表面活性剂亲水-亲油能力对动态界面张力的影响

当两个不互溶的液相接触时,如果其中一相或两相含有表面活性物质,就可能产生动态界面张力。两相间的界面张力随时间连续变化,直到平衡为止。在到达平衡的过程中,经常通过一个最低值。酸性油／碱水体系也会出现类似现象。Englind和Berg把动态界面张力解释为表面活性物质在界面上累积的结果,并观察到1,5－戊二醇由白油向水中传质时存在明显的吸附－脱附位垒。Rubin和Radke首次给出了解释酸性原油与碱水溶液接触时产生动态界面张力的物理模型,他们提出在油水上存在一个表面活性物质的脱附位垒,原油中的酸性物质与氢氧化钠在界面上的反应是迅速完成的,而这些物质的脱附,则比较缓慢,从而合理地解释了这一特征。近年来,由于超低界面张力在强化采油中的重要性,国外研究者对酸性油／碱／表面活性剂体系的动态界面张力特征进行了比较系统的研究,但其机理有待进一步探讨,本文通过对正构烷烃／石油磺酸盐体系动态界面张力的研究,考察了吸附－脱附位垒产生的原因、影响因素及其对动态界面张力曲线的影响,对酸性油／表面活性剂体系动态界面张力的机理进行了更深入的探索。     

CMC系列高分子表面活性剂与原油超低界面张力形成机理的研究

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素系列高分子表面活性剂与大庆原油形成超低界面张力的机理.结果表明,CMC系列高分子表面活性剂具有与低分子量表面活性剂相比拟的表/界面活性,其水溶液的表面张力可达2835mN/m,界面张力达到10^-110mN/m.碱的加入可显著降低高分子表面活性剂与原油的界面张力,在适当条件下界面张力达到超低值(10^-3mN/m),可望作为三次采油的驱油剂.等效烷烃模型研究表明,用碱与原油酸性组分的作用来解释碱能使界面张力下降至超低值的传统观点是不完善的,加入碱能使高分子表面活性剂胶束解缔,胶束数量增多,胶束粒径减小,单分子自由链增加,有利于高分子表面活性剂向界面迁移和排布,这是高分子表面活性剂和碱复配体系与原油界面张力下降至超低值的主要原因.     

由表面活性物质溶液的动界面张力外推求平衡界面张力的研究

表面活性物质溶液的界面张力往往随时间而变,难以测得平衡界面张力J。Kloubek^[1]曾应用经验式:1/(δ_H2O-δ_t)=b/(At^1/2)+1/A,以[1/(δ_H2O-δ_t)]对1/t^1/2作图外推求得溶液的平衡表面张力,但所得结果仅与文献值大致相符。本文从理论上分析该经验式的由来,以及产生偏离的原因,并寻求了解决的办法。     

界面不稳定现象与相间迁移

包含有流动界面的多相体系中的溶质相间迁移在一定条件下可导致表现为界面变形、界面流和多种形式界面运动的不稳定现象．该现象的直接驱动力是界面局部区域出现的张力梯度，表面活性物质在该现象中起重要作用[1，2]．溶质相间迁移通常可考虑为三步：（1）溶质在原所在相内部向     

巴比妥酸与芳香醛的固相反应研究

固相有机化学反应作为绿色化学的重要组成部分是近年来发展起来的新领域 [1,2 ] .固相有机化学反应中 ,反应物分子受晶格的控制 ,运动状态受到很大限制 ,因此表现出比溶液更高的反应效率及反应选择性[3～ 6] .巴比妥酸具有生理活性 ,且有较高的化学反应活性 ,尤其是 C5位的氢 ,由于受相邻两个羰基的吸电子作用而具有较强的酸性 ( p H=4.0 0 ) .因此 ,巴比妥酸与芳香醛易发生 Knoevenagel型缩合反应 ,生成 C5取代的衍生物 - 5 -亚烃基巴比妥酸 .这类缩合反应在溶液中很容易发生 [7,8] ,近年来又发现在蒙脱土 KSF存在下 [9] 及无载体条件下…     

