气体在液体中溶解的分子热力学模型

本文提出气体在液体中溶解的分子热力学模型并应用分子聚集型状态方程对CO_2在直链烷烃中的溶解度进行计算,取得较好结果. 一、前言 化学、环保、生化、能源工业的过程设计和开发需要大量的气体在水或有机溶剂或混     

多组分变压器油溶解气体的傅里叶变换红外光声光谱定量检测

油中溶解气体是表征充油型变压器早期故障的重要特征量之一,其组分和含量的高精度检测在变压器运行状态评估和故障预警中拥有重要的研究意义。光声痕量气体检测技术作为一种光学检测手段,具有无损、高检测灵敏度、大动态范围和样品无需前处理等优点,有望实现多种变压器油溶解气体的在线检测。基于傅里叶变换红外光谱仪,结合高精度T型共振光声池,建立傅里叶变换红外光声光谱检测系统,选用CO2和C2H2作为气体样品,开展多种变压油中溶解气体定量检测研究。所设计的T型共振光声池主要由相互垂直的吸收腔和共振腔构成,声探测器位于共振腔顶端远离入射光路,避免了杂散光引起的噪声对光声信号的干扰。光声池的共振频率主要由共振腔决定,共振腔与入射光路垂直,其长度不受水平面的狭窄空间的影响,故可在有限的尺寸下实现低频共振,满足光谱仪样品空间需求。实验选用380μL·L^-1 CO2∶1 000μL·L^-1 C2H2∶N2的混合气体作为待测样品,应用光谱仪中的宽谱光源,选用6 cm^-1空间分辨率,采集并分析该气体样品的红外光声谱。所有气体吸收峰清晰可见,说明该方法可完成多种气体的同时检测。在常温常压条件下, 2 349 cm^-1入射光能量仅为12.6μW时, CO2气体的检测精度为4μL·L^-1,满足国家电网公司企业标准(Q/GDW 536-2010)变压器油中溶解气体在线监测装置技术规范中在线监测装置技术指标对CO2气体最低监测极限值的要求;1 360 cm^-1入射光能量为30μW时, C2H2气体在的检测精度为5μL·L^-1,达到中华人民共和国电力行业标准变压器油中溶解气体分析和判断导则(DL/T 722-2014)中对运行中220 kV及以下的变压器和电抗器设备油中溶解气体含量C2H2含量上限的限定。实验结果表明基于T增强型光声池气体检测系统结合了傅里叶红外光谱的广谱特性和光声气体检测技术的高灵敏度,可实现多种变压器油中溶解气体的高精度定量检测,有望为变压器运行状态监测和故障类型分析评估提供理论依据。     

基于第一性原理计算Mn掺杂MoS2对油中溶解气体的吸附性能

CO、C₂H₂、CH₄是溶解在变压器油中的典型故障特征气体,其种类和浓度能够反映油浸式变压器绝缘故障的不同类型和严重程度,进行油中溶解气体分析是在线检测变压器运行状态的重要方法.基于第一性原理,通过Mn-MoS₂单层对三种气体的吸附能、转移电荷、态密度和形变电荷密度等参数以及解吸性能分析和灵敏度计算,提出了一种基于Mn-MoS₂材料的气敏传感器对油中溶解气体进行分析的方法.结果表明Mn-MoS₂对CH₄是物理吸附,对CO和C₂H₂是化学吸附.对于Mn-MoS₂来说,CH₄在常温下吸附能力差且灵敏度低,CO在不同温度下均有较强的吸附能力,而C₂H₂在常温下吸附稳定,高温下易解吸且响应灵敏度高.因此,Mn掺杂的MoS₂体系可预期作为CO的气体吸附剂和检测C₂H     

变压器油溶解气体的FTIR定量分析

针对色谱进行变压器溶解气体在线监测需要载气、定期标定、安全性低等缺陷,试图建立一种傅里叶变换红外光谱法的油溶解气体在线分析系统。考虑特征气体量小、成分多、检测限及安全要求高,根据特征气体的吸收光谱特征与分析要求,利用分段比基线校正、改进TR正则化特征变量提取算法,建立稀疏偏最小二乘的定量分析模型。以CH₄,C₂H₆,C₃H₆和CO₂等特征气体为例,给出了分析的测试结果。结果表明,在光谱波数分辨率为1 cm-1,光程为10 cm情况下,可以满足变压器绝缘油溶解气体分析要求。     

