差示扫描量热法测定液体的气化焓和正常沸点

介绍了差示扫描量热 (DSC)测定高沸点液体的气化焓和正常沸点的方法。在升温速率为 80℃ /min、量程为 2 0mJ/s、自然气氛的条件下 ,用邻苯二甲酸二丁酯、乙二醇为标准物 ,测定了正辛醇、甘油和氮酮的气化焓和正常沸点     

掺杂ZrO＿2的Pt／Al＿2O＿3表面氧性质及一氧化碳氧化性能研究

用ＴＰＤ－ＭＳ、ＴＰＳＲ－ＭＳ及ＣＯ氧化活性测定等方法研究了Ｐｔ／Ａｌ２Ｏ３和掺杂超细ＺｒＯ２的样品的表面氧脱出－恢复性能、ＣＯ表面氧化性能及催化氧化性能．结果表明，在Ｐｔ／Ａｌ２Ｏ３中掺杂ＺｒＯ２后，样品表面上的氧物种脱出和氧化恢复性能明显提高，脱氧量也明显增大；并发现在ＣＯ－ＴＰＳＲ过程中程脱物ＣＯ２的脱附量大小及峰顶温度次序与对ＣＯ的催化氧化活性也有一致的关系     

助剂Ag对Cr／γ—Al2O3氧化物催化剂CO氧化性能的影响

本文用硝酸盐水溶液等浸渍法制备了一系列Ｃｒ－Ａｇ／γ－Ａｌ２Ｏ３双金属及单金属的 物催化剂，测定了ＣＯ氧化转化率。用ＢＥＴ，ＸＲＤ，ＴＰＲ，ＴＰＤ－ＭＳ技术研究了助剂Ａｇ对Ｃｒ／γ－Ａｌ２Ｏ３催化剂ＣＯ氧化反应的作用。     

Co／γ—Al2O3催化剂上肉桂醛的选择加氢：催化剂的表征

采用ＸＲＤ,ＴＰＲ,ＸＰＳ技术,分别研究了Ｃｏ３Ｏ４／γ－Ａｌ２Ｏ３样品的晶相结构,还原性能及表面状态,ＸＲＤ结果表明,不同前驱物的钴负载于γ－Ａｌ２Ｏ３后,钴是以Ｃｏ３Ｏ４的结构存在,还原后的钴皆以α－Ｃｏ的形式存在,但以ＣｏＣｌ２为前驱物时,还原后的样品中钴的晶粒较大。     

原子吸收法测定环境水样中化学需氧量

在Ｈ２ＳＯ４介质中用Ｋ２Ｃｒ２Ｏ７同ＣＯＤ水样反应,反应后水相中过量的Ｃｒ（Ⅵ）以Ｃｒ２Ｏ２－７形式被ＴＯＡ萃入有机相中,而生成的Ｃｒ（Ⅲ）则留在水相,用ＡＡＳ测定有机相中的Ｃｒ（Ⅵ）或水相中的Ｃｒ（Ⅲ）都可求得ＣＯＤ含量。本法简便快速、需样量少、且测定结果同标准方法（ＣＯＤＣｒ法）一致,回收率为９８％～１０８％,平均标准偏差为３．３％。     

扫描定点法在Si/Mo多层膜材料深度剖面分析中的应用

用对比方式对分割成二等分的同一Ｓｉ／Ｍｏ多层非晶薄膜样品分别作了ＲＡＳ－ＰＯＩＮＴ ＭＯＤＥ和ＰＯＩＮＴ ＭＯＤＥ的二次离子质谱深度剖面分析,前者是把ＲＡＳ ＭＯＤＥ（扫描法）与ＰＯＩＮＴ ＭＯＤＥ（定点法）有效结合起来的一种方法,即所谓扫描一定点法。实验证明,扫描一定点法有效地克服了弹坑效应（Ｃｒａｔｅｒ ｅｆｆｓｃｔｓ）。     

Zn(Ⅱ)与氯苯基苯并咪唑配合物的合成、表征和晶体结构

带咪唑、苯并咪唑等配位基团的过渡金属配合物是一类很重要的物质[1～ 9] 。本文探讨它与Ｚｎ(Ⅱ )的配位性质及配合物的晶体结构。1　实验部分1 .1　标题配合物的合成及表征将 92ｍｇ 2 (0 氯苯基 )苯并咪唑和 40ｍｇＺｎＣｌ2(ＡＲ)分别溶于无水乙醇(ＡＲ)后混合均匀 ,于室温下静置 3 0天 ,析出长方体形无色晶状物 ,产率为 47%。采用Ｐｅｒｋｉｎ Ｅｌｍｅｒ 2 4 0Ｃ元素分析仪测定配合物中Ｃ、Ｈ、Ｎ含量。用ＤＤＳ 1 1Ｃ数显电导率仪 ,以ＤＭＦ为溶剂测定配合物的摩尔电导。采用Ｎｉｃｏｌｅｔ5ＤＸ Ｂ傅立叶变换红外光谱仪 ,ＫＢｒ压…     

Ag2SO4-CuSO4 催化-微波消解快速测定炼油污水中化学需氧量

以Ａｇ２ＳＯ４－ＣｕＳＯ４为催化剂,探讨了微波消解测定炼油污水中化学需氧量（Ｃｈｅｍｉｃａｌ Ｏｘｙｇｅｎ Ｄｅｍａｎｄ,ＣＯＤｃｒ）的方法。确定了微波消解测定炼油污水ＣＯＤｃｒ的最佳条件;消解功率、消解时间、混酸介质Ｈ３ＰＯ４－Ｈ２ＳＯ４用量、催化剂配比等。用该方法测定炼油水各处理装置出水 的ＣＯＤｃｒ,与经典的ＣＯＤｃｒ回流法所得结果一致。方法适用于临控生产过程。     

掺杂ZrO2的Pt／Al2O3表面氧化性质及一氧化碳氧化性能研究

用ＴＰＤ－ＭＳ，ＴＰＳＲ－ＭＳ及ＣＯ氧化活性测定等方法研究了Ｐｔ／Ａｌ２Ｏ３和掺杂超细ＺｒＯ２的样品的表面氧脱－恢复性能，ＣＯ表面氧化性能有催化氧化性能。结果表明，在Ｐｔ／Ａｌ２Ｏ３中掺杂ＺｒＯ２后，样品表面上的氧物种脱出和氧经恢复性能明显提高，脱氧量也明显增大。     

相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究

对甲氧基肉桂酸 2 乙基己酯是一种有效的ＵＶＢ防晒剂[1 ,2 ] ,一般采用Ｃｌａｉｓｅｎ Ｓｃｈｍｉｄｔ缩合反应制得[3] ,但由于催化剂ＫＯＨ处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (ＰＥＧ)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1　实验部分1 .1　仪器与试剂ＢＩＯ ＲＡＰＦＴ45 0红外光谱仪 ,用液膜法测试 ;Ｂｒｕｒｅｒ ＡＭ 30 0超导核磁共振仪 (溶剂ＤＣ Ｃｌ3) ;ＭＡＴ/44Ｓ ,ＧＣ ＭＳ型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂…     

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。     

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.     

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.     

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.     

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.     

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^-。     

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.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.