Sensitivity Analysis of One-Dimensional Multiphysics Simulation of CO2 Electrolysis Cell.

Electrochemical (EC) carbon dioxide (CO2) reduction, where CO2 is converted to value-added products such as fuel precursors, plays a key role in helping the world's energy system reach net-zero carbon emissions. Simulations of EC cells provide valuable insight into their operation since detailed experimental results on short length and time scales are difficult to obtain. In this work, we construct a 1D simulation of a membrane-electrode-assembly EC cell for CO2 reduction, using a porous silver gas diffusion cathode. We run the simulation under different electrolyte conditions, showing how the cell performance is affected. We then perform a sensitivity analysis of all input parameters to the simulation, which has not been presented before in the literature. We show that the CO partial current density (i CO) is significantly affected by each input parameter of the simulation. i CO is most sensitive to EC kinetic parameters (i 0/α) of all EC reactions, with a 1% change in α resulting in up to 6% change in i CO. Since there is uncertainty associated with the value of each input parameter, this indicates that infidelity between experiment and simulation is likely, and thus, caution should be practiced when comparing experimental results to simulation results. Further, we show that the large range of conditions simulated in literature helps to explain the large variance in reported values of i 0 and α. The results of this paper demonstrate the potential of sensitivity analysis methods to quickly optimize aspects of cell performance (CO2 utilization, Faradaic efficiency, etc.).

Steady states and kinetic modelling of the acid-catalysed ethanolysis of glucose, cellulose, and corn cob to ethyl levulinate.

Ethyl levulinate is a promising advanced biofuel and platform chemical that can be derived from lignocellulosic biomass by ethanolysis processes. It can be blended with both diesel and gasoline and, thus, used in conventional engines and infrastructure. Previously, it has been shown that alkyl levulinate/alcohol/alkyl ether mixtures exhibit significantly enhanced fuel properties relative to any of the individual fuel components, particularly when blended with conventional hydrocarbon liquid fuels. Consequently, this study specifically quantifies the three primary components of the alcoholysis reaction mixture: ethyl levulinate, diethyl ether, and ethanol. The steady state and kinetic phase fractions of ethyl levulinate and diethyl ether produced from glucose, cellulose, and corn cob with 0.5-2 mass% sulphuric acid in ethanol are determined for 5, 10, and 20 mass% of feedstock at 150 °C. Knowledge of the steady state equilibrium mixture fraction is specifically targeted due to its importance in assessing commercial-scale production and in modelling analysis as: (i) it defines the maximum yield possible at a given condition, and (ii) it is equitable to the minimum free energy state. Maximum steady state yields (mass%) of ethyl levulinate of (46.6 ± 3.7), (50.2 ± 5.4), and (27.0 ± 1.9)% are determined for glucose, cellulose, and corn cob, respectively. The conversion of glucose and cellulose to ethyl levulinate in the presence of ethanol and sulphuric acid is shown to be a catalytic process, where the ethyl levulinate yield is not dependent on the acid concentration. For corn-cob biomass, in a new and contrasting finding, the ethyl levulinate yield is shown to strongly depend on the acid concentration. This effect is also observed in the fractions of diethyl ether formed, providing strong evidence that the hydrogen cation is not being replenished in the ethanolysis process and the overall reaction with corncob is not wholly catalytic. Thus, for the acid catalysed alcoholysis of lignocellulosic biomass, acid concentration must be scaled with feedstock concentration. The critical corn cob-to-acid ratio that maximises ethyl levulinate yields while minimizing the formation of undesired co-products (diethyl ether) is in the range 10-20 : 1 at 150 °C. A detailed, hierarchical, mass-conserved chemical kinetic model capable of accurately predicting the relative abundance of the three primary components of the ethanolysis reaction: ethyl levulinate, diethyl ether, and ethanol, from the biochemical composition of the feedstock, is elucidated and validated.

Hemicellulose pyrolysis: mechanism and kinetics of functionalized xylopyranose.

