Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.     

Investigation of the ozone formation potential for ethanol using a smog chamber

The ozone formation reactivity of ethanol has been studied using chamber experiments and model simulations. The computer simulations are based on the MCM v3.1 mechanism with chamber-dependent auxiliary reactions. Results show that the MCM mechanism can well simulate C 2 H 5 OH-NO x chamber experiments in our experimental conditions, especially on ozone formation. C 2 H 5 OH-NO x irradiations are less sensitive to relative humidity than alkane species under our experimental conditions. In order to well simulate the experiments under high relative humidity conditions, inclusion of N 2 O 5 +H 2 O=2HNO 3 in the MCM mechanism is necessary. Under C 2 H 5 OH-limited conditions, the C 2 H 5 OH/NO x ratio shows a positive effect on d(O 3 -NO)/dt and RO 2 +HO 2 . High C 2 H 5 OH/NO x ratios enhance the production of organoperoxide radical and HO 2 radical concentrations, which leads to a much quicker accumulation of ozone. By using ozone isopleths under typical scenarios conditions, the actual ozone formation ability of ethanol is predicted to be 2.3-3.5 part per billion (ppb) in normal cities, 3.5-146 ppb in cities where ethanol gas are widely used, and 0.2-3.2 ppb in remote areas. And maximum ozone formation potential from ethanol is predicted to be 4.0-5.8 ppb in normal cities, 5.8-305 ppb in cities using ethanol gas, and 0.2-3.8 ppb in remote areas.     

A kinetic study of the reaction of ozone with ethylene in a smog chamber under atmospheric conditions

Ozone is one of the key species in the processes of atmospheric chemistry, which can be taken as an indicator of oxidation capacity in the troposphere. The reaction of ozone with reactive gases is an important process in the troposphere. Experimental simulation equipment of smog chamber for atmospheric reactions is used to study the reaction of ozone with ethylene in real atmospheric environment with ozone concentrations of 100―200 ppb. The concentrations of ozone and ethylene were moni-tored during the reaction with the combination of Model 49C-O_3 Analyzer and GC-FID. A rate constant of 1.01×10~(-18) (cm~3·mol~(-1)·s-(~1)) was obtained at 286.5 K, under condition of which the half-life of ozone was 88 min. The results obtained from our experiments are in excellent agreement with those reported previously by other researchers under extremely low pressure in terms of matrixisolation technology. This demonstrates that our equipment of smog chamber for atmospheric reactions is reliable, which can be used for further research of the processes of atmospheric reactions.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

Formation and causes of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> pollution on the east side of the Taihang Mountains in China

Tropospheric column amounts of NO 2 from OMI/Aura products were applied to investigate the seasonal variation of NO x on the east side of the Taihang Mountains (ESTM) in China. The NO 2 concentration varied seasonally, with winter maxima and summer minima. To explore the causes of the heavy NO 2 pollution in this region, wind field simulations were conducted by using the Fifth-Generation NCAR/Penn State Mesoscale Model (MM5). MM5 simulations showed that wind directions in the ESTM region were dominated by northeasterly and northwesterly winds throughout the year and to a lesser degree by southwesterlies. Elevated NO 2 concentrations (higher than 50×10 15 molec/cm 2 ) occurred in three meteorological situations: convergent wind fields (5 days), northeasterly winds (2 days), and calm days (1 day) in January. Although the local anthropogenic NO x emission strength was not so high as that in other developed areas, the calms and frequent occurrence of convergent wind fields, as well as unfavorable terrains for diffusion, resulted in the accumulation of atmospheric pollutants and hence heavy NO x pollution. Furthermore, long-distance NO x transportation from the Beijing-Tianjin-Tangshan region to the ESTM area could be seen when the wind was from a northeasterly direction, especially under high wind speeds.     

Crystal structure and negative thermal expansion of solid solution Lu<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Lu₂W_3−x Mo _x O₁₂ (0.5≤x≤2.5) were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth tungstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Lu₂W_3−x Mo _x O₁₂ are determined as −20.0×10⁻⁶ K⁻¹ for x=0.5 and −16.1×10⁻⁶ K⁻¹ for x=2.5 but -18.6×10⁻⁶ and −16.9×10⁻⁶ K⁻¹ for unsubstituted Lu₂W₃O₁₂ and Lu₂Mo₃O₁₂ in the identical temperature range of 200 to 800°C. High-temperature X-ray diffraction (XRD) data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

