Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials

Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.     

Introduction to pyrolysis of biomass

The pyrolytic properties of biomass are controlled by the chemical composition of its major components, namely cellulose, hemicelluloses and lignin and their minor components including extractives and inorganic materials. Pyrolysis of these materials proceeds through a series of complex, concurrent and consecutive reactions and provides a variety of products.Pyrolysis cellulose at lower temperatures below 300° C involves reduction in molecular weight, evolution of water, carbon dioxide and carbon monoxide and formation of char. On heating at higher temperature 300–500° C, the molecule is rapidly depolymerized to anhydroglucose units that further reacts to provide a XXXX pyrolyXXXXA: still higher temperatures, the anhydrosugar compounds undergo fussion, dehydration disproportionation and decarboxylation reaction to provide a mixture of low molecular weight gaseous and volatile produces. The composition of these produces and mechanism and kinetics of their production are reported.     

Influence of Various Solid Catalysts on the Destruction Kinetics of Sodium Lauryl Sulfate in Aqueous Solutions by DBD

The destruction kinetics of sodium lauryl sulfate (anionic surfactant) in water solutions as well as the formation kinetics of destruction products under the action of an oxygen dielectric barrier discharge at atmospheric pressure both in the presence and in the absence of TiO₂, NiO and Ag₂O catalysts was studied. As it turned out in all cases the main decomposition products were carboxylic acids, aldehydes and carbon dioxide. The catalysts application was shown to result both in the increase of the decomposition efficiency and in a change in the ratio and yields of decomposition products.     

Kinetics, products, and mechanisms of secondary organic aerosol formation

Secondary organic aerosol (SOA) is formed in the atmosphere when volatile organic compounds (VOCs) emitted from anthropogenic and biogenic sources are oxidized by reactions with OH radicals, O(3), NO(3) radicals, or Cl atoms to form less volatile products that subsequently partition into aerosol particles. Once in particles, these organic compounds can undergo heterogenous/multiphase reactions to form more highly oxidized or oligomeric products. SOA comprises a large fraction of atmospheric aerosol mass and can have significant effects on atmospheric chemistry, visibility, human health, and climate. Previous articles have reviewed the kinetics, products, and mechanisms of atmospheric VOC reactions and the general chemistry and physics involved in SOA formation. In this article we present a detailed review of VOC and heterogeneous/multiphase chemistry as they apply to SOA formation, with a focus on the effects of VOC molecular structure on the kinetics of initial reactions with the major atmospheric oxidants, the subsequent reactions of alkyl, alkyl peroxy, and alkoxy radical intermediates, and the composition of the resulting products. Structural features of reactants and products discussed include compound carbon number; linear, branched, and cyclic configurations; the presence of C[double bond, length as m-dash]C bonds and aromatic rings; and functional groups such as carbonyl, hydroxyl, ester, hydroxperoxy, carboxyl, peroxycarboxyl, nitrate, and peroxynitrate. The intention of this review is to provide atmospheric chemists with sufficient information to understand the dominant pathways by which the major classes of atmospheric VOCs react to form SOA products, and the further reactions of these products in particles. This will allow reasonable predictions to be made, based on molecular structure, about the kinetics, products, and mechanisms of VOC and heterogeneous/multiphase reactions, including the effects of important variables such as VOC, oxidant, and NO(x) concentrations as well as temperature, humidity, and particle acidity. Such knowledge should be useful for interpreting the results of laboratory and field studies and for developing atmospheric chemistry models. A number of recommendations for future research are also presented.     

