Problems of the theory of monomolecular dissociation of a one-component gas and dissociation constant of CO2 at high temperatures

Equations determining the temperature of vibrations and dissociation constant of polyatomic molecules with consideration of fast exchange of vibrational quanta are formulated. The equations are simplified considerably if different groups of oscillators have similar temperatures of vibrations. In the case of practical interest, it is sufficient to know the vibrational relaxation time and monomolecular dissociation constant at high densities for solving the problem in a harmonic approximation. Quantitative results are obtained for carbon monoxide.Translated from Zhurnal Prikladnoi Mekhanika i Tekhnicheskaya Fiziki, No. 3, pp. 46–52, May–June, 1972.The author thanks S. A. Losev and N. A. Generalov for additional measurement data and I. S. Zaslonko for useful discussions.     

Nonequilibrium vibration-dissociation phenomena behind a propagating shock wave: Vibrational population calculation

An analysis of nonequilibrium phenomena behind a plane shock is presented concerning the vibrational relaxation and the dissociation of a pure diatomic gas. In the first part, the temperature range is 600 K–2500 K and the dissociation processes are neglected. The population of each vibrational level is computed by solving relaxation and conservation equations. The relaxation process is described by the master equations of each vibrational level. The vibrational transition probabilities appearing in the relaxation equations are calculated analytically and take into account the anharmonicity of molecular vibration and the potential angular dependence. The populations obtained are compared to those calculated using a Treanor model and to those calculated with a nonequilibrium Boltzmann distribution. For moderately high levels significant differences may be observed. The importance of the V-V process is found to be weak for the transitions involving the lowest levels. In the second part, the temperature range is 2500 K–5500K and the dissociation process is taken into account as well as the gas dynamic behavior which did not appear in several recent works. The kinetic equations are transformed to obtain a first order differential system and the resolution of such a system coupled with the conservation equations leads to the population of each vibrational level. The vibrational transition probabilities associated with the atom-molecule interaction are deduced from the cross section calculation used in the first part. The bound-free transition probabilities are obtained, following Marrone and Treanor, assuming that dissociation must occur preferentially from the higher vibrational states: the Marrone and Treanor probability model is extended and employed with an anharmonic oscillator. In the present investigation, behind the shock wave, the evolution of the population distribution expressed as a function of the distance is not monotonous: a lag time appears as shown experimentally in previous works for the macroscopic parameters. For moderately high levels the influence of the anharmonicity and those of the V-V processes appear significant and strongly related. In a general way, in both temperature ranges investigated, the V-V processes reduce the effects of the T-V transfer. Finally the influence of thecharacteristic probability temperature U of Marrone and Treanor is analyzed and a method of determination of local varying U is proposed.     

Quasiequilibrium model of the kinetics of coupled modes of CO2 molecules

The correct allowance for the influence of anharmonicity in the vibrational spectrum of CO₂ on the level distribution of molecules under nonequilibrium conditions, when the vibrational temperature departs significantly from the gas temperature, has become especially urgent in connection with obtaining generation on a number of long-wavelength transitions of CO₂ molecules [1, 2]. The shifts in the levels of coupled modes (symmetric and deformation) are due mainly to Fermi resonance and can reach a considerable value, comparable with the gas temperature even for low levels. In [3] the main features of the quasisteady level distribution of coupled modes were clarified within the framework of the Treanor model of vibrational kinetics. The influence of the ascending flux of quanta, excited by VV exchange under nonequilibrium conditions, on the vibrational distribution was considered in [4–6]. In the present paper we propose a quasiequilibrium model of CO₂ kinetics, obtained without presuming quasisteadiness of the ascending flux of quanta, and making it possible, in contrast to [3–6] to describe the dynamics of the variation of the distribution of molecules among multiplets as a result of processes of VV exchange and VT relaxation between multiplets, with allowance for possible processes of pumping by outside sources. With a Boltzmann population distribution within the multiplets, having the translational temperature of the gas, the problem of studying relaxation in coupled modes is reduced to the equations for an effective anharmonic oscillator with levels corresponding to the multiplets of CO₂ molecules. In this case the levels of the effective oscillator are degenerate with a multiplicity equal to the number of levels in the corresponding multiplet, and they have an anharmonicity constant dependent on the gas temperature. The population distribution of the effective oscillator can be studied by methods developed for the investigation cf a one-mode anharmonic oscillator. The proposed quasiequilibrium model was used for a numerical calculations of the temporal evolution of the distribution function of CO₂ molecules over the levels of coupled modes under the conditions of an extremely maintained discharge.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 3, pp. 16–22, May–June, 1986.     

