ArticleMicrocalorimetric Investigation on the Kinetics of the Oxidation of Ascorbic Acid with Hydrogen Peroxide

Introduction Ascorbic acid is still attractive due to its wide-rang-ing role in biological processes and chemical fields. Consequently the knowledge of the kinetics of ascorbate reduction is highly desirable. In previous papers,1-11 spectroscopy and electronics methods were generally used to study the oxidation of ascorbic acid, and only a first-order reaction rate constant was obtained by these methods. Since the reaction is a complicated process involving several reactive species, the previo…     

Influence of temperature on metal-organic frameworks

Reaction temperature is one of the key parameters in the synthesis of metal-organic frameworks （MOFs）. Though there is no convergence with regard to the various experimental parameters, reaction temperature has been found to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the MOF structures. Theoretically, the reaction temperature affects directly the reaction energy barrier in reaction thermodynamics and the reaction rate in the reaction kinetics. This review aims to show the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and to provide primary information and insights into the design and assernblv of desired MOFs.     

Quasi-classical Trajectory Study of F-I-H20→HF-I-OH Reaction： Influence of Barrier Height,Reactant Rotational Excitation,and Isotopic Substitution

The reaction dynamics of the F＋H20/D20→HF/DF＋OH/OD are investigated on an accurate potential energy surface （PES） using a quasi-classical trajectory method. For both isotopomers, the hydrogen/deuterium abstraction reaction is dominated by a direct rebound mechanism over a very low ＂reactant-like＂ barrier, which leads to a vibrationally hot HF/DF product with an internally cold OH/OD companion. It is shown that the lowered reaction barrier on this PES, as suggested by high-level ab initio calculations, leads to a much better agreement with the experimental reaction cross section, but has little impact on the product state distributions and mode selectivity. Our results further indicate that rotational excitation of the H20 reactant leads to significant enhancement of the reactivity, suggesting a strong coupling with the reaction coordinate.     

SULFATION OF PACHYMAN WITH CHLOROSULFONIC ACID USING THE IMPROVED WOLFROM METHOD

High purity polysaccharide of pachyman was isolated from the powder of Poria cocos sclerotium with an yield of 77.8%. The intrinsic viscosity of polysaccharide was found to be 78.95 mL/g in DMSO solution at 25℃. The isolated polysaccharide was reacted with chlorosulfonic acid to obtain pachyman sulfate using the improved Wolfrom method. The results of the orthogonality experiment on the sulfation reaction identified that the effectiveness of the reaction conditions on the degree of sulfation and the value of intrinsic viscosity is in the following order: molar ratio of chlorosulfonic acid to glucoside (3-5) ＞ reaction temperature (60-80℃) ＞ reaction time (1-2 h). The kinetic studies of the pachyman sulfationindicated that the hydrolysis is accompanied with the sulfation process. The decrease in intrinsic viscosity of the sulfated pachyman is proportional to the increase in the degree of sulfation under the mild reaction conditions of ＜ 80℃,chlorosulfonic acid/glucoside mole ratio ＜ 5, and reaction time ＜ 2 h. Beyond the above reaction conditions, excessive loss of -OH group occurs during hydrolysis. The NMR results indicated a complete sulfation on C-6 and a partial sulfation on the C-2 and C-4 of glucoside.     

The effects of ultrasound frequency and power on the activation energy in Si-KOH reaction system

The activation energy is the minimum amount of energy required to initiate a reaction. It is one of the important indexes for appraising a reaction. The chemical reaction rate is closely related to the value of activation energy, and reducing activation energy is propitious to promoting a chemical reaction. In the present paper, the relationship between the activation energy in Si-KOH reaction system and the ultrasound frequency and power has been discussed for the first time. The range of ultrasound frequency and power is 40-100kHz （interval by 20kHz） and 10-50W （interval by 10W）, respectively. The experimental clata indicate that the activation energy decreases with the increasing ultrasound power. Comparing with the activation energy without ultrasound irradiation, the results in our paper indicate that ultrasound irradiation could reduce the activation energy in Si-KOH reaction system and increase the reaction rate.     

