos

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The energy used in agriculture is a source of global emissions of greenhouse gases. The two main types of this energy are electricity for pumping and diesel for agricultural machinery. In order to reduce these emissions, the European project LIFE REWIND addresses the supply of this demand from renewable sources. First of all, comprehensive data on energy demand and available renewable resources have been obtained in several case studies. Secondly, a set of simulations and optimizations have been performed, in search of the best configuration and sizing, both from an economic and emission reduction point of view. For this purpose, it was used software based on genetic algorithms. Thirdly, a prototype has been designed and installed, that it is being used for the validation in a real case. Finally, throughout a year of operation, various technical and economic parameters are being measured for further analysis. The prototype is not connected to the utility grid, avoiding the cost and environmental impact of a grid extension. The system includes three kinds of photovoltaic fields. One is located on a fixed structure on the terrain. Another one is floating on an irrigation raft. The last one is mounted on a two axis solar tracker. Each has its own solar inverter. The total amount of nominal power is 44 kW. A lead acid battery with 120 kWh of capacity carries out the energy storage. Three isolated inverters support a three phase, 400 V 50 Hz micro-grid, the same characteristics of the utility grid. An advanced control subsystem has been constructed, using free hardware and software. The electricity produced feeds a set of seven pumps used for purification, elevation and pressurization of water in a drip irrigation system located in a vineyard. Since the irrigation season does not include the whole year, as well as a small oversize of the generator, there is an amount of surplus energy. With this surplus, a hydrolyser produces on site hydrogen by electrolysis of water. An off-road vehicle with fuel cell feeds on that hydrogen and carries people in the vineyard. The only emission of the process is high purity water. On the one hand, the results show the technical and economic feasibility of stand-alone renewable energy systems to feed seasonal pumping. In this way, the economic costs, the environmental impacts and the landscape impacts of grid extensions are avoided. The use of diesel gensets and their associated emissions are also avoided. On the other hand, it is shown that it is possible to replace diesel in agricultural machinery, substituting it for electricity or hydrogen of 100% renewable origin and produced on the farm itself, without any external energy input. In addition, it is expected to obtain positive effects on the rural economy and employment, which will be quantified through interviews.

Keywords: drip irrigation, greenhouse gases, hydrogen, renewable energy, vineyard

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Authors: Şeyma Dombaycıoğlu, Hilal Köse, Ali Osman Aydın, Hatem Akbulut

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Rechargeable lithium ion batteries (LIBs) have been considered as one of the most attractive energy storage choices for laptop computers, electric vehicles and cellular phones owing to their high energy and power density. Compared with conventional carbonaceous materials, transition metal oxides (TMOs) have attracted great interests and stand out among versatile novel anode materials due to their high theoretical specific capacity, wide availability and good safety performance. ZnO, as an anode material for LIBs, has a high theoretical capacity of 978 mAh g-1, much higher than that of the conventional graphite anode (∼370 mAhg-1). However, several major problems such as poor cycleability, resulting from the severe volume expansion and contraction during the alloying-dealloying cycles with Li+ ions and the associated charge transfer process, the pulverization and the agglomeration of individual particles, which drastically reduces the total entrance/exit sites available for Li+ ions still hinder the practical use of ZnO powders as an anode material for LIBs. Therefore, a great deal of effort has been devoted to overcome these problems, and many methods have been developed. In most of these methods, it is claimed that carbon nanotubes (CNTs) will radically improve the performance of batteries, because their unique structure may especially enhance the kinetic properties of the electrodes and result in an extremely high specific charge compared with the theoretical limits of graphitic carbon. Due to outstanding properties of CNTs, MWCNT buckypaper substrate is considered a buffer material to prevent mechanical disintegration of anode material during the battery applications. As the bridge connecting the positive and negative electrodes, the electrolyte plays a critical role affecting the overall electrochemical performance of the cell including rate, capacity, durability and safety. Commercial electrolytes for Li-ion batteries normally consist of certain lithium salts and mixed organic linear and cyclic carbonate solvents. Most commonly, LiPF6 is attributed to its remarkable features including high solubility, good ionic conductivity, high dissociation constant and satisfactory electrochemical stability for commercial fabrication. Besides LiPF6, LiBF4 is well known as a conducting salt for LIBs. LiBF4 shows a better temperature stability in organic carbonate based solutions and less moisture sensitivity compared to LiPF6. In this work, free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials were prepared by a sol gel technique giving a high capacity anode material for lithium ion batteries. Electrolyte solutions (including 1 m Li+ ion) were prepared with different Li salts in glove box. For this purpose, LiPF6 and LiBF4 salts and also mixed of these salts were solved in EC:DMC solvents (1:1, w/w). CR2016 cells were assembled by using these prepared electrolyte solutions, the ZnO/MWCNT buckypaper nanocomposites as working electrodes, metallic lithium as cathode and polypropylene (PP) as separator. For investigating the effect of different Li salts on the electrochemical performance of ZnO/MWCNT nanocomposite anode material electrochemical tests were performed at room temperature.

