Search results for: GC-MS and reaction mechanism

Authors: Alireza Bahramian

Abstract:

High-purity TiO₂ nanoparticles (NPs) with size ranging between 50 nm and 100 nm are synthesized from titanium slag through sulphate route under sonochemical procedure. The effect of dissolution parameters such as the sulfuric acid/slag weight ratio, caustic soda concentration, digestion temperature and time, and initial particle size of the dried slag on the extraction efficiency of TiO₂ and removal of iron are examined. By optimizing the digestion conditions, a rutile TiO₂ powder with surface area of 42 m²/g and mean pore diameter of 22.4 nm were prepared. A thermo-kinetic analysis showed that the digestion temperature has an important effect, while the acid/slag weight ratio and initial size of the slag has a moderate effect on the dissolution rate. The shrinking-core model including both chemical surface reaction and surface diffusion is used to describe the leaching process. A low value of activation energy, 38.12 kJ/mol, indicates the surface chemical reaction model is a rate-controlling step. The kinetic analysis suggested a first order reaction mechanism with respect to the acid concentrations.

Keywords: TiO₂ nanoparticles, titanium slag, dissolution rate, sonochemical method, thermo-kinetic study

Procedia PDF Downloads 232

Authors: Deepti Mishra, Arindam Modak, K. K. Pant, Xiu Song Zhao

Abstract:

The promotional effect of mixed ceria-zirconia oxides (CZO) over the Mo/HZSM-5 catalyst for methane dehydroaromatization (MDA) reaction was studied. The surface and structural properties of the synthesized catalyst were characterized using a range of spectroscopic and microscopic techniques, and the correlation between catalytic properties and its performance for MDA reaction is discussed. The impregnation of CZO solid solution on Mo/HZSM-5 was observed to give an excellent catalytic performance and improved benzene formation rate (4.5 μmol/gcat. s) as compared to the conventional Mo/HZSM-5 (3.1 μmol/gcat. s) catalyst. In addition, a significant reduction in coke formation was observed in the CZO-modified Mo/HZSM-5 catalyst. The prevailing comprehension for higher catalytic activity could be because of the redox properties of CZO deposited Mo/HZSM-5, which acts as a selective oxygen supplier and performs hydrogen combustion during the reaction, which is indirectly probed by O₂-TPD and H₂-TPR analysis. The selective hydrogen combustion prevents the over-oxidation of aromatic species formed during the reaction while the generated steam helps in reducing the amount of coke generated in the MDA reaction. Thus, the advantage of CZO incorporated Mo/HZSM-5 is manifested as it promotes the reaction equilibrium to shift towards the formation of benzene which is favourable for MDA reaction.

Keywords: Mo/HZSM-5, ceria-zirconia (CZO), in-situ combustion, methane dehydroaromatization

Procedia PDF Downloads 71

Authors: Manoj K. Sharma, Neha Grover

Abstract:

Dynamical cluster decay model (DCM) is applied to study the decay mechanism of 118Xe* nucleus in reference to recent data on 28Si + 90Zr → 118Xe* reaction, as an extension of our previous work on the dynamics of 112Xe* nucleus. It is relevant to mention here that DCM is based on collective clusterization approach, where emission probability of different decay paths such as evaporation residue (ER), intermediate mass fragments (IMF) and fission etc. is worked out on parallel scale. Calculations have been done over a wide range of center of mass energies with Ec.m. = 65 - 92 MeV. The evaporation residue (ER) cross-sections of 118Xe* compound nucleus are fitted in reference to available data, using spherical and quadrupole (β2) deformed choice of decaying fragments within the optimum orientations approach. It may be noted that our calculated cross-sections find decent agreement with experimental data and hence provide an opportunity to analyze the exclusive role of deformations in view of fragmentation behavior of 118Xe* nucleus. The possible contribution of IMF fragments is worked out and an extensive effort is being made to analyze the role of excitation energy, angular momentum, diffuseness parameter and level density parameter to have better understanding of the decay patterns governed in the dynamics of 28Si + 90Zr → 118Xe* reaction.

Keywords: cross-sections, deformations, fragmentation, angular momentum

Procedia PDF Downloads 286

Authors: Gunasekaran Raja, Rajakumar Arul, Kottilingam Kottursamy, Ramkumar Jayaraman, Sathya Pavithra, Swaminathan Venkatraman

Abstract:

Wireless Interoperability for Microwave Access (WiMAX) utilizes the IEEE 802.1X mechanism for authentication. However, this mechanism incurs considerable delay during handoffs. This delay during handoffs results in service disruption which becomes a severe bottleneck. To overcome this delay, our article proposes a key caching mechanism based on user path prediction. If the user mobility follows that path, the user bypasses the normal IEEE 802.1X mechanism and establishes the necessary authentication keys directly. Through analytical and simulation modeling, we have proved that our mechanism effectively decreases the handoff delay thereby achieving fast authentication.

