Net Reaction Research Articles

Nonprecious Single Atom Catalyst for Methane Pyrolysis.

The development of a suitable catalytic system for methane pyrolysis reactions requires a detailed investigation of the activation energy of C-H bonds on catalysts, as well as their stability against sintering and coke formation. In this work, both single-metal Ni atoms and small clusters of Ni atoms deposited on titanium nitride (TiN) plasmonic nanoparticles were characterized for the C-H bond activation of a methane pyrolysis reaction using ab initio spin-polarized density functional theory (DFT) calculations. The present work shows the complete reaction pathway, including energy barriers for C-H bond activation and dehydrogenated fragments, during the methane pyrolysis reaction on catalytic systems. Interestingly, the C-H bond activation barriers were low for both Ni single-atom and Ni-clusters, showing the energy barriers of ~1.10 eV and ~0.88 eV, respectively. Additionally, single-atom Ni-TiN showed weaker binding to adsorbates, and a net endothermic reaction pathway indicated that the single-atom Ni-TiN was expected to resist coke formation on its surface. However, these Ni single-atom catalysts can sinter, aggregate into a small cluster, and form a coke layer from the highly exothermic reaction pathway that the cluster takes despite the facile reaction pathway.

Electrocatalytic Radical Cation Diels-Alder Reactions Using Enol Ethers As Dienophiles

Single-electron oxidation enables the conversion of electron-rich alkenes such as styrene derivatives to radical cation species. We have been developing various cycloaddition reactions of radical cations produced by single-electron oxidation using electrochemical and TiO2 photochemical methods. Introducing an electron-rich aryl group which we call a redox tag is a critical part of the process to control the reactivity of the radical cations. During carbon-carbon bonds formation the motif functions as both electron donor and electron acceptor. In addition to styrene derivatives, enol ethers can also be readily oxidized by single electron transfer (SET) electrochemically or photochemically to generate the radical cations. For instance, enol ethers tethered redox tag serves efficient radical cation precursors for [2+2] cycloadditions.[1] The cycloadditions are net redox-neutral reactions and are initiated by the formation of a radical cation by single-electron oxidation and completed by reduction after ring formation.Herein, we present [4+2] cycloadditions using enol ethers as dienophiles by electrochemical oxidation in lithium perchlorate (LiClO4)/nitromethane (MeNO2) system. In the case of disubstituted enol ethers prepared from aldehydes, the approach involving redox tag was successful in obtaining the corresponding cycloadducts, while the desired products were not obtained when the substrates without redox tag were subjected.[2] This result suggests that intramolecular electron transfer from the redox tag is crucial for the formation of the cyclohexene ring systems. In contrast, the trisubstituted enol ethers prepared from ketones allowed the cycloaddition reaction to proceed without the involvement of redox tag. It is expected that the methyl group significantly stabilizes the cyclohexene radical cations to have enough lifetime to be reduced by intermolecular SET. Furthermore, since the cycloaddition reaction of enol ether was completed with a catalytic amount of electricity (0.4 F/mol), a radical cation chain mechanism is proposed in which electron acts as a catalyst.

Temperature Effects and Activation Barriers in Aqueous Proton-Uptake Reactions.

Aqueous proton transfer reactions are fundamental in biology and chemistry, yet kinetics and mechanisms of strong base-weak acid reactions are not well understood. In this work, we present a temperature-dependent reaction kinetic study of the water-soluble photobase actinoquinol, in the presence and absence of succinimide, a weak acid reaction partner. We study the temperature dependence of the reaction and connect the observed dynamics to the reaction's thermodynamics. We find that actinoquinol reacts in associated complexes with water/succinimide, creating an intermediate complex that can undergo either dissociation to create products, or reverse proton transfer within the complex to recreate the initial reactants. We find that the intermediates' formation is energetically unfavorable with both reaction partners, which impacts the net reaction rates. We also find that the net reaction rate is additionally strongly influenced by the competition between the dissociation of the intermediates and their reverse reaction.

Numerical Study on Chemical Kinetic Characteristics of Counterflow Diffusion Flame Extinction of Methane/Ammonia/Air Flame under High Pressure or Air Preheating Temperature.