Keywords: anode, electrolyte, Li-ion battery, ZnO/MWCNT

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Authors: A. C. Kumbharkhane

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Time domain dielectric relaxation microwave spectroscopy (TDRMS) is a term used to describe a technique of observing the time dependant response of a sample after application of time dependant electromagnetic field. A TDRMS probes the interaction of a macroscopic sample with a time dependent electrical field. The resulting complex permittivity spectrum, characterizes amplitude (voltage) and time scale of the charge-density fluctuations within the sample. These fluctuations may arise from the reorientation of the permanent dipole moments of individual molecules or from the rotation of dipolar moieties in flexible molecules, like polymers. The time scale of these fluctuations depends on the sample and its relative relaxation mechanism. Relaxation times range from some picoseconds in low viscosity liquids to hours in glasses, Therefore the TDRS technique covers an extensive dynamical process. The corresponding frequencies range from 10-4 Hz to 1012 Hz. This inherent ability to monitor the cooperative motion of molecular ensemble distinguishes dielectric relaxation from methods like NMR or Raman spectroscopy, which yield information on the motions of individual molecules. Recently, we have developed and established the TDR technique in laboratory that provides information regarding dielectric permittivity in the frequency range 10 MHz to 30 GHz. The TDR method involves the generation of step pulse with rise time of 20 pico-seconds in a coaxial line system and monitoring the change in pulse shape after reflection from the sample placed at the end of the coaxial line. There is a great interest to study the dielectric relaxation behaviour in liquid systems to understand the role of hydrogen bond in liquid system. The intermolecular interaction through hydrogen bonds in molecular liquids results in peculiar dynamical properties. The dynamics of hydrogen-bonded liquids have been studied. The theoretical model to explain the experimental results will be discussed.

Keywords: microwave, time domain reflectometry (TDR), dielectric measurement, relaxation time

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Authors: Lenka Morávková, Zuzana Sedláková, Jiří Vejražka, Věra Jandová, Pavel Izák

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The need to minimize the costs of biogas upgrading leads to a continuous search for new and more effective membrane materials. The improvement of biogas combustion efficiency is connected with polar gases removal from a feed stream. One of the possibilities is the use of water–swollen polyamide layer of thin film composite reverse osmosis membrane for simultaneous carbon dioxide and hydrogen sulphide removal. Transport properties and basic characteristics of a thin film composite membrane were compared in the term of appropriate water-swollen membrane choice for biogas upgrading. SEM analysis showed that the surface of the best performing composites changed significantly upon swelling by water. The surface changes were found to be a proof that the selective skin polyamide layer was swollen well. Further, the presence of a sufficient number of associative centers, namely amido groups, inside the upper layer of the hydrophilic thin composite membrane can play an important role in the polar gas separation from a non-polar gas. The next key factor is a high porosity of the membrane support.

