Meso-四-（4-磺基苯基）卟啉钴/过硫酸钠-过氧化氢催化氧化降解农药敌敌畏

研究了CoTPPS4/Na2S2O8-H2O2体系(CoTPPS4:meso-四-（4-磺基苯基）卟啉钴)对农药敌敌畏(DDVP)催化氧化降解效果,探讨了氧化剂种类及比例、催化剂用量、农药初始浓度、pH值及反应温度等因素对催化降解速度的影响,并在优化条件下对降解反应的动力学进行了考察。结果表明,随着催化剂用量增加、初始农药浓度的降低、pH值升高(pH值为5～9)和温度的上升,DDVP降解速率增加。室温时,在pH=9缓冲溶液中,农药初始浓度为1.015×10-4 mol/L、CoTPPS4加入量为2.4×10-3 g时,5 mL 0.050 mol/L Na2S2O8-H2O2（体积比4∶1）混合氧化剂存在条件下,7 h后DDVP农药降解率可达72.8%,反应速率常数为0.190 h-1。降解反应动力学研究表明,CoTPPS4催化混合氧化剂降解DDVP农药为表观一级反应,反应表观活化能Ea为5.052 kJ/mol。     

焦炭溶损反应动力学及其模型研究

利用未反应核收缩模型对高炉焦炭与CO2的反应动力学进行了研究，建立了以可测参数（R）表达的焦炭与CO2的反应动力学关系式。并对反应速率常数和有效扩散系数、表观反应活化能和有效扩散活化能及反应过程中各步骤阻力进行了分析。结果表明，（1）焦炭与CO2的反应符合未反应核收缩模型。（2）反应的表观活化能Ea=124.5kJ/mol，有效扩散活化能ED=642.4 kJ/mol；界面化学反应的阻力随反应温度升高而增加；残余灰层内的内扩散传质阻力相对比例随温度升高而下降。（3）焦炭溶损反应在低温区主要受内扩散控制，随着温度升高，反应由外扩散、化学反应和内扩散三步控制；当进入高温区，反应进行一段时间后主要受内扩散控制。     

松香和枞酸在聚乙烯膜上氧化反应动力学研究

设计了松香和枞酸在聚乙烯膜上的氧化反应器, 建立了枞酸在聚乙烯膜上的紫外分光光度分析方法, 跟踪测定了松香和枞酸氧化反应的过程. 实验结果表明, 松香和枞酸的氧化反应均呈现表观一级反应. 枞酸的氧化反应温度为30, 35, 40, 45, 50和55 ℃时, 表观速率常数分别为0.0036, 0.0041, 0.0062, 0.0087, 0.011和0.0157 min^-1, 表观反应活化能Ea为50.29 kJ/mol. 松香的氧化反应温度为35, 40和45 ℃时, 表观速率常数分别为0.0009, 0.0015和0.0025 min^-1 , 表观反应活化能E_a为80.2 kJ/mol.     

丝裂霉素在β-环糊精修饰电极上的电化学研究

研究了丝裂霉素(MMC)在β-环糊精(β-CD)修饰金电极上的电化学行为。结果表明,β-CD/Au电极能与MMC发生表面包络反应。25℃,pH 7.0时,该电极表面包络常数为3.32×105L/mol,且表面包络常数随温度升高而增大,表现为吸热过程。该电极与MMC的包络呈不可逆的电化学过程。25℃,pH 7.0时,其速率常数为0.0706 s-1,且速率常数值随温度升高而增大,活化能为2.13 kJ/mol。在4~8μmol/L浓度范围内β-CD/Au电极上MMC的还原峰电流与浓度呈线性关系,线性方程Ip=14.86+0.43c,相关系数0.9931,检出限0.75μmol/L。     

牡丹花色苷的热稳定性和降解动力学

研究了pH值和温度对牡丹花色苷热稳定性的影响。动力学数据分析表明,牡丹花色苷的热降解符合一级反应动力学模型。在70～90℃条件下,当pH值为2.6、3.0、3.6、4.0和4.6时,牡丹花色苷的半衰期分别为27.0～7.9、32.1～8.5、27.9～8.9、35.9～9.4和27.3～10.7h。提高温度,花色苷降解反应速率增大;降解反应速率常数与温度的关系附合Arrhenius公式,反应活化能为48.4～69.4kJ/mol。牡丹花色苷单体的降解速率依次为矢车菊-3-O-二葡萄糖苷芍药-3-O-葡萄糖苷矢车菊-3,5-O-二葡萄糖苷芍药-3,5-O-二葡萄糖苷。牡丹花色苷降解生成褐色物质,褐变指数随加热时间的延长、加热温度的升高、pH值的增大而增大。     