三聚氰胺-甲醛加成反应的研究

The addition reaction between melamine and formaldehyde involves the conversion of melamine into nine different methylol melamines.The reaction mechanism of the complex system can be summarized in a simple reaction model as below:(这里有图片19890824-878-1.gif)The rate equations of above reactions are evaluated by using Runge-Kutta method, and the rate constants are determined by means of fitting them to reaction species concentrations at various times.The molecular distribution formula of methylol derivatives of polyamine, which we developed previously, is used to form simultaneous equations with reaction rate equations and the contents of various meth-ylol-melamine are calculated.The results are good in agreement with the experiment data.     

单电子转移反应 I.单电子转移反应引发的碳一氟键异裂——顺-1,2二苯基六氟环丁烷的烷氧基化脱氟取代反应

A novel reaction involving electron transfer and the breakage of a C-F bond has been investigated. In this reactio, 1, 2-diphenylhexafluorocyclobutane(1)reacts with i-PrONa to yield a substitution product 9. The reaction has to be photostimulated, and O2 and p-dinitrobenzene inhibit the reaction. Interestingly and unexpectedly, other alkoxides, viz. MeO-, EtO-, n-PrO- and t-BuO-, do not react with 1. Thus the reaction does not look like a SRN 1. However, the most amazing fact is: only the cis isomer of 1 reacts, whereas the trans isomer does not. Possibly, simultaneous breakage of α-C-H bond (in the i-PrO-) and formation of a (temporary) H-F bond is involved in a very tight transition state of the (caged?) reaction between the radical anion of 1 and the i-PrO.     

Enzymatic Promiscuity： Escherichia coli BioH Esterase-catalysed Aldol Reaction and Knoevenagel Reaction

Esterase BioH,which is obligatory for biotin synthesis in Escherichia coli,was found to exhibit a promiscuous ability to catalyse Aldol and Knoevenagel reactions with moderate to good yields.The reaction conditions including organic solvent,molar ratio of ketone to aldehyde,enzyme amount,and reaction time were investigated to evaluate the effect of different reaction conditions on yield.Target compounds were afforded in the best yield of 91.2％ for Aldol reaction and 54.7％ for Knoevenagel reaction.In addition,because the enzyme could be prepared with a low cost,this protocol could provide an economic route to conduct Aldol and Knoevenagel reactions,which expand the field of enzymatic promiscuity.     

Reaction Mechanism and Kinetics for HCCO Radical with NO

The mechanism and dynamical properties for the reaction of HCCO radicals with NO were investigated theoretically. The minimum energy paths(MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311 G^** level, and the energies along the MEP were further refined at the QCISD(T)/6-311 G^** level. It is found that the reaction mechanism of the title reaction involves three channels, producing HCNO CO, HONC CO and HCN CO2 products, respectively. Channel 1 is the most favorable path. The rate constant for channel 1 were calculated over a temperature range of 800-2500 K by using the canonical variational transition-state theory(CVT). The rate constant for the main path is negatively dependent on temperature, which is a characteristic of radical reactions with negative activation energy, and the variational effect for the rate constant calculation is small in the whole temperature range.     

KINETIC MODEL FOR DIFFUSION-CONTROLLED INTERMOLECULAR REACTION OF HOMOGENOUS POLYMER UNDER STEADY SHEAR

The kinetic model for diffusion-controlled intermolecular reaction of homogenous polymer under steady shear was theoretically studied. The classic formalism and the concept of conformation ellipsoids were integrated to get a new equation, which directly correlates the rate constant with shear rate. It was found that the rate constant is not monotonic with shear rate. The scale of rate constant is N^-1.5 （N is the length of chains）, which is in consistent with de Gennes＇s result.     