Kinetics and mechanism of OH oxidation of small organic dicarboxylic acids in ice: comparison to behavior in aqueous solution

To better understand the oxidation of organic species by OH within frozen solutions, experiments were conducted with a simplified model system consisting of succinic acid (2.5, 5, and 10 mM), using H(2)O(2) (30 mM) as a condensed-phase OH precursor. Frozen (-20 °C) and aqueous (0 °C and room temperature) solutions were irradiated using a xenon arc lamp to study the differences between frozen and nonfrozen reaction media. Formation of products and decay of reactants were measured using ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). Malonic acid was observed as the dominant product, with malic acid formed in significantly smaller amounts, in both frozen and unfrozen substrates, suggesting a common mechanism independent of phase. Notably, a large decrease was observed in the succinic acid first-order decay rate constant when moving from aqueous to frozen samples. This is due not to temperature-dependent second-order kinetics or different OH production rates between the samples, but instead probably arises from physical separation of the succinic acid and H(2)O(2) upon freezing or precipitation of succinic acid upon freeze concentration. The effect is not nearly as pronounced for the decay kinetics of a much more soluble species, namely, malonic acid. From an environmental perspective, this work is the first experimental demonstration that dicarboxylic acids present in the cryosphere might be subject to photochemical degradation into smaller organic acids and carbon dioxide.     

Aging of Transformer Insulation Paper

Abstract

As a transformer ages, the chemical and physical properties of the cellulose insulation materials in the transformer change, and the paper loses its strength and becomes brittle. The average molecular weight of the cellulose chains decrease with age, and degradation products are formed, including water, carbon monoxide, carbon dioxide, and furans. The molecular weight changes in the cellulose have been studied by several methods, but the GPC method for determination of the molecular weight has been shown to offer advantages over other methods because it yields the total molecular weight distribution. The tensile strength of the cellulose insulation in transformers also changes with age as a result of the changing molecular weight of the cellulose. Work carried out in our laboratory on the aging of cellulose insulation is reviewed in this paper. Our studies have included investigations of insulation materials from retired transformers as well as accelerated aging of insulation paper in transformer oil in the temperature range of 129–166°C under vacuum. In the study the relationships between the molecular weight of the cellulose and the furan degradation products and tensile strength have been delineated, and they have been correlated with information on the kinetics of degradation of the insulation paper.     

Process characteristics of exopolysaccharide production by streptococcus thermophilus

The kinetics of growth and exopolysaccharide (EPS) production from Streptococcus thermophilus were studied and optimized for different physical (temperature, pH, aeration rate) and chemical (carbon/nitrogen ratio) factors in milk medium. From these experiments, it was clear that EPS production displays primary metabolite kinetics. Using the optimized conditions, EPS production could also be established in de Man Rogosa Sharpe medium. Growth-associated EPS production, bacterial growth and other fermentation data were translated into a mathematical model.     

稻杆的热溶剂提质及多级分离

采用1-甲基萘(1-MN)为溶剂,在不同温度下(250、300、350 ℃)对稻秆进行热溶剂提质及多级分离,获得3种主要固体产物:低分子量萃取物(soluble)、高分子量萃取物(deposit)和萃取残渣(residue),以及少量气体产物和液体产物。对各组分的元素组成、化学结构、物理化学特性等进行了详细分析,并采用ICP-MS测定了其碱金属和碱土金属(AAEM)含量。结果发现,低分子量萃取物收率随着温度的升高而增大,350 ℃时碳基收率达到33.48%。3种固体产物的碳含量和氧含量随着温度的升高而分别升高和降低,350 ℃时soluble、deposit的碳含量分别高达82.36%、80.59%,氧含量分别低至9.50%、12.03%,稻杆原样中高达86.99%的氧以H₂O或CO₂的形式释放。soluble几乎无灰,deposit的灰含量也低于1.50%。3种固体产物的高位发热量显著高于稻杆原样。FT-IR结果表明,稻杆热溶剂处理过程中除发生了脱水反应、脱羧基反应外,还有明显的芳香化反应。soluble和deposit的Na、Mg和K含量极低,而且随温度的升高其含量逐渐降低。总之,热溶剂提质及多级分离法实现了温和条件下的生物质脱水脱氧提质,并获得低灰低氧含量、高碳含量和发热量的多种产物,此方法有较好的应用前景。     