Keywords: authentication, authorization, and accounting (AAA), handoff, mobile, user path prediction (UPP) and user pattern

Procedia PDF Downloads 367

Authors: Parth Prajapati, A. R. Srinivas

Abstract:

The purpose of this paper is to validate the concept of the Lotus Mechanism using Computer Aided Engineering (CAE) tools considering the statics and dynamics through actual time dependence involving inertial forces acting on the mechanism joints. For a 1.2 m mirror made of hexagonal segments, with simple harnesses and three-point supports, the maximum diameter is 400 mm, minimum segment base thickness is 1.5 mm, and maximum rib height is considered as 12 mm. Manufacturing challenges are explored for the segments using manufacturing research and development approaches to enable use of large lightweight mirrors required for the future space system.

Keywords: dynamics, manufacturing, reflectors, segmentation, statics

Procedia PDF Downloads 345

Authors: Velid Demir, Mesut Akgün

Abstract:

The lanthanum and zinc oxide were synthesized and then loaded with 6 wt% over γ-Al₂O₃ using the wet impregnation method. The samples were calcined at 900 °C to ensure a coherent structure with high catalytic performance. Characterization of the catalysts was verified by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). The effect of catalysts on biodiesel content from jatropha oil was studied under supercritical conditions. The results showed that ZnO/γ-Al₂O₃ was the superior catalyst for jatropha oil with 98.05% biodiesel under reaction conditions of 7 min reaction time, 1:40 oil to methanol molar ratio, 6 wt% of catalyst loading, 90 bar of reaction pressure, and 300 °C of reaction temperature, compared to 95.50% with La₂O₃/γ-Al₂O₃ at the same parameters. For this study, ZnO/γ-Al₂O₃ was the most suitable catalyst due to performance and cost considerations.

Keywords: biodiesel, heterogeneous catalyst, jatropha oil, supercritical methanol, transesterification

Procedia PDF Downloads 69

Authors: Iuliia Zarubiieva, Joyun Tseng, Vishwesh Kulkarni

Abstract:

Recent researches has focused on nucleic acids as a substrate for designing biomolecular circuits for in situ monitoring and control. A common approach is to express them by a set of idealised abstract chemical reaction networks (ACRNs). Here, we present new results on how abstract chemical reactions, viz., catalysis, annihilation and degradation, can be used to implement circuit that accurately computes logarithm function using the method of Arithmetic-Geometric Mean (AGM), which has not been previously used in conjunction with ACRNs.

Keywords: chemical reaction networks, ratio computation, stability, robustness

Procedia PDF Downloads 137

Authors: Haider Aamir, Muhammad Ali Khalid

Abstract:

Electricity harvesting speed bump (EHSB) is speed breaker of conventional shape, but the difference is that it is not fixed, rather it moves up and down, and electricity can be generated from its vibrating motion. This speed bump consists of an upper cover which will move up and down, a shaft mechanism which will be used to drive the generator and a rack and pinion mechanism which will connect the cover and shaft. There is a spring mechanism to return the cover to its initial state when a vehicle has passed over the bump. Produced energy in the past was up to 80 Watts. For this purpose, a clutch mechanism is used so that both the up-down movements of the cover can be used to drive the generator. Mechanical Motion Rectifier (MMR) mechanism ensures the conversion of both the linear motions into rotational motion which is used to drive the generator.

Keywords: electricity harvesting, generator, rack and pinion, stainless steel shaft

Procedia PDF Downloads 246

Authors: Sundaram Chandrasekaran, Seung Hyun Hur

Abstract:

Exploring strategies for oxygen vacancy engineering under mild conditions and understanding the relationship between dislocations and photoelectrochemical (PEC) cell performance are challenging issues for designing high performance PEC devices. Therefore, it is very important to understand that how the oxygen vacancies (VO) or other defect states affect the performance of the photocatalyst in photoelectric transfer. So far, it has been found that defects in nano or micro crystals can have two possible significances on the PEC performance. Firstly, an electron-hole pair produced at the interface of photoelectrode and electrolyte can recombine at the defect centers under illumination of light, thereby reducing the PEC performances. On the other hand, the defects could lead to a higher light absorption in the longer wavelength region and may act as energy centers for the water splitting reaction that can improve the PEC performances. Even if the dislocation growth of ZnO has been verified by the full density functional theory (DFT) calculations and local density approximation calculations (LDA), it requires further studies to correlate the structures of ZnO and PEC performances. Exploring the hybrid structures composed of graphene oxide (GO) and ZnO nanostructures offer not only the vision of how the complex structure form from a simple starting materials but also the tools to improve PEC performances by understanding the underlying mechanisms of mutual interactions. As there are few studies for the ZnO growth with other materials and the growth mechanism in those cases has not been clearly explored yet, it is very important to understand the fundamental growth process of nanomaterials with the specific materials, so that rational and controllable syntheses of efficient ZnO-based hybrid materials can be designed to prepare nanostructures that can exhibit significant PEC performances. Herein, we fabricated various ZnO nanostructures such as hollow sphere, bucky bowl, nanorod and triangle, investigated their pH dependent growth mechanism, and correlated the PEC performances with them. Especially, the origin of well-controlled dislocation-driven growth and its transformation mechanism of ZnO nanorods to triangles on the GO surface were discussed in detail. Surprisingly, the addition of GO during the synthesis process not only tunes the morphology of ZnO nanocrystals and also creates more oxygen vacancies (oxygen defects) in the lattice of ZnO, which obviously suggest that the oxygen vacancies be created by the redox reaction between GO and ZnO in which the surface oxygen is extracted from the surface of ZnO by the functional groups of GO. On the basis of our experimental and theoretical analysis, the detailed mechanism for the formation of specific structural shapes and oxygen vacancies via dislocation, and its impact in PEC performances are explored. In water splitting performance, the maximum photocurrent density of GO-ZnO triangles was 1.517mA/cm-2 (under UV light ~ 360 nm) vs. RHE with high incident photon to current conversion Efficiency (IPCE) of 10.41%, which is the highest among all samples fabricated in this study and also one of the highest IPCE reported so far obtained from GO-ZnO triangular shaped photocatalyst.

