Oxygen vibrational and dissociation relaxation behind regular reflected shocks

1976 ◽  
Vol 74 (3) ◽  
pp. 477-495 ◽  
Author(s):  
H. Oertel

The oxygen vibrational and dissociation relaxation behind regular reflected shocks has been calculated and measured. Numerical calculations using published rate coefficients supplied the relaxation-zone data needed to estimate the range of most useful experimental conditions. Then photographs of the shock reflexion were taken using a complementary double-exposure interferometer. The density profiles in the relaxation zones behind the reflected shocks were measured by means of a multibeam laser-differential interferometer. The results of these experiments confirmed the theoretical model adopted for the calculations within a certain range of experimental conditions, but clearly revealed the need for revising the rate coefficients. New calculations with different vibrational relaxation times and dissociation rate coefficients then had the result that the best fit of calculated to measured profiles was obtained when the following values were inserted.Vibration\begin{eqnarray*} & p\tau_v = A_v\exp(B_vT^{-\frac{1}{3}}),\\ & A_v = (2.1\pm 0.2)\times 10^{-5}\,{\rm kg/ms},\quad B_v = 129\,{}^{\circ}{\rm K}^{\frac{1}{3}}. \end{eqnarray*}Dissociation: O2+ O_2[rlarr ] 2O + O_2\begin{eqnarray*} & {\mathop {k_1}\limits^{\rightharpoonup}} = A_1T^{-2.5}\exp (-\theta_D/T),\\ & A_1 = (6.2 \pm 0.5)\times 10^{18}\,{\rm m}^3\,{}^{\circ}{\rm K}^{2.5}/{\rm mol}\,{\rm s},\quad\theta_D = 59\,136\,{}^{\circ}{\rm K}. \end{eqnarray*}Dissociation: O2+ O[rlarr ]3O\begin{eqnarray*} & {\mathop {k_1}\limits^{\rightharpoonup}} = A_2T^{-1.0}\exp (-\theta_D/T),\\ & A_2 = (4.0 \mp 0.5)\times 10^{-13}\,{\rm m}^3\,{}^{\circ}{\rm K}/{\rm mol}\,{\rm s}. \end{eqnarray*}

1982 ◽  
Vol 60 (23) ◽  
pp. 2927-2942 ◽  
Author(s):  
Heshel Teitelbaum

A semi-empirical analysis based on a rate law for vibrational relaxation of dissociating simple harmonic oscillators allows for a detailed study of measurements of vibrational relaxation times τ and of steady dissociation rate coefficients k0. It is shown that non-equilibrium populations of vibrational energy levels prevent attainment of the thermodynamically expected equilibrium energy. Even under near-isothermal and mild conditions, [Formula: see text], serious experimental errors result when the Bethe–Teller relaxation rate law is used. Closed form expressions are given which permit evaluation of these errors. Measurements should be analyzed using the rate law[Formula: see text]where ε is the vibrational energy per molecule, τ the relaxation time, kd the non-equilibrium rate coefficient, ετ the thermodynamically expected vibrational energy at temperature T, and (ε* + hv) the energy just above the dissociation limit. It is also shown that if[Formula: see text]a local minimum and maximum are predicted for measured density gradients in shock tube dissociations of diatomic molecules, where tine is the incubation time, D′ the effective dissociation energy, and x0 the mole fraction of dissociating molecules in an inert diluent. Expressions are given for extracting incubation times and rate constants from such studies when [Formula: see text]. Analysis of experimental data actually showing such phenomena (J. Chem Phys. 55, 4017 (1971)) is carried out. There are indications that any analysis which does not explicitly account for transient effects could result in errors in measured k0's of factors of 2 or more.


1985 ◽  
Vol 113 ◽  
pp. 139-160 ◽  
Author(s):  
Douglas C. Heggie

This review describes work on the evolution of a stellar system during the phase which starts at the end of core collapse. It begins with an account of the models of Hénon, Goodman, and Inagaki and Lynden-Bell, as well as evaporative models, and modifications to these models which are needed in the core. Next, these models are related to more detailed numerical calculations of gaseous models, Fokker-Planck models, N-body calculations, etc., and some problems for further work in these directions are outlined. The review concludes with a discussion of the relation between theoretical models and observations of the surface density profiles and statistics of actual globular clusters.


1959 ◽  
Vol 30 (6) ◽  
pp. 1614-1615 ◽  
Author(s):  
Morris Salkoff ◽  
Ernest Bauer

1957 ◽  
Vol 27 (5) ◽  
pp. 1149-1155 ◽  
Author(s):  
S. J. Lukasik ◽  
J. E. Young

1998 ◽  
Vol 16 (7) ◽  
pp. 838-846 ◽  
Author(s):  
A. S. Kirillov

Abstract. The first-order perturbation approximation is applied to calculate the rate coefficients of vibrational energy transfer in collisions involving vibrationally excited molecules in the absence of non-adiabatic transitions. The factors of molecular attraction, oscillator frequency change, anharmonicity, 3-dimensionality and quasiclassical motion have been taken into account in the approximation. The analytical expressions presented have been normalized on experimental data of VT-relaxation times in N2 and O2 to obtain the steric factors and the extent of repulsive exchange potentials in collisions N2-N2 and O2-O2. The approach was applied to calculate the rate coefficients of vibrational-vibrational energy transfer in the collisions N2-N2, O2-O2 and N2-O2. It is shown that there is good agreement between our calculations and experimental data for all cases of energy transfer considered.Key words. Ionosphere (Auroral ionosphere; ion chemistry and composition). Atmospheric composition and structure (Aciglow and aurora).


2012 ◽  
Vol 2012 ◽  
pp. 1-9
Author(s):  
K. Bharath Kumar Naik ◽  
B. Ananda Kumar ◽  
S. Raju ◽  
G. Nageswara Rao

Equilibrium study on complex formation of L-histidine with Pb(II), Cd(II), and Hg(II) has been investigated pH metrically in DMSO-water mixtures (0–60% v/v) at 303 K and 0.16 mol L−1 ionic strength. The predominant species detected for Pb(II) and Cd(II) are ML2H4, ML2H3, ML2H2, ML2H, and ML2 and those for Hg(II) are ML2H4, ML2H3, ML2, and ML. The appropriateness of experimental conditions is verified by introducing errors intentionally in the concentrations of ingredients. The models containing different numbers of species were refined by using the computer program MINIQUAD75. The best-fit chemical models were arrived at based on statistical parameters. The trend in variation of stability constants of the complexes with dielectric constant of the medium is attributed to the electrostatic and nonelectrostatic forces. The species distribution and the plausible equilibria for the formation of the species are also presented.


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