Kinetic Modeling of Fermentative Production of 1, 3-Propanediol by Klebsiella pneumoniae HR526 with Consideration of Multiple Product Inhibitions

During the fermentative production of 1, 3-propanediol (1,3-PD), the multiple product inhibitions cannot be negligible to accurately describe the kinetics of fermentation process. A kinetic model for fermentative production of 1,3-PD by Klebsiella pneumoniae HR526 with glycerol as carbon source under aerobic condition was proposed. The inhibitions of multiple products including 1,3-PD, 2, 3-butanediol (2,3-BD), acetate, and succinate were considered in the model. It was found that 1,3-PD, 2,3-BD, and acetate showed strong inhibitions to cell growth depending on their concentrations. The kinetic model was relatively accurate to predict the experimental data of batch, fed-batch, and continuous fermentations. The model thus can serve as a tool for further controlling and optimizing the fermentation process.     

Temperature stability and photodimerization kinetics of beta-cinnamic acid and comparison to its alpha-polymorph as studied by solid-state NMR spectroscopy techniques and DFT calculations

Photoreactions of the alpha- and beta-polymorphs of trans-cinnamic acid were studied by (13)C CPMAS solid-state nuclear magnetic resonance spectroscopy, and the reactants and products were spectroscopically characterized in detail. Chemical shifts and chemical shift anisotropy tensors calculated using density functional theory (DFT) were found to be in good agreement with the experimental results and helped to identify the polymorphs and the individual assignments of reactant and photoproduct carbon atoms. The beta-polymorph is metastable. Its transformation into the alpha-cinnamic acid polymorph is monitored by temperature-dependent (13)C NMR spectroscopy. The transformation occurs at a very slow rate at room temperature but is highly accelerated at elevated temperatures. Analysis of the kinetics of the photoreaction shows that the beta-polymorph progresses at a slower rate compared to that of alpha-cinnamic acid. Based on chemical shift tensor values of reactants and products as obtained from 2D PASS spectra, the difference in reaction rates is suggested to be due to the higher amount of molecular reorientation of functional groups upon photoreaction and the larger distance between the reacting double bonds.     

TiO2 photocatalytic degradation of dimethyl- and diethyl- methylphosphonate, effects of catalyst and environmental factors

Dimethyl methylphosphonate (DMMP) and diethyl methylphosphonate (DEMP) are readily mineralized by photoexcited titanium dioxide (TiO₂). Intermediate products include low molecular weight organic acids and methylphosphonic acid. Complete mineralization yields phosphate and carbon dioxide. The photoactivities of different types of TiO₂ were investigated. The decomposition kinetics of DMMP and effects of DMMP and catalyst concentration, sonication, solar irradiation, oxygen concentration, temperature, and hydrogen peroxide on the rate of decomposition are reported. The degradation rates increase with simultaneous sonication, addition of hydrogen peroxide, and at higher temperatures.     

Nickel-promoted Electrocatalytic Graphitization of Biochars for Energy Storage: Mechanistic Understanding using Multi-scale Approaches

Owing to high-efficiency and scalable advantages of electrolysis in molten salts, electrochemical conversion of carbonaceous resources into graphitic products is a sustainable route for achieving high value-added carbon. To understand the complicated kinetics of converting amorphous carbon (e.g. carbonized lignin-biochar) into highly graphitic carbon, herein this study reports the key processing parameters (addition of Ni, temperature and time) and multi-scale approach of nickel-boosted electrochemical graphitization-catalysis processes in molten calcium chloride. Upon both experiments and modellings, multi-scale analysis that ranges from nanoscale atomic reaction to macroscale cell reveal the multi-field evolution in the electrolysis cell, mechanism of electrochemical reaction kinetics as well as pathway of nickel-boosted graphitization and tubulization. The results of as-achieved controllable processing regions and multi-scale approaches provide a rational strategy of manipulating electrochemical graphitization processes and utilizing the converted biomass resources for high value-added use.     