Keywords: dislocation driven growth, zinc oxide, graphene oxide, water splitting

Procedia PDF Downloads 267

Authors: Zahra Hamedani

Abstract:

Many wonderful technological developments in recent years has opened up the possibility of using intelligent buildings for a number of important applications, ranging from minimizing resource usage as well as increasing building efficiency to maximizing comfort, adaption to inhabitants and responsiveness to environmental changes. The concept of an intelligent building refers to the highly embedded, interactive environment within which by exploiting the use of artificial intelligence provides the ability to know its configuration, anticipate the optimum dynamic response to prevailing environmental stimuli, and actuate the appropriate physical reaction to provide comfort and efficiency. This paper contains a general identification of the intelligence paradigm and its impacts on the architecture arena, that with examining the performance of artificial intelligence, a mechanism to analyze and finally for decision-making to control the environment will be described. This mechanism would be a hierarchy of the rational agents which includes decision-making, information, communication and physical layers. This multi-agent system relies upon machine learning techniques for automated discovery, prediction and decision-making. Then, the application of this mechanism regarding adaptation and responsiveness of intelligent building will be provided in two scales of environmental and user. Finally, we review the identifications of sustainability and evaluate the potentials of intelligent building systems in the creation of sustainable architecture and environment.

Keywords: artificial intelligence, intelligent building, responsiveness, adaption, sustainability

Procedia PDF Downloads 383

Authors: Ulugbek Azimov, Nearchos Stylianidis, Nobuyuki Kawahara, Eiji Tomita

Abstract:

A chemical kinetics and computational fluid-dynamics (CFD) analysis was performed to evaluate the combustion of syngas derived from biomass and coke-oven solid feedstock in a micro-pilot ignited supercharged dual-fuel engine under lean conditions. For this analysis, a new reduced syngas chemical kinetics mechanism was constructed and validated by comparing the ignition delay and laminar flame speed data with those obtained from experiments and other detail chemical kinetics mechanisms available in the literature. The reaction sensitivity analysis was conducted for ignition delay at elevated pressures in order to identify important chemical reactions that govern the combustion process. The chemical kinetics of NOx formation was analyzed for H2/CO/CO2/CH4 syngas mixtures by using counter flow burner and premixed laminar flame speed reactor models. The new mechanism showed a very good agreement with experimental measurements and accurately reproduced the effect of pressure, temperature and equivalence ratio on NOx formation. In order to identify the species important for NOx formation, a sensitivity analysis was conducted for pressures 4 bar, 10 bar and 16 bar and preheat temperature 300 K. The results show that the NOx formation is driven mostly by hydrogen based species while other species, such as N2, CO2 and CH4, have also important effects on combustion. Finally, the new mechanism was used in a multidimensional CFD simulation to predict the combustion of syngas in a micro-pilot-ignited supercharged dual-fuel engine and results were compared with experiments. The mechanism showed the closest prediction of the in-cylinder pressure and the rate of heat release (ROHR).

Keywords: syngas, chemical kinetics mechanism, internal combustion engine, NOx formation

Procedia PDF Downloads 383

Authors: Saad M. Alshehri, Tansir Ahamad

Abstract:

Thiourea-Formaldehyde Pre-Polymer (TUF) was prepared by the reaction thiourea and formaldehyde in basic medium and used as a coating materials for magnetite Fe3O4. The synthesized polymer coated microspheres (TUF@Fe3O4) was characterized using FTIR, TGA SEM and TEM. Its BET surface area was up to 1680 m2 g_1. The adsorption capacity of this ACF product was evaluated in its adsorption of Methylene Blue (MB) in water under different pH values and different temperature. We found that the adsorption process was well described both by the Langmuir and Freundlich isotherm model. The kinetic processes of MB adsorption onto TUF@Fe3O4 were described in order to provide a more clear interpretation of the adsorption rate and uptake mechanism. The overall kinetic data was acceptably explained by a pseudo second-order rate model. Evaluated ∆Go and ∆Ho specify the spontaneous and exothermic nature of the reaction. The adsorption takes place with a decrease in entropy (∆So is negative). The monolayer capacity for MB was up to 450 mg g_1 and was one of the highest among similar polymeric products. It was due to its large BET surface area.