Keywords: biogas upgrading, carbon dioxide separation, hydrogen sulphide separation, water-swollen membrane

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Authors: Alexandre Chagnes

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Lithium-ion battery is the technology of choice in the development of electric vehicles. This technology is now mature, although there are still many challenges to increase their energy density while ensuring an irreproachable safety of use. For this goal, it is necessary to develop new cathodic materials that can be cycled at higher voltages and electrolytes compatible with these materials. But the challenge does not only concern the production of efficient batteries for the electrochemical storage of energy since lithium-ion battery technology relies on the use of critical and/or strategic value resources. It is, therefore, crucial to include Lithium-ion batteries development in a circular economy approach very early. In particular, optimized recycling and reuse of battery components must both minimize their impact on the environment and limit geopolitical issues related to tensions on the mineral resources necessary for lithium-ion battery production. Although recycling will never replace mining, it reduces resource dependence by ensuring the presence of exploitable resources in the territory, which is particularly important for countries like France, where exploited or exploitable resources are limited. This conference addresses the development of a new hydrometallurgical process combining leaching of cathodic material from spent lithium-ion battery in acidic chloride media and solvent extraction process. Most of recycling processes reported in the literature rely on the sulphate route, and a few studies investigate the potentialities of the chloride route despite many advantages and the possibility to develop new chemistry, which could get easier the metal separation. The leaching mechanisms and the solvent extraction equilibria will be presented in this conference. Based on the comprehension of the physicochemistry of leaching and solvent extraction, the present study will introduce a new hydrometallurgical process for the production of cobalt, nickel, manganese and lithium from spent cathodic materials.

Keywords: lithium-ion battery, recycling, hydrometallurgy, leaching, solvent extraction

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Authors: Elmira Ghanbari, Jan Van Esch, Stephen J. Picken, Sahil Aggarwal

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Low-molecular-weight organogelators form gels by self-assembly into the crystalline network which immobilizes the organic solvent. For single bisamide organogelator systems, the effect of the molecular structure on the molecular interaction and their self-assembly behavior has been explored. The spatial arrangement of bisamide molecules in the gel-state is driven by a combination of hydrogen bonding and Van der Waals interactions. The hydrogen-bonding pattern between the amide groups of bisamide molecules is regulated by the number of methylene spacers; the even number of methylene spacers between two amide groups, in even-spaced bisamides, leads to the antiparallel position of amide groups within a molecule. An even-spaced bisamide molecule with antiparallel amide groups can make two pairs of hydrogen bonding with the molecules on the same plane. The odd-spaced bisamide with a parallel directionality of amide groups can form four independent hydrogen bonds with four other bisamide molecules on different planes. The arrangement of bisamide molecules in the crystalline state and the interaction of these molecules depends on the molecular structure, particularly the parity of the spacer length between the amide groups in the bisamide molecule. In this study, the directionality of amide groups has been exploited as a structural characteristic to affect the arrangement of molecules in the crystalline state and produce different binary bisamide gelators with different degrees of crystallinities. Single odd- and even-spaced single bisamides were synthesized and blended to produce binary bisamide organogelators to be characterized in order to understand the effect of the different directionality of amide groups on the molecular interaction in the crystalline state. The pattern of molecular interactions between these blended molecules, mixing or phase separation, has been monitored via differential scanning calorimetry (DSC) and crystallography techniques; X-ray powder diffraction (XRD) and Small-angle X-ray scattering (SAXS). The formation of lamellar structures for odd- and even-spaced bisamide gelators was confirmed by using SAXS and XRD techniques. DSC results have shown that binary bisamide organogelators with different parity of methylene spacers (odd-even binary blends) have a higher tendency for phase separation compared to the binary bisamides with the same parity (odd-odd or even-even binary blends). Phase separation in binary odd-even bisamides was confirmed by the presence of individual (100) reflections of odd and even lamellar structures. The structural characteristic of bisamide organogelators, the parity of spacer length in binary systems, is a promising tool to control the arrangement of molecules and their crystalline structure.