松香改性酚醛环氧树脂的固化反应动力学研究

以自制的松香改性酚醛环氧树脂（RPAE）为对象,采用差示扫描量热法研究了其与4,4．二氨基二苯砜组成的体系（RPAE／DDS）的固化动力学,利用Kissinger方程计算得到体系的固化热约为109．29J／g,表观活化能为51．56kJ／mol,该体系反应级数为0．85,近似为1级反应,反应速率常数为2．69×10^4／s。采用Ozawa-Flynn-Wall方程分析,得到体系的表观活化能为70。1kJ／mol。     

负载双核茂金属催化剂催化乙烯聚合反应动力学研究

以SiO2为载体,制备了负载的双核茂金属[（η5-C5H5）Zr Cl2]2[μ,μ-（SiMe2）2（η5-allyl C5H2）2]/MAO/SiO2催化剂,以己烷为溶剂进行了淤浆条件下乙烯聚合反应,研究了扩散因素、乙烯聚合压力和聚合温度对乙烯淤浆聚合动力学参数的影响,测定了聚合反应级数和表观活化能,采用动力学和相对分子质量法计算了负载催化剂的活性中心浓度,并对链增长速率常数等动力学参数进行了计算.结果表明,以负载双核茂金属催化剂催化乙烯淤浆聚合反应速率对单体浓度呈1.11级依赖,反应活化能Ea为72.47 kJ/mol,活性中心浓度C＊为0.33 mol/mol,链增长速率常数Kp为1.06×106L.（mol.h）-1.     

正、反向共沉淀法对Pr_2Zr_2O_7纳米粒子表观活化能的影响

以氨水作为沉淀剂,采用正、反向共沉淀法制备Pr2Zr2O7纳米粒子。利用XRD、SEM、TEM、TG-DTA等测试手段表征了样品物相及形貌;研究其制备过程中合成动力学和晶粒生长动力学,采用Doyle-Ozawa法和Kissinger法分别计算正、反向沉淀粒子在主要反应阶段的表观活化能。结果表明:反向沉淀的滴定速率为2 mL·min-1、母盐溶液初始浓度0.05 mol·L-1、反应体系温度273 K、pH值11、煅烧温度为1 173 K,保温2 h的条件下获得的样品形貌近球形、无团聚现象、一次粒径约60 nm。Pr2Zr2O7前驱体的分解过程分为3个阶段,正、反向粒子各阶段平均表观活化能分别为:71.2、97.8、183.2 kJ·mol-1和45.37、84.34、152.16kJ·mol-1;晶粒生长活化能分别为19.02和11.95 kJ·mol-1,后者比前者的晶粒生长活化能降低了7.07 kJ·mol-1;反向共沉淀制备工艺优于正向共沉淀法。     

氨基膦酸螯合树脂吸附重稀土的研究

研究了重稀土在氨基膦酸树脂的吸附行为.试验结果表明,氨基膦酸树脂对重稀土的吸附在pH=5.0的HAc-NaAc缓冲溶液时最佳;298K时静态饱和吸附容量为332mg/g干树脂;用2mol/L盐酸洗脱,洗脱率为91.2%;等温吸附服从Freundlich经验式;吸附反应中△H=10.76kJ/mol,表观速率常数k298=1.223×10-4s-1,表观活化能Ea=3.2kJ/mol.     

工业NiW/Al2O3催化剂上二苯并噻吩的加氢脱硫动力学

以二苯并噻吩(DBT)为含硫模型化合物， 在高压滴流床反应装置中，考察了工业NiW/Al2O3催化剂（RN-10）的加氢脱硫(HDS)动力学规律，研究了氢分压（1.5 MPa～4.5 MPa）、氢油体积比（150~700）、液体质量空速(15 h-1~60 h-1）、反应温度（280 ℃~380 ℃）等对DBT的HDS反应结果的影响。结果表明，当氢分压和氢油体积比较大时，两者变化对DBT的转化率基本无影响；温度对DBT的转化率影响较大，提高温度可有效提高DBT的转化率，随着温度的升高，DBT转化率的增加逐渐变缓。采用2级平推流反应动力学模型对不同温度实验数据进行了拟合，求得了不同温度的表观反应速率常数，模型的相关系数>0.989。活化能计算结果表明，RN-10催化剂在高反应温度区(>330 ℃)的DBT的HDS活化能明显低于较低温度时的活化能，分别为13.4 kJ/mol和121.4 kJ/mol。对于RN-10催化剂，不可单纯地通过提高反应温度来大幅度提高HDS转化率。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。