Keywords: TGA, FTIR, magentite, thiourea formaldehyde resin, methylene blue, adsorption

Procedia PDF Downloads 312

Authors: Osman Acar

Abstract:

Sun tracking systems are the systems following the sun ray by a right angle or by predetermined certain angle. In this study, we used theoretical trajectory of sun for latitude of central Anatolia in Turkey. A two degree of freedom spherical mechanism was designed to have a large workspace able to follow the sun's theoretical motion by the right angle during the whole year. An inverse kinematic analysis was generated to find the positions of mechanism links for the predicted trajectory. Force and torque analysis were shown for the first day of the year.

Keywords: sun tracking, theoretical sun trajectory, spherical mechanism, inverse kinematic analysis

Procedia PDF Downloads 388

Authors: Y. L. Sun, L. Shao, Y. Zhao, H. X. Zhou, W. Z. Lu, J. Li, D. W. Zuo

Abstract:

This study introduces an ice fixed-abrasive polishing (IFAP) technology. Using silica solution IFAP pad and Al2O3 IFAP pad, orthogonal tests were performed on polishing high-definition display panel glass, respectively. The results show that the polishing efficiency and effect polished with silica solution IFAP pad are better than those polished with Al2O3 IFAP pad. The optimized silica solution IFAP parameters are: polishing pressure 0.1MPa, polishing time 40min, table velocity 80r/min, and the ratio of accelerator and slurry 1:10. Finally, the IFAP mechanism was studied and it suggests by complicated analysis that IFAP is comprehensive effect of mechanical removal and microchemical reaction, combined with fixed abrasive polishing and free abrasive polishing.

Keywords: ice fixed-abrasive polishing, high-definition display panel glass, material removal rate, surface roughness

Procedia PDF Downloads 360

Authors: Burcu Kiren, Alattin CAkan, Nezihe Ayas

Abstract:

Hydrogen will be arguably the best fuel in the future as it is the most abundant element in the universe. Hydrogen, as a fuel, is notably environmentally benign, sustainable and has high energy content compared to other sources of energy. It can be generated from both conventional and renewable sources. The hydrolysis reaction of metal hydrides provides an option for hydrogen production in the presence of a catalyst. In this study, Ni/dolomite catalyst was synthesized by the wet impregnation method for hydrogen production by hydrolysis reaction of sodium borohydride (NaBH4). Besides, the synthesized catalysts characterizations were examined by means of thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer –Emmett – Teller (BET) and scanning electron microscopy (SEM). The influence of reaction temperature (25-75 °C), reaction time (15-60 min.), amount of catalyst (50-250 mg) and active metal loading ratio (20,30,40 wt.%) were investigated. The catalyst prepared with 30 wt.% Ni was noted as the most suitable catalyst, achieving of 35.18% H₂ and hydrogen production rate of 19.23 mL/gcat.min at 25 °C at reaction conditions of 5 mL of 0.25 M NaOH and 100 mg NaBH₄, 100 mg Ni/dolomite.

Keywords: sodium borohydride, hydrolysis, catalyst, Ni/dolomite, hydrogen

Procedia PDF Downloads 131

Authors: Qin Xia

Abstract:

’National New District’ as a regional overall promotion of strategic thinking has become increasingly mature, but its spatial expansion is still chaotic and disorderly, so it is urgent to summarize the complex and unique driving mechanism contained in its spatial expansion to formulate sustainable urban expansion plan. Under the understanding of the general laws of the driving mechanism of China's space expansion, it is found that the existing research on the driving mechanism of the space expansion of national new districts is insufficient. The research area focuses on the research of the driving mechanism of the space expansion of a single new area. In terms of research methods, qualitative description is the main focus. In terms of research content, it is limited to the expansion speed, intensity, and area of the new district itself and does not involve the expansion and utilization efficiency of space and the spillover efficiency to surrounding cities. The specific connotations of social, economic, political, and geographical categories are not thoroughly explored. It is often a general explanation that a certain factor has promoted it. The logic is not rigorous and convincing, and the description is relatively static, with different time and space. There is less literature on scale interaction. Through the reflection on the key and difficult points of the drive mechanism of the space expansion of the national new area, it is clear that the existing research on the drive mechanism of the space expansion of the national new area should be continued to drive the sustainable expansion of space.