Catalytic Oxidation of NO over La_(0.8)Sr_(0.2)MnO_3 Perovskite

Catalytic oxidation of NO by O2 over La0.8Sr0.2MnO3 was tested in a tubular reactor.The reaction temperature ranged from 373 to 473 K,space time from 0.090 to 0.720 s,inlet NO concentration from 300 to 2000μL/L, and O2 volume fraction from 3%to 9%.The steady-state conversion of NO was increased significantly with increasing reaction temperature and the space time,slightly with increasing the O2 concentration but decreased with increasing the inlet NO concentration at a lower temperature.Under the conditions of 0.720 s space time,500μL/L NO concentration, 5%O2 volume fraction and 473 K,NO conversion reached 90%.A kinetic model including a network of 12 elementary reactions with the desorption of NO2 as the rate-limiting step is established and fits the experimental data well.The activation energy of NO2 desorption from the catalyst surface is determined to be 101 kJ/mol.     

Effects of Experimental Conditions and Kinetics of Photodegradation of Methylene Blue over TiO2

The authors investigated the catalytic activity of TiO2 for methylene blue（MB） degradation under solar light.The reaction parameters such as reaction time,TiO2 content,temperature,pH,MB concentration and light irradiation were in attention.Then,the experimental data was analyzed to investigate the adsorption order and adsorption model.The results indicate that the optimum conditions for the removal of MB are a TiO2 content of 0.5 g/L,0.50 mg/L MB solution,a temperature of 30 ℃ and reaction time of 60 min.It was found that the amount of MB removal was decreased when the pH and temperature increased.This suggests that the removal process is exothermic.However,the solar light irradiation plays a vital role in enhancing the removal amount of MB.In the dark reaction,the ability of TiO2 to remove MB was increased when the pH increased.The kinetics studies confirm that the adsorption of MB is the Pseudo-second-order.And the adsorption model was fitted with the Freundlich isotherm.     

Study on the Deactivation Kinetics of Pd（PPh3）2Cl2 in the Monocarbonylation of Benzyl Chloride

The deactivation kinetics of Pd(PPh3)2Cl2 in the monocarbonylation of benzyl chloride to synthesize phenylacetic acid is studied in this paper. Solid 1-(2-pyridylazo)-2-naphthol (PAN) is used as the colouring agent, and the concentration of Pd(PPh3)2Cl2 in the system is measured through absorptiometry. The result shows that the optimum condition of the chromogenic reaction between Pd2+ and PAN is: 0.5 ml of 0.04% PAN added to 10 ml of Pd2+ solution (1.0×10-6-2.0×10-5 mol/L), and heated in a constant temperature water bath at 40℃ for about 30 min, with pH of the solution being about 3.0. The molar coefficient of absorption is 1.384×104 L/(mol·cm); the orders of the hydrolytic reaction to the concentration of Pd(PPh3)2Cl2, PPh3, phenylacetic acid and NaOH are 0.5, minus 0.8, 2 and 1.2, respectively. The activation energy (E) of the hydrolytic reaction is 75.59 kJ/mol, and the pre-exponential factor is 1.68×1012.     

Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene

We present a theoretical study of the reaction of the hydroxyl radical with ethene using electronic structure calculations and direct-dynamics simulations. High-accuracy electronic structure calculations at the CCSD（T）/aug-cc-pVTZ//MP2/aug-ce-pVDZ level have been carried out to characterize the representative regions of the potential energy surface of various reaction pathways, including OH-addition and H-abstraction. These ab initio calculations have been employed to derive an improved set of parameters for the MSINDO semiempirieal Hamiltonian specific to the OH＋C2H4 reaction. The specific-reaction-parameter Hamilto- nian captures the ab initio data accurately, and has been used to perform direct quasiclassica] trajectory simulations of the OH＋C2H4 reaction at collision energies in the range of 2-10 kcal/mol. The calculated cross sections reveal that the OH-addition reaction domi- nates at all energies over H-abstraction. In addition, the excitation function of addition is reminiscent of a barrierless capture process, while that for abstraction corresponds to an activated one, and these trends can be connected to the transition-state energies of both reactions. We note that the development of an accurate semiempirical Hamiltonian for the OH＋C2H4 reaction in this work required the inclusion of empirical dispersion corrections, which will be important in future applications for which long-range intermoleeular attraction becomes significant.     