Keywords: binary bisamide organogelators, crystalline structure, phase separation, self-assembly behavior

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Authors: Mohammad Syahirin Aisha, Khairul Imran Sainan

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The PEM fuel cell is a device that generate electric by electrochemical reaction between hydrogen fuel and oxygen in the fuel cell stack. PEM fuel cell consists of an anode (hydrogen supply), a cathode (oxygen supply) and an electrolyte that allow charges move between the two positions of the fuel cell. The only product being developed after the reaction is water (H2O) and heat as the waste which does not emit greenhouse gasses. The performance of fuel cell affected by numerous parameters. This study is restricted to cathode parameters that affect fuel cell performance. At the anode side, the reactant is not going through any changes. Experiments with variation in air velocity (3m/s, 6m/s and 9m/s), temperature (10oC, 20oC, 35oC) and relative humidity (50%, 60%, and 70%) have been carried out. The experiments results are presented in the form of fuel cell stack power output over time, which demonstrate the impacts of the various air condition on the execution of the PEM fuel cell. In this study, the experimental analysis shows that with variation of air conditions, it gives different fuel cell performance behavior. The maximum power output of the experiment was measured at an ambient temperature of 25oC with relative humidity and 9m/s velocity of air.

Keywords: air-breathing PEM fuel cell, cathode side, performance, variation in air condition

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Authors: Disha Gupta

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The aim of this research is to conduct X-ray and e-beam characterization techniques on lithium-ion battery materials for the improvement of battery performance. The key characterization techniques employed are the synchrotron X-ray Absorption Spectroscopy (XAS) combined with X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to obtain a more holistic approach to understanding material properties. This research effort provides additional battery characterization knowledge that promotes the development of new cathodes, anodes, electrolyte and separator materials for batteries, hence, leading to better and more efficient battery performance. Both ex-situ and in-situ synchrotron experiments were performed on LiFePO₄, one of the most common cathode material, from different commercial sources and their structural analysis, were conducted using Athena/Artemis software. This analysis technique was then further extended to study other cathode materials like LiMnxFe(₁₋ₓ)PO₄ and even some sulphate systems like Li₂Mn(SO₄)₂ and Li₂Co0.5Mn₀.₅ (SO₄)₂. XAS data were collected for Fe and P K-edge for LiFePO4, and Fe, Mn and P-K-edge for LiMnxFe(₁₋ₓ)PO₄ to conduct an exhaustive study of the structure. For the sulphate system, Li₂Mn(SO₄)₂, XAS data was collected at both Mn and S K-edge. Finite Difference Method for Near Edge Structure (FDMNES) simulations were also conducted for various iron, manganese and phosphate model compounds and compared with the experimental XANES data to understand mainly the pre-edge structural information of the absorbing atoms. The Fe K-edge XAS results showed a charge compensation occurring on the Fe atom for all the differently synthesized LiFePO₄ materials as well as the LiMnxFe(₁₋ₓ)PO₄ systems. However, the Mn K-edge showed a difference in results as the Mn concentration changed in the materials. For the sulphate-based system Li₂Mn(SO₄)₂, however, no change in the Mn K-edge was observed, even though electrochemical studies showed Mn redox reactions.

Keywords: li-ion batteries, electrochemistry, X-ray absorption spectroscopy, XRD

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Authors: Avijit Datta

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We have presented a phase control scheme in population transfer using chirped laser fields. A chirped pulse can do population transfer from one level to another level via adiabatic rapid passage accessible by one photon dipole transition. We propose to use a pair of phase-locked chirped pulses of the same frequency w(t) instead of a singly chirped-pulse frequency w(t). Simultaneous action of phase controlled interference in addition to rapid adiabatic passages due to chirped pulses lead to phase control over this population transfer dynamics. We have demonstrated the proposed phase control scheme over the population distribution from the initial level X(v=0,j=0) to C(v=2,j=1) level of hydrogen molecule using a pair of phase-locked and similarly chirped laser pulses. We have extended this two-level system to three-level 1+1 ladder system of hydrogen molecule from X level to final J(v=2,j=2) level via C intermediate level using two pairs of laser pulses having frequencies w(t) and w'(t) respectively and obtained laudable control over the population distribution among three levels. We also have presented some results of interference effects of w₁(t) and its third harmonics w₃(t).