Keywords: national new district, space expansion, driving mechanism, existing research

Procedia PDF Downloads 146

Authors: André Luis Lima de Oliveira, Vera Lúcia Viana do Nascimento, Victória Maura Silva Bermudez, Mauricio Nunes Kleinberg, João Carlos da Costa Assunção, José Osvaldo Beserra Carioca

Abstract:

The objective of this study was to synthesize a triglyceride with high content of unsaturated fatty acids from salmon oil (Salmo salar L.) by esterification with glycerol catalyzed dealuminized zeolite. A kinetic study was conducted to determine the reaction order and the activation energy. A statistical study was conducted to determine optimal reaction conditions. Initially, the crude oil was refined salmon physically and chemically. The crude oil was hydrolyzed and unsaturated free fatty acids were separated by urea complexation method. An experimental project to verify the parameters (temperature, glycerin and catalyst) with the greatest impact on the reaction was developed. In experiments aliquots were taken at predetermined times to measure the amount of free fatty acids. Pareto, surface, contour and hub graphs were used to determine the factors that maximized the reaction. According to the graphs the best reaction conditions were: temperature 80 ° C, the proportion glycerine/oil 5: 1 and 1% of catalyst. The kinetic data showed that the system was compatible with a second-order reaction. After analyzing the rate constant versus temperature charts a value of 85.31 kJ/mol was obtained for the reaction activation energy.

Keywords: esterification, kinect, oil, salmon

Procedia PDF Downloads 489

Authors: Mehdi Habibagahi, Shami Nejadi, Ata Aminfar

Abstract:

A significant degradation factor that impacts the durability of concrete structures is the alkali-silica reaction. Engineers are frequently charged with the challenges of conducting a thorough safety assessment of concrete structures that have been impacted by ASR. The alkali-silica reaction has a major influence on the structural capacities of structures. In most cases, the reduction in compressive strength, tensile strength, and modulus of elasticity is expressed as a function of free expansion and crack widths. Predicting the effect of ASR on flexural strength is also relevant. In this paper, a nonlinear three-dimensional (3D) finite-element model was proposed to describe the flexural strength degradation induced byASR.Initial strains, initial stresses, initial cracks, and deterioration of material characteristics were all considered ASR factors in this model. The effects of ASR on structural performance were evaluated by focusing on initial flexural stiffness, force–deformation curve, and load-carrying capacity. Degradation of concrete mechanical properties was correlated with ASR growth using material test data conducted at Tech Lab, UTS, and implemented into the FEM for various expansions. The finite element study revealed a better understanding of the ASR-affected RC beam's failure mechanism and capacity reduction as a function of ASR expansion. Furthermore, in this study, decreasing of the residual mechanical properties due to ASRisreviewed, using as input data for the FEM model. Finally, analysis techniques and a comparison of the analysis and the experiment results are discussed. Verification is also provided through analyses of reinforced concrete beams with behavior governed by either flexural or shear mechanisms.

Keywords: alkali-silica reaction, analysis, assessment, finite element, nonlinear analysis, reinforced concrete

Procedia PDF Downloads 144

Authors: Merve Aygün Esastürk, Deren Ataç Yılmaz, Görkem Oğur, Emre Özgen Kuzu, Sadık Ödemiş

Abstract:

Hydrocracker plants are one of the most complicated and most profitable units in the refinery process. It takes long chain paraffinic hydrocarbons as feed and turns them into smaller and more valuable products, mainly kerosene and diesel under high pressure with the excess amount of hydrogen. Controlling the product qualities well directly contributes to the unit profit. Control of a plant is mainly based on PID and MPC controllers. Controlling the reaction section is important in terms of reaction severity. However, controlling the fractionation section is more crucial since the end products are separated in fractionation section. In this paper, the importance of well-configured base layer control mechanism, composed of PID controllers, is highlighted. For this purpose, two different base layer control scheme is applied in a hydrocracker fractionator column performances of schemes, which is a direct contribution to better product quality, are compared.

Keywords: controller, distillation, configuration selection, hydrocracker, model predictive controller, proportional-integral-derivative controller

Procedia PDF Downloads 415

Authors: Gabriela D. Silva, Rodrigo L. O. R. Cunha, Mauricio D. Coutinho-Neto

Abstract:

In the last four decades the biological activities of selenium compounds has received great attention, particularly for hypervalent derivates from selenium (IV) used as enzyme inhibitors. The unregulated activity of cysteine proteases are related to the development of several pathologies, such as neurological disorders, cardiovascular diseases, obesity, rheumatoid arthritis, cancer and parasitic infections. These enzymes are therefore a valuable target for designing new small molecule inhibitors such as selenuranes. Even tough there has been advances in the synthesis and design of new selenuranes based inhibitors, little is known about their mechanism of action. It is a given that inhibition occurs through the reaction between the thiol group of the enzyme and the chalcogen atom. However, several open questions remain about the nature of the mechanism (associative vs. dissociative) and about the nature of the reactive species in solution under physiological conditions. In this work we performed a theoretical investigation on model systems to study the possible routes of substitution reactions. Nucleophiles may be present in biological systems, our interest is centered in the thiol groups from the cysteine proteases and the hydroxyls from the aqueous environment. We therefore expect this study to clarify the possibility of a route reaction in two stages, the first consisting of the substitution of chloro atoms by hydroxyl groups and then replacing these hydroxyl groups per thiol groups in selenuranes. The structures of selenuranes and nucleophiles were optimized using density function theory along the B3LYP functional and a 6-311+G(d) basis set. Solvent was treated using the IEFPCM method as implemented in the Gaussian 09 code. Our results indicate that hydrolysis from water react preferably with selenuranes, and then, they are replaced by the thiol group. It show the energy values of -106,0730423 kcal/mol for dople substituition by hydroxyl group and 96,63078511 kcal/mol for thiol group. The solvatation and pH reduction promotes this route, increasing the energy value for reaction with hydroxil group to -50,75637672 kcal/mol and decreasing the energy value for thiol to 7,917767189 kcal/mol. Alternative ways were analyzed for monosubstitution (considering the competition between Cl, OH and SH groups) and they suggest the same route. Similar results were obtained for aliphatic and aromatic selenuranes studied.

