On the interpretation of measured rotational and vibrational relaxation times. II. Sudden change experiments

Abstract

This paper examines, in terms of the normal-mode analysis developed earlier (Part I), the nature of relaxations in which a diatomic gas, highly diluted in a heat bath of inert gas atoms, is subjected to a sudden change as in shock-wave excitation or laser schlieren experiments.It is shown in detail how the observed relaxation time in a shock-wave excitation to a fixed final temperature depends on the initial temperature. At the same time, it is confirmed that the characterisation as 'mainly rotational' of the measured relaxation time in H2 when it is heated from room temperature to 1500 K in a shock wave is perfectly plausible.On the other hand, the calculations show that in laser schlieren experiments in which the v = 1, J = 1 level of H2 is overpopulated, the vibrational relaxation time of H2 at the temperature in question is recovered, although interesting effects should appear if other J levels were populated initially, or if the experiments were carried out at much higher ambient temperatures.The calculations also demonstrate that it is not generally possible to derive relaxation times by following the variation in population of any particular level of the molecule: multiple overshoots sometimes occur, and apparent relaxation times both longer or shorter than the true relaxation times could often result from attempts to follow level populations as a function of time.