Keywords: phase control, population transfer, chirped laser pulses, rapid adiabatic passage, laser-molecule interaction

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Authors: K. Sruthi, Sai Snehitha Yadavalli, Swathi Gosh Acharyya

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Water is the most crucial element for sustaining life on earth. Increasing water pollution directly or indirectly leads to harmful effects on human life. Most of the heavy metal ions are harmful in their cationic form. These heavy metal ions are released by various activities like disposing of batteries, industrial wastes, automobile emissions, and soil contamination. Ions like (Pb, Co, Cd) are carcinogenic and show many harmful effects when consumed more than certain limits proposed by WHO. The simultaneous detection of the heavy metal ions (Pb, Co, Cd), which are highly toxic, is reported in this study. There are many analytical methods for quantifying, but electrochemical techniques are given high priority because of their sensitivity and ability to detect and recognize lower concentrations. Square wave voltammetry was preferred in electrochemical methods due to the absence of background currents which is interference. Square wave voltammetry was performed on GCE for the quantitative detection of ions. Three electrode system consisting of a glassy carbon electrode as the working electrode (3 mm diameter), Ag/Agcl electrode as the reference electrode, and a platinum wire as the counter electrode was chosen for experimentation. The mechanism of detection was done by optimizing the experimental parameters, namely pH, scan rate, and temperature. Under the optimized conditions, square wave voltammetry was performed for simultaneous detection. Scan rates were varied from 5 mV/s to 100 mV/s and found that at 25 mV/s all the three ions were detected simultaneously with proper peaks at particular stripping potential. The variation of pH from 3 to 8 was done where the optimized pH was taken as pH 5 which holds good for three ions. There was a decreasing trend at starting because of hydrogen gas evolution, and after pH 5 again there was a decreasing trend that is because of hydroxide formation on the surface of the working electrode (GCE). The temperature variation from 25˚C to 45˚C was done where the optimum temperature concerning three ions was taken as 35˚C. Deposition and stripping potentials were given as +1.5 V and -1.5 V, and the resting time of 150 seconds was given. Three ions were detected at stripping potentials of Cd²⁺ at -0.84 V, Pb²⁺ at -0.54 V, and Co²⁺ at -0.44 V. The parameters of detection were optimized on a glassy carbon electrode for simultaneous detection of the ions at lower concentrations by square wave voltammetry.

Keywords: cadmium, cobalt, lead, glassy carbon electrode, square wave anodic stripping voltammetry

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Authors: Hammadi Larbi

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The treatment of wastewater in sewage plants usually results in the formation of a large amount of sludge. These appear at the outlet of the treatment plant as a viscous fluid loaded with a high concentration of dry matter. This sludge production presents environmental, ecological, and economic risks. That is why it is necessary to find many solutions for minimizing these risks. In the present article, the effect of hydrogen peroxide, thermal treatment, and quicklime on the characteristics of the activated sludge produced in urban wastewater plant were evaluated in order to avoid any risk in the plants. The study shows increasing of the dose of H2O2 from 0 to 0.4 g causes an increase in the solubilization rate of COD from 12% to 45% and a reduction in the organic matter content of sludge (VM/SM) from 74% to 36% . The results also show that the optimum efficiency of the heat treatment corresponds to a temperature of 80 ° C for a treatment time of 40 min is 47% and 51.82% for a temperature equal to 100 ° C and 76.30 % for a temperature of 120 ° C, and 79.38% for a temperature of 140 ° C. The treatment of sludge by quicklime gives the optimum efficiency of 70.62 %. It was shown the increasing of the temperature from 80°C to 140°C, the pH of sludge was increased from 7.12 to 9.59. The obtained results showed that with increasing the dose of quicklime from 0 g/l to 1g/l in activated sludge led to an increase of their pH from 7.12 to 12.06. The study shows the increasing the dose of quicklime from 0 g/l to 1g/l causes also an increase in the solubilization of COD from 0% to 70.62 %

Keywords: activated sludge, hydrogen peroxide, thermal treatment, quicklime

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Authors: Merve Nur Güven Biçer

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Conductive inks are used extensively in electronic devices like sensors, batteries, photovoltaic devices, antennae, and organic light-emitting diodes. These inks are typically made from silver. Wearable technology is another industry that requires inks to be flexible. The aim of this study is the fabrication of low-temperature silver paste by synthesis long silver nanowires.