Green ammonia has become an increasingly popular fuel in recent years because of its combustion process without carbon oxide release. Adding ammonia to methane fuel for co-combustion has become one of the important research topics in the current combustion field. In the present study, the CH4/NH3/Air counterflow diffusion flame was taken as the research object, and Chemkin-2019 R3 software was used to explore and analyze the flame extinction limit and chemical kinetics characteristics under different ammonia mixing ratios, initial pressures, and air preheating temperatures. It was obtained that the flame extinction stretch rate was decreased by increasing the NH3 mole fraction in the CH4/NH3 mixed fuel. The increase in pressure or air preheating temperature would accelerate the chemical reaction rate of each component in the combustion process, increase the flame extinction limit, and counteract the "stretching effect" of the flame, thus restraining the flame extinguishing phenomenon. The results of a path analysis show that the formation and consumption of OH had an important influence on flame extinction in the chain reaction. The net reaction rate of OH increases with increasing the initial pressure or air preheating temperature, which leads to an increase in flame intensity, combustion stability, and the extinction limit. Furthermore, the function curve between the reaction influences the RIF factor and the stretch rate of the first-to-ten reactions, affected by the heat release of flame combustion, was drawn and quantitatively analyzed. Eventually, a sensitivity analysis of the flame under different working conditions was completed, which found that promoting the forward reaction R39 H + O2<=>O + OH also promotes the positive combustion as a whole when the flame was near extinction. The sensitivity coefficient of R39 in the CH4/NH3/Air flame increases with the growing initial pressure. The increasing air preheating temperature was capable of switching the reaction of R248 NH2 + OH<=>NH + H2O in the CH4/NH3/Air flame from an inhibiting reaction to a promoting reaction, while decreasing the sensitivity coefficient of inhibiting the forward reaction R10 O + CH3<=>H + CH2O, R88 OH + HO2<=>O2 + H2O, and R271 H + NO + M<=>HNO + M. Thus, the inhibition effect of flame extinction was weakened, and the positive progress of combustion was promoted.

Experimental and numerical study on the influence of N2/H2 on the laminar combustion characteristics of syngas premixed flames

This paper primarily analyzes the influence of N2 and H2 content on the laminar combustion characteristics of low calorific value syngas, using a constant-volume combustion bomb to measure the laminar combustion velocity (SL) of the fuel and compare it with five commonly used mechanisms. The study reveals that higher N2 content significantly reduces the SL of CO/CH4/CO2 mixed fuels, primarily due to a general decrease in the mole fractions of key intermediates and net reaction rates. Increasing H2 content leads to an increase in the SL of CO/CH4/CO2/N2 mixed fuels. The thermal effect becomes increasingly prominent with the elevation of H2 content, while the proportion of thermal effect initially decreases and subsequently increases as the equivalence ratio rises. With the increase in N2 content, the mole fraction of NO experiences a significant decrease, and the rate of decline in thermal NO production is even faster. Conversely, with the increase in H2 content, the rate of rise in non-thermal NO generation is faster, and the mole fraction of NO tends to increase.

Numerical Investigation of Combustion Characteristics in a Binary Fuel Blend of C &lt;sub&gt;8&lt;/sub&gt; H &lt;sub&gt;18&lt;/sub&gt; and H &lt;sub&gt;2&lt;/sub&gt;

&lt;div&gt;The escalating energy demand in today’s world has amplified exhaust emissions, contributing significantly to climate change. One viable solution to mitigate carbon dioxide emissions is the utilization of hydrogen alongside gasoline in internal combustion engines. In pursuit of this objective, combustion characteristics of iso-octane/hydrogen/air mixtures are numerically investigated to determine the impact of hydrogen enrichment. Simulations are conducted at 400 K over a wide range of equivalence ratio 0.7 ≤ Ф ≤ 1.4 and pressure 1–10 atm. Adiabatic flame temperature, thermal diffusivity, laminar burning velocity, and chemical participation are assessed by varying hydrogen concentration from 0 to 90% of fuel molar fraction. As a result of changes in thermal properties and chemical participation, it is noticed that the laminar burning velocity (LBV) increases with higher hydrogen concentration and decreases as pressure increases. Chemical participation and mass diffusion were found to be the main contributors to the LBV increase in binary fuel blends. To circumvent NO&lt;sub&gt;X&lt;/sub&gt; formation, a binary fuel blend at Ф = 0.7 and 80% H&lt;sub&gt;2&lt;/sub&gt; is selected to increase combustion intensity while maintaining a relatively low flame temperature and retaining 85% of energy density by volume. It is noted that the concentration of H, O, and OH radicals increase with hydrogen enrichment. Furthermore, the analysis revealed that the LBV increases linearly with the peak mole fraction of radicals. Key reactions are identified through sensitivity analysis and net reaction rates. A significant increase in net reaction rate is observed for H&lt;sub&gt;2&lt;/sub&gt; + O &amp;lt;=&amp;gt; H + OH and H&lt;sub&gt;2&lt;/sub&gt; + OH &amp;lt;=&amp;gt; H + H&lt;sub&gt;2&lt;/sub&gt;O, which in turn increases the pool of radicals. This is evident by the increase in the net production rate of H, O, and OH radicals.&lt;/div&gt;

