Non-Fourier heat conduction model with dual phase lag wave-diffusion model was analyzed by using well-conditioned asymptotic wave evaluation (WCAWE) and finite element method (FEM). The non-Fourier heat conduction has been investigated where the maximum likelihood (ML) and Tikhonov regularization technique were used successfully to predict the accurate and stable temperature responses without the loss of initial nonlinear/high frequency response. To reduce the increased computational time by Tikhonov WCAWE using ML (TWCAWE-ML), another well-conditioned scheme, called mass effect (ME) T-WCAWE, is introduced. TWCAWE with ME (TWCAWE-ME) showed more stable and accurate temperature spectrum in comparison to asymptotic wave evaluation (AWE) and also partial Pade AWE without sacrificing the computational time. However, the TWCAWE-ML remains as the most stable and hence accurate model to analyze the fast transient thermal analysis of non-Fourier heat conduction model.
Gas Hydrate modelling has gained huge attention in the past decade due to its increase in usage for various energy as well as environmental applications at an industrial scale. As the experimental approach is highly expensive and time-consuming, modelling is the best way to predict the conditions before the actual applications at industrial scales. The commercial software currently existing uses the equation of states (EOS) to predict the thermodynamic conditions of gas hydrates. But, in certain cases, the prediction by using EOS fails to predict the hydrate conditions accurately. Therefore, there arose a need for an accurate prediction model to estimate the hydrate formation conditions. So, in this work, an accurate prediction model has been proposed to predict the thermodynamic equilibrium conditions of the gas hydrate formation. The performance of prediction accuracy for the proposed model is compared with those of the SRK equation of state and Peng Robinson (PR) Equation of state. It was observed that in most of the cases the proposed model has predicted the thermodynamic conditions more accurately than the PR and SRK equation of state. This work helps in understanding the limitations of EOS for the prediction hydrate conditions. Also, the current work helps in strengthening the conventional statistical modelling technique to predict the hydrate conditions for a broader range.
Among numerous methods developed in purification and separation industries, the adsorption process has received considerable attention due to its inexpensive, facile, and eco-friendly nature. The importance of the adsorption process causes extraordinary endeavors for modeling the adsorption isotherms during the years; thus, myriads of research have been conducted and many reviews have been published. In this paper, we have attempted to gather the most widely used adsorption isotherms and their related definitions, along with examples of correlated work of the recent decade. In the present review, 37 adsorption isotherms with about 400 references have been collected from the research published in the period of 2010-2020. The adsorption isotherms utilized are alphabetically organized for ease of access. The parameters of each isotherm, as well as the applicable definitions, are presented in the table, in addition to being discussed in the text. Another table is provided for the practical use of researchers, featuring the usage of the related isotherms in peer-reviewed studies.
In this study, a sustainable NH2-MIL-101(Al) is synthesized and subjected to characterization for cryogenic CO2 adsorption, isotherms, and thermodynamic study. The morphology revealed a highly porous surface. The XRD showed that NH2-MIL-101(Al) was crystalline. The NH2-MIL-101(Al) decomposes at a temperature (>500 °C) indicating excellent thermal stability. The BET investigation revealed the specific surface area of 2530 m2/g and the pore volume of 1.32 cm3/g. The CO2 adsorption capacity was found to be 9.55 wt% to 2.31 wt% within the investigated temperature range. The isotherms revealed the availability of adsorption sites with favorable adsorption at lower temperatures indicating the thermodynamically controlled process. The thermodynamics showed that the process is non-spontaneous, endothermic, with fewer disorders, chemisorption. Finally, the breakthrough time of NH2-MIL-101(Al) is 31.25% more than spherical glass beads. The CO2 captured by the particles was 2.29 kg m-3. The CO2 capture using glass packing was 121% less than NH2-MIL-101(Al) under similar conditions of temperature and pressure.
Limited information is available about the thermodynamic evaluation for biomass gasification process using updraft gasifier. Therefore, to minimize errors, the gasification of dry refinery sludge (DRS) is carried out in adiabatic system at atmospheric pressure under ambient air conditions. The objectives of this paper are to investigate the physical and chemical energy and exergy of product gas at different equivalent ratios (ER). It will also be used to determine whether the cold gas, exergy, and energy efficiencies of gases may be maximized by using secondary air injected to gasification zone under various ratios (0, 0.5, 1, and 1.5) at optimum ER of 0.195. From the results obtained, it is indicated that the chemical energy and exergy of producer gas are magnified by 5 and 10 times higher than their corresponding physical values, respectively. The cold gas, energy, and exergy efficiencies of DRS gasification are in the ranges of 22.9-55.5%, 43.7-72.4%, and 42.5-50.4%, respectively. Initially, all 3 efficiencies increase until they reach a maximum at the optimum ER of 0.195; thereafter, they decline with further increase in ER values. The injection of secondary air to gasification zone is also found to increase the cold gas, energy, and exergy efficiencies. A ratio of secondary air to primary air of 0.5 is found to be the optimum ratio for all 3 efficiencies to reach the maximum values.
