An exact and vigorous kinetic Monte Carlo simulation to determine the properties of bimodal HDPE synthesized with a dual-site metallocene catalyst.

A vigorous and progressed Monte Carlo strategy was developed to precisely simulate the ethylene and 1-butene copolymerization within the presence of hydrogen by dual-site metallocene catalyst. The results showed up that the ethylene and 1-butene consumption rates at the second catalyst site were approximately 5 times higher than at the first site, and hydrogen transfer rates at the first catalyst site were over 3 times more rapid than at the second site. It was found that the most elevated molar percentage of 1-butene inside the copolymers synthesized from the second site was around 12% and within the copolymers gotten from the first site was around 2%. At a steady hydrogen concentration, with 8 times increase in the 1-butene concentration within the initial feed, the overall weight average molecular weight (M‾w) and an overall number average molecular weight (M‾n) extended by approximately 50% and 40%, respectively. Besides, at a consistent 1-butene concentration, with 8 times increase in the concentration of hydrogen, M‾w and M‾n diminished by approximately 18% and 22%, separately. Due to the synthesis of two groups of chains with distinct molecular weights, the overall dispersity (D) was slightly higher than the dispersity resulting from each catalyst site (1.5-2.1). With increasing 1-butene concentrations, the overall bimodal molecular weight distribution (MWD) widened, and the peak sizes grew smaller and moved towards higher molecular weights. As hydrogen concentration increased, peaks became taller and move toward shorter chain lengths. It was observed that the first site created chain lengths between 102 and 103 while the second site generated chain lengths between 102 and 106. As the concentration of 1-butene was increased in the initial feed, the number of short chain branching per 1000 carbon atoms (SCB/1000C) increased from 10 to 50. Compared to the first site, there were 5 times as many SCBs at the chains produced from the second site. By diminishing the ratio of ethylene to 1-butene, the melt index (MI) tended towards smaller numbers (0.2≤MI≤2). With an increase in the ratio of ethylene to 1-butene and ethylene to hydrogen, the weight fraction of crystals raised from 67.4 to 69.5% and diminished from 71 to 69.5%, respectively. At last, increasing the temperature led to a diminish in molecular weight, a narrowing of the bimodal MWD, an increment within the thickness and weight fraction of crystals, and an increment within the density of HDPE.

Combination of nZVI and DC for the in-situ remediation of chlorinated ethenes: An environmental and economic case study.

Over the past two decades, the use of nanoscale zero-valent iron (nZVI) has emerged as a standard method of contaminated groundwater remediation. The effectiveness of this method depends on key intrinsic hydrogeological parameters, which can affect both reactivity of the nanoparticles and their migration in the aquifer. In the case of low hydraulic permeability, the migration of nanoparticles is limited, which negatively influences remediation. An application of nZVI reinforced with a DC electric field led to a significant increase in the efficiency of remediation, as demonstrated by long-term monitoring at a former industrial site in Horice (Czech Republic). For the method testing, a 12 × 9 m polygon was defined around well IS4, where the original contamination was predominantly composed of DCE (7300 µg/l), and with a total concentration of chlorinated ethenes of 8880 µg/l. During the first stage of the activities, 49 kg of nZVI was injected and monitored for two years. Subsequently, the electrodes were installed, and for three years, the synergistic action of nZVI within an applied DC field was monitored. Based on 32 monitoring campaigns performed over the six years, the combined method was compared with an application of the only nZVI in technical, environmental and economic terms. Technically, the method requires annual reinstallation of anodes as a result of their oxidative disintegration. Environmentally, the method provides significantly improved chlorinated ethane reduction, remediation of low permeable zones, and extended efficiency. Economically, the method is five times cheaper when compared to the nZVI used alone.

Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model.

The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT), local excitations, and triplet excited states, several ab initio and density functional theory (DFT) methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE) complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT) with the Tamm-Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed.

Shale Gas Implications for C2-C3 Olefin Production: Incumbent and Future Technology.

Substantial natural gas liquids recovery from tight shale formations has produced a significant boon for the US chemical industry. As fracking technology improves, shale liquids may represent the same for other geographies. As with any major industry disruption, the advent of shale resources permits both the chemical industry and the community an excellent opportunity to have open, foundational discussions on how both public and private institutions should research, develop, and utilize these resources most sustainably. This review summarizes current chemical industry processes that use ethane and propane from shale gas liquids to produce the two primary chemical olefins of the industry: ethylene and propylene. It also discusses simplified techno-economics related to olefins production from an industry perspective, attempting to provide a mutually beneficial context in which to discuss the next generation of sustainable olefin process development.