Studies on properties of laminar premixed oxygen-enriched NH3/H2/O2/N2 flames at elevated temperature and pressure

In this work, the effects of oxygen enrichment coefficient (Ω = 0.21 − 0.42) and initial temperature (Tu = 298 − 448 K) on the laminar burning properties of NH3/H2/O2/N2 flames are systematically investigated by using the spherical flame propagation method at equivalence ratios (Φ = 0.8 − 1.4) and initial pressure (Pu = 3 atm). LBV is analyzed by obtaining experimental data. In order to analyze flame instability, thermal diffusion and hydrodynamic instability are separated by linear stability theory. The thermal and chemical effects of oxygen enrichment on LBV and its effect on heat release rate are analyzed by numerical simulation. The results show that the laminar burning velocity (LBV) exhibits a positive correlation with both the oxygen enrichment coefficient and the initial temperature. The temperature index (α) exhibits a non-monotonic variation in response to the initial temperature of the NH3/H2/O2/N2 flame. Leeff is insensitive to temperature and positively correlated with the oxygen enrichment coefficient. The NH3/H2/O2/N2 flame is mainly affected by hydrodynamic instability when the oxygen enrichment coefficient is large. The peak NHRR scales positively with the oxygen enrichment coefficient. Oxygen enrichment helps to contribute to the overall net reaction rate.

Isolation and characterization of a bis(dithiolene)-supported tungsten-acetylenic complex as a model for acetylene hydratase

Acetylene hydratase is currently the only known mononuclear tungstoenzyme that does not catalyze a net redox reaction. The conversion of acetylene to acetaldehyde is proposed to occur at a W(IV) active site through first-sphere coordination of the acetylene substrate. To date, a handful of tungsten complexes have been shown to bind acetylene, but many lack the bis(dithiolene) motif of the native enzyme. The model compound, [W(O)(mnt)2]2−, where mnt2− is 1,2-dicyano-1,2-dithiolate, was previously reported to bind an electrophilic acetylene substrate, dimethyl acetylenedicarboxylate, and characterized by FT-IR, UV–vis, potentiometry, and mass spectrometry (Yadav, J; Das, S. K.; Sarkar, S., J. Am. Chem. Soc., 1997, 119, 4316–4317). By slightly changing the electrophilic acetylene substrate, an acetylenic-bis(dithiolene)‑tungsten(IV) complex has been isolated and characterized by FT-IR, UV–vis, NMR, X-ray diffraction, and X-ray absorption spectroscopy. Activation parameters for complex formation were also determined and suggest coordination-sphere reorganization is a limiting factor in the model complex reactivity.

Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones

Epoxides, as a prominent small ring O-heterocyclic and the privileged pharmacophores for medicinal chemistry, have recently represented an ideal substrate for the development of single-atom replacements. The previous O-to-C replacement strategy for epoxides to date typically requires high temperatures to achieve low yields and lacks substrate range and functional group tolerance, so achieving this oxygen-carbon exchange remains a formidable challenge. Here, we report a silver-catalyzed direct conversion of epoxides into trifluoromethylcyclopropanes in a single step using trifluoromethyl N-triftosylhydrazones as carbene precursors, thereby achieving oxygen-carbon exchange via a tandem deoxygenation/[2 + 1] cycloaddition. The reaction shows broad tolerance of functional groups, allowing routine cheletropic olefin synthesis in a strategy for the net oxygen-carbon exchange reaction. The utility of this method is further showcased with the late-stage diversification of epoxides derived from bioactive natural products and drugs. Mechanistic experiments and DFT calculations elucidate the reaction mechanism and the origin of the chemo- and stereoselectivity.