An in-situ DRIFTS study in the reaction between NO x and soot on BaAl2O4

The interactions between NO, O2 and their mixture on BaAl2O4, as well as the reaction of NOx with soot in the presence of O2, have been investigated using Diffuse Reflectance Infrared Fourier Transform Spectroscopy （DRIFTS）. NO adsorption produces only nitrites species in the absence of O2. NO2 adsorption produces nitrates species besides nitrites species. The produced nitrites will further react with O2, Osurf^-. and Olattice^2- to form nitrates. The reaction of NOx with soot begins with the reaction of nitrates with soot oxygenated complex （C（O））, which is regarded as the key and rate determining step. A reaction pathway is proposed for the catalyzed reaction of NOx with soot in the presence of O2.     

Decarburization rate of RH refining for ultra low carbon steel

The decarburization behaviors of ultra low carbon steel in a 210-t RH vacuum degasser were investigated under practical operating conditions. According to the apparent decarburization rate constant (K_C) calculated by the carbon content in the samples taken from the hot melt in a ladle at an interval of 1–2 min, it is observed that the total decarburization reaction period in RH can be divided into the quick decarburization period and the stagnant decarburization period, which is quite different from the traditional one with three stages. In this study, the average apparent decarburization rate constant during the quick decarburization period is 0.306 min-1, and that of the stagnant period is 0.072 min-1. Increasing the initial carbon content and enhancing the exhausting capacity can increase the apparent decarburization rate constant in the quick decarburization period. The decarburization reaction comes into the stagnant decarburization period when the carbon content in molten steel is less than 14×10-6 after 10 min of decarburization.     

Organic media enhanced spectrofluorimetric determination of L-ascorbic acid

A novel spectrofluorimetric method for the determination of L-ascorbic acid is proposed. It is based on the inhibition of L-ascorbic acid on the formation of 2,3-diaminophenazine, which is an oxidation product ofo-phenylenediamine catalyzed by laccase. The fluorescence (at λ_cx/λ_cm=464 nm /530 nnm) was enhanced strongly in the presence of organic media. The mechanism ofo-phenylenediamine oxidation reaction catalyzed by laccase in the presence of L-ascorbic acid is discussed. L-ascorbic acid is determined in the ethanol, 1,4-dioxane and acetone over the linear range of 4.0×10⁻⁷≈1.2×10⁻⁴ mol/L, 4.0×10⁻⁷≈8.0×10⁻⁵ mol/L and 4.0×10⁻⁷≈1.0×10⁻⁴ mol/L with a detection limit of 1.20×10⁻⁵ mol/L, 1.19×10⁻⁵ mol/L and 1.24×10⁻⁸ mol/L, respectively. The method has been successfully applied to the simple and rapid determination of L-ascorbic acid in pharmaceuticals and milk powder. Supported by National Natural Science Foundation of China and the Special Funds of State Education Committe for Doctorate Research Huang Zuyun: born in Aug. 1963. Ph.D     

柴油机SCR尿素喷射方式研究

鉴于柴油机选择性催化还原系统尿素喷射特性与氮氧（NO_x）转化效率密切相关,本文搭建SCR系统小样试验台,NO和NH₃作为主要试验用气,研究了不同氨氮比和不同温度条件下V₂O₅-WO₃/TiO₂催化剂的氨存储、氨泄漏以及NO_x转化效率的影响.结果表明:氨氮比越大,氨存储量的建立时间越短,NO_x转化效率的提升就越快;氨氮比为0.22时,15 s内NO_x转化效率从0增大到4.3%;当氨氮比为0.30时,15 s内NO_x转化效率从0增大到8.7%;随着氨氮比的增大氨泄漏会提前出现;氨氮比先大后小的喷射方法有利于改善NO_x转化效率.采用氨氮比先大后小的喷射方法,进行ETC标准循环测试,NO_x比排放从8.26 g/（kW·h）减少到1.91 g/（kW·h）,NH₃泄漏均值为5×10-6,峰值为18×10-6,满足国V排放法规要求.      