Numerical investigation of the heat transfer and friction factor characteristics of a circular fitted with V-cut twisted tape (VCT) insert with twist ratio (y = 2.93) and different cut depths (w = 0.5, 1, and 1.5 cm) were studied for laminar flow using CFD package (FLUENT-6.3.26). The data obtained from plain tube were verified with the literature correlation to ensure the validation of simulation results. Classical twisted tape (CTT) with different twist ratios (y = 2.93, 3.91, 4.89) were also studied for comparison. The results show that the enhancement of heat transfer rate induced by the classical and V-cut twisted tape inserts increases with the Reynolds number and decreases with twist ratio. The results also revealed that the V-cut twisted tape with twist ratio y = 2.93 and cut depth w = 0.5 cm offered higher heat transfer rate with significant increases in friction factor than other tapes. In addition the results of V-cut twist tape compared with experimental and simulated data of right-left helical tape inserts (RLT), it is found that the V-cut twist tape offered better thermal contact between the surface and the fluid which ultimately leads to a high heat transfer coefficient. Consequently, 107% of maximum heat transfer was obtained by using this configuration.
Research into the speciation of sulfur and hydrogen molecules produced through the complex process of thermophilic dark fermentation has been conducted. Detailed surface studies of solid-gas systems using real biogas (biohydrogen) streams have unveiled the mechanisms and specific interactions between these gases and the physicochemical properties of a zeolite as an adsorbent. These findings highlight the potential of zeolites to effectively capture and interact with these molecules. In this study, the hydrogen sulphide removal analysis was conducted using 0.8 g of the adsorbent and at various reaction temperatures (25-125 °C), a flow rate of 100 mL min-1, and an initial concentration of approximately 5000 ppm hydrogen sulphide. The reaction temperature has been observed to be an essential parameter of Zeolite Socony Mobil - 5 adsorption capacity. The optimum adsorption capacity attains a maximum value of 0.00890 mg g-1 at an optimal temperature of 25 °C. The formation of sulphur species resulting from the hydrogen sulphide adsorption on the zeolite determines the kinetics, thermodynamics, and mass transfer behaviours of Zeolite Socony Mobil - 5 in hydrogen sulphide removal and Zeolite Socony Mobil - 5 is found to improve the quality of biohydrogen produced in thermophilic environments. Biohydrogen (raw gas) yield was enhanced from 2.48 mol H2 mol-1 hexose consumed before adsorption to 2.59 mol H2 mol-1 hexose consumed after adsorption at a temperature of 25 °C. The Avrami kinetic model was fitted for hydrogen sulphide removal on Zeolite Socony Mobil - 5. The process is explained well and fitted using the Temkin isotherm model and the investigation into thermodynamics reveals that the adsorption behaviour is exothermic and non-spontaneous. Furthermore, the gas molecule's freedom of movement becomes random. The adsorption phase is restricted by intra-particle diffusion followed by film diffusion during the transfer of hydrogen sulphide into the pores of Zeolite Socony Mobil - 5 prior to adsorption on its active sites. The utilisation of Zeolite Socony Mobil - 5 for hydrogen sulphide removal offers the benefit of reducing environmental contamination and exhibiting significant applications in industrial operations.
Using traditional weight-loss tests, as well as different electrochemical techniques (potentiodynamic polarization and electrochemical impedance spectroscopy), we investigated the corrosion-inhibition performance of 2,2′-(1,4-phenylenebis(methanylylidene)) bis(N-(3-methoxyphenyl) hydrazinecarbothioamide) (PMBMH) as an inhibitor for mild steel in a 1 M hydrochloric acid solution. The maximum protection efficacy of 0.0005 M of PMBMH was 95%. Due to the creation of a protective adsorption layer instead of the adsorbed H2O molecules and acidic chloride ions, the existence of the investigated inhibitor reduced the corrosion rate and increased the inhibitory efficacy. The inhibition efficiency increased as the inhibitor concentration increased, but it decreased as the temperature increased. The PMBMH adsorption mode followed the Langmuir adsorption isotherm, with high adsorption-inhibition activity. Furthermore, the value of the ∆Gadso indicated that PMBMH contributed to the physical and chemical adsorption onto the mild-steel surface. Moreover, density functional theory (DFT) helped in the calculation of the quantum chemical parameters for finding the correlation between the inhibition activity and the molecular structure. The experimental and theoretical findings in this investigation are in good agreement.