Implementing an accelerometer-based pelvis segment for low back kinetic analyses during dynamic movement tasks

An accelerometer-based pelvis has been employed to study segment and joint kinematics during scenarios involving close human-object interface and/or line-of-sight obstructions. However, its accuracy for examining low back kinetic outcomes is unknown. This study compared reaction moments and contact forces of the L5S1 joint calculated with an accelerometer-based and optically tracked pelvis segment. An approach to correct the global pelvis position as a function of thigh angle was developed. One participant performed four dynamic tasks: forward bend, squat, sit-to-stand-to-sit, and forward lunge. A standard bottom-up inverse dynamics approach was used and the root mean square error (RMSE) and coefficient of determination (R2) were calculated to examine kinetic differences between the optical and accelerometer approaches. The RMSE observed for L5S1 reaction flexion-extension moments ranged from 1.32 Nm to 2.20 Nm (R2 ≥ 0.98). The RMSE for net shear and compression reaction forces ranged from 2.13 to 10.45 N and 0.63 – 4.96 N, respectively. Similarly, the RMSE for L5S1 joint contact shear and compression ranged from 13.45 N to 19.51 N (R2 ≥ 0.85) and 31.18 N – 55.97 N (R2 ≥ 0.97), respectively. In conclusion, the accelerometer-based pelvis together with the approach to correct the global pelvis position is a feasible approach for computing low back kinetics with a single equivalent muscle model. The observed error in joint contact forces represents less than 5 % of the NIOSH recommended action limits and is unlikely to alter the interpretation of low back injury risk.

Molecular Dynamic Simulations of Aqueous Micellar Organometallic Catalysis: Methane Functionalization as a Case Study.

Molecular Dynamics (MD) simulations constitute a powerful tool that provides a 3D perspective of the dynamical behavior of chemical systems. Herein the first MD study of the dynamics of a catalytic organometallic system, in micellar media, is presented. The challenging methane catalytic functionalization into ethyl propionate through a silver-catalyzed process has been targeted as the case study. The intimate nature of the micelles formed with the surfactants sodium dodecylsulfate (SDS) and potassium perfluorooctane sulfonate (PFOS) has been ascertained, as well as the relative distribution of the main actors in this transformation, namely methane, the diazo reagent and the silver catalyst, the latter in two different forms: the initial compound and a silver-carbene intermediate. Catalyst deactivation occurs with halide containing surfactants dodecyltrimethylammonium chloride (DTAC) and Triton X-100. Computed simulations allow explaining the experimental results, indicating that micelles behave differently regarding the degree of accumulation and the local distribution of the reactants and their effect in the molecular collisions leading to net reaction.

Molecular Dynamic Simulations of Aqueous Micellar Organometallic Catalysis: Methane Functionalization as a Case Study

AbstractMolecular Dynamics (MD) simulations constitute a powerful tool that provides a 3D perspective of the dynamical behavior of chemical systems. Herein the first MD study of the dynamics of a catalytic organometallic system, in micellar media, is presented. The challenging methane catalytic functionalization into ethyl propionate through a silver‐catalyzed process has been targeted as the case study. The intimate nature of the micelles formed with the surfactants sodium dodecylsulfate (SDS) and potassium perfluorooctane sulfonate (PFOS) has been ascertained, as well as the relative distribution of the main actors in this transformation, namely methane, the diazo reagent and the silver catalyst, the latter in two different forms: the initial compound and a silver‐carbene intermediate. Catalyst deactivation occurs with halide containing surfactants dodecyltrimethylammonium chloride (DTAC) and Triton X‐100. Computed simulations allow explaining the experimental results, indicating that micelles behave differently regarding the degree of accumulation and the local distribution of the reactants and their effect in the molecular collisions leading to net reaction.