Keywords: silver ink, conductive ink, low temperature conductive ink, silver nanowire

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Authors: Natasha Botha, Gary Corderely, Helen M. Inglis

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With the move to cleaner energy applications the transport industry is working towards on-board hydrogen, or compressed natural gas-fuelled vehicles. A popular method for storage is to use composite overwrapped pressure vessels (COPV) because of their high strength to weight ratios. The proper design of these COPVs are according to international standards; this study aims to provide a preliminary design for a 350 Bar Type IV COPV (i.e. a polymer liner with a composite overwrap). Netting analysis, a popular analytical approach, is used as a first step to generate an initial design concept for the composite winding. This design is further improved upon by following the American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel standards, Section X: Fibre-reinforced composite pressure vessels. A design program based on these two approaches is developed using Python. A numerical model of a burst test simulation is developed based on the two approaches and compared. The results indicate that the netting analysis provides a good preliminary design, while the ASME-based design is more robust and accurate as it includes a better approximation of the material behaviour. Netting analysis is an easy method to follow when considering an initial concept design for the composite winding when not all the material characteristics are known. Once these characteristics have been fully defined with experimental testing, an ASME-based design should always be followed to ensure that all designs conform to international standards and practices. Future work entails more detailed numerical testing of the design for improvement, this will include the boss design. Once finalised prototype manufacturing and experimental testing will be conducted, and the results used to improve on the COPV design.

Keywords: composite overwrapped pressure vessel, netting analysis, design, American Society of Mechanical Engineers section x, fiber-reinforced, hydrogen storage

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Authors: Rouzbeh Jafari, Joe Nava

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This study includes learnings from an engineering practice normally performed on large scale biohydrogen processes. If properly scale-up is done, biohydrogen can be a reliable pathway for biowaste valorization. Most of the studies on biohydrogen process development have used model feedstock to investigate process key performance indicators (KPIs). This study does not intend to compare different technologies with model feedstock. However, it reports economic drivers and technical challenges which help in developing a road map for expanding biohydrogen economy deployment in Canada. BBA is a consulting firm responsible for the design of hydrogen production projects. Through executing these projects, activity has been performed to identify, register and mitigate technical drawbacks of large-scale hydrogen production. Those learnings, in this study, have been applied to the biohydrogen process. Through data collected by a comprehensive literature review, a base case has been considered as a reference, and several case studies have been performed. Critical parameters of the process were identified and through common engineering practice (process design, simulation, cost estimate, and life cycle assessment) impact of these parameters on the commercialization risk matrix and class 5 cost estimations were reported. The process considered in this study is food waste and woody biomass dark fermentation. To propose a reliable road map to develop a sustainable biohydrogen production process impact of critical parameters was studied on the end-to-end process. These parameters were 1) feedstock composition, 2) feedstock pre-treatment, 3) unit operation selection, and 4) multi-product concept. A couple of emerging technologies also were assessed such as photo-fermentation, integrated dark fermentation, and using ultrasound and microwave to break-down feedstock`s complex matrix and increase overall hydrogen yield. To properly report the impact of each parameter KPIs were identified as 1) Hydrogen yield, 2) energy consumption, 3) secondary waste generated, 4) CO2 footprint, 5) Product profile, 6) $/kg-H2 and 5) environmental impact. The feedstock is the main parameter defining the economic viability of biohydrogen production. Through parametric studies, it was found that biohydrogen production favors feedstock with higher carbohydrates. The feedstock composition was varied, by increasing one critical element (such as carbohydrate) and monitoring KPIs evolution. Different cases were studied with diverse feedstock, such as energy crops, wastewater slug, and lignocellulosic waste. The base case process was applied to have reference KPIs values and modifications such as pretreatment and feedstock mix-and-match were implemented to investigate KPIs changes. The complexity of the feedstock is the main bottleneck in the successful commercial deployment of the biohydrogen process as a reliable pathway for waste valorization. Hydrogen yield, reaction kinetics, and performance of key unit operations highly impacted as feedstock composition fluctuates during the lifetime of the process or from one case to another. In this case, concept of multi-product becomes more reliable. In this concept, the process is not designed to produce only one target product such as biohydrogen but will have two or multiple products (biohydrogen and biomethane or biochemicals). This new approach is being investigated by the BBA team and the results will be shared in another scientific contribution.