基于微型光声传感器的油中溶解气体检测技术

为满足油浸式变压器在线监测的需求,根据非共振光声光谱和无孔膜油气分离理论,将直径为40 mm的聚全氟乙丙烯(FEP)高分子膜与体积仅为0.3 mL的光声气室结合,设计了集成光声气体传感器和油气分离膜的微型传感模块,该模块具有体积小、油气分离时间短及可实时在线检测的优点。油中溶解的故障特征气体扩散进入气室中,利用近红外激光光声光谱技术、波长调制和二次谐波检测技术对气室中的气体进行高灵敏度检测。对特征气体C_2H_2检测的实验结果表明,在油温为60℃时,油中溶解气体传感系统可在3 h内实现油气分离平衡,其中对于体积分数为10~(-6)的油中溶解C_2H_2气体的体积分数测量误差在±30%之内。     

水银的清洁法

水银和多种液体是不相溶解的,所以当水银弄湿后,只要用容易吸附液体的脱脂棉或吸水纸一吸就可以了。水银弄脏后只要用细径漏斗过滤一下,也可光亮如镜,清洁异常。水银     

液体密度测量仪

利用纯水作为比较液体,用2个玻璃管与注射器内的气体相通,另一端分别插入水和待测密度的液体中,拉动注射器的活塞,使注射器的压强减小,使液体和水同时在玻璃管中升高,液体上升稳定后,利用封闭在注射器内气体压强与外界大气压强的关系,即可方便测出液体密度.     

光反馈腔增强吸收光谱技术的痕量乙烷检测研究

乙烷是电力变压器油中溶解的主要故障特征气体之一,其高精度、高灵敏度检测是进行油中溶解气体分析的关键。基于光反馈原理及腔增强吸收光谱技术,结合量子级联激光器,建立了一套变压器油中溶解乙烷气体检测系统。基于腔内单腔模对称理论,通过LabVIEW编程来实现反馈光与腔谐振的相位匹配。研究并实现了光学反馈效应(激光将在延迟一定的时间后,返回激光腔并锁定腔模式共振频率)、偶数和奇数模式效应(交替出现强度较大和较小的腔模式)、激光器阈值电流降低效应(约1.2mA)。利用腔衰荡光谱检测技术测得的系统有效反射率、腔品质因素分别为99.978%和7138.4,系统光谱分辨率达到0.005 2cm-1。标准大气压、温度20℃下,1s的积分时间内,对乙烷PQ3吸收线进行检测,系统检测准确率及检测极限分别达到95.72%±0.17%和(1.97±0.06)×10-3μL·L-1,满足了变压器油中溶解乙烷气体检测的需要。     

铀裂变产物中^133Xe的分离

照射过的UO2经7d冷却后装入有回流装置的溶解槽中，溶解槽抽真空后，充入He气，加适量5-7mol．L^-1HNO3，调节He气流速至60mL／min，加热溶解。当溶液开始沸腾时，立即添加20mL的稳定Xe作为载气。溶解过程中释放的氪、氙、碘化氢、氮的氧化物、游离碘、痕量碳氢化合物及少量空气由He气流带出，经两级Na2SO3吸收除去游离碘和酸气后，进入CaCl2干燥器和低温干燥器除去微量水蒸气。留在He气中的氪、氙及部分杂质气体被液氮冷却的分子筛吸附柱吸附。当吸附柱回温到室温时，用60mL／min的He气洗去氪和杂质气体，氙的组分则引入液氮温度下的分子筛纯化柱重新吸附。当纯化柱回到室温，也用60mL／min的He气冲洗。纯化过的氤被收集到液氮温度下的收集瓶中。实验流程如图1所示。最后，将收集的氙转至气体源盒进行放射性强度测量和产品核纯度分析鉴定。     

离子液体-MEA混合工质平板降膜吸收CO_2

设计了CO_2降膜吸收反应器,对比了四种工质20%MEA、20%IL、5%IL+15%MEA、10%IL+10%MEA吸收CO_2性能。结果表明:工质5%[N_(1111)][Gly]+15%MEA每摩尔胺吸收的CO_2量最大,且其CO_2吸收能力被完全利用程度高达89.0%。选取5%[N_(1111)][Gly]+15%MEA为吸收剂,考察了液体流量,液体温度,气体流量,气体进口CO_2浓度对5%[N1111][Gly]+15%MEA吸收剂降膜吸收性能的影响.结果表明:吸收速率随液体流量先增加之后下降,随液体温度、气体流量及气体进口CO_2浓度的增加而增加.     