EFFECT OF MICROSTRUCTURES ON MASS TRANSFER INSIDE A HIERARCHICALLY STRUCTURED POROUS CATALYST

In this paper, the pore network model to investigate the reaction-diffusion process in the hierarchically structured porous catalyst particle is extended to consider the phenomenon of deactivation by coking. In this framework, the interaction of internal particle pore structure and mass transfer under the condition of coke deposition is examined. Then, the effect of structural features, namely macroporosity and pore size ratio, the deactivation properties, the maximum loading of coke, as well as the transport properties, the pore Damk&amp;#246;hler number on the net reaction rate, and deactivation of the particle have been investigated. Three deactivation mechanisms are accounted for, namely, the site coverage, the pore narrowing, and the pore blockage. It is found that the deactivation of the catalyst particle can be divided into two conditions: the kinetic deactivation and the structural deactivation. It is shown that depending on the Damk&amp;#246;hler number, increasing the macroporosity does not necessarily improve the reactivity and deactivation resistance of the catalyst. The key finding of this work is to demonstrate and quantify how changing the typical fresh catalyst microstructure into a hierarchical one influences the reactivity and deactivation.

Hydrogen Reduction Reduction (HRR)

The year 2023 marks the bicentennial of the discovery of heterogeneous H2 catalysis. Nowadays, the hydrogen oxidation reaction (HOR), which converts H2 to protons (H+), is one of the most important transformations in energy research. Meanwhile, hydrogenation reactions, which transfer net H-atoms (H·) to organic substrates from H2, play pivotal roles in various chemical industries. In comparison, it is surprising to see that a heterogenous catalytic reaction that directly converts H2 to hydrides (H–) still remains elusive. Hydride transfer is a critical elementary reaction step that spans biological catalysis, organic synthesis and energy conversion. Conventionally, hydride transfer reactions are performed using (bio)molecular hydride reagents under homogeneous conditions. Here we report a conceptually distinct heterogeneous hydride transfer reaction via the net electrocatalytic hydrogen reduction reaction (HRR), which reduces H2 to hydrides. The reaction proceeds by H2 dissociative adsorption on a metal electrode to form surface M−H species, which are then negatively polarized to drive hydride transfer to molecular hydride acceptors with up to 91% Faradaic efficiency. The hydride transfer reactivity of surface M−H species is highly tunable, and, depending on the electrode potential, the thermodynamic hydricity of Pt−H on the same Pt electrode can continuously span a range of >40 kcal/mol.In addition to this electrochemical transformation, we further developed an alternative strategy to achieve heterogeneous hydride transfer on dispersed metal catalysts under non-electrochemical conditions. In the presence of a base, deprotonation of surface M-H builds up electron density at the metal surface and thereby causes spontaneous polarization which can then drive hydride transfer from metal nanoparticles. Based on this, HRR can be performed under standard hydrogenation conditions with the addition of a base using dispersed metal catalysts, and the surface hydricity is now controlled by the solution basicity. We further demonstrate that this non-electrochemical HRR method can be applied to NADH regeneration which is closely related to industrial biocatalysis. The discovery of HRR reveals the fundamental hydride transfer reactivity of surface M-H species as well as its polarization-dependent nature. Both the electrochemical and non-electrochemical HRR methods establish sustainable strategies for accessing reactive hydrides directly from H2. Figure 1

Reynolds number-based global modification of EDC constants and simulation of a syngas and a piloted CH4/air flames

The Eddy Dissipation Concept (EDC), as a promising flame prediction model, is reviewed comprehensively. Instead of strong modifications of the standard EDC constants to fit experiments, a modification method of the EDC constants based on the fuel jet Reynolds number is presented in this work and used to predict a simple jet nonpremixed syngas Sandia Flame CHN–B and a piloted CH4/air partially premixed Sandia Flame D. Compared with the experiments, the predictions show the two flames are properly reproduced with the modified EDC constants. Some over-predictions might be attributed to the under-estimation of turbulence. The microscale and the macroscale Damköhler numbers are presented showing decreasing trends with the increased Reynolds number. Three clear combustion regions in the two flames are firstly identified from the results of the net reaction rate of OH. The reaction heat in the fuel-rich region is found larger than that in the fuel-lean region for Flame D. The contours of the net reaction rate of OH show a stronger reaction region in the fuel-lean side for Flame CHN–B and in the fuel-rich side for Flame D. The predictions with the modified EDC constants agree with the experiments better than those with the standard EDC constants.