A DFT Study of Thiophene Adsorption on the Rh（111） Surfaces

Thiophene adsorption on the Rh(111) surfaces has been investigated by density functional theory.The results show that the adsorption at the hollow and bridge sites is the most stable.The molecular plane of the thiophene ring is distorted,the C=C bond is stretched to 1.448  and the C-C bond is shortened to 1.390.The C-H bonds tilt 22～42oaway from the surface.The calculated adsorption geometries are in reasonable agreement with population analysis and density of states.The thiophene molecule obtains 0.74 electrons,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.The reaction paths and transition states for desulfurization of the molecule have been investigated.The bridge adsorption structure of thiophene leads to a thiol via an activated reaction with an energetic barrier of 0.30 eV.This second step is slightly difficult,and dissociation into a C4H4 fragment and a sulfur atom is possible,with an energetic barrier of 0.40 eV.     

A Study on the Kinetics of the Catalytic Reforming Reaction of CH4 with CO2： Determination of the Reaction Order

The kinetics of the catalytic reforming reaction of methane with carbon dioxide to produce synthesis gas on a Ni/(α-A1203 and a HSD-2 type commercial catalyst has been studied. The results indicate that the reaction orders are one and zero for methane and carbon dioxide, respectively, when the carbon dioxide partial pressure was about 12.5-30.0 kPa and the temperature was at 1123-1173 K. However, when the carbon dioxide partial pressure was changed to 30.0-45.0 kPa under the same temperature range of 1123-1173 K, the reaction orders of methane and carbon dioxide are one. Furthermore, average rate constants at different temperatures were determined.     

A Facile and Efficient Oxidation of α,β-Unsaturated Alcohols with Manganese Dioxide in Ionic Liquids under Mild Conditions

The oxidation of α,β-unsaturated primary and secondary alcohols to corresponding aldehydes and ketones by manganese dioxide in ionic liquids as a safe recyclable and accelerative reaction medium under mild conditions are described. The rate of the oxidation reaction is faster and the yield is higher than that with conventional procedures.     

Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate

Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is （28.795 ± 0.182） kJ/mol （298.15 K）, and the standard molar enthalpy of formation of the title complex is （-2185.43 ± 13.80） kJ/mol （298.15 K）. Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction： an nth-order reaction （Fn） with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction （F2） with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1.     

Studies on the Molecular Chain Conformation Stability of Aminated Konjac Glucomannan

Konjac glucomannan （KGM） was aminated by 2-chloroethyl-amine （CEA） as reagent so as to study the influence of concentration of CEA （based on the amount of KGM）, concentration of NaOH, reaction time and temperature on the extent of amination. And the molecular simulation technology was adopted to analyze the conformation stability of aminate （AKGM）. The results indicate that when the amount of CEA is higher, the extent of amination is higher. The optimum concentration of NaOH, reaction time and temperature are 10% NaOH, 70 ℃ and 45 rain, respectively. IR shows KGM is successfully aminated. The conformation of AKGM is in a random clew-like shape.     

Kinetic Modeling of Plasma Methane Conversion Using Gliding Arc

Plasma methane (CH4) conversion in gliding arc discharge was examined. The result data of experiments regarding the performance of gliding arc discharge were presented in this paper. A simulation which is consisted some chemical kinetic mechanisms has been provided to analyze and describe the plasma process. The effect of total gas flow rate and input frequency refers to power consumption have been studied to evaluate the performance of gliding arc plasma system and the reaction mechanism of decomposition.Experiment results indicated that the maximum conversion of CH4 reached 50% at the total gas flow rate of 1 L/min. The plasma reaction was occurred at the atmospheric pressure and the main products were C (solid), hydrogen, and acetylene (C2H2). The plasma reaction of methane conversion was exothermic reaction which increased the product stream temperature around 30～50℃.