VOID FORMATION IN UNIDIRECTIONAL SOLIDIFICATION

Abstract

Visual and photographic observations of unidirectional solidification of liquids that shrink by about 10%% is reported. The liquid is contained in a constant-volume (sealed) cylindrical cell. To estimate the effect of gravity, cooling is provided from above or below. For degassed liquids, when solidified from below, it is observed that the shrinkage is accommodated at the top (like a cavity). However, when solidified from above, the shrinkage is accommodated by formation of voids and worms filled with vapor. The effect of dissolved gases is also investigated. It is observed that dissolved gases tend to distribute the voids for both solidification from below and above. Hence, dissolved gases may be used to control the location of shrinkage voids. Some discussions and predictions are made regarding the location of voids formed under zero gravity.     

All-optical switching based on inverse Raman scattering in liquid-core optical fibers

We report on a new platform for all-optical switching based on inverse Raman scattering in liquids. Narrowband switching, which could be suitable for wavelength-division-multiplexed applications, is demonstrated using integrated liquid-core optical fiber infiltrated with both neat liquids (CCl(4) and CS(2)) as well as an organic chromophore (β-carotene) dissolved in CCl(4). Compared to standard glass optical fibers, these liquids have much larger Raman loss coefficients, which help reduce the pump power by at least an order of magnitude. Further improvements can be expected with the development of highly soluble organic compounds possessing large Raman cross sections.     

Hekla cold springs (Iceland): groundwater mixing with magmatic gases

We have analysed the chemical and stable isotope compositions of four spring waters situated just northwest of the Hekla volcano, where cold water emerges from the base of the lava flows. The stable isotope ratios of water (H, O), dissolved inorganic carbon (C) and sulphate (S) were used to determine whether magmatic gases are mixing with the groundwater. The waters can be characterised as Na-HCO₃ type. The results show that deep-seated gases mix with groundwater, substantially affecting the concentration of solutes and the isotopic composition of dissolved carbon and sulphate.     

Optoacoustic phenomena in insulating oils

Sonoluminescence is a process by which light is emitted from collapsing ultrasound-driven gas bubbles in a liquid. Recent works on sonoluminescence have shown that many parameters of the dissolved gas, surrounding liquid and external conditions influences this phenomenon [10]. The light intensity and emitted light spectra depends mainly on the fluid and dissolved gases properties [9,13]. These features indicate the possibility of estimating the amount of dissolved chemical compounds in liquids. The use of sonoluminescence for aging properties diagnostic of insulation oils was proposed. This article presents the schematic of used measurement setup and points out the difficulties in the research resulted from subtleness of the process and no fully accepted sonoluminescence theory.     

A molecular dynamics simulation study on the cavitation inception of water with dissolved gases

The promotion/prevention mechanism of dissolved gases on cavitation inception is essential for many high-tech industries and research. In the present study, large-scale molecular dynamics simulations are performed to investigate the effects of water cavitation caused by different gas types by using nitrogen and oxygen gases with TIP4P/2005 water. The cavitation inception behaviour is analyzed via Mean First Passage Time method. Water with dissolved gases has a higher nucleation rate and is easier to cavitate than pure water. At the same gas concentration, the cavitation of water with nitrogen is promoted to a greater extent than that with oxygen. The number and energy of hydrogen bond (HB) are further calculated by the Acceptor-Hydrogen-Donor method to explain this promotion mechanism. The number and energy of HB in water with gases decrease compared with those in pure water. The introduction of gases weakens the HB network and promotes cavitation inception because of weaker interactions between gas and water molecules. A model is developed to describe the relationship between nucleation rate and HB energy. Gas molecules assemble on the surface of bubbles during water cavitation, which may decrease the free energy of bubble surface, maintain the existing bubble, and contribute to the growth process.     