Dihydropyrimidine dehydrogenase from Escherichia coli: Transient state analysis reveals both reductive activation prior to turnover and diminished substrate effector roles relative to the mammalian form

Dihydropyrimidine dehydrogenase (DPD) is an enzyme that uses an elaborate architecture to catalyze a simple net reaction: the reduction of the vinylic bond of uracil and thymine. Known DPDs have two active sites separated by approximately 60 Å. One active site has an FAD cofactor and binds NAD(P) and the other has an FMN cofactor and binds pyrimidines. The intervening distance is spanned by four Fe4S4 centers that act as an electron conduit. Recent advancements with porcine DPD have revealed unexpected chemical sequences where the enzyme undergoes reductive activation by transferring two electrons from NADPH to the FMN via the FAD such that the active form has the cofactor set FAD•4(Fe4S4)•FMNH2. Here we describe the first comprehensive kinetic investigation of a bacterial form of DPD. Using primarily transient state methods, DPD from E. coli (EcDPD) was shown to have a similar mechanism to that observed with the mammalian form in that EcDPD is observed to undergo reductive activation before pyrimidine reduction and displays half-of-sites activity. However, two distinct aspects of the EcDPD reaction relative to the mammalian enzyme were observed that relate to the effector roles for substrates: (i) the enzyme will rapidly take up electrons from NADH, reducing a flavin in the absence of pyrimidine substrate, and (ii) the activated form of the enzyme can become fully oxidized by transferring electrons to pyrimidine substrates in the absence of NADH.

Investigation of water effects on hydrogen dissolution, diffusion, and reaction in high temperature proton exchange membrane fuel cell

High-temperature proton exchange membrane fuel cell with phosphoric acid-doped polybenzimidazole membrane is typically utilized with a methanol steam reformer due to its high CO tolerance. However, methanol reformate commonly contains 20 % water, and its effect on the high temperature fuel cell is unclear. A comprehensive 3D multiphase non-isothermal model with an enhanced electrochemical kinetics model considering the water influence mechanism is developed. The water influence mechanism includes the proton conductivity, hydrogen dissolution on the pore-ionomer interface, hydrogen diffusion inside the ionomer, and hydrogen surface reaction on the platinum. The sensitivity analysis found that hydrogen dissolution on the pore-ionomer and hydrogen surface reaction on the platinum significantly affect cell performance. The influences of water on ionomer hydrogen concentration, platinum surface hydrogen concentration, and surface reaction rates are investigated under the voltage range of 0.9–0.4 V. The increase of water content can improve the net adsorption rate and benefit electrochemical reaction. Besides, the anode water is better for the uniformity of surface reaction rate distributions while not affecting the hydrogen distributions inside the ionomer and on the platinum surface. Additionally, the positive influence of water on CO poisoning is investigated in terms of surface reaction. The water's beneficial effect on decreasing platinum loading is also discussed. The results show that 20 % water can reduce the platinum loading by 20 %.

Effect of diluent N2 addition on NH3/H2/air combustion characteristics

As a clean energy source with high-energy hydrogen carriers, ammonia has a promising application prospect in gas turbine power production. The existence of N2 as an ammonia combustion product and as an ammonia decomposition product at high temperatures influences ammonia combustion characteristics. Accordingly, this paper measured the combustion characteristics of the NH3/H2/air flame by the method of a constant-pressure spherical flame under different N2 dilution ratios and different equivalent ratios (0.7–1.5), with initiating temperatures of 303 K and 500 K and an initiating pressure of 1 atm, respectively. The experimental results show that the influence of diluent N2 leads to a downward trend in the laminar burning velocities (LBVs) of the NH3/H2/N2/air mixture, and the dilution effect inhibits the propagation of the NH3/H2/N2/air flame. The laminar flame propagation of the mixture is aided by the initiating temperature increase. The existence of diluent N2 reduces the major branching reactions’ net reaction and net heat production rates while enhancing inhibition of the H/OH radical pool and the rate-limiting effect of the primitive reactions. The initiating temperature reduces the impact of the radical reactions on the flame rate and enhances the chemotaxis of NHi (i = 1, 2). The diluent N2 changed the NH3 consumption and effectively suppressed the NOx production, showing the NO emission potential of NH3/H2/N2/air mixtures combustion under fuel-rich conditions.

The Computational Acid-Base Chemistry of Hepatic Ketoacidosis.