Efficient input variable selection for soft-senor design based on nearest correlation spectral clustering and group Lasso.

Appropriate input variables have to be selected for building highly accurate soft sensor. A novel input variable selection method based on nearest correlation spectral clustering (NCSC) has been proposed, and it is referred to as NCSC-based variable selection (NCSC-VS). Although NCSC-VS can select appropriate input variables, a lot of parameters have to be tuned carefully for selecting proper variables. The present work proposes a new methodology for efficient input variable selection by integrating NCSC and group Lasso. The proposed NCSC-based group Lasso (NCSC-GL) can not only reduce the number of tuning parameters but also achieve almost the same performance as NCSC-VS. The usefulness of the proposed NCSC-GL is demonstrated through applications to soft sensor design for a pharmaceutical process and a chemical process.

Comparative life cycle assessment of biogas plant configurations for a demand oriented biogas supply for flexible power generation.

The environmental performance of biogas plant configurations for a demand - oriented biogas supply for flexible power generation is comparatively assessed in this study. Those configurations indicate an increased energy demand to operate the operational enhancements compared to conventional biogas plants supplying biogas for baseload power generation. However, findings show that in contrast to an alternative supply of power generators with natural gas, biogas supplied on demand by adapted biogas plant configurations saves greenhouse gas emissions by 54-65 g CO(2-eq) MJ(-1) and primary energy by about 1.17 MJ MJ(-1). In this regard, configurations with flexible biogas production profit from reduced biogas storage requirements and achieve higher savings compared to configurations with continuous biogas production. Using thicker biogas storage sheeting material reduces the methane permeability of up to 6m(3) d(-1) which equals a reduction of 8% of the configuration's total methane emissions.

Modelling microbial dechlorination of trichloroethene: investigating the trade-off between quality of fit and parameter reliability.

This work puts forth a heuristic approach for investigating compromises between quality of fit and parameter reliability for the Monod-type kinetics employed to model microbial reductive dechlorination of trichloroethene. The methodology is demonstrated with three models of increasing fidelity and complexity. Model parameters were estimated with a stochastic global optimization algorithm, using scarce and inherently noisy experimental data from a mixed anaerobic microbial culture, which dechlorinated trichloroethene to ethene completely. Parameter reliability of each model was assessed using a Monte Carlo technique. Finally, an alternate quantity of applied interest was evaluated in order to assist with model discrimination. Results from the application of our approach suggest that the modeler should examine the implementation of conceptually simple models, even if they are a crude abstraction of reality, as they can be computationally less demanding and adequately accurate when model performance is assessed with criteria of applied interest, such as chloroethene elimination time.

Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules.

Quantum-chemical computational methods are benchmarked for their ability to describe conical intersections in a series of organic molecules and models of biological chromophores. Reference results for the geometries, relative energies, and branching planes of conical intersections are obtained using ab initio multireference configuration interaction with single and double excitations (MRCISD). They are compared with the results from more approximate methods, namely, the state-interaction state-averaged restricted ensemble-referenced Kohn-Sham method, spin-flip time-dependent density functional theory, and a semiempirical MRCISD approach using an orthogonalization-corrected model. It is demonstrated that these approximate methods reproduce the ab initio reference data very well, with root-mean-square deviations in the optimized geometries of the order of 0.1 Å or less and with reasonable agreement in the computed relative energies. A detailed analysis of the branching plane vectors shows that all currently applied methods yield similar nuclear displacements for escaping the strong non-adiabatic coupling region near the conical intersections. Our comparisons support the use of the tested quantum-chemical methods for modeling the photochemistry of large organic and biological systems.

Simple, low-cost styrene-ethylene/butylene-styrene microdevices for electrokinetic applications.

Styrene-ethylene/butylene-styrene (SEBS) copolymers combine thermoplastic and elastomeric properties to provide microdevices with the advantageous properties of hard thermoplastics and ease of fabrication similar to PDMS. This work describes the electrical surface properties of SEBS block copolymers using current monitoring experiments to determine zeta potential. We show that SEBS exhibits a stable and relatively high zeta potential magnitude compared to similar polymers. The zeta potential of SEBS is stable when stored in air over time, and no significant differences are observed between different batches and devices, demonstrating reproducibility of results. We show zeta potential trends for varying pH and counterion concentration and demonstrate that SEBS has a repeatable surface potential comparable to glass. Oxygen plasma treatment greatly increases the zeta potential magnitude immediately following treatment before undergoing a moderate hydrophobic recovery to a stable zeta potential. SEBS copolymers also offer simple rapid prototyping fabrication and mass production potential. The presented electrokinetic properties combined with simple, low-cost fabrication of microdevices make SEBS a quality material for electrokinetic research and application development.