室温下Pt电极上CO的脱附机理

利用流动电解池与电化学原位红外光谱技术研究了温度和阴离子竞争吸附等因素对室温下Pt电极上COad的脱附机理与动力学的影响.研究表明当溶液中有Cl-或硫酸根等离子时,室温下未观察到COad从电极表面脱附.但是当溶液相存在与COad的吸附能相当甚至比之更大的粒子如CO或CN-时,COad可以被取代而从电极表面脱附.红外光谱表明吸、脱附过程中CN-ad与COad的红外谱带强度存在反线性的关系,而且变温实验估算得到COad的脱附能垒小于40kJmol-1,该脱附能垒远比CO的吸附能（〉60kJmol-1）小.上述结果进一步验证了室温下COad在Pt电极上的脱附不是热激发脱附.据此结果,本文详细地讨论了我们早先提出的吸附驱动的脱附机理的历程与能量来源.     

表面活性素分子结构对其胶束化行为的影响

采用表面张力、界面张力、荧光、动态光散射(DLS)和冷冻刻蚀电镜(FF-TEM)等方法, 研究了由Bacillus subtilis HSO121所产生的一组表面活性素的胶束化行为. 通过对表面活性素溶液表面张力、表面活性素对水/正己烷界面张力的影响、表面活性素胶束微极性以及胶束粒径和形态的研究, 发现随着表面活性素脂肪链长度的增加, 其表界面活性增强, 溶液中趋向于形成更大的聚集体.     

醇在α-A12O3和硅胶G表面上的脱附规律

吸附质在两相界面上的吸附行为对多相催化、界面化学等有重要意义[1,2]。本文采用程序升温法分别测定了13种醇在α Al2O3和硅胶G表面上的脱附温度td,发现td与醇的沸点及烷基化效应指数[3](PEI)有定量关系。1　实验红外干燥箱100℃干燥30分钟后的吸附剂在所研究的吸附质的饱和蒸汽压、室温下平衡24-48h,以达到吸附平衡;取20-25mg吸附平衡后的吸附剂,用PCT 1A型差热天平进行TG/DTA分析,升温速率为2 5℃/min,升温范围从室温到250℃,由计算机进行数据采集(RSZ 200热分析系统软件),从DTA曲线的最高峰值确定脱附温度,每个样品重复3-5…     

假二元微乳液体系标度律

微乳液是在表面活性物质存在下形成的油 -水混合热力学稳定体系 ,在一定条件下 ,表面活性剂双 -2 -乙基己基硫代琥珀酸钠 (AOT) -水 -正构烷烃可形成油包水型微乳液体系 ,其中分散颗粒的大小仅由水与 AOT的物质的量比 x确定[1] .这类微乳液体系有一个低临界温度 Tc,当温度高于 Tc时体系分成两相 ,两相中分散颗粒的大小相同 ,但颗粒浓度不同 ,因此 ,可看成一个假二元体系 .近年来 ,有关这类微乳液体系在临界区域与温度相关的标度律是否符合 3 D-Ising模型方面存在争论 [2～ 4 ] .本文通过精确测量 AOT-水 -正构烷烃假二元微乳液体系在…     

吸附热脱附-气质联用技术分析烟丝中挥发及半挥发性成分

卷烟致香成分是卷烟质量的重要指标,利用吸附热脱附-气相色谱-质谱技术分析了烟丝中挥发及半挥发性成分79种,其中酸性物质17种,碱性物质5种,中性物质57种,为烟草化学研究提供了简单快速的分析方法.     

Polyelectrolyte/surfactant mixtures in the bulk and at water/oil interfaces

Stabilization of emulsions by mixed polyelectrolyte/surfactant systems is a prominent example for the application in modern technologies. The formation of complexes between the polymers and the surfactants depends on the type of surfactant (ionic, non-ionic) and the mixing ratio. The surface activity (hydrophilic–lipophilic balance) of the resulting complexes is an important quantity for its efficiency in stabilizing emulsions. The interfacial adsorption properties observed at liquid/oil interfaces are more or less equivalent to those observed at the aqueous solution/air interface, however, the corresponding interfacial dilational and shear rheology parameters differ quite significantly. The interfacial properties are directly linked to bulk properties, which support the picture for the complex formation of polyelectrolyte/surfactant mixtures, which is the result of electrostatic and hydrophobic interactions. For long alkyl chain surfactants the interfacial behavior is strongly influenced by hydrophobic interactions while the complex formation with short chain surfactants is mainly governed by electrostatic interactions.     