The fundamental mechanism of biochemistry lies on the reaction kinetics, which is determined by the reaction pathways. Interestingly, the reaction pathway is a challenging concept for undergraduate students. Experimentally, it is difficult to observe, and theoretically, it requires some degree of physics knowledge, namely statistical and quantum mechanics. However, students can utilize computational methods to study the reaction kinetics without paying too much attention but not wholly neglecting the comprehension of physics. We hereby provided an approach to study the reaction kinetics based on density-functional calculations. We particularized the study of the isomerization case involving five molecules at three different temperatures and emphasized the importance of the transition state in the study of reaction kinetics. The results we presented were in good agreement with the experiments and provided useful insights to assist students in the application of their knowledge into their research.
We study the reduced dynamics of a pair of nondegenerate oscillators coupled collectively to a thermal bath. The model is related to the trilinear boson model where the idler mode is promoted to a field. Due to nonlinear coupling, the Markovian master equation for the pair of oscillators admits non-Gaussian equilibrium states, where the modes distribute according to the Bose-Einstein statistics. These states are metastable before the nonlinear coupling is taken over by linear coupling between the individual oscillators and the field. The Gibbs state for the individual modes lies in the subspace with infinite occupation quantum number. We present the time evolution of a few states to illustrate the behaviors of the system.
Hybrid material of surgical mask activated carbon (SMAC) and Fe2O3 (SMAC-Fe2O3) composite was prepared by simple co-precipitation method and used as potential material for the remediation of 2,4-dicholrophenol (2,4-DCP). The XRD patterns exhibited the presence of SMAC and Fe2O3, FTIR spectrum showed the FeO-carbon stretching at the wavenumber from 400 to 550 cm-1. UV-Vis DRS results showed the band gap was 1.97 eV and 2.05 eV for SMAC-Fe2O3 and Fe2O3, respectively. The SEM images revealed that the Fe2O3 doped onto the fiber morphology of SMAC. The outcomes of the BET examination exhibited a surface area of 195 m2/g and a pore volume of 0.2062 cm3/g for the SMAC/Fe2O3 composite. The batch mode study shows the maximum adsorption and photocatalytic degradation efficacies which were 97% and 78%, respectively. The experimental data was studied with both linear and nonlinear adsorption isotherm and kinetics models. The nonlinear Langmuir isotherm and pseudo-second-order kinetics (PSOK) models have well fit compared with other models. The Langmuir maximum adsorption capacity (qmax) was found 161.60 mg/g. Thermodynamic analysis shows that the 2,4-DCP adsorption onto SMAC-Fe2O3 was a spontaneous and exothermic process. The PSOK assumes that the adsorption process was chemisorption. The photocatalytic degradation rate constant of 2,4-DCP was calculated using pseudo-first-order kinetics (PFOK) and the rate constant for SMAC-Fe2O3 and Fe2O3 were 0.859 × 10-2 min-1 and 0.616 × 10-2 min-1, correspondingly. In addition, the obtained composite exhibited good reusability after a few cycles. These results confirmed that SMAC-Fe2O3 composite is an effective adsorbent and photocatalyst for removing 2,4-DCP pollutants.
Excessive use of tetracycline (TC) is alarming owing to its increased detection in water systems. In this study, a photocatalyst was developed to degrade TC using a Ce-N-co-doped AC/TiO2 photocatalyst, denoted as Ce/N-AC/TiO2, prepared using the sol-gel method assisted by microwave radiation, speeding up the synthesis process. Ce/N-AC/TiO2 achieved maximum TC degradation of 93.1% under UV light with optimum sorption system conditions of an initial concentration of 10 mg L-1, pH 7, and 30 ℃, under 120 min. Scavenger experiments revealed that holes and superoxide radicals were the active species influencing the photodegradation process. The TC degradation was appropriately fitted with Langmuir isotherms and a pseudo-second-order (PSO) kinetic model. The change in enthalpy (ΔH) (2.43 kJ mol-1), entropy (ΔS) (0.024 kJ mol-1), and Gibbs free energy (ΔG) (- 4.941 to - 5.802 kJ mol-1) suggested that the adsorption process was spontaneous, favourable, and endothermic. Electrostatic interaction, hydrogen bonding, pore-filling, cationic-π, n-π, and π-π interaction were among the interactions involved between TC and Ce/N-AC/TiO2. Furthermore, Ce/N-AC/TiO2 stability was confirmed through 80% removal efficiency even after the fifth reuse cycle. Notably, this work provides new insight into the production of efficient, reusable, and enhanced photocatalysts using a rapid and cost-effective microwave-assisted synthesis process for pollutant remediation.