Unusual two-stage kinetics of ethylene adsorption on Si(100) unraveled by surface optical spectroscopy and Monte Carlo simulation.

The adsorption of ethylene on a Si(100)-2×1 surface in an ultrahigh vacuum has been monitored at room temperature by use of real-time surface differential reflectance spectroscopy, which clearly demonstrated that the adsorption follows a two-stage process. About half a monolayer is obtained for 1 L, while the second stage is much slower, yielding the complete monolayer for an exposure of ∼400 L. The kinetics over the full range has been successfully reproduced by a Monte Carlo calculation. The key point of this two-stage adsorption kinetic lies in the reduced adsorption probability (by a factor of several hundreds) on the Si dimers, neighbors of dimers which have already reacted, with respect to the adsorption probability on isolated dimers. This new kind of adsorption kinetics, due to a repulsion between already adsorbed molecules and additional molecules impinging on the surface, makes it a textbook case for a "cooperative" adsorption process.

Economic feasibility of the sugar beet-to-ethylene value chain.

As part of a long-term strategy toward renewable feedstock, a feasibility study into options for the production of bioethylene by integrating the sugar beet-to-ethanol-to-ethylene value chain. Seven business cases were studied and tested for actual economic feasibility of alternative sugar-to-ethanol-to-ethylene routes in comparison to fossil-fuel alternatives. An elaborate model was developed to assess the relevant operational and financial aspects of each business case. The calculations indicate that bioethylene from sugar beet is not commercially viable under current market conditions. In light of expected global energy and feedstock prices it is also reasonable to expect that this will not change in the near future. To consider biorenewable sources as starting material, they need to be low in cost (compared to sugar beets) and also require less capital and energy-intensive methods for the conversion to chemicals. In general, European sugar prices will be too high for many chemical applications. Future efforts for in sugar-to-chemicals routes should, therefore, focus on integrated process routes and process intensification and/or on products that contain a significant part of the original carbohydrate backbone.

Expedient synthesis of α-substituted fluoroethenes.

A mild and efficient synthesis of 1-aryl-1-fluoroethenes from benzothiazolyl (aryl)fluoromethyl sulfones and paraformaldehyde, under DBU- or Cs(2)CO(3)-mediated conditions at room temperature, is described. A comparable diethyl fluoro(naphthalen-2-yl)methylphosphonate reagent does not react with paraformaldehyde under these mild conditions. The utility of the methodology for synthesis of terminal α-fluoroalkenes bearing electron-withdrawing functionalities is also shown.

Computational study of the effect of confinement within microporous structures on the activity and selectivity of metallocene catalysts for ethylene oligomerization.

The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite (host) frameworks displaying different pore sizes, have been studied as solid hosts: mazzite (MAZ), AIPO-8 (AET), UTD-1F (DON), faujasite (FAU), and VPI-5 (VFI). Intermediates and transition states involved in the ethylene trimerization reaction catalyzed by a Ti-based catalyst [(η(5)-C(5)H(4)CMe(2)C(6)H(5))TiCl(3)/MAO] have been used as sorbates (guests). We have demonstrated linear correlations with slope a(H,j) between the adsorption enthalpy and the molecular volume V(m) of the sorbates, each holding for a given microporous host below a host-specific threshold V(mmax,j). Beyond this maximal molecular volume, the adsorption vanishes due to steric exclusion. a(H,j) increases, and V(mmax,j) decreases with decreasing host pore size, in line with the confinement concept. We moreover showed that, in the limit of vanishing loading (Henry regime), the enthalpies and entropies of adsorption in a given host are linearly correlated. We have defined a host-specific confinement compensation temperature a(j), which refers to a temperature where the stabilizing adsorption enthalpic interactions are canceled out against the loss in entropy. However, calculated a(j) are much larger than the operating temperatures. With a setup microkinetic model, we predict that the activity and selectivity of the confined Ti-catalyst in ethylene oligomerization can be significantly altered with respect to homogeneous phase conditions, since the adsorption free energies of transition states and intermediates also become functions of a(H,j) and V(m). We have applied this theory to predict the optimum host pore size to get maximum α-octene production, instead of α-hexene, which is primarily produced in the homogeneous phase. We also predict a significantly increased activity for confined catalysts.

