可激发气体分子声弛豫过程振动模式能量转移速率计算

研究可激发气体中振动模式能量转移速率和声弛豫过程形成的关系,将单一气体Tanczos弛豫方程理论[J.Chem.Phys.25,439(1956)]扩展应用于混合气体中振动模式的振动-振动(V-V)和振动-平动(V-T)能量转移速率的计算。在室温下CO₂,CH₄,CL₂,N₂和O₂组成的多种混合气体中,振动模式能量转移速率的计算结果表明:对于多个振动模式所形成的声复合弛豫过程,各振动模式的声激发能可由V-V能量转移相互耦合后传递给具有最快V-T转移速率的最低振动频率振动模式,再通过该振动模式的V-T转移退激发形成主弛豫过程。这种选择最快转移路径的声激发量弛豫方式,造成了大多数可激发气体中声弛豫吸收谱的实测数据只存在一个吸收峰的现象。从而提供了一个可通过计算微观振动能量转移速率分析混合气体声弛豫过程形成机理的理论模型。      

基于声弛豫频率的可激发气体压强合成算法

声弛豫频率是声吸收谱峰值点的频率,包含可激发气体成分、环境温度和压强信息.利用声弛豫频率线性正比气体压强的特性,提出一种通过两频点声吸收系数和声速测量值计算声弛豫频率,并通过查表方式合成气体压强的算法.算法的声弛豫频率测量误差具有随声测量值误差线性变换的特性,且当两频点的声吸收测量误差相等时,压强的合成误差为零.对于一定温度下的甲烷及其混合气体,仿真计算证明算法的有效性和声测量误差的稳健性.提供一种简单、稳健性好、可实时连续在线检测可激发气体腔体压强的声学方法.     

常温下氢气声转动弛豫模型研究

氢气声弛豫过程主要由氢气分子的转动弛豫决定.然而,当前大部分声弛豫模型是基于气体分子的振动弛豫,并不适用于氢气.本文利用理想气体焓变与定压热容的关系,提出了一种基于氢气分子转动的弛豫模型,并讨论了转动弛豫和振动弛豫的相似与不同.该模型不仅适用于氢气,还能够和其他气体的振动弛豫模型相结合求解混合气体的声弛豫吸收谱和声速频谱.仿真结果表明,对于H_2,N_2/H_2,CO_2/H_2等气体,该模型生成的声速、声弛豫谱曲线与实验数据符合.本模型为包含氢气的混合气体声学探测提供了一个有效的理论模型.     

可激发气体振动弛豫时间的两频点声测量重建算法

振动弛豫时间是可激发气体分子内外自由度能量转移速率的宏观体现,它决定了声吸收谱峰值点对应的弛豫频率.本文给出了等温、绝热定压和绝热定容三种不同热力学过程下振动弛豫时间的相互关系;基于Petculescu和Lueptow[2005 Phys.Rev.Lett.94 238301]的弛豫过程合成算法,推导了单一压强下两频点声测量值的弛豫时间重建算法.该算法可应用于等温、绝热定压、绝热定容弛豫时间和弛豫频率的重建测量,并避免了弛豫时间传统声测量方法需要不断改变气体腔体压强的问题.仿真结果表明,对于室温下CO_2,CH_4,Cl_2,N_2和O_2组成的多种气体,重建的弛豫时间和弛豫频率与实验数据相符.     

多元可激发气体声弛豫频率的环境影响分析

推导多元可激发气体中声弛豫频率和环境温度、压强的解析关系.理论分析和仿真计算表明：声弛豫频率线性反比于主弛豫过程的弛豫时间,正比于主弛豫过程的振动耦合热容,反比于外自由度热容;温度升高导致振动耦合热容增加、内外自由度能量转移速率增大引起弛豫时间减少,进而造成声弛豫频率正比于环境温度;压强增加使得分子碰撞速率增加引起弛豫时间减少,进而使得声弛豫频率线性正比于环境压强.     

