Search results for: thermodynamic

Authors: Jyoti Sahu, Vinay A. Juvekar

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Electrolytes are often used to bring about salting-in and salting-out of organic molecules and polymers (e.g. polyethylene glycols/proteins) from the aqueous solutions. For quantification of these phenomena, a thermodynamic model which can accurately predict activity coefficient of electrolyte as a function of temperature is needed. The thermodynamics models available in the literature contain a large number of empirical parameters. These parameters are estimated using lower/upper critical solution temperature of the solution in the electrolyte/organic molecule at different temperatures. Since the number of parameters is large, inaccuracy can bethe creep in during their estimation, which can affect the reliability of prediction beyond the range in which these parameters are estimated. Cloud point of solution is related to its free energy through temperature and composition derivative. Hence, the Cloud point measurement can be used for accurate estimation of the temperature and composition dependence of parameters in the model for free energy. Hence, if we use a two pronged procedure in which we first use cloud point of solution to estimate some of the parameters of the thermodynamic model and determine the rest using osmotic coefficient data, we gain on two counts. First, since the parameters, estimated in each of the two steps, are fewer, we achieve higher accuracy of estimation. The second and more important gain is that the resulting model parameters are more sensitive to temperature. This is crucial when we wish to use the model outside temperatures window within which the parameter estimation is sought. The focus of the present work is to prove this proposition. We have used electrolyte (NaCl/Na2CO3)-water-organic molecule (Iso-propanol/ethanol) as the model system. The model of Robinson-Stokes-Glukauf is modified by incorporating the temperature dependent Flory-Huggins interaction parameters. The Helmholtz free energy expression contains, in addition to electrostatic and translational entropic contributions, three Flory-Huggins pairwise interaction contributions viz., and (w-water, p-polymer, s-salt). These parameters depend both on temperature and concentrations. The concentration dependence is expressed in the form of a quadratic expression involving the volume fractions of the interacting species. The temperature dependence is expressed in the form .To obtain the temperature-dependent interaction parameters for organic molecule-water and electrolyte-water systems, Critical solution temperature of electrolyte -water-organic molecules is measured using cloud point measuring apparatus The temperature and composition dependent interaction parameters for electrolyte-water-organic molecule are estimated through measurement of cloud point of solution. The model is used to estimate critical solution temperature (CST) of electrolyte water-organic molecules solution. We have experimentally determined the critical solution temperature of different compositions of electrolyte-water-organic molecule solution and compared the results with the estimates based on our model. The two sets of values show good agreement. On the other hand when only osmotic coefficients are used for estimation of the free energy model, CST predicted using the resulting model show poor agreement with the experiments. Thus, the importance of the CST data in the estimation of parameters of the thermodynamic model is confirmed through this work.

Keywords: concentrated electrolytes, Debye-Hückel theory, interaction parameters, Robinson-Stokes-Glueckauf model, Flory-Huggins model, critical solution temperature

Procedia PDF Downloads 358

Authors: Leyla Noroozbabaee, David Nickerson

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We introduce a modular, consistent, reusable bond graph model of the renal nephron’s proximal convoluted tubule (PCT), which can reproduce biological behaviour. In this work, we focus on ion and volume transport in the proximal convoluted tubule of the renal nephron. Modelling complex systems requires complex modelling problems to be broken down into manageable pieces. This can be enabled by developing models of subsystems that are subsequently coupled hierarchically. Because they are based on a graph structure. In the current work, we define two modular subsystems: the resistive module representing the membrane and the capacitive module representing solution compartments. Each module is analyzed based on thermodynamic processes, and all the subsystems are reintegrated into circuit theory in network thermodynamics. The epithelial transport system we introduce in the current study consists of five transport membranes and four solution compartments. Coupled dissipations in the system occur in the membrane subsystems and coupled free-energy increasing, or decreasing processes appear in solution compartment subsystems. These structural subsystems also consist of elementary thermodynamic processes: dissipations, free-energy change, and power conversions. We provide free and open access to the Python implementation to ensure our model is accessible, enabling the reader to explore the model through setting their simulations and reproducibility tests.

Keywords: Bond Graph, Epithelial Transport, Water Transport, Mathematical Modeling

Procedia PDF Downloads 57

Authors: Nabila Mohamed, Santiago Aparicio, Bahman Tohidi, Mert Atilhan

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Qatar's one of the biggest problem in processing its natural resource, which is natural gas, is the often occurring blockage in the pipelines caused due to uncontrolled gas hydrate formation in the pipelines. Several millions of dollars are being spent at the process site to dehydrate the blockage safely by using chemical inhibitors. We aim to establish national database, which addresses the physical conditions that promotes Qatari natural gas to form gas hydrates in the pipelines. Moreover, we aim to design and test novel hydrate inhibitors that are suitable for Qatari natural gas and its processing facilities. From these perspectives we are aiming to provide more effective and sustainable reservoir utilization and processing of Qatari natural gas. In this work, we present the initial findings of a QNRF funded project, which deals with the natural gas hydrate formation characteristics of Qatari type gas in both experimental (PVTx) and computational (molecular simulations) methods. We present the data from the two fully automated apparatus: a gas hydrate autoclave and a rocking cell. Hydrate equilibrium curves including growth/dissociation conditions for multi-component systems for several gas mixtures that represent Qatari type natural gas with and without the presence of well known kinetic and thermodynamic hydrate inhibitors. Ionic liquids were designed and used for testing their inhibition performance and their DFT and molecular modeling simulation results were also obtained and compared with the experimental results. Results showed significant performance of ionic liquids with up to 0.5 % in volume with up to 2 to 4 0C inhibition at high pressures.

