Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH_3OOH on the atmospheric concentration of OH radicals

Peroxides play an i mportant role in atmosphericchemistry,because they are not only amongthe prin-ciple oxidants in the chemical conversion of O3andSO2,but also act as an atmospheric sink and tempo-rary reservoir for i mportant oxidizing radicals such asOH, HO2and RO2[1 ,2]. With the development ofmeasurement techniques , several organic peroxideswere identified in the atmosphere in addition to hy-drogen peroxide (H2O2)[3—5]. And among these or-ganic peroxides , methyl hydroperoxide ( MH…     

The impact of HS radicals on the measured rate constant of H<Subscript>2</Subscript>S with OH radicals

The rate constant for the reaction of OH radicals and hydrogen sulfide (H₂S) was studied in different bath gases (including N₂, air, O₂ and He) by using relative technique at 298 K. The small difference of the measured rate constants between N₂ and those with the presence of O₂ suggested possible influence of HS self reaction. Further experiments with NO_x presence for scavenging HS demonstrated this assumption. The rate constant of (5.48±0.12) ×10^–12 cm³ molecule^–1 s^–1 obtained with 4.09 ×10^–4 mol m₃ NO presence may be accurate for estimating the atmospheric lifetime of H2S. The results provided circumstantial evidence that the rapid reaction of HS with N₂O is suspected.     

Density functional theory study of the reaction paths of reactions of CH3C(O)O2 radicals with HO2 in the gas phase

A DFT study on the reactions between CH₃C(O)O₂ and HO₂ radicals has been carried out. It is suggested that both the triplet and singlet potential surfaces involve a complex mechanism with the formation of loosely bound intermediate complexes of reactants and products. The reaction prefers to occur on the triplet surface to produce peracetic acid (CH₃C(O)O₂H) and triplet O₂ molecule. The CH₃C(O)O₂H can further convert into CH₃C(O)O and HO radicals.     

Density functional theory study of the reaction paths of reactions of CH3C(O)O2 radicals with HO2 in the gas phase

A DFT study on the reactions between CH₃C(O)O₂ and HO₂ radicals has been carried out. It is suggested that both the triplet and singlet potential surfaces involve a complex mechanism with the formation of loosely bound intermediate complexes of reactants and products. The reaction prefers to occur on the triplet surface to produce peracetic acid (CH₃C(O)O₂H) and triplet O₂ molecule. The CH₃C(O)O₂H can further convert into CH₃C(O)O and HO radicals.     

OH自由基与CS2反应机理的理论研究

用量子化学密度泛函理论(DFT)和G3方法，对OH自由基与CS2的反应进行了研究,在B3LYP／6-31G*,B3LYP／6-311 G(3df，3pd)G3计算水平上,优化了反应势能面上各驻点的几何构型，并对它们进行了内禀反应坐标(IRC)计算和振动分析，以确定中间体和过渡态的真实性，研究结果表明：OH自由基与CS2反应的产物为COS和SH，计算结果与实验结果一致。     

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Using an improved smog chamber system,the temperature dependence of OH radical reaction with EMS was investigated over the temperature range of 297-346 K at 1.01×105 Pa pressure of air. The Arrhenius expression of the reaction was obtained for the first time. The mechanism of the reaction was also investigated.     

基于MLS卫星临边探测数据研究大气OH时空分布

 OH自由基是大气中重要的氧化剂,对大气中其他气体成分和气溶胶的形成和转化起着重要作用。本文利用MLS(micro-wave limb sounder)卫星观测资料,对大气平流层上层和中间层OH自由基的时空分布和变化以及中国上空OH自由基的垂直分布进行分析。结果显示,大气平流层上层和中间层OH自由基含量存在明显的季节变化和昼夜变化,在空间上的分布也随着太阳直射点的不同而呈现一定的周期性。比较了中国上空与同纬度纬向平均值,发现白天和夜间的观测值只有个别位置有较明显偏差,中国地区上空的OH含量比在整体上与同纬度比起来无明显异常,中国局地上空廓线的比较更加详细地反映了OH自由基的昼夜垂直结构。总之,中层大气OH自由基含量存在显著的昼夜变化、季节变化,同时也受太阳活动的影响,年际变化则不明显。     

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.     

无声放电场中OH自由基发生及其氧化碳烟的动力学模拟

在实验研究声声放电作用于Ｎ２－Ｈ２Ｏ简单介质而发生ＯＨ自由基，并给出基本定量结果的基础上，建立电子碰撞模型和单元反应方程组，模拟无声放电场中ＯＨ自由基发生及其氧化碳烟的动力学过程，计算结果与实验数据相吻合。确认ＯＨ自由基在碳烟氧化过程中的关键作用和对其进行动力学模拟的可行性。     

NaOH-Ca(OH)2分解独居石精矿的研究

为降低独居石分解工艺的加碱量,并提高独居石分解率,本研究在NaOH-Ca(OH)₂体系中对独居石精矿进行焙烧分解,采用XRD对焙烧产物进行物相分析,并结合焙烧矿中稀土元素在盐酸中的浸出率判断独居石分解效果.实验分别研究了NaOH添加量、Ca(OH)₂添加量、焙烧温度以及焙烧时间对独居石精矿分解的影响.结果表明,在NaOH-Ca(OH)₂体系中,独居石精矿分解的最佳工艺条件:NaOH添加量为25%,Ca(OH)₂添加量为20%,焙烧温度为800℃,焙烧时间为1.5h.该焙烧条件下独居石全部分解为稀土氧化物,浓盐酸对稀土浸出率可达到98%左右.与现有工业生产工艺相比,本研究工艺中碱添加量降低55%左右,独居石分解率提高2%左右.     