Effect of vibrational relaxation of molecules on dissociating air characteristics behind a strong shock front

Molecular vibrational relaxation has a considerable effect on the dissociation rate in a gas consisting of molecules of a single type [1]. In gas mixtures such as air, vibrational relaxation also affects the other reaction rates, which may be important in solving several problems of hypersonic aerodynamics. This is due to the fact that in air at temperatures above 5000° the vibrational excitation of nitrogen molecules and the dissociation of oxygen molecules proceed almost simultaneously. We study the effect of vibrational relaxation on the conditions behind a strong shock front.     

Comparison of different approaches to the calculation of chemically nonequilibrium flow with allowance for vibrational relaxation

Chemically nonequilibrium flows with allowance for vibrational relaxation are investigated numerically within the framework of the hypersonic viscous shock layer equations with reference to the example of the flow in the neighborhood of the critical line of the “Buran” orbital vehicle in its motion along a re-entry trajectory. It is found that the vibrational temperatures of the molecular components differ markedly. The distinctive feature of the model in question, as compared with a model with one average vibrational temperature, is the stronger effect on the flow characteristics over the thermally stressed part of the trajectory. The models proposed in the literature for dissociation from an effective vibrational level are compared with the model for dissociation with a certain probability from all the vibrational levels. It is shown that the use of an approximation of the total dissociation constant as a function of translational temperature only may lead to a considerable variation from the results of calculations with allowance for vibrational relaxation on the basis of the equilibrium dissociation rate constant. Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 138–146, March–April, 1994.     

凝聚态物质振动-平动能量弛豫过程的分子动力学模拟

本文利用分子动力学计算机模拟方法,研究了稠密态双原子分子振动-平动弛豫速率与分子离解能、密度和温度的关系。发现振动弛豫速率随着分子离解能的增高而下降。这一现象与由光谱数据得到的结果是一致的。它可以用振动频率的下降来解释;分子振动弛豫速率随密度增大而加快,在我们所作的范围内,似乎看不到弛豫速率与温度有关。     

Vibrational-translational relaxation of anharmonic oscillators at low temperatures

An approximate analytic solution is found to the problem of the vibrational-translational relaxation of anharmonic oscillators at translational temperatures which are small compared with the energy difference between adjacent levels of the oscillator. The deviation of the obtained distribution from the Boltzmann distribution in the relaxation process is analyzed. A study is made of the behavior of the vibrational energy near equilibrium at temperatures such that dissociation has only a small effect on the rate of vibrational relaxation.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 2, pp. 3–8, March–April, 1976.The author wishes to thank M. B. Zheleznyak and A. Kh. Mnatsakanyan for a useful discussion of the work.     

高温非平衡流动中的氧分子振动态精细分析

高超声速流动在头激波压缩后常处于高 温条件下的热化学非平衡状态. 本文采用态-态方法和双温度模型计算分析了一维正激波后和高超声速钝体绕流驻点线上的氧气热化学非平衡流动. 态-态方法将氧气的每个振动能级当成独立的组分,通过耦合 Euler 方程或驻点线上的降维 Navier-Stokes 方程,数值求解得 到了高温流动中的精细热化学非平衡状态. 而双温度模型假设氧气的振动能级服从 Boltzmann 分布,通过求解振动能方程得到振动温度. 一维正激波后热化学松弛过程的计算结果表明,态-态计算预测的温度分布和氧原子浓度分布较好地吻合了文 献中的实验结果,而经典的双温度模型的预测结果误差较大,且不同双温度模型的计算结果比较发散. 态-态方法详细地给出了所有振动能级的变化过程. 无论是正激波还是脱体激波后的流场,都是高振动能级首先得到激发;但是数密度大的低振动能级先达到热平衡,而高能级 分子要经过很长距离后才能达到热平衡. 在驻点附近,复合反应生成的氧气分子处于高振动能级,导致高振动能级分子数密度显著高于平衡分布. 计算还发现,经典双温度模型的离解反应速率明显偏离态-态计算结果,无法准确体现振动离解耦合效应对离解反应 速率的影响,但是 Park 双温度模型将离解失去的振动能取为 0.3$\sim 高超声速流动在头激波压缩后常处于高 温条件下的热化学非平衡状态. 本文采用态-态方法和双温度模型计算分析了一维正激波后和高超声速钝体绕流驻点线上的氧气热化学非平衡流动. 态-态方法将氧气的每个振动能级当成独立的组分,通过耦合 Euler 方程或驻点线上的降维 Navier-Stokes 方程,数值求解得 到了高温流动中的精细热化学非平衡状态. 而双温度模型假设氧气的振动能级服从 Boltzmann 分布,通过求解振动能方程得到振动温度. 一维正激波后热化学松弛过程的计算结果表明,态-态计算预测的温度分布和氧原子浓度分布较好地吻合了文 献中的实验结果,而经典的双温度模型的预测结果误差较大,且不同双温度模型的计算结果比较发散. 态-态方法详细地给出了所有振动能级的变化过程. 无论是正激波还是脱体激波后的流场,都是高振动能级首先得到激发;但是数密度大的低振动能级先达到热平衡,而高能级 分子要经过很长距离后才能达到热平衡. 在驻点附近,复合反应生成的氧气分子处于高振动能级,导致高振动能级分子数密度显著高于平衡分布. 计算还发现,经典双温度模型的离解反应速率明显偏离态-态计算结果,无法准确体现振动离解耦合效应对离解反应 速率的影响,但是 Park 双温度模型将离解失去的振动能取为 0.3$\sim $0.5 倍分子离解能是比较合理的.     