Aerobic biodegradation of chlorinated ethenes in a fractured bedrock aquifer: quantitative assessment by compound-specific isotope analysis (CSIA) and reactive transport modeling.

A model-based analysis of concentration and isotope data was carried out to assess natural attenuation of chlorinated ethenes in an aerobic fractured bedrock aquifer. Tetrachloroethene (PCE) concentrations decreased downgradient of the source, but constant delta13C signatures indicated the absence of PCE degradation. In contrast, geochemical and isotopic data demonstrated degradation of trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) under the prevailing oxic conditions. Numerical modeling was employed to simulate isotopic enrichment of chlorinated ethenes and to evaluate alternative degradation pathway scenarios. Existing field information on groundwater flow, solute transport, geochemistry, and delta13C signatures of the chlorinated ethenes was integrated via reactive transport simulations. The results provided strong evidence for the occurrence of aerobic TCE and DCE degradation. The chlorinated ethene concentrations together with stable carbon isotope data allowed us to reliably constrain the assessment of the extent of biodegradation at the site and plume simulations quantitatively linked aerobic biodegradation with isotope signatures in the field. Our investigation provides the first quantitative assessment of aerobic biodegradation of chlorinated ethenes in a fractured rock aquifer based on compound specific stable isotope measurements and reactive transport modeling.

Heavier group 2 metals and intermolecular hydroamination: a computational and synthetic assessment.

A density functional theory assessment of the use of the group 2 elements Mg, Ca, Sr, and Ba for the intermolecular hydroamination of ethene indicated that the efficiency of the catalysis is dependent upon both the polarity and the deformability of the electron density within the metal-substituent bonds of key intermediates and transition states. The validity of this analysis was supplemented by a preliminary study of the use of group 2 amides for the intermolecular hydroamination of vinyl arenes. Although strontium was found to provide the highest catalytic activity, in line with the expectation provided by the theoretical study, a preliminary kinetic analysis demonstrated that this is possibly a consequence of the increased radius and accessibility of this cation rather than a reflection of a reduced barrier for rate-determining alkene insertion.

Mass spectrometric characterization of 4-oxopentanoic acid and gas-phase ion fragmentation mechanisms studied using a triple quadrupole and time-of-flight analyzer hybrid system and density functional theory.

4-Oxopentanoic acid was characterized experimentally by electrospray ionization using a triple quadrupole and time-of-flight analyzer hybrid system. This compound was chosen as a model substance for small organic compounds bearing an acetyl and a carboxyl group. Collision-induced dissociation experiments at different activation energies were performed to elucidate possible fragmentation pathways. These pathways were also studied on the theoretical level using density functional theory (DFT) B3LYP/6-311++G(3df,3pd)//B3LYP/6-31+G(d)+ZPVE calculations. CO2 ejection from the [M-H](-) anion of 4-oxopentanoic acid was observed and the fragmentation pathway studied by DFT reveals a new concerted mechanism for CO2 elimination accompanied by an intramolecular proton transfer within a pentagonal transition state structure. Successive elimination of water and CO from the [M-H](-) anion of 4-oxopentanoic acid was also observed. A rearrangement in the primary deprotonated ketene anion produced after water elimination was found on the theoretical level and leads to CO elimination from the primary product anion [M-H-H2O](-). Energy diagrams along the reaction coordinates of the fragmentation pathways are presented and discussed in detail. Mulliken charge distributions of some important structures are presented.

Molecular dynamics simulation of unsaturated lipid bilayers at low hydration: parameterization and comparison with diffraction studies.

A potential energy function for unsaturated hydrocarbons is proposed and is shown to agree well with experiment, using molecular dynamics simulations of a water/octene interface and a dioleoyl phosphatidylcholine (DOPC) bilayer. The simulation results verify most of the assumptions used in interpreting the DOPC experiments, but suggest a few that should be reconsidered. Comparisons with recent results of a simulation of a dipalmitoyl phosphatidylcholine (DPPC) lipid bilayer show that disorder is comparable, even though the temperature, hydration level, and surface area/lipid for DOPC are lower. These observations highlight the dramatic effects of unsaturation on bilayer structure.