Search results for: kinetically

Authors: Olumayede Emmanuel Gbenga, Adeniyi Azeez Adebayo

Abstract:

Carbonyls are the first-generation products from tropospheric degradation reactions of volatile organic compounds (VOCs). This computational study examined the mechanism of removal of carbonyls from the atmosphere via hydroxyl radical. The kinetics of the reactions were computed from the activation energy (using enthalpy (ΔH**) and Gibbs free energy (ΔG**). The minimum energy path (MEP) analysis reveals that in all the molecules, the products have more stable energy than the reactants, which implies that the forward reaction is more thermodynamically favorable. The hydrogen abstraction of the aromatic aldehyde, especially without methyl substituents, is more kinetically favorable compared with the other aldehydes in the order of aromatic (without methyl or meta methyl) > alkene (short chain) > diene > long-chain aldehydes. The activation energy is much lower for the forward reaction than the backward, indicating that the forward reactions are more kinetically stable than their backward reaction. In terms of thermodynamic stability, the aromatic compounds are found to be less favorable in comparison to the aliphatic. The study concludes that the chemistry of the carbonyl bond of the aldehyde changed significantly from the reactants to the products.

Keywords: Atmospheric carbonyls, oxidation, mechanism, kinetic, thermodynamic.

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Authors: Reza Bazargan-Lari, Mohammad Ebrahim Bahrololoom, Afshin Nemati

Abstract:

Heavy metals have bad effects on environment and soils and it can uptake by natural HAP .natural Hap is an inexpensive material that uptake large amounts of various heavy metals like Zn (II) .Natural HAP (N-HAP), extracted from bovine cortical bone ash, is a good choice for substitution of commercial HAP. Several experiments were done to investigate the sorption capacity of Zn (II) to N-HAP in various particles sizes, temperatures, initial concentrations, pH and reaction times. In this study, the sorption of Zinc ions from a Zn solution onto HAP particles with sizes of 1537.6 nm and 47.6 nm at three initial pH values of 4.50, 6.00 and 7.50 was studied. The results showed that better performance was obtained through a 47.6 nm particle size and higher pH values. The experimental data were analyzed using Langmuir, Freundlich, and Arrhenius equations for equilibrium, kinetic and thermodynamic studies. The analysis showed a maximum adsorption capacity of NHAP as being 1.562 mmol/g at a pH of 7.5 and small particle size. Kinetically, the prepared N-HAP is a feasible sorbent that retains Zn (II) ions through a favorable and spontaneous sorption process.

Keywords: Natural Hydroxyapatite, Heavy metal ions, Adsorption, Zn removal, kinetic model, bone ash

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Authors: M. Hossain, H. P. Zhu, A. B. Yu

Abstract:

This paper presents a numerical investigation of regime transition of flow of ellipsoidal particles and a comparison with that of spherical particle assembly. Particle assemblies constituting spherical and ellipsoidal particle of 2.5:1 aspect ratio are examined at separate instances in similar flow conditions in a shear cell model that is numerically developed based on the discrete element method. Correlations among elastically scaled stress, kinetically scaled stress, coordination number and volume fraction are investigated, and show important similarities and differences for the spherical and ellipsoidal particle assemblies. In particular, volume fractions at points of regime transition are identified for both types of particles. It is found that compared with spherical particle assembly, ellipsoidal particle assembly has higher volume fraction for the quasistatic to intermediate regime transition and lower volume fraction for the intermediate to inertial regime transition. Finally, the relationship between coordination number and volume fraction shows strikingly distinct features for the two cases, suggesting that different from spherical particles, the effect of the shear rate on the coordination number is not significant for ellipsoidal particles. This work provides a glimpse of currently running work on one of the most attractive scopes of research in this field and has a wide prospect in understanding rheology of more complex shaped particles in light of the strong basis of simpler spherical particle rheology.

Keywords: Discrete element method, granular rheology, non-spherical particles, regime transition

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Authors: O. Onoriode Emoyan, E. Eyitemi Akporhonor, Charles Otobrise

Abstract:

Polycyclic Aromatic Hydrocarbons (PAHs) are formed mainly because of incomplete combustion of organic materials during industrial, domestic activities or natural occurrence. Their toxicity and contamination of terrestrial and aquatic ecosystem have been established. However, with limited validity index, previous research has focused on PAHs isomer pair ratios of variable physicochemical properties in source identification. The objective of this investigation was to determine the empirical validity of Pearson Correlation Coefficient (PCC) and Cluster Analysis (CA) in PAHs source identification along soil samples of different land uses. Therefore, 16 PAHs grouped, as Endocrine Disruption Substances (EDSs) were determined in 10 sample stations in top and sub soils seasonally. PAHs was determined the use of Varian 300 gas chromatograph interfaced with flame ionization detector. Instruments and reagents used are of standard and chromatographic grades respectively. PCC and CA results showed that the classification of PAHs along pyrolitic and petrogenic organics used in source signature is about the predominance PAHs in environmental matrix. Therefore, the distribution of PAHs in the studied stations revealed the presence of trace quantities of the vast majority of the sixteen PAHs, which may ultimately inhabit the actual source signature authentication. Therefore, factors to be considered when evaluating possible sources of PAHs could be; type and extent of bacterial metabolism, transformation products/substrates, and environmental factors such as salinity, pH, oxygen concentration, nutrients, light intensity, temperature, co-substrates, and environmental medium are hereby recommended as factors to be considered when evaluating possible sources of PAHs.

Keywords: Comparative correlation, kinetically, polynuclear aromatic hydrocarbons, thermodynamically- favored PAHs, sources evaluation.

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

Abstract:

Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO hydro-deoxygenation, DFT, liquid fuels, XPS, XTL.

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