Dissociation of anharmonic molecules by means of high-power infrared emission

The kinetics of nonequilibrium molecular dissociation when vibrations are excited by high-power infrared emission is investigated for a model of anharmonic oscillators. The case when exchange of vibrational quanta during collision with molecules in the lower states plays a fundamental role in the formation of the vibratory distributionfunction at the upper level is analyzed. Dependences of the “vibration temperature” and the rate constant for nonequilibrium dissociation, as a function of the optical pumping probability are obtained for different pumping conditions. The results are compared with similar calculations for a harmonic model.     

On the theory of vibrational relaxation of diatomic molecules

The relaxation of diatomic molecules (harmonic oscillators) in a relatively light inert gas, which plays the part of a thermostat, is considered within the framework of classical mechanics. The gas-kinetic equation for the distribution function of diatomic molecules is approximated by the Fokker-Planck equation in the space of the energies of translational, rotational and vibrational motions on the assumption of strong nonadiabaticity of the collisions. In the approximation discussed, relaxation processes with different degrees of freedom develop independently, although the characteristic times of these processes are quantities of the same order. The vibrational relaxation time, expressed in terms of the gas-kinetic integral ^*(1,1) (T*), is obtained.     

Calculation of the characteristics of a gas-dynamic laser

The dependence of the radiated power on the characteristics of optical cavities in the case of flow systems has been investigated in a number of papers [1–3], in which it is assumed that population inversion of the laser levels is obtained until entry into the cavity. The operation of a cavity is analyzed in [1] in the geometric-optical approximation with allowance for vibrational relaxation in the gas flow. A simplified system of relaxation equations is solved under steady-state lasing conditions and an expression derived for the laser output power on the assumption of constant temperature, density, and flow speed. The vibrational relaxation processes in the cavity itself are ignored in [2, 3]. It is shown in those studies that the solution has a singularity at the cavity input within the context of the model used. In the present article the performance characteristics of a CO₂-N₂-He gas-dynamic laser with a plane cavity are calculated. A set of equations describing the processes in the cavity is analyzed and solved numerically. Population inversion of the CO₂ laser levels is created by pre-expansion of the given mixture through a flat hyperbolic nozzle. The dependence of the output power on the reflectivities of the mirrors, the cavity length, the pressure, and the composition of the active gas medium is determined.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi FiziM, No. 5, pp. 33–40, September–October, 1972.     

A master equation study of vibration-dissociation coupling in shock-heated oxygen molecules

The vibration-dissociation coupling phenomena in shock-heated oxygen molecules highly dilute in an argon heat-bath have been studied numerically. State-to-state transition rate coefficients were evaluated by using relatively simple models developed through the information theoretical approach. The master equation was solved by numerical integration to obtain time-resolved vibrational population distributions. The results of the master equation analysis are compared with those obtained by using a widely-used phenomenological vibration-dissociation coupling model. The results show that during the relaxation process the depletion of high-lying vibrational energy levels is severe and significantly affects bulk properties related to dissociation and that the phenomenological model can reproduce qualitatively the bulk relaxation process found in the master equation analysis. Received 26 June 2001 / Accepted 3 December 2002 Published online 4 February 2003     

Estimation of the effect of vibrational excitation of diatomic molecules on their diffusional transport and dissociation in a boundary layer

Relations for the diffusion fluxes of vibrationally highly excited diatomic molecules are found by means of the Chapman-Enskog method. On the basis of these relations a quantitative estimate of the changes in the diffusion coefficients under vibrational excitation and the corresponding changes in the macroscopic dissociation rate is obtained under conditions of disequilibrium of the upper vibrational levels of the dissociating molecules caused by the diffusion processes. The diffusion relations obtained are used in deriving the boundary conditions for the equations of level vibrational kinetics. A simplified version of this derivation is presented for noncatalytic and catalytic surfaces.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 1, pp. 169–182, January–February, 1996.     