Keywords: chalcogenes, computational study, cysteine proteases, enzyme inhibitors

Procedia PDF Downloads 278

Authors: L. Parisi

Abstract:

In this research work, neural networks were applied to classify two types of hip joint implants based on the relative hip joint implant side speed and three components of each ground reaction force. The condition of walking gait at normal velocity was used and carried out with each of the two hip joint implants assessed. Ground reaction forces’ kinetic temporal changes were considered in the first approach followed but discarded in the second one. Ground reaction force components were obtained from eighteen patients under such gait condition, half of which had a hip implant type I-II, whilst the other half had the hip implant, defined as type III by Orthoload®. After pre-processing raw gait kinetic data and selecting the time frames needed for the analysis, the ground reaction force components were used to train a MLP neural network, which learnt to distinguish the two hip joint implants in the abovementioned condition. Further to training, unknown hip implant side and ground reaction force components were presented to the neural networks, which assigned those features into the right class with a reasonably high accuracy for the hip implant type I-II and the type III. The results suggest that neural networks could be successfully applied in the performance assessment of hip joint implants.

Keywords: kinemic gait data, neural networks, hip joint implant, hip arthroplasty, rehabilitation engineering

Procedia PDF Downloads 329

Authors: Hashim Isam Jameel Al-Safi, P. Ranjan Sarukkalige

Abstract:

Climate change is likely to impact the Australian continent by changing the trends of rainfall, increasing temperature, and affecting the accessibility of water quantity and quality. This study investigates the possible impacts of future climate change on the hydrological system of the Harvey River catchment in Western Australia by using the conceptual modelling approach (HBV mode). Daily observations of rainfall and temperature and the long-term monthly mean potential evapotranspiration, from six weather stations, were available for the period (1961-2015). The observed streamflow data at Clifton Park gauging station for 33 years (1983-2015) in line with the observed climate variables were used to run, calibrate and validate the HBV-model prior to the simulation process. The calibrated model was then forced with the downscaled future climate signals from a multi-model ensemble of fifteen GCMs of the CMIP3 model under three emission scenarios (A2, A1B and B1) to simulate the future runoff at the catchment outlet. Two periods were selected to represent the future climate conditions including the mid (2046-2065) and late (2080-2099) of the 21^st century. A control run, with the reference climate period (1981-2000), was used to represent the current climate status. The modelling outcomes show an evident reduction in the mean annual streamflow during the mid of this century particularly for the A1B scenario relative to the control run. Toward the end of the century, all scenarios show a relatively high reduction trends in the mean annual streamflow, especially the A1B scenario, compared to the control run. The decline in the mean annual streamflow ranged between 4-15% during the mid of the current century and 9-42% by the end of the century.

Keywords: climate change impact, Harvey catchment, HBV model, hydrological modelling, GCMs, LARS-WG

Procedia PDF Downloads 230

Authors: Kyohei Yoshino, Masahiko Matsumiya, Yuji Sasaki

Abstract:

Recently, studies have been conducted on Au(III) extraction using ionic liquids (ILs) as extractants or diluents. ILs such as piperidinium, pyrrolidinium, and pyridinium have been studied as extractants for noble metal extractions. Furthermore, the polarity, hydrophobicity, and solvent miscibility of these ILs can be adjusted depending on their intended use. Therefore, the unique properties of ILs make them functional extraction media. The extraction mechanism of Au(III) using phosphonium-based ILs and relevant thermodynamic studies are yet to be reported. In the present work, we focused on the mechanism of Au(III) extraction and related thermodynamic analyses using phosphonium-based ILs. Triethyl-n-pentyl, triethyl-n-octyl, and triethyl-n-dodecyl phosphonium bis(trifluoromethyl-sulfonyl)amide, [P₂₂₂ₓ][NTf₂], (X = 5, 8, and 12) were investigated for Au(III) extraction. The IL–Au complex was identified as [P₂₂₂₅][AuCl₄] using UV–Vis–NIR and Raman spectroscopic analyses. The extraction behavior of Au(III) was investigated with a change in the [P₂₂₂ₓ][NTf₂]IL concentration from 1.0 × 10–4 to 1.0 × 10–1 mol dm−3. The results indicate that Au(III) can be easily extracted by the anion-exchange reaction in the [P₂₂₂ₓ][NTf₂]IL. The slope range 0.96–1.01 on the plot of log D vs log[P₂₂₂ₓ][NTf2]IL indicates the association of one mole of IL with one mole of [AuCl4−] during extraction. Consequently, [P₂₂₂ₓ][NTf₂] is an anion-exchange extractant for the extraction of Au(III) in the form of anions from chloride media. Thus, this type of phosphonium-based IL proceeds via an anion exchange reaction with Au(III). In order to evaluate the thermodynamic parameters on the Au(III) extraction, the equilibrium constant (logKₑₓ’) was determined from the temperature dependence. The plot of the natural logarithm of Kₑₓ’ vs the inverse of the absolute temperature (T–1) yields a slope proportional to the enthalpy (ΔH). By plotting T–1 vs lnKₑₓ’, a line with a slope range 1.129–1.421 was obtained. Thus, the result indicated that the extraction reaction of Au(III) using the [P₂₂₂ₓ][NTf₂]IL (X=5, 8, and 12) was exothermic (ΔH=-9.39〜-11.81 kJ mol-1). The negative value of TΔS (-4.20〜-5.27 kJ mol-1) indicates that microscopic randomness is preferred in the [P₂₂₂₅][NTf₂]IL extraction system over [P₂₂₂₁₂][NTf₂]IL. The total negative alternation in Gibbs energy (-5.19〜-6.55 kJ mol-1) for the extraction reaction would thus be relatively influenced by the TΔS value on the number of carbon atoms in the alkyl side length, even if the efficiency of ΔH is significantly influenced by the total negative alternations in Gibbs energy. Electrochemical analysis revealed that extracted Au(III) can be reduced in two steps: (i) Au(III)/Au(I) and (ii) Au(I)/Au(0). The diffusion coefficients of the extracted Au(III) species in [P₂₂₂ₓ][NTf₂] (X = 5, 8, and 12) were evaluated from 323 to 373 K using semi-integral and semi-differential analyses. Because of the viscosity of the IL medium, the diffusion coefficient of the extracted Au(III) increases with increasing alkyl chain length. The 4f7/2 spectrum based on X-ray photoelectron spectroscopy revealed that the Au electrodeposits obtained after 10 cycles of continuous extraction and electrodeposition were in the metallic state.

Keywords: au(III), electrodeposition, phosphonium-based ionic liquids, solvent extraction

Procedia PDF Downloads 65

Authors: Lifar M. S., Tereshchenko A. A., Bulgakov A. N., Guda S. A., Guda A. A., Soldatov A. V.

Abstract:

Metal nanoparticles are widely used as heterogeneous catalysts to activate adsorbed molecules and reduce the energy barrier of the reaction. Reaction product yield depends on the interplay between elementary processes - adsorption, activation, reaction, and desorption. These processes, in turn, depend on the inlet feed concentrations, temperature, and pressure. At stationary conditions, the active surface sites may be poisoned by reaction byproducts or blocked by thermodynamically adsorbed gaseous reagents. Thus, the yield of reaction products can significantly drop. On the contrary, the dynamic control accounts for the changes in the surface properties and adjusts reaction parameters accordingly. Therefore dynamic control may be more efficient than stationary control. In this work, a reinforcement learning algorithm has been applied to control the simulation of CO oxidation on a catalyst. The policy gradient algorithm is learned to maximize the CO₂ production rate based on the CO and O₂ flows at a given time step. Nonstationary solutions were found for the regime with surface deactivation. The maximal product yield was achieved for periodic variations of the gas flows, ensuring a balance between available adsorption sites and the concentration of activated intermediates. This methodology opens a perspective for the optimization of catalytic reactions under nonstationary conditions.

Keywords: artificial intelligence, catalyst, co oxidation, reinforcement learning, dynamic control

Procedia PDF Downloads 88

Authors: N. Dumitru, S. Dumitru, C. Copilusi, N. Ploscaru

Abstract:

On this research, experimental analyses have been performed in order to determine the oil pump mechanism dynamics and stability from an oil unit mechanical structure. The experimental tests were focused on the vibrations which occur inside of the rod element during functionality of the oil pump unit. The oil pump mechanism dynamic parameters were measured and also determined through numerical computations. Entire research is based on the oil pump unit mechanical system virtual prototyping. For a complete analysis of the mechanism, the frequency dynamic response was identified, mainly for the mechanism driven element, based on two methods: processing and virtual simulations with MSC Adams aid and experimental analysis. In fact, through this research, a complete methodology is presented where numerical simulations of a mechanism with deformed elements are developed on a dynamic mode and these can be correlated with experimental tests.

Keywords: modal dynamic analysis, oil pump, vibrations, flexible elements, frequency response

Procedia PDF Downloads 288

Authors: Vikram Singh, Parmod Kumar Sethi

Abstract:

The objective of the study was to study the effectiveness of common yoga protocol on reaction time (choice visual reaction time, measured in milliseconds/seconds) of male football players in the age group of 16 to 21 years. The 40 boys were measured initially on parameters of years of experience, level of participation. They were randomly assigned into two groups i.e. control and experimental. CVRT for both the groups was measured on day-1 and post intervention (common yoga protocol here) was measured after 45 days of training to the experimental group after they had finished with their regular fitness and soccer skill training. One way ANOVA (Univariate analysis) and Independent t-test using SPSS 23 statistical package were applied to get and analyze the results. The experimental yoga protocol group showed a significant reduction in CVRT, whereas the insignificant difference in reaction times was observed for control group after 45 days. The effect size was more than 52% for CVRT indicating that the effect of treatment was large. Power of the study was also found to be high (> .80). There was a significant difference after 45 days of yoga protocol in choice visual reaction time of experimental group (p = .000), t (21.93) = 6.410, p = .000 (two-tailed). The null hypothesis (that there would be no difference in reaction times of control and experimental groups) was rejected. Where p< .05. Therefore alternate hypothesis was accepted.