Determination of sample temperature and temperature stability with 129Xe NMR

The (129)Xe chemical shift of xenon dissolved in isotropic liquids is very sensitive to solvent density, which in turn is dependent on the sample temperature. Therefore, the (129)Xe chemical shift can be used as the basis of a thermometer for measuring actual sample temperatures in NMR experiments. Good accuracy can be achieved, but the thermometer is particularly useful in monitoring temperature stability. In the present case, carbon tetrachloride (CCl(4)), ethylbromide (C(2)H(5)Br), and deuterated chloroform (CDCl(3)) were chosen as solvents because of their large thermal expansion coefficient.     

Visualization of flow fields in a Bubble Eliminator

Bubbles and dissolved gases in liquids greatly influence the performance of fluid power systems, coating solutions, plants in the food industry and so on. To eliminate bubbles from working fluids and to prevent degradation of liquids as well as to avoid possible damage of fluid components is an important engineering issue. Recently one of the authors, Ryushi Suzuki, has developed a new device using swirling flow with the capability of eliminating bubbles and of decreasing dissolved gases in fluids. This device is called “Bubble Eliminator.” The swirling flow pattern and pressure distributions in the bubble eliminator greatly influence the effective performance of the bubble removal. In this paper the swirl flow pattern in a transparent bubble eliminator is experimentally visualized and processed as digital images by a high-speed video camera system. Velocity profiles and pressure distributions in the bubble eliminator are calculated and graphically visualized by a three-dimensional numerical simulation. The results of the flow visualization are compared with the numerical simulation. The performance evaluation of the bubble removal effectiveness is numerically and experimentally verified. It is also proposed to augment understanding of 3D flow fields for the swirling flow in the bubble eliminator with scientific flow visualization methods, which combine graphics or real images with haptic displays.     

三维荧光结合平行因子分析在东海溶解有机物研究中的应用

利用三维荧光光谱（EEMs）结合平行因子分析（PARAFAC）,研究了东海夏、秋两季溶解有机物（DOM）的荧光组分特征,并对其种类、分布和来源进行了分析和讨论。共识别出三个荧光组分,分别为类蛋白荧光组分C1（235, 280/330）、陆源或海源类腐殖质组分C2(255, 330/400)以及陆源类腐殖质组分C3（275, 360/480）。两个类腐殖质组分C2和C3之间呈显著正相关,表明他们有相同的来源或在结构上存在某种联系。三组分在两个季节不同水层的分布总体呈现近岸高,远海低的特点。各组分与叶绿素a和盐度的关系表明调查海域的DOM受现存浮游植物的直接影响很小,夏季长江输入是长江口三组分的重要来源,而秋季受长江输入的影响减弱。本研究显示了三维荧光与平行因子分析相结合在海洋溶解有机物的研究中具有很好的应用前景。     

Effects of dissolved gases and an echo contrast agent on ultrasound mediated in vitro gene transfection

The effects of acoustic cavitation on in vitro transfection by ultrasound were investigated. HeLa cells were exposed to 1.0 MHz continuous ultrasound in culture media containing the luciferase gene. Transfection efficiency was elevated when an echo contrast agent, Levovist was added or air was dissolved in the medium. When cells were sonicated in medium saturated with Ar, N2 or N2O which have different gamma values (Cp/Cv), or were saturated with He, Ar or Ne with different thermal conductivities, the effectiveness for the dissolved gases in the ultrasound mediated transfection was Ar > N2 > N2O or Ar > Ne > He, respectively. When free radical formation in water by ultrasound was monitored as a measure of inertial cavitation, it was similarly affected by dissolved gases. These results indicate that the efficiency of ultrasound mediated transfection was significantly affected either by occurrence of or by modification of inertial cavitation due to various gases.     

How do dissolved gases affect the sonochemical process of hydrogen production? An overview of thermodynamic and mechanistic effects – On the “hot spot theory”

Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H₂) from water, namely the radical attack of H₂O and H₂O₂ and the free radicals recombination, several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals, and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas, i.e., N₂, O₂, Ar and air, may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects, i.e., dynamics of bubble oscillation and collapse events if any, against indirect chemical effects, i.e., the chemical reactions of free radicals formation and consequently hydrogen emergence, it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works, due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera, in the case of CO₂-saturated water where degassing bubbles are formed instead of transient cavitation.