Shock layers over blunt and conical bodies in hypersonic non-equilibrium flow

It is well known that the flow-field over blunt and pointed bodies is sensitive to the non-equilibrium phenomena characteristic of high enthalpy hypersonic flows. Till date, most experiments and modelling were related to flows essentially dominated by the dissociation rate. However, in practical cases of a re-entry low density flow, the aerodynamic quantities such as the shock shape and location may also be strongly influenced by vibrational relaxation coupled with dissociation and chemical reactions. Thus, the flow about various bodies such as spheres, hemisphere–cylinders and cones is recomputed using a chemical model recently proposed by the authors and by taking into account the coupling between the vibrational relaxation and the chemical kinetics. Then, the computed shock shapes in air flow are compared to recent experimental results obtained in a ballistic range for flight velocities between 2,500 and 4,000 m/s, and in a shock tunnel for enthalpies close to 5 and 10 MJ/kg. The computed density field around hemispherical bodies is also compared to the experimental one. A good agreement, within 5%, between computed and measured results is observed. A few comparisons are also proposed with the results obtained with another well-known (empirical) model. A comparison is also made between the flow quantities along the stagnation line obtained over cylindrical and spherical bodies using the present model and those coming from a quasi-one-dimensional model recently developed, showing also a satisfactory agreement.     

高超声速三维热化学非平衡流场的数值模拟

对三维高超声速热化学非平衡流场进行数值模拟,采用双温度热化学非平衡、11组元空气模型,考虑振动-离解耦合．差分格式采用沈清博士提出的“迎风型NND”格式,用熵修正方法消除了高超声速流数值模拟中的“carbuncle现象”．与LU-SGS方法结合,提高了单步计算效率和收敛性．数值模拟结果与文献结果进行了对比,并在弹道靶中进行了钢质圆球的弓形激波位置实验验证．计算结果与文献、实验的对比说明,三维热化学非平衡流计算程序可以精确地捕捉到强弓形激波,得到合理的空气动力系数．     

Diffusion equation in the theory of vibrational relaxation of diatomic molecules

A kinetic equation is obtained for the distribution function of anharmonic oscillators with respect to the vibrational energy; it enables one in the diffusion approximation to describe the vibrational relaxation of diatomic molecules in a medium of inert gas when there is a weak interaction between the oscillators and a thermal bath. The main difference from the equation for harmonic oscillators is in the appearance in the diffusion coefficient of an adiabaticity function that characterizes the variation of the adiabaticity factor because of the anharmoni-city of the vibrations. It follows from the form of this function that the greatest difference between the relaxation of anharmonic and harmonic oscillators is to be expected in the case of adiabatic interaction of oscillators with particles of the inert gas.     

Gekoppelte Relaxation mehratomiger Gase

Übersicht Die Relaxationsgleichungen und die Dissoziationsraten für gekoppelte Relaxation werden aus der sog. Master-Gleichung, welche die Besetzung der einzelnen Energiezustände der Moleküle durch Übergangswahrscheinlichkeiten miteinander in Beziehung bringt, hergeleitet. Zur numerischen Auswertung der Gleichungen wird angenommen, daß ein Molekül dissoziieren kann, wenn die bei einem Stoß ausgetauschte Energie die Differenz aus Dissoziationsenergie und Vibrationsenergie übersteigt. Die Ergebnisse für Moleküle mit bis zu 7 verschiedenen Schwingungsformen zeigen, inwieweit die gekoppelte Relaxation von der Translationstemperatur, den Vibrationstemperaturen und der Anzahl der Schwingungsformen abhängt.

---

Summary The relaxation-equations and the dissociation rate-equations for coupled relaxation are derived from the master equation, which gives a relation between the population of the energy-levels of a molecule by means of transition-probabilities. For a numerical evaluation the assumption is made that a molecule may dissociate, if during a collision the relative line of center translational energy exceeds the difference between the dissociation energy and the vibrational energy. Results for molecules with up to 7 different modes of vibration show the effects of the translational and vibrational temperatures and of the number of vibrational modes.

     

Vibrational distribution functions and relaxation rate in anharmonic-oscillator systems

Analytical expressions were derived for the vibrational distribution function in a system of anharmonic oscillators under conditions where the supply of vibrational energy considerably exceeded the equilibrium value. Distribution was found by considering the effect of vibrational-vibrational and vibrational-translational energy exchange, as well as spontaneous radiative transitions. Analytical expressions were also obtained for the relaxation rate of vibrational energy. It was shown that where there is a strong deviation from equilibrium this rate can significantly exceed the corresponding value for a model of harmonic oscillators and is determined by the probability of vibrational-vibrational exchange in the molecules.