离子液体表面活性剂1-丁基-3-甲基咪唑烷基硫酸酯的合成及其在水溶液中的聚集行为

采用离子交换法,由1-丁基-3甲基咪唑氯盐（C4mimCl）和烷基硫酸钠合成了一系列无卤素的阴离子表面活性离子液体—1-丁基-3-甲基咪唑烷基硫酸酯[C4mim][CnH2n 1SO4](n=8,12,16),利用表面张力仪、稳态荧光光谱等手段考察了表面活性离子液体在水溶液表面及体相中的聚集行为,结果表明,与传统无机反离子相比,有机咪唑阳离子[C4mim] 作为反离子的离子液体型表面活性剂具有较高的表面活性,[C4mim] 产生的氢键引起的抑制分子规则排列的作用小于其促进分子有序排列的疏水作用。长烷基链的阴离子是界面膜及胶束的主要组成成分,阴离子疏水烷基碳链的增长虽然可促进胶束的形成,但却在一定程度上抑制[C4mim] 离子参与界面或胶束的形成;阴离子所带烷基链越长,越不利于阳离子[C4mim]＋参与界面膜或胶束的形成,界面膜或胶束中表面活性剂排布越松散,即界面张力越大,体系中胶束聚集数较小。     

表面活性剂双水相界面性质的研究

表面活性剂双水相是指正、负离子表面活性剂混合水溶液在一定浓度及混合比 范围内，自发分离形成的两个互不相溶的水相。前文报道了将其作为一种新型萃取 体系，用于生物活性物质的分离。目前有关其相行为、化学物质和生物大分子的分 配方面已有较多研究，但未见两相之间界面化学性质研究的报道。表面活性剂双水 相的形成是一种奇特的相分离现象，两个稀水溶液（含水量可高达99%以上）互不 相溶、平衡共存，其界面结构和界面张力必有其特殊性。     

Studies of Interfacial Activities of Four Kinds of Surfactants at Oil/Water Interface

This article aims to compare the interfacial activities of different kinds of surfactants in the same oil/water system. The anionic surfactants of alkylbenzene sulfonates, the polyoxyethylenated nonionic surfactants, the cationic surfactants of alkyl trimethyl ammonium chlorides, and the zwitterionic surfactants of alkyl hydroxyl sulfobetaines were used, and the interfacial tensions of the surfactant solutions against kerosene at different NaCl concentrations were measured. It is found that the interfacial activities of the alkylbenzene sulfonates are high and ultralow interfacial tensions (<0.01 mN/m) can be obtained at proper salinities. While, the nonionic surfactants have relatively low interfacial activities and the minimum tensions are around 0.01 mN/ms. The salinity scanning curves of the alkylbenzene sulfonates and nonionic surfactants decrease first, then increase, showing their interfacial activities can be changed by the salinity effectively. The cationic and zwitterionic surfactants have very low interfacial activities, of which all the tensions are higher than 0.1 mN/ms and are hard to be changed by the salinity. The experimental results may have important reference values for enhanced oil recovery.     

Interfacial tension between water and high pressure CO2 in the presence of hydrocarbon surfactants

Interfacial tension of water–CO₂ interface was measured by pendant drop method in the presence of a surfactant of various concentrations. The surfactants used were three surfynols which are non-ionic blanched hydrocarbon with different length of the alkyl side chain. Prior to the interfacial tension measurements, the solubility of the surfynols in CO₂ were determined from cloud point method. The measured interfacial tensions indicated that an addition of small amount surfactant did reduce the interfacial tension. The interfacial activities of surfactants were evaluated from the slope of the interfacial tension reduction curve against the surfactant concentration and rationalized in terms of the molecular natures such as hydrophobic alkyl chain length.     