Keywords: biohydrogen, process scale-up, economic evaluation, commercialization uncertainties, hydrogen economy

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Authors: Harpreet Singh Kainth

Abstract:

Rubidium salts have been commonly used as an electrolyte to improve the efficiency cycle of Li-ion batteries. In recent years, it has been implemented into the large scale for further technological advances to improve the performance rate and better cyclability in the batteries. X-ray absorption spectroscopy (XAS) is a powerful tool for obtaining the information in the electronic structure which involves the chemical state analysis in the active materials used in the batteries. However, this technique is not well suited for the industrial applications because it needs a synchrotron X-ray source and special sample file for in-situ measurements. In contrast to this, conventional wavelength dispersive X-ray fluorescence (WDXRF) spectrometer is nondestructive technique used to study the chemical shift in all transitions (K, L, M, …) and does not require any special pre-preparation planning. In the present work, the fluorescent Lα, Lβ₁ , Lβ₃,₄ and Lγ₂,₃ X-ray spectra of rubidium in different chemical forms (Rb₂CO₃ , RbCl, RbBr, and RbI) have been measured first time with high resolution wavelength dispersive X-ray fluorescence (WDXRF) spectrometer (Model: S8 TIGER, Bruker, Germany), equipped with an Rh anode X-ray tube (4-kW, 60 kV and 170 mA). In ₃₇Rb compounds, the measured energy shifts are in the range (-0.45 to - 1.71) eV for Lα X-ray peak, (0.02 to 0.21) eV for Lβ₁ , (0.04 to 0.21) eV for Lβ₃ , (0.15 to 0.43) eV for Lβ₄ and (0.22 to 0.75) eV for Lγ₂,₃ X-ray emission lines. The chemical shifts in rubidium compounds have been measured by considering Rb₂CO₃ compounds taking as a standard reference. A Voigt function is used to determine the central peak position of all compounds. Both positive and negative shifts have been observed in L shell emission lines. In Lα X-ray emission lines, all compounds show negative shift while in Lβ₁, Lβ₃,₄, and Lγ₂,₃ X-ray emission lines, all compounds show a positive shift. These positive and negative shifts result increase or decrease in X-ray energy shifts. It looks like that ligands attached with central metal atom attract or repel the electrons towards or away from the parent nucleus. This pulling and pushing character of rubidium affects the central peak position of the compounds which causes a chemical shift. To understand the chemical effect more briefly, factors like electro-negativity, line intensity ratio, effective charge and bond length are responsible for the chemical state analysis in rubidium compounds. The effective charge has been calculated from Suchet and Pauling method while the line intensity ratio has been calculated by calculating the area under the relevant emission peak. In the present work, it has been observed that electro-negativity, effective charge and intensity ratio (Lβ₁/Lα, Lβ₃,₄/Lα and Lγ₂,₃/Lα) are inversely proportional to the chemical shift (RbCl > RbBr > RbI), while bond length has been found directly proportional to the chemical shift (RbI > RbBr > RbCl).

Keywords: chemical shift in L emission lines, bond length, electro-negativity, effective charge, intensity ratio, Rubidium compounds, WDXRF spectrometer

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