This work analyzes the thermochemical kinetic influence of the most prominent functionalizations of the ß-D-xylopyranose motif, specifically 4-methoxy, 5-carboxyl, and 2-O-acetyl, regarding the pyrolytic depolymerization mechanism. The gas-phase potential energy surface of the initial unimolecular decomposition reactions is computed with M06-2X/6-311++G(d,p), following which energies are refined using the G4 and CBS-QB3 composite methods. Rate constants are computed using the transition state theory. The energies are integrated within the atomization method to assess for the first time the standard enthalpy of formation of ß-D-xylopyranose, 4-methoxy-5-carboxy-ß-D-xylopyranose, and 2-O-acetyl-ß-D-xylopyranose: -218.2, -263.1, and -300.0 kcal mol-1, respectively. For all isomers, the activation enthalpies of ring-opening are considerably lower, 43.8-47.5 kcal mol-1, than the ring-contraction and elimination processes, which show higher values ranging from 61.0-81.1 kcal mol-1. The functional groups exert a notable influence, lowering the barrier of discrete elementary reactions by 1.9-8.3 kcal mol-1, increasing thus the reaction rate constant by 0-4 orders of magnitude relative to unsubstituted species. Regardless of the functionalization, the ring-opening process appears to be the most kinetically favored, characterized by a rate constant on the order 101 s-1, exceeding significantly the values associated with ring-contraction and elimination, which fall in the range 10-4-10-10 s-1. This analysis shows the decomposition kinetics are contingent on the functionalization specificities and the relative orientation of reacting centers. A relatively simple chemical reactivity and bonding analysis partially support the elaborated thermokinetic approach. These insights hold significance as they imply that many alternative decomposition routes can be quickly, yet accurately, informed in forthcoming explorations of potential energy surfaces of diverse hemicellulose motifs under pyrolysis conditions.

Ab Initio and Kinetic Modeling of ß-d-Xylopyranose under Fast Pyrolysis Conditions.

Lignocellulosic biomass is an abundant renewable resource that can be upgraded to chemical and fuel products through a range of thermal conversion processes. Fast pyrolysis is a promising technology that uses high temperatures and fast heating rates to convert lignocellulose into bio-oils in high yields in the absence of oxygen. Hemicellulose is one of the three major components of lignocellulosic biomass and is a highly branched heteropolymer structure made of pentose, hexose sugars, and sugar acids. In this study, ß-d-xylopyranose is proposed as a model structural motif for the essential chemical structure of hemicellulose. The gas-phase pyrolytic reactivity of ß-d-xylopyranose is thoroughly investigated using computational strategies rooted in quantum chemistry. In particular, its thermal degradation potential energy surfaces are computed employing Minnesota global hybrid functional M06-2X in conjunction with the 6-311++G(d,p) Pople basis set. Electronic energies are further refined by performing DLPNO-CCSD(T)-F12 single-point calculations on top of M06-2X geometries using the cc-pVTZ-F12 basis set. Conformational analysis for minima and transition states is performed with state-of-the-art semiempirical quantum chemical methods coupled with metadynamics simulations. Key thermodynamic quantities (free energies, barrier heights, enthalpies of formation, and heat capacities) are computed. Rate coefficients for the initial steps of thermal decomposition are computed by means of reaction rate theory. For the first time, a detailed elementary reaction kinetic model for ß-d-xylopyranose is developed by utilizing the thermodynamic and kinetic information acquired from the aforementioned calculations. This model specifically targets the initial stages of ß-d-xylopyranose pyrolysis in the high-pressure limit, aiming to gain a deeper understanding of its reaction kinetics. This approach establishes a systematic strategy for exploring reactive pathways, evaluating competing parallel reactions, and selectively accepting or discarding pathways based on the analysis. The findings suggest that acyclic d-xylose plays a significant role as an intermediary in the production of key pyrolytic compounds during the pyrolysis of xylose. These compounds include furfural, anhydro-d-xylopyranose, glycolaldehyde, and dihydrofuran-3(2H)-one.

A passive leg-support exoskeleton adversely affects reactive balance after simulated slips and trips on a treadmill.

Occupational exoskeletons have become more prevalent as an ergonomic control to reduce the physical demands of workers. While beneficial effects have been reported, there is relatively little evidence regarding potential adverse effects of exoskeletons on fall risk. The purpose of this study was to investigate the effects of a leg-support exoskeleton on reactive balance after simulated slips and trips. Six participants (three females) used a passive, leg-support exoskeleton that provided chair-like support in three experimental conditions (no exoskeleton, low-seat setting, high-seat setting). In each of these conditions, participants were exposed to 28 treadmill perturbations from an upright standing posture simulating a backward slip (0.4-1.6 m/s) or a forward trip (0.75-2.25 m/s). The exoskeleton increased the probability of a failed recovery, and adversely affected reactive balance kinematics, after simulated slips and trips. After simulated slips, the exoskeleton decreased initial step length 0.039 m, decreased mean step speed 0.12 m/s, anteriorly displaced touchdown position of the initial recovery step by 0.045 m, and decreased PSIS height at initial step touchdown by 1.7 % sof its standing height. After simulated trips, the exoskeleton increased trunk angle at step 2.4 degrees, and decreased initial step length 0.033 m. These effects appeared to result from the exoskeleton inhibiting regular stepping motion due to its posterior placement on the lower limbs, added mass, and mechanical constraints on participant movement. Our results suggest care may be needed among leg-support exoskeleton users when at risk of slips or trips and motivate potential exoskeleton design modifications to reduce fall risk.