A Study of Dynamic Interfacial Properties as Related to Foaming Properties of Sodium 2,5-dialkyl Benzene Sulfonates

In this article, foaming properties and dynamic interfacial properties of a series of sodium 2,5-dialkyl benzene sulfonates in aqueous solutions were carried out to elucidate the relationship between foaming properties and dynamic interfacial properties. The properties of foams generated from bubbling air through different surfactant solutions were measured using a modified Bikerman device. The dynamic surface tension and surface dilational elasticity were obtained from an image analysis technique based on the oscillating bubble method. The surfactants molecular adsorption at the air/water interface was introduced with Rosen empirical equation and the rate of adsorption was determined from measurements of the dynamic surface tension. The surfactant with the longest alkyl chain shows the lowest dynamic surface activity, which lead to the lowest foam volume. The short ortho straight alkyl chain has little effect on the arrangement of molecules at the interface and the foam stability changes a little with the changing of the ortho alkyl chain length. The foam stability is correlated with both the higher surface dilational elasticity and the larger surface monolayer strength.     

Fluorescent pH sensors with negligible sensitivity to ionic strength

Optical pH determination has the fundamental disadvantage of measuring a signal that depends on the ionic strength of the sample. The problem originates from the complex relationship between the proton activity and the concentration of the pH-sensitive dye. The effect of ionic strength on the signal depends on the charge of the indicator and its environment, e.g. the immobilisation matrix. We present novel lipophilic fluorescein esters carrying one negative charge. They are embedded in an uncharged, highly proton-permeable hydrogel to give optical pH sensors that show a negligible cross-sensitivity towards ionic strength. The fluorescent dyes differ in their substituents. This variation of substituents results in dissociation constants between 5.5 and 8.5. The indicators were made lipophilic by esterification of the carboxy group with a C(18) alkyl chain. Since their spectral properties are quite similar, two indicators may be used in one sensor. This results in an optical pH sensor with a dynamic range that extends from pH 4.5 to 8.     

Enhanced interfacial properties of novel amino acid-derived surfactants: Effects of headgroup chemistry and of alkyl chain length and unsaturation

Amino acid-derived surfactants have increasingly become a viable biofriendly alternative to petrochemically based amphiphiles as speciality surfactants. Herein, the Krafft temperatures and critical micelle concentrations (cmc) of three series of novel amino acid-derived surfactants have been determined by differential scanning microcalorimetry and surface tension measurements, respectively. The compounds comprise cationic molecules based on serine and tyrosine headgroups and anionic ones based on 4-hydroxyproline headgroups, with varying chain lengths. A linear dependence of the logarithm of cmc on chain length is found for all series, and in comparison to conventional ionic surfactants of equal chain length, the new amphiphiles present lower cmc and lower surface tension at the cmc. These observations highlight their enhanced interfacial performance. For the 18-carbon serine-derived surfactant the effects of counterion change and of the presence of a cis-double bond in the alkyl chain have also been investigated. The overall results are discussed in terms of headgroup and alkyl chain effects on micellization, in the light of available data for conventional surfactants and other types of amino acid-based amphiphiles reported in the literature.     

Ring-opening polymerization of nitrogen– and phosphorus-containing monomers: Polymerization mechanism and polymer properties

The first part of this paper describes cationic polymerizations of cyclic imino ethers, 2-oxazolines and 5,6-dihydro–4H–1,3–oxazines, which proceed via cyclic onium propagating species or via covalently bonded alkyl halide species. In an extreme case, both ionic and covalent species are present in equilibrium and propagate concurrently. The propagation rate constants due to the respective species were determined. A poly(cyclic imino ether) becomes hydrophilic or lipophilic dependent on the substituent of the monomer. Based on this principle, various types of nonionic polymer surfactants have been prepared, e.g., diblock and triblock copolymers, graft copolymers, and surfactants having one 2-oxazoline chain. The second part is concerned with ring-opening polymerizations of new eight cyclic trivalent phosphorus monomers. These polymerizations produced phosphorus-containing functional polymers such as a chelating resin. ³¹P NMR analyses of polymerization of cyclic phosphinite monomers led to propose a new mechanism of “Electrophilic Ring-Opening Polymerization”.