Keywords: gas hydrates, natural gas, ionic liquids, inhibition, thermodynamic inhibitors, kinetic inhibitors

Procedia PDF Downloads 1281

Authors: Shenghong Huang, Weirong Wang, Xisheng Luo, Xinzhu Li, Xinwen Zhao

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Understanding of material mixing induced by Richtmyer-Meshkov instability (RMI) at extreme shock compressing conditions (high energy density environment: P >> 100GPa, T >> 10000k) is of great significance in engineering and science, such as inertial confinement fusion(ICF), supersonic combustion, etc. Turbulent mixing induced by RMI is a kind of complex fluid dynamics, which is closely related with hydrodynamic conditions, thermodynamic states, material physical properties such as compressibility, strength, surface tension and viscosity, etc. as well as initial perturbation on interface. For phenomena in ordinary thermodynamic conditions (low energy density environment), many investigations have been conducted and many progresses have been reported, while for mixing in extreme thermodynamic conditions, the evolution may be very different due to ionization as well as large difference of material physical properties, which is full of scientific problems and academic interests. In this investigation, the first principle based molecular dynamic method is applied to study metal Lithium and gas Hydrogen (Li-H2) interface mixing in micro/meso scale regime at different shock compressing loading speed ranging from 3 km/s to 30 km/s. It's found that, 1) Different from low-speed shock compressing cases, in high-speed shock compresing (>9km/s) cases, a strong acceleration of metal/gas interface after strong shock compression is observed numerically, leading to a strong phase inverse and spike growing with a relative larger linear rate. And more specially, the spike growing rate is observed to be increased with shock loading speed, presenting large discrepancy with available empirical RMI models; 2) Ionization is happened in shock font zone at high-speed loading cases(>9km/s). An additional local electric field induced by the inhomogeneous diffusion of electrons and nuclei after shock font is observed to occur near the metal/gas interface, leading to a large acceleration of nuclei in this zone; 3) In conclusion, the work of additional electric field contributes to a mechanism of RMI in micro/meso scale regime at extreme shock compressing conditions, i.e., a Rayleigh-Taylor instability(RTI) is induced by additional electric field during RMI mixing process and thus a larger linear growing rate of interface spike.

Keywords: ionization, micro/meso scale, material mixing, shock

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Authors: Youssef Mazloum, Haytham Sayah, Maroun Nemer

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The penetration of renewable energy sources into the electric grid is significantly increasing. However, the intermittence of these sources breaks the balance between supply and demand for electricity. Hence, the importance of the energy storage technologies, they permit restoring the balance and reducing the drawbacks of intermittence of the renewable energies. This paper discusses the modeling and the cost-effectiveness of an isobaric adiabatic compressed air energy storage (IA-CAES) system. The proposed system is a combination among a compressed air energy storage (CAES) system with pumped hydro storage system and thermal energy storage system. The aim of this combination is to overcome the disadvantages of the conventional CAES system such as the losses due to the storage pressure variation, the loss of the compression heat and the use of fossil fuel sources. A steady state model is developed to perform an energy and exergy analyses of the IA-CAES system and calculate the distribution of the exergy losses in the latter system. A sensitivity analysis is also carried out to estimate the effects of some key parameters on the system’s efficiency, such as the pinch of the heat exchangers, the isentropic efficiency of the rotating machinery and the pressure losses. The conducted sensitivity analysis is a local analysis since the sensibility of each parameter changes with the variation of the other parameters. Therefore, an exergoeconomic study is achieved as well as a cost optimization in order to reduce the electricity cost produced during the production phase. The optimizer used is OmOptim which is a genetic algorithms based optimizer.

Keywords: cost-effectiveness, Exergoeconomic analysis, isobaric adiabatic compressed air energy storage (IA-CAES) system, thermodynamic modeling

Procedia PDF Downloads 219

Authors: Payam Haghparast, Mikhail V. Sorin, Hakim Nesreddine

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The complex oblique shock phenomenon can be simply assumed as a normal shock at the constant area section to simulate a sharp pressure increase and velocity decrease in 1-D thermodynamic models. The assumed normal shock location is one of the greatest sources of error in ejector thermodynamic models. Most researchers consider an arbitrary location without justifying it. Our study compares the effect of normal shock place on ejector dimensions in 1-D models. To this aim, two different ejector experimental test benches, a constant area-mixing ejector (CAM) and a constant pressure-mixing (CPM) are considered, with different known geometries, operating conditions and working fluids (R245fa, R141b). In the first step, in order to evaluate the real value of the efficiencies in the different ejector parts and critical back pressure, a CFD model was built and validated by experimental data for two types of ejectors. These reference data are then used as input to the 1D model to calculate the lengths and the diameters of the ejectors. Afterwards, the design output geometry calculated by the 1D model is compared directly with the corresponding experimental geometry. It was found that there is a good agreement between the ejector dimensions obtained by the 1D model, for both CAM and CPM, with experimental ejector data. Furthermore, it is shown that normal shock place affects only the constant area length as it is proven that the inlet normal shock assumption results in more accurate length. Taking into account previous 1D models, the results suggest the use of the assumed normal shock location at the inlet of the constant area duct to design the supersonic ejectors.

Keywords: 1D model, constant area-mixing, constant pressure-mixing, normal shock location, ejector dimensions

Procedia PDF Downloads 169

Authors: Khaled Alshamari

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Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.

Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon

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Authors: Palash Kumar Mollick, Leire Olazar, Laura Santamaria, Pablo Comendador, Manomita Mollick, Gartzen Lopez, Martin Olazar

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The entire world is skeptical towards a silver line technology of converting plastic waste into valuable synthetic gas. At this junction, besides an adequately studied conventional catalytic process for steam reforming, a non-thermal plasma is being introduced. Organic volatiles are produced in the first step, pyrolysing the plastic materials. Resultant lightweight olefins and carbon monoxide are the major components that undergo a steam reforming process to achieve syngas. A non-thermal plasma consists of ionized gases and free electrons with an electronic temperature as high as 10³ K. Organic volatiles are, in general, endorganics inactive and thus demand huge bond-breaking energy. Conventional catalyst is incapable of providing the required activation energy, leading to poor thermodynamic equilibrium, whereas a non-thermal plasma can actively collide with reactants to produce a rich mix of reactive species, including vibrationally or electronically excited molecules, radicals, atoms, and ions. In addition, non-thermal plasma provides nonequilibrium conditions leading to electric discharge only in certain degrees of freedom without affecting the intrinsic chemical conditions of the participating reactants and products. In this work, we report thermodynamic and kinetic aspects of the conversion of organic volatiles into syngas using a non-thermal plasma. Detailed characteristics of plasma and its effect on the overall yield of the process will be presented.