An explanation to the high efficiency ofm-THPC (temporfin) used in photodynamic therapy

Meso-tetrahydroxylphenyl chlorin (m-THPC) is one of the most efficient prospective sensitizers used in photodynamic therapy (PDT). ESR spectroscopy, fluorescence quenching experiments and cyclic voltammogram measurement were used to study its redox properties. The results showed that the ability of m-THPC generating superoxide radical anions was very strong, and the rate constant of m-THPC fluorescence quenching by oxygen k_q (O₂)=1.46×10¹⁰ mol^-1·s^-1. The values of fluorescence quen- ching rate constant of m-THPC by some other electron acceptors, such as methyl viologen (MV²⁺) and anthraquinone (An), were also measured. And they were k_q (MV²⁺)=5.51×10⁹ mol^-1·s^-1, k_q (An)=7.81×10⁹ mol^-1·s^-1. The oxidation potential of m-THPC was examined to be +0.62 V (vs. NHE) in acetonitrile. All these suggested that m-THPC should be a much stronger electron donor than photofrin, the currently used in clinical photodrug, and may react easily through electron transfer with biological matter to yield various radicals. So it seemed reasonable that the type Ⅰ reaction may play an important role in the high activity of m-THPC-PDT.     

FTIR-ATR chamber for observation of efflorescence and deliquescence processes of NaClO4 aerosol particles on ZnSe substrate

NaClO4 aerosol particles with diameter of 5-20 microns are deposited on the ZnSe substrate. An FTIR-ATR chamber on the ZnSe substrate is set up to observe the structural changes of NaClO4 aerosol particles at crystallization relative humidity （CRH） and deliquescence relative humidity （DRH）. With the decrease of RH （relative humidity） from 96% to 24% in the efflorescence process, the absorbance of O-H stretching band of the aerosol solutions continuously decreases. A sudden decrease of the water peak is observed at RH20%, where solid particles form. Very small amount of residual interfacial water, with two weak peaks at 3602 and 3533 cm^-1, can still be resolved in the FTIR-ATR spectra of the solid particles. In the deliquescence process of the same sample, little spectral changes are observed when the value of RH varies from 5% to 29%. Before the abrupt increase of the O-H stretching band at the DRH of about RH46%, a pre-deliquescence process is observed, i.e. in the RH range between 33% and 46%, there is really a slow absorbance increase for the peak area of O-H stretching band. The O-H stretching band shows an arciform O-H en- velope, totally different from not only the FTIR-ATR spectra of ClO4^- solutions either under supersaturated state or in diluted state, but also the characteristic of the residually interfacial water discussed in the efflorescence process. Such kind of water is considered as pure water, indicating that small amount of water aggregates in the microspaces of solid aerosol particles due to the capillary cohesion effect. When the RH arrives at RH44%, two weak shoulders at 3384 and 3260 cm^-1 can be resolved, and the solid NaClO4 particles begin to be dissolved by increasing capillary cohesion water. The spectral characteristic of the v3-ClO4^- band also shows the transition from solid particles to mainly solvated ClO4^- ions.     

Kinetic investigation of <Emphasis Type="Italic">in situ</Emphasis> growth of CdMoO<Subscript>4</Subscript> nano-octahedra

CdMoO₄ nano-octahedra were grown in situ at room temperature by reverse-microemulsion. Energy evolution from this growth process was monitored using microcalorimetry. The microcalorimetric heat flow (MCHF) curve showed a characteristic endothermic peak for the initial reaction, and double discontinuous exothermic peaks for the subsequent crystal growth. Combined with complementary characterization techniques, the evolution of morphology and size of the CdMoO₄ nano-octahedra were correlated with the MCHF peaks. Calculations based on the microcalorimetric results at 298.15 K provided rate constants of 7.56×10⁻⁵ s⁻¹ for the reaction and nucleation process and 1.59×10⁻⁴ s⁻¹ for the crystallization process.     

HPLC determination of ascorbic acid using luminol-Cu (II) chemiluminescence-application to the analysis of Juice beverage

The chemiluminescence (CL) of luminol-Cu (II) was applied to HPLC determination of ascorbic acid, which was separated by a C₁₈ reverse-phase column with a mobile phase of 0.25 mol/L HAc. The eluted ascorbic acid was mixed with 0.3 mmol/L luminol and 0.05 mol/L CuSO₄. The light emission from the reaction of Cu(II) oxidized ascorbic acid and luminol was detected by a modified luminometer. The detection limit was 3.6×10⁻⁶ mol/L for ascorbic acid at aS/N ratio of 3, and the linear calibration range was 2×10⁻⁴–2×10⁻³ mol/L. The relative standard deviation for 5 replicate injections of 1×10⁻³ mol/L ascorbic acid was calculated as 4.3%. The method was successfully applied to determination of ascorbic acid in juice beverage. Foundation item: National Natural Science Foundation of China (29605001) Biography: Wu Feng-wu(1963-), male, research direction: analytical chemistry.     

