十六烷基甲苯磺酸钠的界面性能研究

用自制的3种十六烷基甲苯磺酸钠,研究了其正构烷烃/水体系的界面性能。分别考察了磺酸盐支化程度及浓度等内部因素以及外加助剂脂肪醇类型和无机盐浓度等外界因素对磺酸盐最小烷烃碳数n_min以及界面张力值的影响。结果表明,磺酸盐支化程度增加,其n_min变大,最低界面张力值变小;而随着磺酸盐浓度的增加,界面张力值先下降后上升;随着助剂脂肪醇碳链长度的增加,其n_min逐渐变大;无机盐的影响则表现为随着盐浓度的增加界面张力值先下降后上升,超低界面张力值出现在一个适宜的盐浓度范围内。     

系列烷基苯磺酸盐对烷烃的动态界面张力研究

从表面活性剂分子量、表面活性剂浓度、电解质浓度、烷烃碳数等方面考察了系列烷基苯磺酸盐异构体纯化合物的油水动态界面张力行为.研究表明,表面活性剂分子量增大和电解质浓度增加使界面张力动态变化减慢,达到平衡所需时间延长;表面活性剂浓度增加和烷烃碳数增加使界面张力动态变化加快,达到平衡所需时间减少.     

系列烷基苯磺酸盐对烷烃的动态界面性能研究

从表面活性剂分子量、表面活性剂浓度、电解质浓度、 烷烃碳数等方面考察了系列烷基苯磺酸盐异构体纯化合物的油水动态界面张力行为。研究表明,表面活性剂分子量越大和电解质浓度增加使界面张力动态变化越慢,达到平衡所需时间越长;表面活性剂浓度增加和烷烃碳数增加使界面张力动态变化加快,达到平衡所需时间减少。     

不同链长烷基芳基磺酸盐形成微乳液的性质

以Winsor相态图法和拟三元相图法研究了自制的3种不同链长烷基芳基磺酸盐在多组分体系中形成的微乳液的性质, 并考察了分子结构、无机盐和短链醇等的影响. 结果表明, 无机盐浓度的增加导致表面活性剂/正丁醇/正辛烷/NaCl/水形成的微乳液体系在一定温度下发生由WinsorⅠ→ WinsorⅢ→ WinsorⅡ型转变; 随着烷基芳基磺酸盐分子的长烷基链碳原子数的增加, 耐盐能力减弱, 增溶能力提高; 随着醇碳链的增大, 微乳区面积先增大后减小. 当烷基芳基磺酸盐分子结构固定时, 最大微乳液区域醇的选择依据符合Bansal理论. 醇的链长一定时, 随着烷基芳基磺酸盐分子的长烷基链碳原子数的增加, 微乳液的区域变小.     

重烷基苯磺酸盐的界面性质和驱油机理

重烷基苯磺酸盐是在三次采油中广泛采用的表面活性剂之一，但重烷基苯原料组成复杂导致最终磺化产物的驱油效果差异很大.实验通过柱层析的方法将重烷基苯分离成6个族组分，并对其中的二烷基苯、单烷基苯和二烷基茚萘满、烷基萘、多苯烷进行磺化，中和提纯后对各磺酸盐进行界面张力测定.通过对比不同矿化度下界面张力以及各组分复配后的界面张力，对原油等效烷烃数(EACN)以及各组分碳数最低值(nmin)测定，得出各组分之间协同效应的规律和复配机理，从而阐明了重烷基苯磺酸盐的驱油机理.通过研究十二烷基苯磺酸钠(LAS)与各组分之间的复配作用对上述规律和机理进行了进一步验证.     

表面活性剂与油相动态界面张力影响因素研究

对不同类型表面活性剂烷基糖苷(APG1214)、咪唑啉(IAS)、十二烷基苯磺酸钠(SDBS)、烷基酚醚羧酸盐(ss-231)的油水动态界面张力进行了研究。在60℃,5 000 r·min-1条件下,考察了表面活性剂的浓度、表面活性剂的结构、正构烷烃碳数以及原油中活性物质对形成低界面张力影响。实验结果表明:表面活性剂亲水基的亲水性越强,亲水基之间排斥力越小,使得在油水界面排布的密度越大,降低界面张力的效果会更好;当表面活性剂疏水碳链与烷烃碳链相似时,降低界面张力的效果会更明显;无碱体系中原油中的活性物质可在油水界面上形成粘弹性界面膜,这种界面膜的形成减少了表面活性剂分子在界面的吸附,使界面张力升高。     

石油磺酸盐体系中相微乳液研究

宽分子量分布的石油磺酸盐在低浓度时有正丁醇、正构烷烃、盐存在的情况下能成中相微乳液。研究了盐浓度、烷烃种类、醇浓度对该体系中相微乳液的形成及特性影响,得到中相微乳液的特性参数;最佳含盐量Ｓ＾＊、增溶参数σ、盐宽△Ｓ、界面张力γ等,并从理论上进行了探讨。采用模拟驱油装置测定了体系的驱油效率,对优化驱油体系设计具有重要意义。     

