物理化学实验装置改进点滴

几年来,我室对物理化学实验装置进行了一些改进;这些改进虽小,但在教学实践中收到了良好的效果。现就液体饱和蒸汽压的测定、表面张力测定两实验改进前后的情况对比加以说明。     

EXCEL在物理化学实验数据处理中的应用

应用Excel对数据进行作图、线性拟合、非线性曲线拟合等处理,以测定液体表面张力实验数据的处理为例,介绍Excel软件在物理化学实验数据处理中的具体操作方法.     

离子液体[emim][Tf_2N]的表面张力、密度、黏度及电导率实验测定

在298.15~338.15 K 0.1 MPa工况下测定了离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([emim][Tf_2N])的表面张力、密度、黏度及电导率;采用最小二乘法拟合了实验数据,得到了表面张力和密度随温度的回归方程;在相同工况下,同其他实验数据以及采用基团贡献法得到的数据进行了对比;同时,研究了相关物性参数同离子液体结构和温度的关系。研究结果表明:离子液体的表面张力随阳离子取代基碳链长度的增大而减小,随阴离子尺寸的增加而减小;其表面张力和密度随温度的升高均呈线性减小变化;黏度随着温度的升高逐渐降低;电导率随着温度的升高而增大。以上物性的测定和研究,填补了离子液体[emim][Tf_2N]相关物性参数的空白,同时也为该种离子液体的应用,尤其是在吸收式制冷系统中的应用,提供了参考。     

近化学专业“液体物性测定”综合实验研究

通过物性测定综合实验,判定无色透明纯液体A和B。综合运用数字式真空计测定不同温度下纯液体A和B的饱和蒸气压,用图解法求得该液体在实验温度范围内平均摩尔汽化热与正常沸点;用最大泡压法测定液体A和B的表面张力;用阿贝折光仪测定A和B液体的摩尔折光率等参数。系列物化综合探索试验显示,液体A应是环已醇,而液体B应是环已烷。     

1-乙基-3-甲基咪唑醋酸盐离子液体的基础物性研究

新型功能性离子液体[emim]Ac吸收CO_2性能良好,但物性研究匮乏。在298.15—338.15 K温度范围内测定了离子液体[emim]Ac的黏度和表面张力及308.15—428.15 K温度范围内的比热容。结果表明:当压力一定时,离子液体[emim]Ac的黏度和表面张力均随温度的升高逐渐减小;比热容随温度的升高先减小后逐渐增大;分别采用Litovitz方程和Eotvos方程进行黏度、表面张力数据的关联,比热容与温度的关联式符合温度的N次函数,得出平均相对偏差分别为:0.04%,1.11%,3.53%,理论关联与实验测定结果一致。通过研究补充了离子液体[emim]Ac的相关物性,验证了模型关联对离子液体基础物性关联的可行性。     

三硅氧烷离子液体水溶液的动态表面张力研究

采用气泡压力张力仪测定了三硅氧烷吡啶类离子液体([Si(3)Py]Cl)和三硅氧烷咪唑类离子液体([Si(3)Mim]Cl)水溶液的动态表面张力,考察了浓度和温度对其动态表面张力的影响。根据Word-Tordai方程对所得数据进行分析,计算得出不同测定条件下离子液体分子吸附初始阶段和长时吸附阶段的扩散系数,得出上述2种离子液体在水中的吸附机理均属于混合动力控制吸附。     

液体黏度和表面张力对滤材气液过滤性能的影响

利用滤材实验装置,研究了黏度和表面张力等液体物性参数对气液过滤性能的影响。结果表明:液体黏度对滤材压降影响较小,滤材稳态压降基本不变,液体黏度较小时滤材出口液滴浓度较大,且出口有较多粒径较大的液滴;而液体表面张力对滤材压降有较大影响,液体表面张力较大时出口液滴浓度较大。并利用Ohnesorge数对滤材出口液滴浓度进行了分析,Ohnesorge数越大,则出口液滴浓度越低。     

时间对液体表面张力测定影响的实验探讨

使用DCAT21表面张力仪的挂片法测定液体表面张力。讨论了待测溶液配制后的时间因素对液体表面张力测定值的影响。     

界面化学(二)表面张力测定方法的共同原理

<正> 表面张力是液体的最基本性质,涉及广泛的表面现象。表面张力测定的方法极多,但测得数值的准确度除了决定于实验误差外,很大程度决定于从实验观察到的数据来计算表面张力的数学分析是否成功。本文推荐了Bashforth-Adams 方法。该方法所用的基本公式是Lapalace 方程,这是因为我们实际所要解决的对象多是液体曲面,而且这些曲面都是轴对称的。Lapalace 方程的具体形式为:     

表面张力变化对含气泡液体射流破裂的影响

使用高速相机研究了表面张力变化对含气泡液体射流破裂过程的影响。通过改变表面活性剂浓度获得了不同表面张力的液体射流。实验发现当液体射流速度保持不变时,减小液体表面张力会增加射流破裂长度。表面活性剂一方面降低了液体动态表面张力,减小了射流表面不稳定波的增长率,增大了射流破裂长度;另一方面表面活性剂在射流表面的非均匀分布会产生Marangoni应力,促使液体向射流变形区运动,从而推迟了射流破裂的发生,增大了射流破裂长度。通过理论分析得到了液体射流破裂长度表达式。发现射流内部气泡会显著缩短含表面活性剂射流的破裂长度。通过气泡扰动射流速度和吸附表面活性剂的分析,揭示了内部气泡对含表面活性剂射流破裂的影响规律。     

Comparison of drop-time and electrocapillary methods for study of adsorption of a neutral molecule at the mercury electrode

The question of the reliability of the electrocapillary technique for measurement of relative changes of surface tension is investigated for the case of aqueous. 0·03N NaClO₄ and for solutions containing the rigid symmetrical molecule pyrazine. Surface tension and adsorption measurements have been made by drop-time and electrocapillary techniques. Only very small differences of surface tension changes, due to adsorption of pyrazine at various electrode charges, can be detected between the two methods. The surface excess/chemical potential relations derived from the results of the two methods are almost identical. It is concluded that systematic errors in the study of electrochemical adsorption by the electrocapillary method do not normally arise.     