Opposing evidence exists for the source of the hydrogen ions (H+) during ketoacidosis. Organic and computational chemistry using dissociation constants and alpha equations for all pertinent ionizable metabolites were used to (1) document the atomic changes in the chemical reactions of ketogenesis and ketolysis and (2) identify the sources and quantify added fractional (~) H+ exchange (~H+e). All computations were performed for pH conditions spanning from 6.0 to 7.6. Summation of the ~H+e for given pH conditions for all substrates and products of each reaction of ketogenesis and ketolysis resulted in net reaction and pathway ~H+e coefficients, where negative revealed ~H+ release and positive revealed ~H+ uptake. Results revealed that for the liver (pH = 7.0), the net ~H+e for the reactions of ketogenesis ending in each of acetoacetate (AcAc), β-hydroxybutyrate (β-HB), and acetone were -0.9990, 0.0026, and 0.0000, respectively. During ketogenesis, ~H+ release was only evident for HMG CoA production, which is caused by hydrolysis and not ~H+ dissociation. Nevertheless, there is a net ~H+ release during ketogenesis, though this diminishes with greater proportionality of acetone production. For reactions of ketolysis in muscle (pH = 7.1) and brain (pH = 7.2), net ~H+ coefficients for β-HB and AcAc oxidation were -0.9649 and 0.0363 (muscle), and -0.9719 and 0.0291 (brain), respectively. The larger ~H+ release values for β-HB oxidation result from covalent ~H+ release during the oxidation-reduction. For combined ketogenesis and ketolysis, which would be the metabolic condition in vivo, the net ~H+ coefficient depends once again on the proportionality of the final ketone body product. For ketone body production in the liver, transference to blood, and oxidation in the brain and muscle for a ratio of 0.6:0.2:0.2 for β-HB:AcAc:acetone, the net ~H+e coefficients for liver ketogenesis, blood transfer, brain ketolysis, and net total (ketosis) equate to -0.1983, -0.0003, -0.2872, and -0.4858, respectively. The traditional theory of ketone bodies being metabolic acids causing systemic acidosis is incorrect. Summation of ketogenesis and ketolysis yield H+ coefficients that differ depending on the proportionality of ketone body production, though, in general, there is a small net H+ release during ketosis. Products formed during ketogenesis (HMG-CoA, acetoacetate, β-hydroxybutyrate) are created as negatively charged bases, not acids, and the final ketone body, acetone, does not have pH-dependent ionizable groups. Proton release or uptake during ketogenesis and ketolysis are predominantly caused by covalent modification, not acid dissociation/association. Ketosis (ketogenesis and ketolysis) results in a net fractional H+ release. The extent of this release is dependent on the final proportionality between acetoacetate, β-hydroxybutyrate, and acetone.

Investigating Reforming Kinetics of a Synthetic Biogas Mixture on Ni: Model Development and Experimental Validation

A thermodynamically consistent mechanistic rate model for steam reforming (SRM) and catalytic partial oxidation (CPOx) of a synthetic biogas mixture on a Ni catalyst is derived in this work. A microkinetic model (MKM) consisting of 42 irreversible reactions served as the starting point for the development of the model equations presented in this study. A global sensitivity analysis based on ANOVA using Sobol sampling is conducted on the MKM to identify important reactions that describe SRM, CPOx, and water–gas shift reaction (WGSR), which occur alongside CH4 reforming. The unimportant reactions are eliminated to obtain a reduced elementary reaction model, which is subjected to validation by reproducing the predictions of 42 reactions of the MKM. The rate-determining steps (rds) are identified for SRM, WGSR, and CPOx, from the reduced mechanism by using a net reaction rate and partial equilibrium analysis. Mechanistic rate expressions are derived from the identified rds by adopting the Langmuir–Hinshelwood–Hougen–Watson approach. The parameters of these mechanistic rate models for SRM, WGSR, and CPOx are estimated by using a real coded genetic algorithm. The rate models with the estimated parameters could reproduce the experimental observations with good accuracy. The predictive capability of the derived rate models is established by comparing the model predictions with the experimental measurements of SRM, combined steam and dry reforming, and trireforming. The reforming experiments were performed for a synthetic biogas mixture containing CH4/CO2 = 2, in a packed bed reactor using 10 wt % Ni/γ-Al2O3. Overall the mechanistic models were able to predict the experimental measurements with good accuracy.