Keywords: non thermal plasma, plasma catalysis, steam reforming, syngas, plastic waste, green energy

Procedia PDF Downloads 33

Authors: Shahram Naghizadeh Raeisi, Ali Alghooneh, Seyed Jalal Razavi Zahedkolaei

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Herein, a shelf stable (no refrigeration required) UHT processed, aseptically packaged whey protein drink was formulated by using a new strategy in microparticulate process. Applying thermal and two-dimensional mechanical treatments simultaneously, a modified protein (MWPC-80) was produced. Then the physical, thermal and thermodynamic properties of MWPC-80 were assessed using particle size analysis, dynamic temperature sweep (DTS), and differential scanning calorimetric (DSC) tests. Finally, using MWPC-80, a new RTD beverage was formulated, and shelf stability was assessed for three months at ambient temperature (25 °C). Non-isothermal dynamic temperature sweep was performed, and the results were analyzed by a combination of classic rate equation, Arrhenius equation, and time-temperature relationship. Generally, results showed that temperature dependency of the modified sample was significantly (Pvalue<0.05) less than the control one contained WPC-80. The changes in elastic modulus of the MWPC did not show any critical point at all the processed stages, whereas, the control sample showed two critical points during heating (82.5 °C) and cooling (71.10 °C) stages. Thermal properties of samples (WPC-80 & MWPC-80) were assessed using DSC with 4 °C /min heating speed at 20-90 °C heating range. Results did not show any thermal peak in MWPC DSC curve, which suggested high thermal resistance. On the other hands, WPC-80 sample showed a significant thermal peak with thermodynamic properties of ∆G:942.52 Kj/mol ∆H:857.04 Kj/mole and ∆S:-1.22Kj/mole°K. Dynamic light scattering was performed and results showed 0.7 µm and 15 nm average particle size for MWPC-80 and WPC-80 samples, respectively. Moreover, particle size distribution of MWPC-80 and WPC-80 were Gaussian-Lutresian and normal, respectively. After verification of microparticulation process by DTS, PSD and DSC analyses, a 10% why protein beverage (10% w/w/ MWPC-80, 0.6% w/w vanilla flavoring agent, 0.1% masking flavor, 0.05% stevia natural sweetener and 0.25% citrate buffer) was formulated and UHT treatment was performed at 137 °C and 4 s. Shelf life study did not show any jellification or precipitation of MWPC-80 contained beverage during three months storage at ambient temperature, whereas, WPC-80 contained beverage showed significant precipitation and jellification after thermal processing, even at 3% w/w concentration. Consumer knowledge on nutritional advantages of whey protein increased the request for using this protein in different food systems especially RTD beverages. These results could make a huge difference in this industry.

Keywords: high protein whey beverage, micropartiqulation, two-dimentional mechanical treatments, thermodynamic properties

Procedia PDF Downloads 41

Authors: H. Aksas, H. Babaci, K. Louhab

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In this paper, a comparative study of the adsorption of Chromium and dyes, onto mixture biosorbents, olive stones and date pits at different percentage was investigated in aqueous solution. The study of various parameters: Effect of contact time, pH, temperature and initial concentration shows that these materials possess a high affinity for the adsorption of chromium for the adsorption of dye bezaktiv yellow HE-4G. To deepen the comparative study of the adsorption of chromium and dye with the use of different blends of olive stones and date pits, the following models are studied: Langmuir, Freundlich isotherms and Dubinin- Radushkvich (D-R) were used as the adsorption equilibrium data model. Langmuir isotherm model was the most suitable for the adsorption of the dye bezaktiv HE-4G and the D-R model is most suitable for adsorption Chrome. The pseudo-first-order model, pseudo-second order and intraparticle diffusion were used to describe the adsorption kinetics. The apparent activation energy was found to be less than 8KJ/mol, which is characteristic of a controlled chemical reaction for the adsorption of two materials. t was noticed that adsorption of chromium and dye BEZAKTIV HE-YELLOW 4G follows the kinetics of the pseudo second order. The study of the effect of temperature was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes. The resulting thermodynamic parameters indicate the endothermic nature of the adsorption of Cr (VI) ions and the dye Bezaktiv HE-4G. But these materials are very good adsorbents, as they represent a low cost. in addition, it has been noticed that the greater the quantity of olive stone in the mixture increases, the adsorption ability of the dye or chromium increases.

Keywords: chromium ions, anions dye, sorption, mixed adsorbents, olive stone, date pits

Procedia PDF Downloads 203

Authors: Mohamad Saab, Florent Real, Francois Virot, Laurent Cantrel, Valerie Vallet

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All spent nuclear fuel reprocessing plants use the PUREX process (Plutonium Uranium Refining by Extraction), which is a liquid-liquid extraction method. The organic extracting solvent is a mixture of tri-n-butyl phosphate (TBP) and hydrocarbon solvent such as hydrogenated tetra-propylene (TPH). By chemical complexation, uranium and plutonium (from spent fuel dissolved in nitric acid solution), are separated from fission products and minor actinides. During a normal extraction operation, uranium is extracted in the organic phase as the UO₂(NO₃)₂(TBP)₂ complex. The TBP solvent can form an explosive mixture called red oil when it comes in contact with nitric acid. The formation of this unstable organic phase originates from the reaction between TBP and its degradation products on the one hand, and nitric acid, its derivatives and heavy metal nitrate complexes on the other hand. The decomposition of the red oil can lead to violent explosive thermal runaway. These hazards are at the origin of several accidents such as the two in the United States in 1953 and 1975 (Savannah River) and, more recently, the one in Russia in 1993 (Tomsk). This raises the question of the exothermicity of reactions that involve TBP and all other degradation products, and calls for a better knowledge of the underlying chemical phenomena. A simulation tool (Alambic) is currently being developed at IRSN that integrates thermal and kinetic functions related to the deterioration of uranyl nitrates in organic and aqueous phases, but not of the n-butyl phosphate. To include them in the modeling scheme, there is an urgent need to obtain the thermodynamic and kinetic functions governing the deterioration processes in liquid phase. However, little is known about the thermodynamic properties, like standard enthalpies of formation, of the n-butyl phosphate molecules and of the UO₂(NO₃)₂(TBP)₂ UO₂(NO₃)₂(HDBP)(TBP) and UO₂(NO₃)₂(HDBP)₂ complexes. In this work, we propose to estimate the thermodynamic properties with Quantum Methods (QM). Thus, in the first part of our project, we focused on the mono, di, and tri-butyl complexes. Quantum chemical calculations have been performed to study several reactions leading to the formation of mono-(H₂MBP), di-(HDBP), and TBP in gas and liquid phases. In the gas phase, the optimal structures of all species were optimized using the B3LYP density functional. Triple-ζ def2-TZVP basis sets were used for all atoms. All geometries were optimized in the gas-phase, and the corresponding harmonic frequencies were used without scaling to compute the vibrational partition functions at 298.15 K and 0.1 Mpa. Accurate single point energies were calculated using the efficient localized LCCSD(T) method to the complete basis set limit. Whenever species in the liquid phase are considered, solvent effects are included with the COSMO-RS continuum model. The standard enthalpies of formation of TBP, HDBP, and H2MBP are finally predicted with an uncertainty of about 15 kJ mol⁻¹. In the second part of this project, we have investigated the fundamental properties of three organic species that mostly contribute to the thermal runaway: UO₂(NO₃)₂(TBP)₂, UO₂(NO₃)₂(HDBP)(TBP), and UO₂(NO₃)₂(HDBP)₂ using the same quantum chemical methods that were used for TBP and its derivatives in both the gas and the liquid phase. We will discuss the structures and thermodynamic properties of all these species.