MILD燃烧条件下掺氢比对甲烷-氢气湍流扩散火焰的影响

采用二维轴对称的仿真方法对JHC实验中的第二级MILD燃烧进行数值模拟,研究了燃料体积流量不变时,掺氢比对甲烷-氢气湍流扩散火焰的影响规律.结果表明:随着掺氢比增加,燃料与氧化剂的混合程度逐渐提高,混合气体的总流速及其径向分量不断减小,火焰锋面逐渐向氧化剂侧倾斜,OH自由基的最大质量分数呈现出先上升后下降的趋势;在燃烧温度方面,虽然MILD燃烧主要放热反应区域内的燃烧温度随掺氢比的增加不断增大,但当掺氢比大于20%时,掺氢比的进一步提高对最高燃烧温度影响很小.     

大黄提取物对羟基自由基的清除效果研究

采用四氯化碳和无水乙醇提取大黄中的有效成分，用比色法测定不同浓度的大黄提取物对羟基自由基的清除率。结果表明：大黄的提取物对羟基自由基具有明显的清除作用。找到了在实验条件下，大黄提取物对羟基自由基清除作用的最佳值，即四氯化碳和无水乙醇提取物浓度分别为0．3％和0．15％时，清除率分别为25．3％和50．1％。     

Ca(OH)2-Na2CO3激发矿渣-粉煤灰混凝土的抗裂性能分析

采用Ca(OH)2和Na2CO3（摩尔比1:1）为激发剂制备碱矿渣-粉煤灰混凝土（ASFC）,分别研究了碱当量（Ca(OH)2和Na2CO3反应生成的Na2O与（矿渣+粉煤灰）的质量比为4%、6%、8%和10%）和粉煤灰掺量（粉煤灰与（矿渣+粉煤灰）的质量比为0、20%和40%）对ASFC抗压强度、劈裂抗拉强度、内钢环应变、环向拉应力和抗裂性能的影响,通过开裂系数ζt(t)和抗裂性能评价指标Acr(t)表征ASFC的抗裂性能。研究结果表明：随着碱当量的增加,ASFC的抗压强度和劈裂抗拉强度先增大后减小;当碱当量较小时(4%和6%),ζt(t)和Acr(t)基本不变,继续增大至8%和10%时,二者明显增大,抗裂性能明显降低;随着粉煤灰掺量的增加,ASFC的抗压强度和劈裂抗拉强度先增大后减小;粉煤灰掺量为20%时,ζt(t)和Acr(t)明显下降,抗裂性能提高;继续增大粉煤灰掺量至40%,ζt(t)和Acr(t)变化不大,抗裂性能没有明显提升。碱当量为6%,粉煤灰掺量为20%时,力学性能和抗裂性能最优。     

铝酸钠溶液中Al(OH)3吸附草酸盐行为研究

通过模拟拜耳法晶种分解过程研究了铝酸钠溶液中Al(OH)₃对草酸盐的吸附平衡和动力学行为,并考察了草酸盐初始浓度和Al(OH)₃粒度对吸附的影响规律. 结果表明:Al(OH)₃对草酸钠有较大的吸附能力,随草酸钠浓度的升高和Al(OH)₃粒度的细化,草酸钠吸附率随之升高,达到平衡的时间也相应缩短;不同粒度Al(OH)₃的吸附能力不同,这跟Al(OH)₃的比表面积有很大关系;Al(OH)₃对草酸钠的等温吸附符合Freundlich模型,吸附动力学符合准二级动力学方程,吸附行为为多分子层吸附,同时存在物理和化学吸附过程.     

HCNO＋OH反应机理的理论研究

为揭示HCNO与OH自由基反应的微观机理,采用密度泛函理论（DFT）在B3LYP／6—311G（d,P）水平上对该体系可能出现的7个反应通道上各反应物、中间体、过渡态和产物的几何构型进行了搜索、几何全优化和振动分析验证,并在QCISD（T）／6-311G（d,P）水平上进行了能量校正．计算结果表明：各反应通道均为多步过程,反应的主产物为H2NO＋CO和HCO＋HNO,它们分别经历通道3和通道7而最后生成．     

Density functional theory study of the reaction paths of reactions of CH_3C(O)O_2 radicals with HO_2 in the gas phase

Acetyl peroxyradicals play a major roleinthe at-mospheric degradation of organic compounds .In pol-luted atmospheres ,the reaction between CH3C(O)O2radical and NO2forms the well-known PAN(peroxy-acetyl nitrate , CH3C(O)OONO2) ,an i mportant or-ganic contributor to photochemical smog.Inless pol-luted atmospheres ,the reactions between CH3C(O)O2and HO2radicals become critical as NOxlevels maybe low[1 ,2]. Niki et al . were the first to examine thereactions of CH3C(O)O2with HO2radic…     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

1,25(OH)_2VD_3在过敏原特异性免疫治疗花粉过敏哮喘中的应用

以1,25(OH)₂VD₃为佐剂制备软叶针葵花粉变应原疫苗,以小鼠致敏哮喘模型为研究对象进行特异性免疫治疗.通过检测小鼠气道高反应性、血清中特异性抗体、细胞因子以及肺组织病理学切片等指标对治疗模型的构建进行评价,探讨1,25(OH)₂VD₃在过敏原特异性免疫治疗花粉过敏哮喘免疫机制中的作用.结果表明:以1,25(OH)₂VD₃为变应原疫苗能有效抑制花粉特异性IgE的产生和Th2细胞因子IL-4分泌,促进封闭性抗体IgG2a产生和Th1细胞因子IFN-γ的分泌,增加耐受性细胞因子IL-10生产,使Th2反应向Th1反应转变.1,25(OH)₂VD₃在花粉过敏性哮喘治疗中能大幅提高过敏原特异性免疫治疗的疗效.