胜利和孤岛减压渣油中的硫醚硫和噻吩硫的测定

用ＫＩＯ３电位滴定法测定了胜利和孤岛减压渣油及其色谱分离组分中的硫醚硫，用管式炉定硫法测总硫量，差减得到噻吩类硫的含量。对胜利和孤岛渣油及其亚组分的测定结果表明，胜利减压渣油中的硫约有３６．６％为硫醚硫，６３．４％为噻吩硫；孤岛减压渣油的相应值分别为４０．１％和５９．９％；胜利减渣的芳香分中硫醚硫含量高于其胶质中的硫醚硫含量，且相差较大；而孤岛减渣的这两个组分中的硫醚硫含量相近。硫醚硫在这两个渣油     

初馏~523℃馏分油的碳、硫元素模拟蒸馏方法研究

采用气相色谱-原子发射光谱检测器（GC-AED），建立了同时测定减压馏分油（初馏～523℃）中碳、硫收率随沸点变化的色谱模拟蒸馏分析方法．优化了减压馏分油模拟蒸馏的色谱条件和光谱条件．以C5～C40正构烷烃为试样，建立了正构烷烃的沸点与保留时间的校正曲线，进而得到硫色谱图的保留时间与沸点之间的校正曲线．扣除空白实验下碳、硫的基线后，采用自行研制的切片积分软件，得到减压馏分油中碳、硫的收率随沸点变化的关系曲线，并将碳的模拟蒸馏计算结果与ASTMD2887标准方法进行了对比，结果具有较好的一致性．已将该方法用于催化裂化原料中碳、硫分布随沸点变化的研究中．     

气相色谱法测定催化柴油中硫化物类型分布及数据对比

采用气相色谱-氢火焰离子化检测器-硫化学发光检测器（GC—FID—SCD）联用技术,建立了催化柴油中各种硫化物类型分布的分析方法。考察了色谱条件对催化柴油中各种硫化物分离的影响,定性了某催化柴油中的120多个硫化物,该方法还可以同时提供催化柴油中正构烷烃含量的分布信息。硫化物中的硫在1．5—700mg／L时其峰面积与质量浓度呈较好的线性关系,相关系数达0．9999,响应与硫化物的类型无关。催化柴油中苯并噻吩、4-甲基苯并噻吩、二苯并噻吩、4-甲基二苯并噻吩和4,6-二甲基二苯并噻吩等主要硫化物浓度测定的相对标准偏差（RSD）均小于5．0％。当信噪比（S／N）为3时,测得苯并噻吩硫的检出限为0．1mg／L。将该方法用于不同来源柴油中各种硫化物类型分布的研究,并与气相色谱一原子发射光谱检测器（GC—AED）测硫的数据进行了对比,两种检测器的定量结果大多数具有较好的相关性,相关系数大于0．95。     

催化裂化汽油中类型硫含量分布

利用催化裂化汽油中各类硫化物的系统分析方法,对催化裂化(FCC)汽油和重油催化裂化(RFCC)汽油中各类型硫进行了分析测定,碱洗后FCC汽油和RFCC汽油中类型硫的布规律为:硫醇硫和二硫化物硫的含量较少,硫醚硫含量中等,而噻吩类硫的含量最多,占总硫含量的60%以上.     

用色谱-脉冲火焰光度(GC-PFPD)法分析汽油中的总硫

实验了脉冲火焰光度检测器(PFPI))对汽油中微量有机硫化物的响应性和重现性，用色谱-脉冲火焰光度检测器法(GC-PFPI))和外标法定量测定了齐鲁和胜华FCC汽油全馏分及其窄馏分中的硫含量，并与微库仑法进行了对比，分析结果表明：(1)脉冲火焰光度(PFPD)检测器能够有效排除烃信号的干扰，只输出硫信号，定性简单，重现性好，是分析汽油中总硫含量的理想检测器。(2)采用色谱-脉冲火焰光度(GC-PFPD)法分析汽油中的总硫，操作简单，分析时间短，分析结果准确可靠，标准偏差小于1％。     

水溶性丙烯酸树脂相对分子质量及其分布的测定

选用HPll00型高效液相色谱仪、HP PLgel MIXED—B双柱串联，以四氢呋喃作流动相，采用紫外吸收检测器测定了水溶性丙烯酸树脂的平均相对分子质量及其分布。确定了凝胶色谱(GPC)的最佳实验条件：流动相流速为1.5mL／min，进样质量浓度为1．0g／L，进样体积为40μg/L。该方法测定结果与粘度法测定结果相比相对误差小于6％。     

微库仑法测定石油硫含量

建立了测定石油中硫含量的微库仑法。用硫标准样品对库仑仪的最佳工作参数进行试验和调整,结果表明:裂解段温度为1 000℃,空气流量为1 L/min,裂解段停留时间至少2.5 min时测定结果较为理想。低硫含量、中硫含量、高硫含量油品的取样量分别为10~20 mg,9.5~11.5 mg,5.5 mg左右。该方法测量结果的相对标准偏差小于3%(n=6),两种硫标准样品回收率分别为100.2%,101.9%。该法适用于石油中硫含量的测定。     

高频红外吸收光谱法测定铝土矿赤泥中总碳和总硫含量

试样放入高频燃烧器中,在富氧条件下高频感应加热燃烧。其中的总碳和总硫分别被氧化为二氧化碳和二氧化硫,根据红外气体分析仪的检测器能量的变化,检测总碳和总硫含量。进行了称样量实验,助溶剂选择及加入量实验,通过工作曲线法、增量法、加标回收实验、重复性实验等研究确立了红外吸收光谱法测定赤泥中总碳、总硫含量的方法;测定结果准确度满足要求,通过测定结果比对并与测定方法值对照,方法准确度高,误差小,实用性强。     

关于高频感应炉燃烧-红外光谱法测定碳、硫所用坩埚空白值

近年来,越来越多地采用高频感应炉燃烧-红外光谱法测定材质中碳、硫含量。在使用此方法测定材质中碳、硫时,所用瓷坩埚的质量对分析有一定的影响,瓷坩埚本身所含碳、硫的量对测定结果有影响。尤其是待测材质中碳、硫含量比较低（0.00xx%～0．000x％）时,要求所用瓷坩埚中碳、硫的含量尽可能低且含量稳定。这样在分析中,预先准确地测定出包括瓷坩埚本身的空白值,在测定材质的碳、硫值中予以校正或扣除,才能准确地测出材质中碳、硫含量。按ISO9556—1989和ISO4935—1989感应炉燃烧红外线吸收法测定碳、硫含量的规定,系统空白值（主要是坩埚和助熔剂碳、硫含量之和）是在坩埚中加入与试样等量的纯铁和助熔剂,按照试样分析方法测定含量,     

高频燃烧-红外吸收法测定大气粉尘中碳硫

使用美国LecoCS-344碳硫测定仪以W－Fe为助熔剂测定大气粉尘中碳硫含量，考察了空白值、助熔剂、分析时间对碳硫释放的影响，并应用microsoft Excel 2000软件处理试验数据，最终得到粉尘样品中碳硫含量，方法快速准确，测定范围为0.1%-3%,相对标准偏差优于7％。     

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。     

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.

     

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.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。