Keywords: PUREX process, red oils, quantum chemical methods, hydrolysis

Procedia PDF Downloads 166

Authors: Kyohei Yoshino, Masahiko Matsumiya, Yuji Sasaki

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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

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Authors: Belcher Fulele, W. A. A. Ddamba

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Study of solvent systems contributes to the understanding of intermolecular interactions that occur in binary mixtures. These interactions involves among others strong dipole-dipole interactions and weak van de Waals interactions which are of significant application in pharmaceuticals, solvent extractions, design of reactors and solvent handling and storage processes. Binary mixtures of solvents can thus be used as a model to interpret thermodynamic behavior that occur in a real solution mixture. Densities of pure DFM, n-alkanes (n-pentane, n-hexane, n-heptane and n-octane) and amides (N-methylformamide, N-ethylformamide, N,N-dimethylformamide and N,N-dimethylacetamide) as well as their [DFM + ((C5-C8) n-alkane or amide)] binary mixtures over the entire composition range, have been reported at temperature 293.15, 298.15 and 303.15 K and atmospheric pressure. These data has been used to derive the thermodynamic properties: the excess molar volume of solution, apparent molar volumes, excess partial molar volumes, limiting excess partial molar volumes, limiting partial molar volumes of each component of a binary mixture. The results are discussed in terms of possible intermolecular interactions and structural effects that occur in the binary mixtures. The variation of excess molar volume with DFM composition for the [DFM + (C5-C7) n-alkane] binary mixture exhibit a sigmoidal behavior while for the [DFM + n-octane] binary system, positive deviation of excess molar volume function was observed over the entire composition range. For each of the [DFM + (C5-C8) n-alkane] binary mixture, the excess molar volume exhibited a fall with increase in temperature. The excess molar volume for each of [DFM + (NMF or NEF or DMF or DMA)] binary system was negative over the entire DFM composition at each of the three temperatures investigated. The negative deviations in excess molar volume values follow the order: DMA > DMF > NEF > NMF. Increase in temperature has a greater effect on component self-association than it has on complex formation between molecules of components in [DFM + (NMF or NEF or DMF or DMA)] binary mixture which shifts complex formation equilibrium towards complex to give a drop in excess molar volume with increase in temperature. The Prigogine-Flory-Patterson model has been applied at 298.15 K and reveals that the free volume is the most important contributing term to the excess experimental molar volume data for [DFM + (n-pentane or n-octane)] binary system. For [DFM + (NMF or DMF or DMA)] binary mixture, the interactional term and characteristic pressure term contributions are the most important contributing terms in describing the sign of experimental excess molar volume. The mixture systems contributed to the understanding of interactions of polar solvents with proteins (amides) with non-polar solvents (alkanes) in biological systems.

Keywords: alkanes, amides, excess thermodynamic parameters, Prigogine-Flory-Patterson model

Procedia PDF Downloads 326

Authors: Padmesh Tirunelveli Narayanapillai, Joel Sharwinkumar, Gaitri Saravanan

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The biosorption of Xylenol Orange (XO) and Eriochrome Black T (EBT) from aqueous solutions by chemically activated Cocos nucifera and mango seed as a low-cost, natural, and eco-friendly biosorbents was investigated. The study for biosorption of XO and EBT was optimized by different experimental parameters, initial pH 2–7, temperature 30–60 °C, biosorbent dosage 0.1 – 0.5 g, and XO: EBT dye proportions 0 – 100 by weight %. Physicochemical characteristic studies were conducted by Fourier Transform Infrared (FTIR). The equilibrium uptake was increased with an increase in the initial dye concentrations in the solution. Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The experimental isotherms data were analyzed using Langmuir, Freundlich, Redlich-Peterson, and Toth isotherm equations. Thermodynamic parameters ∆Go, ∆Ho, and ∆So were calculated indicating that the biosorption of Xo and EBT dye is a spontaneous and endothermic process. The Langmuir model gave the best fit by higher correlation coefficient (R2 =0.9971) for both biosorbents at optimum circumstances as pH 3, temperature 30°C, dosage 0.5 g for chemically activated Cocos nucifera and 0.4 g for chemically activated mango seeds it assumes as monolayer adsorption. The maximum dye removal efficiency was determined as 79.75% with chemically activated mango seeds compared to chemically activated Cocos nucifera. In summary, this research work showed that chemically modified activated mango seed can be effectively used as a promising low-cost biosorbent for the removal of different XO and EBT mixed dye combinations from aqueous solutions.