The Role of Life Satisfaction in Predicting Youth Violence and Offending: A Prospective Examination.

Life satisfaction in adolescence has been shown to protect against numerous negative outcomes (e.g., substance use, sexual risk-taking), but limited work has directly explored the relationship between life satisfaction and youth violence and offending. As such, we conducted a prospective assessment to explore this relationship among community (n = 334) and at-risk youth (n = 99). Findings suggest life satisfaction is significantly associated with decreased offending and violence within both samples and adds incremental value above established risk factors in predicting violent and total offending among community youth. Furthermore, moderation analyses indicate that the protective value of life satisfaction is greater for youth with high callous-unemotional traits. Mediation analyses suggest that youth who are unsatisfied with their lives may seek out substance use, in turn elevating risk of offending. Together, these findings indicate that efforts to improve overall life satisfaction may help prevent adolescent offending. However, future research is needed.

Mechanism and theory of d-glucopyranose homogeneous acid catalysis in the aqueous solution phase.

A detailed systematic theoretical study of the mechanism of the homogeneous Brønsted-acid catalysis of d-glucose in aqueous solution phase ("acid hydrolysis") is reported. G4MP2 with the SMD solvation model at B3LYP/6-31G(2df,p) are employed to compute the free energies of the molecular and ionic species pertaining to the isomerization, protonation, hydrogen cation transfer and decomposition processes of d-glucopyranose in aqueous solution phase. This information is used to hypothesise a reaction mechanism that is of improved accuracy and completeness from the existing art. It is found that rotation of the d-glucose alkyl carbon-carbon bond is a facile process and is very important to the subsequent catalytic mechanism. This rotation produces two rotameric isomers which are of notably different thermodynamic stability and reactivity, even with regard to the products of this acid catalysis. As a low energy process (ΔG‡ = ∼3.8-6.7 kcal mol-1), the alkyl carbon-carbon bond may rotate toward the hydroxyl group at the adjacent "4" position reducing the energy required to protonate that position by 3.0-7.2 kcal mol-1 (or 15-30%). The combination of two rotomeric isomers with the six structural isomers owing to the oxygen atoms, means that protonated d-glucose cations embark on a complex competition of interconversion and decomposition that is both thermodynamically and kinetically influenced. The calculations support the hypothesis that the acid-catalysed hydrolysis of d-glucose may yield a number of platform chemicals that have not previously been suggested. These include the prospect of three isomers of 5-hydroxymethylfurfural (HMF); 5-(hydroxymethyl)furan-2-carbaldehyde, 5-(hydroxymethyl)furan-3-carbaldehyde and 5-(hydroxymethyl)furan-4-carbaldehyde. Vibrational spectra of these HMF isomers are also computed and compared to experimentally determined infrared spectra of "humins". On this basis, it is cautiously speculated that the alternative HMF isomers, may be monomeric constituent of the polymeric "humins".

Becoming the Standard: Expanding the Conventional Use of Interventional Embolization for Ruptured Pulmonary Artery Aneurysms.

Behcet's disease is inflammatory vasculitis that has a high incidence of mortality in patients with pulmonary artery aneurysm (PAA) formation. Traditionally, patients with Behcet's disease and PAA rupture undergo invasive surgical management. Surgical intervention; however, has been shown to have high complication, failure, and mortality rates. It has become a more contemporary practice to utilize the interventional embolization of pulmonary artery aneurysms (PAAs) in patients with Behcet's disease and other various etiologies because of its inherent minimally invasive nature and decreased risk for complications. The management paradigm for treating PAAs has shifted toward endovascular embolization even in severe or emergent cases where surgical management was once thought to be the standard. The following case is a testimony to the practicality of interventional embolization in the setting of a symptomatic patient presenting with PAAs.

Incremental and Predictive Validity of the Antisocial Process Screening Device in a Community Sample of Male and Female Ethnic Minority and Caucasian Youth.