The aim of this study was to understand the influence of catalyst in thermal degradation behavior of rice husk (RH) in catalytic fast pyrolysis (CFP) process. An iso-conversional Kissinger kinetic model was introduced into this study to understand the activation energy (EA), pre-exponential value (A), Enthalpy (ΔH), Entropy (ΔS) and Gibb's energy (ΔG) of non-catalytic fast pyrolysis (NCFP) and CFP of RH. The study revealed that the addition of natural zeolite catalyst enhanced the rate of devolatilization and decomposition of RH associated with lowest EA value (153.10 kJ/mol) compared to other NCFP and CFP using nickel catalyst. Lastly, an uncertainty estimation was applied on the best fit non-linear regression model (MNLR) to identify the explanatory variables. The finding showed that it had the highest probability to obtain 73.8-74.0% mass loss in CFP of rice husk using natural zeolite catalyst.
Fabrication of functional DNA nanostructures operating at a cellular level has been accomplished through molecular programming techniques such as DNA origami and single-stranded tiles (SST). During implementation, restrictive and constraint dependent designs are enforced to ensure conformity is attainable. We propose a concept of DNA polyominoes that promotes flexibility in molecular programming. The fabrication of complex structures is achieved through self-assembly of distinct heterogeneous shapes (i.e., self-organised optimisation among competing DNA basic shapes) with total flexibility during the design and assembly phases. In this study, the plausibility of the approach is validated using the formation of multiple 3×4 DNA network fabricated from five basic DNA shapes with distinct configurations (monomino, tromino and tetrominoes). Computational tools to aid the design of compatible DNA shapes and the structure assembly assessment are presented. The formations of the desired structures were validated using Atomic Force Microscopy (AFM) imagery. Five 3×4 DNA networks were successfully constructed using combinatorics of these five distinct DNA heterogeneous shapes. Our findings revealed that the construction of DNA supra-structures could be achieved using a more natural-like orchestration as compared to the rigid and restrictive conventional approaches adopted previously.
Metal nanoclusters have been considered as a new class of chemical sensors due to their unique electronic structures and the particular physicochemical properties. The interaction of N2 molecule with neutral and ionic magnesium nanoclusters Mg17q(q=0,±1), as well as neutral magnesium nanoclusters with the centrality of beryllium and calcium Mg16M (M=Be, Mg, and Ca) have been investigated using CAM-B3LYP/6-311+G(d) level of theory in the gas phase. The electronic properties of magnesium nanoclusters were significantly affected by the adsorption of N2 molecule. The NBO analysis revealed a charge transfer from the adsorbed N2 molecule to the nanocluster. Based on the adsorption energies and enthalpies, a thermodynamically favorable chemisorption process was predicted for the Mg16Ca-N2 complex. The negative value of the Gibbs free energy of Mg16Ca-N2 confirmed the spontaneous adsorption process. The estimated recovery time for Mg16Ca-N2 complex for 8-MR (0.089 s) and 4-MRs (0.075 s) illustrated a possible desorption process for N2 molecule from the surface of Mg16Ca. Our finding also revealed the Mg16Ca has the ability to use as a sensor for detection and absorption of N2 molecule.
Pyrolysis of agricultural biomass is a promising technique for producing renewable energy and effectively managing solid waste. In this study, groundnut shell (GNS) was processed at 500 °C in an inert gas atmosphere with a gas flow rate and a heating rate of 10 mL/min and 10 °C/min, respectively, in a custom-designed fluidized bed pyrolytic-reactor. Under optimal operating conditions, the GNS-derived pyrolytic-oil yield was 62.8 wt.%, with the corresponding biochar (19.5 wt.%) and biogas yields (17.7 wt.%). The GC-MS analysis of the GNS-based bio-oil confirmed the presence of (trifluoromethyl)pyridin-2-amine (18.814%), 2-Fluoroformyl-3,3,4,4-tetrafluoro-1,2-oxazetidine (16.23%), 5,7-dimethyl-1H-Indazole (11.613%), N-methyl-N-nitropropan-2-amine (6.5%) and butyl piperidino sulfone (5.668%) as major components, which are used as building blocks in the biofuel, pharmaceutical, and food industries. Furthermore, a 2 × 5 × 1 artificial neural network (ANN) architecture was developed to predict the decomposition behavior of GNS at heating rates of 5, 10, and 20 °C/min, while the thermodynamic and kinetic parameters were estimated using a non-isothermal model-free method. The Popescu method predicted activation energy (Ea) of GNS biomass ranging from 111 kJ/mol to 260 kJ/mol, with changes in enthalpy (ΔH), Gibbs-free energy (ΔG), and entropy (ΔS) ranging from 106 to 254 kJ/mol, 162-241 kJ/mol, and -0.0937 to 0.0598 kJ/mol/K, respectively. The extraction of high-quality precursors from GNS pyrolysis was demonstrated in this study, as well as the usefulness of the ANN technique for thermogravimetric analysis of biomass.