Keywords: mixed dye proportions, xylenol orange and eriochrome black t, chemically activated cocos nucifera and mango seed, kinetic, isotherm and thermodynamic studies, FTIR

Procedia PDF Downloads 40

Authors: Zhuoran Li, Guan Qin

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A robust and efficient compositional equilibrium characterization model for hydrate-containing systems is required, especially for time-critical simulations such as subsea pipeline flow assurance analysis, compositional simulation in hydrate reservoirs etc. A multiphase flash calculation framework, which combines Gibbs energy minimization function and cubic plus association (CPA) EoS, is developed to describe the highly non-ideal phase behavior of hydrate-containing systems. A non-iterative eigenvalue problem-solving approach for the trust-region sub-problem is selected to guarantee efficiency. The developed flash model is based on the state-of-the-art objective function proposed by Michelsen to minimize the Gibbs energy of the multiphase system. It is conceivable that a hydrate-containing system always contains polar components (such as water and hydrate inhibitors), introducing hydrogen bonds to influence phase behavior. Thus, the cubic plus associating (CPA) EoS is utilized to compute the thermodynamic parameters. The solid solution theory proposed by van der Waals and Platteeuw is applied to represent hydrate phase parameters. The trust-region method combined with the trust-region sub-problem non-iterative eigenvalue problem-solving approach is utilized to ensure fast convergence. The developed multiphase flash model's accuracy performance is validated by three available models (one published and two commercial models). Hundreds of published hydrate-containing system equilibrium experimental data are collected to act as the standard group for the accuracy test. The accuracy comparing results show that our model has superior performances over two models and comparable calculation accuracy to CSMGem. Efficiency performance test also has been carried out. Because the trust-region method can determine the optimization step's direction and size simultaneously, fast solution progress can be obtained. The comparison results show that less iteration number is needed to optimize the objective function by utilizing trust-region methods than applying line search methods. The non-iterative eigenvalue problem approach also performs faster computation speed than the conventional iterative solving algorithm for the trust-region sub-problem, further improving the calculation efficiency. A new thermodynamic framework of the multiphase flash model for the hydrate-containing system has been constructed in this work. Sensitive analysis and numerical experiments have been carried out to prove the accuracy and efficiency of this model. Furthermore, based on the current thermodynamic model in the oil and gas industry, implementing this model is simple.

Keywords: equation of state, hydrates, multiphase equilibrium, trust-region method

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Authors: Vladimir Messerle, Alfred Mosse, Alexandr Ustimenko, Oleg Lavrichshev

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Hygiene and sanitary study of typical medical-biological waste made in Kazakhstan, Russia, Belarus and other countries show that their risk to the environment is much higher than that of most chemical wastes. For example, toxicity of solid waste (SW) containing cytotoxic drugs and antibiotics is comparable to toxicity of radioactive waste of high and medium level activity. This report presents the results of the thermodynamic analysis of thermal processing of SW and experiments at the developed plasma unit for SW processing. Thermodynamic calculations showed that the maximum yield of the synthesis gas at plasma gasification of SW in air and steam mediums is achieved at a temperature of 1600K. At the air plasma gasification of SW high-calorific synthesis gas with a concentration of 82.4% (СO – 31.7%, H2 – 50.7%) can be obtained, and at the steam plasma gasification – with a concentration of 94.5% (СO – 33.6%, H2 – 60.9%). Specific heat of combustion of the synthesis gas produced by air gasification amounts to 14267 kJ/kg, while by steam gasification - 19414 kJ/kg. At the optimal temperature (1600 K), the specific power consumption for air gasification of SW constitutes 1.92 kWh/kg, while for steam gasification - 2.44 kWh/kg. Experimental study was carried out in a plasma reactor. This is device of periodic action. The arc plasma torch of 70 kW electric power is used for SW processing. Consumption of SW was 30 kg/h. Flow of plasma-forming air was 12 kg/h. Under the influence of air plasma flame weight average temperature in the chamber reaches 1800 K. Gaseous products are taken out of the reactor into the flue gas cooling unit, and the condensed products accumulate in the slag formation zone. The cooled gaseous products enter the gas purification unit, after which via gas sampling system is supplied to the analyzer. Ventilation system provides a negative pressure in the reactor up to 10 mm of water column. Condensed products of SW processing are removed from the reactor after its stopping. By the results of experiments on SW plasma gasification the reactor operating conditions were determined, the exhaust gas analysis was performed and the residual carbon content in the slag was determined. Gas analysis showed the following composition of the gas at the exit of gas purification unit, (vol.%): СO – 26.5, H2 – 44.6, N2–28.9. The total concentration of the syngas was 71.1%, which agreed well with the thermodynamic calculations. The discrepancy between experiment and calculation by the yield of the target syngas did not exceed 16%. Specific power consumption for SW gasification in the plasma reactor according to the results of experiments amounted to 2.25 kWh/kg of working substance. No harmful impurities were found in both gas and condensed products of SW plasma gasification. Comparison of experimental results and calculations showed good agreement. Acknowledgement—This work was supported by Ministry of Education and Science of the Republic of Kazakhstan and Ministry of Education and Science of the Russian Federation (Agreement on grant No. 14.607.21.0118, project RFMEF160715X0118).

Keywords: coal, efficiency, ignition, numerical modeling, plasma-fuel system, plasma generator

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Authors: Claudia Matassa, Matthias Hohne, Dominic Ormerod, Yamini Satyawali

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Chiral amines integrate the backbone of several active pharmaceutical ingredients (APIs) used in modern medicine for the treatment of a vast range of diseases. Despite the demand, their synthesis remains challenging. Besides a range of chemicals and enzymatical methods, chiral amine synthesis using transaminases (EC 2.6.1.W) represents a useful alternative to access this important class of compounds. Even though transaminases exhibit excellent stereo and regioselectivity and the potential for high yield, the reaction suffers from a number of challenges, including the thermodynamic equilibrium, product inhibition, and low substrate solubility. In this work, we demonstrate a membrane assisted strategy for addressing these challenges. It involves the use of high molecular weight (HMW) amine donors for the transaminase-catalyzed synthesis of 4-phenyl-2-butylamine in both aqueous and organic solvent media. In contrast to common amine donors such as alanine or isopropylamine, these large molecules, provided in excess for thermodynamic equilibrium shifting, are easily retained by commercial nanofiltration membranes; thus a selective permeation of the desired smaller product amine is possible. The enzymatic transamination in aqueous media, combined with selective product removal shifted the equilibrium enhancing substrate conversion by an additional 25% compared to the control reaction. Along with very efficient amine product removal, there was undesirable loss of ketone substrate and low product concentration was achieved. The system was therefore further improved by performing the reaction in organic solvent (n-heptane). Coupling the reaction system with membrane-assisted product removal resulted in a highly concentrated and relatively pure ( > 97%) product solution. Moreover, a product yield of 60% was reached, compared to 15% without product removal.