The Antisocial Process Screening Device (APSD) is a well-supported tool for assessing psychopathic features in youth. However, most research with the APSD has been derived from clinical and forensic samples comprised mainly of male Caucasian and African American adolescents. In this prospective study, the incremental and predictive validity of the self-report APSD for violent and non-violent offending was examined in an ethnically diverse community sample of male and female youth (N = 335) aged 12 to 14. High-school students from a moderate sized city in Western Canada completed the self-report APSD and then completed the Self-Report of Offending 6 months later. Receiver Operating Characteristics analysis indicated that APSD total and subscale scores were predictive of violent and non-violent offending at 6-month follow-up with moderate to large effect sizes. In addition, total scores on the APSD added incremental predictive utility above and beyond traditional criminogenic predictors of youth offending (i.e., prior offending, delinquent peer affiliation, poor school achievement, substance use, low parental monitoring). Although sex differences emerged in the predictive utility of the Impulsivity subscale of the APSD vis-à-vis violent offending, sex did not moderate the relationship between APSD total, Narcissism, or Callous/Unemotional scores and offending. In addition, the predictive utility of the APSD did not vary as a function of the youth's ethnic background. These findings suggest that: (1) the self-report APSD may have utility for risk or threat assessment with normative school populations, (2) APSD findings from higher risk samples generalize to a lower risk sample of high-school youth, and (3) predictive utility of APSD total scores do not differ across male and female Caucasian and ethnic minority youth.

Dehydration rate measurements for tertiary-butanol in a variable pressure flow reactor.

Fundamentally, the dehydration reaction of tertiary-butanol is frequently used as an internal standard for relative rate studies of other decomposition reactions. We report here a study using radical trappers to isolate this path in tertiary-butanol pyrolysis experiments conducted in the Princeton variable pressure flow reactor between 658 and 980 K. A novel technique that determines the rate constant value by applying a global least-squares fit incorporating all experimental species (tertiary-butanol, isobutene, and water) evolution data is developed and applied to yield six rate constant values at two reaction pressures (6.1 and 18 atm) and at temperatures between 949 and 980 K. Data from previously reported studies are reanalyzed to evaluate their "absolute" uncertainties, and new Arrhenius parameters are derived based upon the present and previous measurements. The recommended rate constant (uncertainties) for the dehydration reaction is k = 2.88(0.91) × 10(7)T(2.21(0.10)) s(-1) exp(-62.4(0.9) kcal mol(-1)/RT). The new correlation is in excellent agreement with other independent experimental and theoretical studies appearing in the literature.

Enthalpies of formation, bond dissociation energies and reaction paths for the decomposition of model biofuels: ethyl propanoate and methyl butanoate.

The complete basis set method CBS-QB3 has been used to study the thermochemistry and kinetics of the esters ethyl propanoate (EP) and methyl butanoate (MB) to evaluate initiation reactions and intermediate products from unimolecular decomposition reactions. Using isodesmic and isogeitonic equations and atomization energies, we have estimated chemically accurate enthalpies of formation and bond dissociation energies for the esters and species derived from them. In addition it is shown that controversial literature values may be resolved by adopting, for the acetate radical, CH3C(O)O(.-), DeltaH(o)(f)298.15K) = -197.8 kJ mol(-1) and for the trans-hydrocarboxyl radical, C(.-)(O)OH, -181.6 +/- 2.9 kJ mol(-1). For EP, the lowest energy decomposition path encounters an energy barrier of approximately 210 kJ mol(-1) (approximately 50 kcal mol(-1)), which proceeds through a six-membered ring transition state (retro-ene reaction) via transfer of the primary methyl H atom from the ethyl group to the carbonyl oxygen, while cleaving the carbon-ether oxygen to form ethene and propanoic acid. On the other hand, the lowest energy path for MB has a barrier of approximately 285 kJ mol(-1), producing ethene. Other routes leading to the formation of aldehydes, alcohols, ketene, and propene are also discussed. Most of these intramolecular hydrogen transfers have energy barriers lower than that needed for homolytic bond fission (the lowest of which is 353 kJ mol(-1) for the C(alpha)-C(beta) bond in MB). Propene formation is a much higher energy demanding process, 402 kJ mol(-1), and it should be competitive with some C-C, C-O, and C-H bond cleavage processes.

Biosensor-based diagnostics of contaminated groundwater: assessment and remediation strategy.

Shallow groundwater beneath a former airfield site in southern England has been heavily contaminated with a wide range of chlorinated solvents. The feasibility of using bacterial biosensors to complement chemical analysis and enable cost-effective, and focussed sampling has been assessed as part of a site evaluation programme. Five different biosensors, three metabolic (Vibrio fischeri, Pseudomonas fluorescens 10568 and Escherichia coli HB101) and two catabolic (Pseudomonas putida TVA8 and E. coli DH5alpha), were employed to identify areas where the availability and toxicity of pollutants is of most immediate environmental concern. The biosensors used showed different sensitivities to each other and to the groundwater samples tested. There was generally a good agreement with chemical analyses. The potential efficacy of remediation strategies was explored by coupling sample manipulation to biosensor tests. Manipulation involved sparging and charcoal treatment procedures to simulate remediative engineering solutions. Sparging was sufficient at most locations.