On the formation of ozone in oxygen-rich solar system ices via ionizing radiation

The irradiation of pure molecular oxygen (O(2)) and carbon dioxide (CO(2)) ices with 5 keV H(+) and He(+) ions was investigated experimentally to simulate the chemical processing of oxygen rich planetary and interstellar surfaces by exposure to galactic cosmic ray (GCR), solar wind, and magnetospheric particles. Deposited at 12 K under ultra-high vacuum conditions (UHV), the irradiated condensates were monitored on-line and in situ in the solid-state by Fourier transform infrared spectroscopy (FTIR), revealing the formation of ozone (O(3)) in irradiated oxygen ice; and ozone, carbon monoxide (CO), and cyclic carbon trioxide (c-CO(3)) in irradiated carbon dioxide. In addition to these irradiation products, evolution of gas-phase molecular hydrogen (H(2)), atomic helium (He) and molecular oxygen (O(2)) were identified in the subliming oxygen and carbon dioxide condensates by quadrupole mass spectrometry (QMS). Temporal abundances of the oxygen and carbon dioxide precursors and the observed molecular products were compiled over the irradiation period to develop reaction schemes unfolding in the ices. These reactions were observed to be dependent on the generation of atomic oxygen (O) by the homolytic dissociation of molecular oxygen induced by electronic, S(e), and nuclear, S(n), interaction with the impinging ions. In addition, the destruction of the ozone and carbon trioxide products back to the molecular oxygen and carbon dioxide precursors was promoted over an extended period of ion bombardment. Finally, destruction and formation yields were calculated and compared between irradiation sources (including 5 keV electrons) which showed a surprising correlation between the molecular yields (～10(-3)-10(-4) molecules eV(-1)) created by H(+) and He(+) impacts. However, energy transfer by isoenergetic, fast electrons typically generated ten times more product molecules per electron volt (～10(-2)-10(-3) molecules eV(-1)) than exposure to the ions. Implications of these findings to Solar System chemistry are also discussed.     

Conversion of food industrial wastes into bioplastics with municipal activated sludge

Plastics have become an integral part of our contemporary life because of many desirable properties including durability and resistance to degradation. However, these non-degradable, petrochemicals-derived plastics accumulate in the environment at a rate of 25 million tons per year. Recently there is an interest in the development of a class of microbially produced bioplastics, e.g., polyhydroxyalkanoates (PHAs) which retain the desired physical and chemical properties of conventional synthetic plastics. Broader usage of biodegradable plastics in packaging and disposable products as a solution to the environmental problem would heavily depend on further reduction of costs and the discovery of novel biodegradable plastics with improved properties. In this paper, the microbial production of PHAs by activated sludge utilizing food industrial wastes is reported. The melting points of the products as well as the co-polymer composition of the products investigated by GC and NMR were compared. By use of activated sludge to convert the carbon source into PHAs not only environment-friendly bioplastics are produce, but also part of the problem of the disposal of municipal activated sludge is solved. The selection of food industrial waste as carbon resource can also further reduce the cost of production of PHAs.     

Effect of ultrasound on a mixed oxide-based catalyst for synthesis of nanostructured carbon materials

The effect of ultrasonic activation on the performance of a mixed oxide-based (Ni/Mg) catalyst in the synthesis of multiwalled carbon nanotubes via chemical vapor deposition was studied. The molecular geometry of the solution of initial catalyst components (feed solution) was calculated and simulated according to a molecular mechanics method. Activation of the catalyst performed for 10 s during its preparation stage resulted in a considerable increase (of about 40 %) in the specific yield of nanotubes due to enhanced catalytic activity. Moreover, the kinetics of nanotube synthesis over the activated catalyst was studied, and the morphology of the obtained nanoproduct was investigated. Finally, the possibility of employing the present method for catalyst activation in experimental–industrial production of nanotubes was evaluated.     