Comparative analysis of the dissolution kinetics of galena in binary solutions of HCl/FeCl<Subscript>3</Subscript> and HCl/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comparative study of the dissolution kinetics of galena ore in binary solutions of FeCl₃/HCl and H₂O₂/HCl has been undertaken. The dissolution kinetics of the galena was found to depend on leachant concentration, reaction temperature, stirring speed, solid-to-liquid ratio, and particle diameter. The dissolution rate of galena ore increases with the increase of leachant concentration, reaction temperature, and stirring speed, while it decreases with the increase of solid-to-liquid ratio and particle diameter. The activation energy (E _a) of 26.5 kJ/mol was obtained for galena ore dissolution in 0.3 M FeCl₃/8.06 M HCl, and it suggests the surface diffusion model for the leaching reaction, while the E _a value of 40.6 kJ/mol was obtained for its dissolution in 8.06 M H₂O₂/8.06 M HCl, which suggests the surface chemical reaction model for the leaching reaction. Furthermore, the linear relationship between rate constants and the reciprocal of particle radius supports the fact that dissolution is controlled by the surface reaction in the two cases. Finally, the rate of reaction based on the reaction-controlled process has been described by a semiempirical mathematical model. The Arrhenius and reaction constants of 11.023 s⁻¹, 1.25×10⁴ and 3.65×10² s⁻¹, 8.02×10⁶ were calculated for the 0.3 M FeCl₃/8.06 M HCl and 8.06 M H₂O₂/8.06 M HCl binary solutions, respectively.     

200 MW四角切圆锅炉燃烧器浓淡比对NOx排放影响的数值研究

以某热电厂200MW四角切圆浓淡煤粉燃烧锅炉为对象,通过数值模拟获得了该炉最大连续出力工况(BMCR)下炉膛内的流场、温度场及炉膛出口的NO_x浓度,并进一步通过数值模拟探讨了改变水平浓淡煤粉燃烧器浓淡比时对炉内燃烧及NO_x生成情况的影响.数值结果表明:在BMCR工况下,计算值与实际运行的在线仪表的记录值基本一致;当浓淡比增大时,NO_x生成量并不是单调的,而是先降低后升高;其中最佳浓淡比为5∶1,且在此基础上采用"缩腰型"配风有助于进一步降低NO_x生成量.其计算结果可供同类锅炉实际运行时参考.     

Studies on reduced extent method for inhibited thermokinetics of enzyme-catalyzed reaction

The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distinguishing inhibition type was given and the methods for calculating kinetic parameters,K _M,K _i andv _m were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation ofo-dihydroxybenzene bym-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type,K _M=6.224×10⁻³ mol·L⁻¹,K _i=2.363×10⁻² mol·L⁻¹. Xiong Ya: born Sep. 1961, Ph. D. graduate student. Curent research interest is in biothermochemistry research Supported by the National Natural Science Foundation of China     

壁面绿化及热效应对浅型街谷内污染物扩散与转化的影响研究

采用经风洞实验验证的CFD数值模型,就壁面绿化和热效应对浅型街谷内污染物扩散和NO_x-O₃光化学转化的影响开展研究。考虑了4种壁面受热模式以及4种叶面积密度的壁面绿化模式,并采用臭氧消耗率衡量光化学反应的剧烈程度。结果表明,壁面受热会改变街道峡谷内的流动结构,背风面受热和地面受热能够增加峡谷内顺时针旋涡的尺度,迎风面受热会削弱该旋涡的尺度,全壁面受热则会破坏旋涡结构。壁面绿化的设置能够有效降低峡谷内平均温度,促进峡谷内旋涡结构的重构,并且不同程度降低平均臭氧消耗率。因此,壁面绿化对缓解城市热岛效应和光化学污染具有积极的意义。     

Chemiluminescence determination of thiourea using tris (1,10-phenanthroline)-ruthenium (II) KMnO4 system

The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) ₂ ^{3 +} is used to determine 1.0×10⁻⁵ −1.0×10⁻⁵ mol/L thiourea. The limit of detection is 9.8×10⁻⁹ mol/L and the relative standard deviation is 1.1% for a 1.0×10⁻⁵ mol/L thiourea solution (n=10). The method was applied satisfactorily to the determination of thiourea. Foundation item, Support by Ministry of Education, Wuhan University and Alumni Association of it Biography: Wu Feng-wu(1963-), Male, Ph. D, research direction: analytical chemistry.