Keywords: reaction time, yoga protocol, t-test, soccer players

Procedia PDF Downloads 214

Authors: Joel Y. Y. Loh, Geoffrey A. Ozin, Charles A. Mims, Nazir P. Kherani

Abstract:

A major goal in the emerging field of solar fuels is to realize an ‘artificial leaf’ – a material that converts light energy in the form of solar photons into chemical energy – using CO2 as a feedstock to generate useful chemical species. Enabling this technology will allow the greenhouse gas, CO2, emitted from energy and manufacturing production exhaust streams to be converted into valuable solar fuels or chemical products. Indium Oxide (In2O3) with surface hydroxyl (OH) groups have been shown to reduce CO2 in the presence of H2 to CO with a reaction rate of 15 μmol gcat−1 h−1. The likely mechanism is via a Frustrated Lewis Pair sites heterolytically splitting H2 to be absorbed and form protonic and hydric sites that can dissociate CO2. In this study, we investigate the dependence of oxygen composition of In2O3 on the CO2 reduction rate. In2O3-x films on quartz fiber paper were DC sputtered with an Indium target and varying O2/Ar plasma mixture. OH surface groups were then introduced by immersing the In2O3-x samples in KOH. We show that hydroxylated In2O3-x reduces more CO2 than non-hydroxylated groups and that a hydroxylated and higher O2/Ar ratio sputtered In2O3-x has a higher reaction rate of 45 μmol gcat-1 h-1. We show by electrical resistivity-temperature curves that H2 is adsorbed onto the surface of In2O3 whereas CO2 itself does not affect the indium oxide surface. We also present activation and ionization energy levels of the hydroxylated In2O3-x under vacuum, CO2 and H2 atmosphere conditions.

Keywords: solar fuels, photocatalysis, indium oxide nanoparticles, carbon dioxide

Procedia PDF Downloads 219

Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

Abstract:

Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

Procedia PDF Downloads 267

Authors: Jyh J. Chen, Fu H. Yang, Ming H. Liao

Abstract:

This study describes a capillary-based device integrated with the heating and cooling modules for polymerase chain reaction (PCR). The device consists of the reaction polytetrafluoroethylene (PTFE) capillary, the aluminum blocks, and is equipped with two cartridge heaters, a thermoelectric (TE) cooler, a fan, and some thermocouples for temperature control. The cartridge heaters are placed into the heating blocks and maintained at two different temperatures to achieve the denaturation and the extension step. Some thermocouples inserted into the capillary are used to obtain the transient temperature profiles of the reaction sample during thermal cycles. A 483-bp DNA template is amplified successfully in the designed system and the traditional thermal cycler. This work should be interesting to persons involved in the high-temperature based reactions and genomics or cell analysis.

Keywords: polymerase chain reaction, thermal cycles, capillary, TE cooler

Procedia PDF Downloads 424

Authors: Vemula Amalakrishna, S. Pushpavanam

Abstract:

Change and motion characterize and persistently reshape the world around us, on scales from molecular to global. The subtle interplay between change (Reaction) and motion (Diffusion) gives rise to an astonishing intricate spatial or temporal pattern. These pattern formation in nature has been intellectually appealing for many scientists since antiquity. Periodic precipitation patterns, also known as Liesegang patterns (LP), are one of the stimulating examples of such self-assembling reaction-diffusion (RD) systems. LP formation has a great potential in micro and nanotechnology. So far, the research on LPs has been concentrated mostly on how these patterns are forming, retrieving information to build a universal mathematical model for them. Researchers have developed various theoretical models to comprehensively construct the geometrical diversity of LPs. To the best of our knowledge, simulation studies of LPs assume an arbitrary value of RD parameters to explain experimental observation qualitatively. In this work, existing models were studied to understand the mechanism behind this phenomenon and challenges pertaining to models were understood and explained. These models are not computationally effective due to the presence of discontinuous precipitation rate in RD equations. To overcome the computational challenges, smoothened Heaviside functions have been introduced, which downsizes the computational time as well. Experiments were performed using a conventional LP system (AgNO₃-K₂Cr₂O₇) to understand the effects of different gels and temperatures on formed LPs. The model is extended for real parameter values to compare the simulated results with experimental data for both 1-D (Cartesian test tubes) and 2-D(cylindrical and Petri dish).

Keywords: reaction-diffusion, spatio-temporal patterns, nucleation and growth, supersaturation

Procedia PDF Downloads 132