Sustainable Diesel from Pyrolysis of Unsaturated Fatty Acid Basic Soaps: The Effect of Temperature on Yield and Product Composition

The production of sustainable diesel without hydrogen addition remains a challenge for low-cost fuel production. In this work, the pyrolysis of unsaturated fatty acid (UFA) basic soaps was studied for the production sustainable diesel (bio-hydrocarbons). UFAs were obtained from palm fatty acids distillate (PFAD), which was purified by the fractional crystallization method. Metal hydroxides were used to make basic soap composed of a Ca, Mg, and Zn mixture with particular composition. The pyrolysis reactions were carried out in a batch reactor at atmospheric pressure and various temperatures from 375 to 475 °C. The liquid products were obtained with the best yield (58.35%) at 425 °C and yield of diesel fraction 53.4%. The fatty acids were not detected in the pyrolysis liquid product. The gas product consisted of carbon dioxide and methane. The liquid products were a mixture of hydrocarbon with carbon chains in the range of C₇ and C₂₀ containing n-alkane, alkene, and iso-alkane.     

Divalent Transition‐Metal‐Ion Stress Induces Prodigiosin Biosynthesis in Streptomyces coelicolor M145: Formation of Coeligiosins

The bacterium Streptomyces coelicolor M145 reacts to transition‐metal‐ion stress with myriad growth responses, leading to different phenotypes. In particular, in the presence of Co²⁺ ions (0.7 mM ) S. coelicolor consistently produced a red phenotype. This phenotype, when compared to the wild type, differed strongly in its production of volatile compounds as well as high molecular weight secondary metabolites. LC‐MS analysis revealed that in the red phenotype the production of the prodigiosins, undecylprodigiosin and streptorubin B, was strongly induced and, in addition, several intense signals appeared in the LC‐MS chromatogram. Using LC‐MS/MS and NMR spectroscopy, two new prodigiosin derivatives were identified, that is, coeligiosin A and B, which contained an additional undecylpyrrolyl side chain attached to the central carbon of the tripyrrole ring system of undecylprodigiosin or streptorubin B. This example demonstrates that environmental factors such as heavy metal ion stress can not only induce the production of otherwise not observed metabolites from so called sleeping genes but alter the products from well‐studied biosynthetic pathways.     

Kinetics of the adsorption of polystyrene macromolecules from dilute solutions in methyl ethyl ketone on carbon black

The kinetics of the adsorption of a mixture of three polystyrenes (the weight-average molecular weight M _w = 8300, 34000, and 195000) on nonporous carbon (carbon black pretreated in the argon flow at 3800 K) from dilute solutions in methyl ethyl ketone at 298 K is studied. The kinetic dependences of the adsorption of polystyrenes on carbon black nanoparticles from solutions in methyl ethyl ketone are described by adsorption kinetics equations previously used for describing the adsorption of aromatic hydrocarbons from aqueous solutions by active carbon. The correlation between the kinetic coefficients and the molecular weights of polystyrenes is discussed.     

二氧化硫与戊烷的气相光化学反应研究

Baclock等^[1]的研究表明,在SO2与烃的光化学反应体系中,单重态SO2通过系间窜跃转化为三重态SO2参与光化学反应,Penzhorn等^[2,3]的研究表明,在SO2与C4以下气相烃的光化学反应中有多种产物存在,产物的复杂性预示反应为自由基链反应。Smith等^[4]等认为体系中存在烃的逐步氧化,同时证明SO2与烷烃光化学反应中自由基链反应的重要性,文献报道的研究多以凝聚态产物为切入点^[5],为避免器壁对光化学反应的影响,本文以气相物质为研究对象,对挥发性烷烃中结构最简单的戊烷与二氧化硫的光化学反应的气相反应产物,反应机理和影响因素等进行了研究。