Keywords: amine donor, chiral amines, in situ product removal, transamination

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Authors: Richard Adu Antwako

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Coastal wetland destruction and its consequences have recently taken the center stage of global discussions. This phenomenon is no gray area to humanity as coastal wetland-human interaction seems inevitably ingrained in the earliest civilizations, amidst the demanding use of its resources to meet their necessities. The severity of coastal wetland destruction parallels with growing civilizations, and it is against this backdrop that, this paper interrogated the causes of coastal wetland destruction in Harper City in Liberia, compared the degree of coastal wetland stressors to the non-equilibrium thermodynamic scale as well as suggested an integrated coastal zone management to address the problems. Literature complemented the primary data gleaned via global positioning system devices, field observation, questionnaire, and interviews. Multi-sampling techniques were used to generate data from the sand miners, institutional heads, fisherfolk, community-based groups, and other stakeholders. Non-equilibrium thermodynamic theory remains vibrant in discerning the ecological stability, and it would be employed to further understand the coastal wetland destruction in Harper City, Liberia and to measure the coastal wetland stresses-amplitude and elasticity. The non-equilibrium thermodynamics postulates that the coastal wetlands are capable of assimilating resources (inputs), as well as discharging products (outputs). However, the input-output relationship exceedingly stretches beyond the thresholds of the coastal wetlands, leading to coastal wetland disequilibrium. Findings revealed that the sand mining, mangrove removal, and crude dumping have transformed the coastal wetlands, resulting in water pollution, flooding, habitat loss and disfigured beaches in Harper City in Liberia. This paper demonstrates that the coastal wetlands are converted into developmental projects and agricultural fields, thus, endangering the future society against nature.

Keywords: amplitude, crude dumping, elasticity, non-equilibrium thermodynamics, wetland destruction

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Authors: Sobia Mushtaq, Firdaus E. Bareen, Asma Tayyeb

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This study conducted to investigate the metal biosorption potential of indigenous Trichoderma species (T. harzianum KS05T01, T. longibrachiatum KS09T03, Trichoderma sp KS17T09., T. viridi KS17T011, T. atrobruneo KS21T014, and T. citrinoviride) that have been isolated from contaminated soil of Kasur Tannery Waste Management Agency. The effect of different biosorption parameters as initial metal ion concentration, pH, contact time , and temperature of incubation was investigated on the biosorption potential of these species. The metal removal efficiency and (E%) and metal uptake capacity (mg/g) increased along with the increase of initial metal concentration in media. The Trichoderma species can tolerate and survive under heavy metal stress up to 800mg/L. Among the two isotherm models were applied on the biosorption data, Langmuir isotherm model and Freundlich isotherm model, maximum correlation coefficients values (R 2 ) of 1was found for Langmuir model, which showed the better fitted model for the Trichoderma biosorption. The metal biosorption was increased with the increase of temperature and pH of the media. The maximum biosorption was observed between 25-30 o C and at pH 6.-7.5, while the biosorption rate was increased from 3-6 days of incubation, and then the rate of biosorption was slowed down. The biosorption data was better fitted for Pseudo kinetic first order during the initial days of biosorption. Thermodynamic parameters as standard Gibbs free energy (G), standard enthalpy change (H), and standard entropy (S) were calculated. The results confirmed the heavy metal biosorption by Trichoderma species was endothermic and spontaneous reaction in nature. The FTIR spectral analysis and SEM-EDX analysis of the treated and controlled mycelium revealed the changes in the active functional sites and morphological variations of the outer surface. The data analysis envisaged that high metal tolerance exhibited by Trichoderma species indicates its potential as efficacious and successful mediator for bioremediation of the heavy metal polluted environments.

Keywords: heavy metal, fungal biomass, biosorption, kinetics

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Authors: Makhlouf Mourad, Messabih Sidi Mohamed, Bouchher Omar, Houali Farida, Benrachedi Khaled

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Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH₃)₃ was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values ​​obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.

Keywords: adsorption, kinetics, isotherm, mesoporous materials, Phenol, P-hydroxy benzoique acid

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Authors: Keltoum Bouherine, Olivier Leroy

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The present work is dedicated to study a three–dimensional (3D) self-consistent fluid simulation of microwave discharges of argon plasma in PECVD reactor. The model solves the Maxwell’s equations, continuity equations for charged species and the electron energy balance equation, coupled with Poisson’s equation, and Navier-Stokes equations by finite element method, using COMSOL Multiphysics software. In this study, the simulations yield the profiles of plasma components as well as the charge densities and electron temperature, the electric field, the gas velocity, and gas temperature. The results show that the microwave plasma reactor is outside of local thermodynamic equilibrium.The present work is dedicated to study a three–dimensional (3D) self-consistent fluid simulation of microwave discharges of argon plasma in PECVD reactor. The model solves the Maxwell’s equations, continuity equations for charged species and the electron energy balance equation, coupled with Poisson’s equation, and Navier-Stokes equations by finite element method, using COMSOL Multiphysics software. In this study, the simulations yield the profiles of plasma components as well as the charge densities and electron temperature, the electric field, the gas velocity, and gas temperature. The results show that the microwave plasma reactor is outside of local thermodynamic equilibrium.

Keywords: electron density, electric field, microwave plasma reactor, gas velocity, non-equilibrium plasma

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Authors: Taiheng Zhang, Hongbin Zhao

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Compressed air energy storage become increasingly vital for solving intermittency problem of some renewable energies. In this study, a new hybrid system on a combination of compressed air energy storage (CAES), solid oxide fuel cell (SOFC), gas turbine (GT), and organic Rankine cycle (ORC) is proposed. In the new system, excess electricity during off-peak time is utilized to compress air. Then, the compressed air is stored in compressed air storage tank. During peak time, the compressed air enters the cathode of SOFC directly instead of combustion chamber of traditional CAES. There is no air compressor consumption of SOFC-GT in peak demand, so SOFC- GT can generate power with high-efficiency. In addition, the waste heat of exhaust from GT is recovered by applying an ORC. Three different organic working fluid (R123, R601, R601a) of ORC are chosen to evaluate system performance. Based on Aspen plus and Engineering Equation Solver (EES) software, energy and exergoeconomic analysis are used to access the viability of the combined system. Besides, the effect of two parameters (fuel flow and ORC turbine inlet pressure) on energy efficiency is studied. The effect of low-price electricity at off-peak hours on thermodynamic criteria (total unit exergy cost of products and total cost rate) is also investigated. Furthermore, for three different organic working fluids, the results of round-trip efficiency, exergy efficiency, and exergoeconomic factors are calculated and compared. Based on thermodynamic performance and exergoeconomic performance of different organic working fluids, the best suitable working fluid will be chosen. In conclusion, this study can provide important guidance for system efficiency improvement and viability.