物理化学实验“滴重法测定液体表面张力”改革方案设计与实践

文章是在学生思考和教研室同仁的交流基础上,针对原实验方法中需要两个人协作完成、操作熟练要求高、偏差较大的特点,对滴重法测定表面张力方法进行了改革。新实验方案基于原有的实验原理,采用分析天平称重的方法进行,精度高、偏差小,一个人可以独立完成,具有较高的应用价值。同时,对文章新方案的误差来源进行了分析,提出了注意事项和适合范围。     

Predicting the surface tension of biodiesel fuels from their fatty acid composition

The emergence of biodiesel fuels as diesel fuel substitutes has led to several studies on their properties. Surface tension, which plays a role in atomization, has lacked attention compared to other properties. This paper presents a method to predict the surface tension of biodiesel fuels based on the fatty acid composition. Several binary, ternary, and quaternary mixtures of fatty acid ethyl ester gas chromatographic (GC) standards were prepared, and we found that a mass-average equation predicted the surface tension of these mixtures within ±3.5% of their measured values. Six complex mixtures of fatty acid methyl ester GC standards that simulated typical oils used as biodiesel fuels were also prepared. For these complex mixtures the predicted surface tensions of the mixtures, calculated from a mass-average equation, were 2–6% higher than the measured values. A mass-average equation was developed in which we used a weighted surface tension for the individual components, and we found that this method predicted the surface tension of the simulated oils within ±4.5% of their measured values. Five natural vegetable oils were used to produce biodiesel fuels by the transesterification process. The predicted surface tensions of these fuels were all within ±3.5% of their measured values. The surface tensions of 15 biodiesel types were then predicted, based on their fatty acid composition as published in the literature. These results show that the differences in surface tension between biodiesel types are not the main cause of the reported differences in engine tests.     

表(界)面张力测定方法的研究进展

综述了表(界)面张力的测量原理和方法;详细分析了适合高温、高压、不同气氛影响以及动态表面张力的测量方法、表面张力仪器建立时需要注意的问题和影响测量结果准确度的因素以及其发展趋势;指出了在煤液化工艺和石油加氢工艺中考察气氛对表面张力影响时最好采用最大气泡法和悬滴法。     

Correlation between surface tension and physical paint properties

Surface tension is a parameter of decisive importance for characterizing painted and unpainted surfaces related to wetting and adhesion phenomena. Measurements of the surface tension of solids by means of an automatic contact angle measurement device are presented. The theoretical evaluations provide for a separation of the surface tension into polar and disperse components. In addition, this paper briefly touches on other more far-reaching approaches (acid/base) and discusses a method for the determination of the dynamic surface tension of liquids.     

Wettability of HF-CVD diamond films

Wettability of HF-CVD diamond films grown in different conditions has been investigated. Wettability depends on surface tension: solids with high surface tension, as diamond, should be hydrophilic, while solids with low surface tension should be hydrophobic. In spite of these arguments, natural diamond exhibits a moderate hydrophobicity [J. Coll. Inter. Sci. 130 (1999) 35], depending on surface termination (hydrogen or oxygen terminated). In this work we find that CVD diamond films show wettability behaviours ranging from a small, up to clear hydrophobicity, probably according to surface carbon termination functionalities. Wettability does not seem to be influenced by characteristics as film structural morphology or growth orientation direction, which were analysed by SEM, while it seems dependent on surface reconstruction, as detected by Raman and XPS analysis. Moreover, in contrast with natural diamond [J. Coll. Inter. Sci. 130 (1999) 35] we found an enhancement to water wettability when CVD diamond films were treated in a hot filament activated hydrogen atmosphere. We argue that this effect may be due to the hydrogen etching of reconstructed surface layers with lower surface tension.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.     

ZrO2对高硼硅玻璃高温粘度和表面张力的影响

高硼硅玻璃由于熔化温度高,对耐火材料侵蚀严重,ZrO2溶解到玻璃中后使其高温粘度和表面张力发生变化,是产生玻璃缺陷的重要原因之一。通过在母体玻璃中引入少量ZrO2,采用旋转粘度法测试玻璃的高温粘度,采用静滴法测试玻璃的高温表面张力。结果表明,随着含量的增加,ZrO2对玻璃在1530℃以上的粘度影响不大,但可使1530℃以下的粘度有较大提高。玻璃的高温表面张力随着ZrO2含量的增加单调递增,随着温度的升高而降低。     

Measurement of surface tension by the forming bubble method

The present work proposed a modified technique of the forming bubble method for measuring surface tension, and compared surface tension data by this method with other reported data. This method shows an applicability to the study of surface aging effect in a surfactant system.     

Surface activity of foam fractions of a calcium lignosulphonate

Successive foam fractionation has been used to divide a processed calcium lignosulphonate into tractions differing appreciably in surface activity. Static surface tension has been measured by the de Nouy tensiometer and surface tension aging by the sessile bubble (photographic) method. The effect of concentration on surface tension has been determined. The effect of pH at 1% concentration on dynamic surface tension has been determined on freshly prepared solutions.