基于混合气体分子复合弛豫模型的一氧化碳浓度检测算法

研究了声波通过混合气体时,复合弛豫声吸收和声速与气体各成分浓度和声频率之间的依赖关系.以一氧化碳气体、水蒸气、氮气和氧气的混合气体为例,分别建立了弛豫声吸收和声速与气体浓度的三维模型,以及弛豫声吸收与声频率的二维模型.完成了通过测量弛豫声吸收和声速计算一氧化碳气体浓度的算法推导,提出了一种依据弛豫声吸收和声速检测气体浓度的简化算法.仿真实验结果不仅证明了算法的理论可行性,还给出了算法的最佳适用声频率范围,并估计了将算法应用于实验的误差原因,证明了算法具有实际可行性. 关键词： 气体浓度声学检测 一氧化碳浓度检测 复合弛豫声吸收 声速     

基于分子弛豫模型的混合气体多物理场二维重建算法

基于气体分子弛豫模型,研究声波传播的弛豫吸收与混合气体浓度及温度的关系,以CO-N₂-O₂混合气体为例,分别建立声速和声弛豫吸收同混合气体温度、浓度关系的三维模型.提出一种在二维空间中同时重建混合气体的温度场、浓度场和流场的算法,并对混合气体多物理场进行仿真重建.数值实验证明了算法的可靠性及实际应用的可行性,并可以将此算法应用到其它混合气体的测量,为混合气体的复杂多物理场测量提供了一种新的有效测量方法.     

基于声吸收谱峰值点的天然气燃烧特性检测理论

天然气的成分构成会随产地来源变化而不同, 使其具有不同的燃烧特性和经济价值.本文利用声吸收谱峰值点随气体成分变化而改变的声分子弛豫现象, 提出一种天然气燃烧特性检测理论.它基于两频点上声测量值可合成声吸收谱峰值点, 且依赖于频率的声吸收谱可由峰值点重建的物理原理; 可利用峰值点对应的特征量——弛豫频率和弛豫吸收最大值与气体成分的关系, 从两个维度同时定量检测天然气成分.该理论避免了传统上测量声吸收谱峰值点方法需要不断改变气体腔体压强的问题, 还具有无需测量气体密度的优点.     

混合气体声复合弛豫频谱的解析模型

为研究声传播和分子多模式振动能量弛豫的相互关系,本文提出了一种混合气体声 复合弛豫频谱的解析模型.该模型从振动模式微观能量转移及其耦合形成宏观弛豫过程两个角度, 分析了依赖于声频率的混合气体有效热容.并通过求解振动模式能量转移的通用弛豫方程, 最终得到可同时体现主副弛豫过程的声弛豫吸收和声频散的解析结果.仿真结果表明, 对于CO₂, CH₄, N₂和O₂组成的多种混合气体, 该模型的声吸收谱与实验数据相符,峰值误差在1%以内,且反映了多振动模式形成的 声复合弛豫吸收谱上通常仅会显现1-2个吸收波峰的物理现象.与已有模型相比, 本解析模型可直接求出混合气体声弛豫频谱上特征点的解析形式,并利于对其进行定性定量分析. 从而为研究声传播特性与气体分子弛豫特性的相互关系提供了一个有效理论模型.     

BCl3振动激发弛豫的红外吸收研究

本工作用红外双共振技术测量了BCl₃分子的振动激发态吸收光谱。观察了分子间的多种弛豫过程及能量转移过程。得到关系式Pτ_V-V^(11BCl₃)=3微秒·托。观察到径向声波对双共振信号的调制,声速为2×10⁴厘米/秒,与计算值相符。 关键词：     

Calculating vibrational mode contributions to sound absorption in excitable gas mixtures by decomposing multi-relaxation absorption spectroscopy