Keywords: CAES, SOFC, ORC, energy and exergoeconomic analysis, organic working fluids

Procedia PDF Downloads 91

Authors: M. Gomaa Abdoelatef, Robert M. Field, Lee, Yong-Kwan

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Growing human populations have placed increased demands on water supplies and a heightened interest in desalination infrastructure. Key elements of the economics of desalination projects are thermal and electrical inputs. With growing concerns over the use of fossil fuels to (indirectly) supply these inputs, coupling of desalination with nuclear power production represents a significant opportunity. Individually, nuclear and desalination technologies have a long history and are relatively mature. For desalination, Reverse Osmosis (RO) has the lowest energy inputs. However, the economically driven output quality of the water produced using RO, which uses only electrical inputs, is lower than the output water quality from thermal desalination plants. Therefore, modern desalination projects consider that RO should be coupled with thermal desalination technologies (MSF, MED, or MED-TVC) with attendant steam inputs to permit blending to produce various qualities of water. A large nuclear facility is well positioned to dispatch large quantities of both electrical and thermal power. This paper considers the supply of thermal energy to a large desalination facility to examine heat balance impact on the nuclear steam cycle. The APR1400 nuclear plant is selected as prototypical from both a capacity and turbine cycle heat balance perspective to examine steam supply and the impact on electrical output. Extraction points and quantities of steam are considered parametrically along with various types of thermal desalination technologies to form the basis for further evaluations of economically optimal approaches to the interface of nuclear power production with desalination projects. In our study, the thermodynamic evaluation will be executed by DE-TOP which is the IAEA desalination program, it is approved to be capable of analyzing power generation systems coupled to desalination systems through various steam extraction positions, taking into consideration the isolation loop between the APR-1400 and the thermal desalination plant for safety concern.

Keywords: APR-1400, desalination, DE-TOP, IAEA, MSF, MED, MED-TVC, RO

Procedia PDF Downloads 503

Authors: Niharika Keot, Manabendra Sarma

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A thorough investigation of Ln3+ complexes with more than one inner-sphere water molecule is crucial for designing high relaxivity contrast agents (CAs) used in magnetic resonance imaging (MRI). This study accomplished a comparative stability analysis of two hexadentate (H3cbda and H3dpaa) and two heptadentate (H4peada and H3tpaa) ligands with Ln3+ ions. The higher stability of the hexadentate H3cbda and heptadentate H4peada ligands has been confirmed by the binding affinity and Gibbs free energy analysis in aqueous solution. In addition, energy decomposition analysis (EDA) reveals the higher binding affinity of the peada4− ligand than the cbda3− ligand towards Ln3+ ions due to the higher charge density of the peada4− ligand. Moreover, a mechanistic overview of water exchange kinetics has been carried out based on the strength of the metal–water bond. The strength of the metal–water bond follows the trend Gd–O47 (w) > Gd–O39 (w) > Gd–O36 (w) in the case of the tris-aquated [Gd(cbda)(H2O)3] and Gd–O43 (w) > Gd–O40 (w) for the bis-aquated [Gd(peada)(H2O)2]− complex, which was confirmed by bond length, electron density (ρ), and electron localization function (ELF) at the corresponding bond critical points. Our analysis also predicts that the activation energy barrier decreases with the decrease in bond strength; hence kex increases. The 17O and 1H hyperfine coupling constant values of all the coordinated water molecules were different, calculated by using the second-order Douglas–Kroll–Hess (DKH2) approach. Furthermore, the ionic nature of the bonding in the metal–ligand (M–L) bond was confirmed by the Quantum Theory of Atoms-In-Molecules (QTAIM) and ELF along with energy decomposition analysis (EDA). We hope that the results can be used as a basis for the design of highly efficient Gd(III)-based high relaxivity MRI contrast agents for medical applications.

Keywords: MRI contrast agents, lanthanide chemistry, thermodynamic stability, water exchange kinetics

Procedia PDF Downloads 46

Authors: Kevin A. Droguett, Edwin G. Pérez, Denis Fuentealba, Margarita E. Aliaga, Angélica M. Fierro

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Supramolecular chemistry is a field of growing interest. Moreover, studying the formation of host-guest complexes between macrocycles and dyes is highly attractive due to their potential applications. Examples of the above are drug delivery, catalytic process, and sensing, among others. There are different dyes of interest in the literature; one example is the quinolinone derivatives. Those molecules have good optical properties and chemical and thermal stability, making them suitable for developing fluorescent probes. Secondly, several macrocycles can be seen in the literature. One example is the cucurbiturils. This water-soluble macromolecule family has a hydrophobic cavity and two identical carbonyl portals. Additionally, the thermodynamic analysis of those supramolecular systems could help understand the affinity between the host and guest, their interaction, and the main stabilization energy of the complex. In this work, two 7-(diethylamino) quinoline-2 (1H)-one derivative (QD1-2) and their interaction with cucurbit[7]uril (CB[7]) were studied from an experimental and in-silico point of view. For the experimental section, the complexes showed a 1:1 stoichiometry by HRMS-ESI and isothermal titration calorimetry (ITC). The inclusion of the derivatives on the macrocycle lends to an upward shift in the fluorescence intensity, and the pKa value of QD1-2 exhibits almost no variation after the formation of the complex. The thermodynamics of the inclusion complexes was investigated using ITC; the results demonstrate a non-classical hydrophobic effect with a minimum contribution from the entropy term and a constant binding on the order of 106 for both ligands. Additionally, dynamic molecular studies were carried out during 300 ns in an explicit solvent at NTP conditions. Our finding shows that the complex remains stable during the simulation (RMSD ~1 Å), and hydrogen bonds contribute to the stabilization of the systems. Finally, thermodynamic parameters from MMPBSA calculations were obtained to generate new computational insights to compare with experimental results.

Keywords: host-guest complexes, molecular dynamics, quinolin-2(1H)-one derivatives dyes, thermodynamics

Procedia PDF Downloads 59

Authors: Diwan Singh

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The ability of non-living Spirogyra sp. biomass for biosorption of copper(II) ions from aqueous solutions was explored. The effect of contact time, pH, initial copper ion concentration, biosorbent dosage and temperature were investigated in batch experiments. Both the Freundlich and Langmuir Isotherms were found applicable on the experimental data (R2>0.98). Qmax obtained from the Langmuir Isotherms was found to be 28.7 mg/g of biomass. The values of Gibbs free energy (ΔGº) and enthalpy change (ΔHº) suggest that the sorption is spontaneous and endothermic at 20ºC-40ºC.