The properties of fibre-reinforced composites are dependent not only on the strength of the reinforcementfibre but also on the distribution of fibre strength and the composition of the chemicals or additivesaddition within the composites. In this study, the tensile properties of abaca fibre reinforced high impactpolystyrene (HIPS) composites, which had been produced with the parameters of fibre loading (30,40,50wt.%), coupling agent maleic anhydride (MAH) (1,2,3 wt%) and impact modifier (4,5,6 wt.%) weremeasured. The optimum amount of MAH is 3% and the impact modifier is 6% and these give the besttensile properties. Meanwhile, Differential Scanning Calorimetry (DSC) was used to study the thermalbehaviour within the optimum conditions of the composites. In this research, glass transitions temperature(Tg) of neat HIPS occurred below the Tg of the optimum condition of composites as the temperature ofan amorphous state. The endothermic peak of the composites was in the range of 430-4350C, includingneat HIPS. It was observed that enthalpy of the abaca fibre reinforced HIPS composites yielded belowthe neat HIPS of 748.79 J/g.
Molecular dynamics reaction simulation showed that the rate constant is not constant over the concentration profile of reactants and products over a fixed temperature regime, and this variation is expressed in terms of the defined reactivity coefficients. The ratio of these coefficients for the forward and backward reactions were found to equal that of the activity coefficient ratio for the product and reactant species. A theory was developed to explain kinetics in general based on these observations. Several other theorems had first to be developed, most striking of all was the inference that the excess Helmholtz free energy was the thermodynamical function which had a direct relation to these activity factors than the Gibbs free energy. The theory is applied to a class of ionic reactions which could not be rationalized using the standard Bjørn-Bjerrum theory of ionic reactions.
This study investigates the thermal decomposition, thermodynamic and kinetic behavior of rice-husk (R), sewage sludge (S) and their blends during co-pyrolysis using thermogravimetric analysis at a constant heating rate of 20 °C/min. Coats-Redfern integral method is applied to mass loss data by employing seventeen models of five major reaction mechanisms to calculate the kinetics and thermodynamic parameters. Two temperature regions: I (200-400 °C) and II (400-600 °C) are identified and best fitted with different models. Among all models, diffusion models show high activation energy with higher R2(0.99) of rice husk (66.27-82.77 kJ/mol), sewage sludge (52.01-68.01 kJ/mol) and subsequent blends (45.10-65.81 kJ/mol) for region I and for rice husk (7.31-25.84 kJ/mol), sewage sludge (1.85-16.23 kJ/mol) and blends (4.95-16.32 kJ/mol) for region II, respectively. Thermodynamic parameters are calculated using kinetics data to assess the co-pyrolysis process enthalpy, Gibbs-free energy, and change in entropy. Artificial neural network (ANN) models are developed and employed on co-pyrolysis thermal decomposition data to study the reaction mechanism by calculating Mean Absolute Error (MAE), Root Mean Square Error (RMSE) and coefficient of determination (R2). The co-pyrolysis results from a thermal behavior and kinetics perspective are promising and the process is viable to recover organic materials more efficiently.
The performance of aptamers as versatile tools in numerous analytical applications is critically dependent on their high target binding specificity and selectivity. However, only the technical or methodological aspects of measuring aptamer-target binding affinities are focused, ignoring the equally important mathematical components that play pivotal roles in affinity measurements. In this study, we aim to provide a comprehensive review regarding the utilization of different mathematical models and equations, along with a detailed description of the computational steps involved in mathematically deriving the binding affinity of aptamers against their specific target molecules. Mathematical models ranging from one-site binding to multiple aptameric binding site-based models are explained in detail. Models applied in several different approaches of affinity measurements such as thermodynamics and kinetic analysis, including cooperativity and competitive-assay based mathematical models have been elaborately discussed. Mathematical models incorporating factors that could potentially affect affinity measurements are also further scrutinized.