MoO3和Nb2O5助剂对Pt/ZrO2催化剂上短链烷烃燃烧反应的不同促进作用

贵金属Pt催化剂具有高活性和热稳定性,广泛应用于催化挥发性有机物的完全氧化反应(燃烧反应).短链烷烃(甲烷、乙烷、丙烷等)化学性质稳定,是最难氧化的一类有机物,常用作考察燃烧反应催化剂性能的模型反应物.然而,目前报道的研究工作通常仅限于针对某一种烷烃底物的催化燃烧,系统考察催化剂以及助剂对不同短链烷烃的催化燃烧活性鲜有报道.在短链烷烃中,甲烷只有C–H键;而其它烷烃除了C–H键;还有C–C键.因此,研究催化剂对甲烷、乙烷和丙烷燃烧反应催化性能的差异性,对于认识催化剂上C–H键和C–C键的活化具有非常重要的意义.本文制备了MoO3或Nb2O5修饰的Pt/ZrO2催化剂并用于短链烷烃的燃烧反应.研究发现,MoO3助剂对甲烷燃烧有明显的抑制作用,但对乙烷,丙烷和正己烷燃烧反应具有促进作用,促进作用随着烷烃碳链的增长逐渐增加;Nb2O5助剂对甲烷、乙烷、丙烷和正己烷燃烧反应均具有促进作用,然而促进作用随着碳链的增长而逐渐减弱.MoO3和Nb2O5助剂的不同促进作用与助剂影响催化剂表面酸性以及Pt物种的氧化或还原态有关.NH3-TPD结果表明,MoO3助剂可以显著增加Pt/ZrO2催化剂表面强酸位点数量,而Nb2O5助剂可以显著增加Pt/ZrO2催化剂表面中强酸位点数量.HTEM结果表明,两种助剂的添加都不会明显改变Pt物种的颗粒尺寸.在Pt-Mo/ZrO2催化剂上,MoO3覆盖部分Pt物种形成丰富的Pt-MoO3界面,促进了金属Pt物种和强表面酸性位点的生成,提高了丙烷燃烧反应活性;Pt-Nb/ZrO2催化剂上载体表面的部分Nb2O5被Pt物种包覆,使得生成的表面Pt-Nb2O5界面低于Pt-Mo/ZrO2催化剂,但由于催化剂表面酸性位的提升,也促进了丙烷燃烧反应活性的提高.XPS结果表明,在甲烷燃烧反应中,Pt-Nb/ZrO2催化剂上Ptn+物种能够更加稳定地存在,这可能是Nb2O5助剂提高Pt-Nb/ZrO2催化剂上甲烷燃烧活性的关键.而Pt-Mo/ZrO2催化剂上Ptn+物种在甲烷反应中可以更容易地被还原,并且由于MoO3的包裹导致暴露的Pt位点数量降低,使催化剂催化甲烷燃烧的活性受到抑制.可见,MoO3助剂更有利于C–C键活化,而Nb2O5助剂更有利于高键能的C–H键活化.综上,本文系统性地研究MoO3助剂和Nb2O5助剂对Pt/ZrO2催化剂上不同短链烷烃的燃烧反应的影响,证实了两种助剂的促进作用与碳链长度的关系是截然不同的.     

NaCl对烷基苯磺酸盐Gemini表面活性剂水溶液性质的影响

采用旋滴法测定了烷基苯磺酸盐Gemini表面活性剂Ia水溶液与正庚烷的界面张力,用超微电极循环伏安法测定了水溶液中Ia的胶束扩散系数.结果发现,NaCl的加入能够使界面张力降低2倍左右,使Ia的胶束扩散系数变大;Ia浓度增大,胶束扩散系数变小,而NaCl浓度增大,胶束扩散系数变大.这些变化说明NaCI的加入使得Ia胶束大小发生了变化.这是由于NaCl的加入降低了Ia离子头基之间的静电斥力,使得Ia分子排列更加紧密,更有效降低了油水的界面张力,使胶束形状变小;同时胶束表面电荷得到中和,胶束的静电斥力相应减小,胶束流动性相应增加,从而表现出较大的胶柬扩散系数.     

十四烷基芳基磺酸盐形成的分子有序组合体

以表面张力法、碘光谱法、水增溶法和相态图法研究了自制的三种十四烷基芳基磺酸盐在不同条件下形成的分子有序组合体(胶束、反胶束和微乳液),并考察了分子结构、溶剂、无机盐和短链醇等对其的影响.结果表明:增加十四烷基芳基磺酸盐分子亲油基支化度,不利于其在水溶液或混合极性溶剂(乙二醇-水)中形成胶束而有利于其在非极性溶剂正庚烷中形成反胶束;溶剂极性的降低,促使表面活性剂溶液由胶束溶液→单体溶液→反胶束溶液转变;无机盐或短链醇的加入促进了水溶液中胶束的形成,且反离子价态数或醇烷基碳原子数越大,越有利于胶束形成;无机盐浓度的增加导致表面活性剂/正丁醇/正辛烷/NaCl/水形成的微乳液体系在一定温度下发生由WinsorI→WinsorIII→WinsorII型的转变.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

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.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。