Keywords: biosorption, Spirogyra sp., contact time, pH, dose

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Authors: George N. Prodromidis, Frank A. Coutelieris

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Biogas can be currently considered as an alternative option for electricity production, mainly due to its high energy content (hydrocarbon-rich source), its renewable status and its relatively low utilization cost. Solid Oxide Fuel Cell (SOFC) stacks convert fuel’s chemical energy to electricity with high efficiencies and reveal significant advantages on fuel flexibility combined with lower emissions rate, especially when utilize biogas. Electricity production by biogas constitutes a composite problem which incorporates an extensive parametric analysis on numerous dynamic variables. The main scope of the presented study is to propose a detailed thermodynamic model on the optimization of SOFC-based power plants’ operation based on fundamental thermodynamics, energy and exergy balances. This model named THERMAS (THERmodynamic MAthematical Simulation model) incorporates each individual process, during electricity production, mathematically simulated for different case studies that represent real life operational conditions. Also, THERMAS offers the opportunity to choose a great variety of different values for each operational parameter individually, thus allowing for studies within unexplored and experimentally impossible operational ranges. Finally, THERMAS innovatively incorporates a specific criterion concluded by the extensive energy analysis to identify the most optimal scenario per simulated system in exergy terms. Therefore, several dynamical parameters as well as several biogas mixture compositions have been taken into account, to cover all the possible incidents. Towards the optimization process in terms of an innovative OPF (OPtimization Factor), presented here, this research study reveals that systems supplied by low methane fuels can be comparable to these supplied by pure methane. To conclude, such an innovative simulation model indicates a perspective on the optimal design of a SOFC stack based system, in the direction of the commercialization of systems utilizing biogas.

Keywords: biogas, exergy, efficiency, optimization

Procedia PDF Downloads 342

Authors: Samaneh Soroush, Tommy Golczynski, Tony Spratt

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One of the new technologies for CO₂ capture, storage, and utilization (CCSU) is forming clathrate hydrate. This technology has some unknowns and challenges that make it difficult to apply in the real world. The low formation rate is one of the main difficulties of CO₂ hydrate. In this work, the effect of different promotors on the hydrate formation rate has been studied. Two surfactants, sodium dodecyl sulfate (SDS), tetra-n-butylammonium bromide (TBAB), and cyclopentane (CP) as a thermodynamic promotor and their combination have been used for the experiments. The results showed that the SDS is a powerful kinetic promotor and its combination with CP helps to convert more CO₂ to hydrate in a short time.

Keywords: carbon capture, carbon dioxide, hydrate, promotor

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Authors: Pedro A. Marques, Francisco Monteiro, Alessandra Zumbo, Alessia Simonini, Miguel A. Mendez

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Cryogenic fuels such as Liquid Hydrogen (LH₂) must be transported and stored at extremely low temperatures. Without expensive active cooling solutions, preventing fuel boil-off over time is impossible. Hence, one must resort to venting systems at the cost of significant energy and fuel mass loss. These losses increase significantly in propellant tanks installed on vehicles, as the presence of external accelerations induces sloshing. Sloshing increases heat and mass transfer rates and leads to significant pressure oscillations, which might further trigger propellant venting. To make LH₂ economically viable, it is essential to minimize these factors by using advanced control techniques. However, these require accurate modelling and a full understanding of the tank's thermodynamics. The present research aims to implement a simple thermodynamic model capable of predicting the state of a cryogenic fuel tank under different operating conditions (i.e., filling, pressurization, fuel extraction, long-term storage, and sloshing). Since this model relies on a set of closure parameters to drive the system's transient response, it must be calibrated using experimental or numerical data. This work focuses on the former approach, wherein the model is calibrated through an experimental campaign carried out on a reduced-scale model of a cryogenic tank. The thermodynamic model of the system is composed of three control volumes: the ullage, the liquid, and the insulating walls. Under this lumped formulation, the governing equations are derived from energy and mass balances in each region, with mass-averaged properties assigned to each of them. The gas-liquid interface is treated as an infinitesimally thin region across which both phases can exchange mass and heat. This results in a coupled system of ordinary differential equations, which must be closed with heat and mass transfer coefficients between each control volume. These parameters are linked to the system evolution via empirical relations derived from different operating regimes of the tank. The derivation of these relations is carried out using an inverse method to find the optimal relations that allow the model to reproduce the available data. This approach extends classic system identification methods beyond linear dynamical systems via a nonlinear optimization step. Thanks to the data-driven assimilation of the closure problem, the resulting model accurately predicts the evolution of the tank's thermodynamics at a negligible computational cost. The lumped model can thus be easily integrated with other submodels to perform complete system simulations in real time. Moreover, by setting the model in a dimensionless form, a scaling analysis allowed us to relate the tested configurations to a representative full-size tank for naval applications. It was thus possible to compare the relative importance of different transport phenomena between the laboratory model and the full-size prototype among the different operating regimes.

Keywords: destratification, hydrogen, modeling, pressure-drop, pressurization, sloshing, thermodynamics

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Authors: Mutalubi Aremu Akintunde, John Isa

Abstract:

The negative impact on the atmosphere, of chlorofluorocarbon refrigerants (CFC) radical changes and measures were put in place to replace them. This has led to search for alternative refrigerants over the past decades. This paper presents thermal conductivity, diffusivity and performance of two alternative refrigerants as replacement to R12, which has been a versatile refrigerant which had turned the refrigeration industries around for decades, but one of the offensive refrigerants. The new refrigerants were coded RA1 (50%R600a/50%R134a;) and RA2 (70%R600a/30%R134a). The diffusivities for RA1 and RA2 were estimated to be, 2.76384 X 10-8 m2/s and 2.74386 X 10-8 m2/s respectively, while that of R12 under the same experimental condition is 2.43772 X 10-8 m2/s. The performances of the two refrigerants in a refrigerator initially designed for R12, were very close to that of R12. Other thermodynamic parameters showed that R12 can be replaced with both RA1 and RA2.

Keywords: alternative refrigerants, conductivity, diffusivity, performance, refrigerants

Procedia PDF Downloads 127