Sound relaxational absorption spectroscopy of excitable gas mixtures is potentially applied for gas composition detection. The relaxation of vibrational modes of gas molecules determines the sound relaxational absorption. However, to our knowledge, the contribution of each vibrational mode available in gas mixtures to sound multi-relaxation absorption has not been calculated in existing literature. In this paper, based on the decoupled expression of the effective isochoric molar heat for a gas mixture, a sound multi-relaxation absorption spectrum is decomposed into the sum of single-relaxation spectra. From this decomposable characteristic, the contribution of each vibrational mode available in the gaseous medium to the multi-relaxation absorption is obtained at room temperature. For various gas compositions including carbon dioxide, methane, nitrogen etc., the calculated contributions of vibrational modes are verified by the comparison with experiment data. We prove the following views with quantifiable outcomes that the primary molecular relaxation process associated with the lowest mode plays the major role in acoustic relaxational absorption of gas mixtures; the mode with lower vibrational frequency provides higher contribution to the primary relaxation process. This work could provide a deeper insight into the relationship between the sound relaxational absorption spectroscopy and gas molecules.     

Synthesizing primary molecular relaxation processes in excitable gases using a two-frequency reconstructive algorithm

Identifying molecular relaxation processes in excitable gases remains challenging. An algorithm that reconstructs the primary relaxation processes is presented. Based on measurements of acoustic attenuation and sound speed at two frequencies, it synthesizes the entire frequency dependence of the complex effective specific heat of the gas, which is the macroscopic "footprint" of relaxation effects. The algorithm is based on the fact that for a simple relaxation process, such as occurs in many polyatomic gases at temperatures around 300 K, the effective specific heat traces a semicircle in the complex plane as a function of frequency. Knowing the high-frequency or instantaneous value of the specific heat provides the capability to not only sense the presence, but also infer the nature and, for mixtures of unlike-symmetry molecules, the concentration of foreign molecules leaking in a host gas.     

基于三频点声速测量的气体压强合成算法

利用声速测量精度高, 测量方法简单的特点, 提出一种基于三个频率点测量声速合成气体压强的算法。首先在三个频率点测量声速, 然后计算得到声速频散谱拐点的弛豫频率, 最后根据弛豫频率与压强成线性正比的关系得到气体压强, 仿真结果验证了该算法的可行性。为在线实时检测气体腔体压强提供了一种技术简单、精度高的超声方法。     

Decoupling multimode vibrational relaxations in multi-component gas mixtures: Analysis of sound relaxational absorption spectra

Decoupling the complicated vibrational-vibrational (V-V) coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 (2012)], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrational- translational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.     

Calculation of vibrational energy transition rates in acoustic relaxation processes for excitable gas molecules

To research the correlation between vibrational energy transition rates and acoustic relaxation processes in excitable gases, the vibrational relaxation theory provided by Tanczos [J.Chem. Phys. 25, 439(1956)] is applied to calculate the energy transition rates of VibrationalVibrational(V-V) and Vibrational-Translational(V-T) energy transfer in gas mixtures. The results of calculation for the multi-relaxation processes in various gas mixtures, consisting of carbon dioxide, methane, chlorine, nitrogen, and oxygen at room temperature, demonstrate that the acoustic energy stagnated in every vibrational mode is coupled with each other through V-V energy exchanges. The vibrational excitation energy will relax through the V-T de-excitation path of the lowest mode because of its fastest V-T transition rate, resulting in that only one absorption peak can be measured for most of excitable gas mixtures. Thus, an effective model is provided to analyze how the vibrational energy transition rates affect the characteristics of acoustic relaxation processes and acoustic propagation in excitable gas mixtures.     

基于光声光谱技术的NO,NO2气体分析仪研究

NO, NO₂是大气污染源中的常见气体, 对环境具有严重的危害性. 为检测污染源中这两种气体的浓度, 构建了成本较低的基于红外热辐射光源的光声光谱气体检测系统. 分析计算得到了NO, NO₂ 在2500–6667 nm波段吸收谱线. 通过建立光声传输线RLC振荡电路模型和仿真得到品质因数、声压大小与谐振腔长、内腔半径以及调制频率的关系, 据此设计了光声池几何结构. 实验表明该系统所测得的光声信号与气体浓度有很好的线性关系, 并且对NO, NO₂气体极限检测灵敏度分别达到4.01 和1.07 μL. 通过调节激光发射波长和选取滤波片, 该系统还可用于其他微量气体的浓度检测. 关键词： 大气污染 光声光谱 气体检测