The predictions of non-equilibrium radiation for a Titan aerocapture aeroshell vary significantly amongst Computational Fluid Dynamics (CFD) analyses and are limited by the physical models of the non-equilibrium flow. Of particular interest are the non-equilibrium processes associated with the cyanogen (CN) molecule which is known to be a strong radiator. It is therefore important to have experimental data for these radiating shock layers which will allow for validation of CFD models. Furthermore, a more detailed understanding of the chemical processes that lead to the formation of CN above equilibrium concentration is required. This thesis describes the modelling of the radiation behind a shock using a collisional-radiative (CR) model and presents measurements of radiation intensity behind a shock in simulated Titan and Martian atmospheres. The uncertainties in radiation is more significant at lower speeds (around 5-8 km/s) with these atmospheres when compared to Earth entry. This is due to the formation of CN and because of the highly non-equilibrium nature of the flow. The motivation for this work began with the successful landing of the Huygens probe on the surface of Titan which led to the renewed interest in inter-planetary missions. Thus radiative heating during atmospheric entry to Titan and Mars was the subject of several experimental campaigns and extensive computational analyses. In order to better understand the formation of CN, and the nonequilibrium radiation emitted under such atmospheric conditions, NASA Ames Research Center conducted a series of experiments on their Electric Arc Shock Tube facility, EAST. Furthermore, several research groups in Europe and the United States independently developed CR models to predict the measured levels of radiation. The results from these simulations showed some ma jor discrepancies and highlighted a lack of knowledge and understanding about the fundamental physics behind the formation and decay of the CN molecule and its associated excited states. Based on a comparison of the various simulations with the CR models and the EAST experimental data, it was concluded that the absolute level of peak radiation was well predicted, however, there was a significant discrepancy related to the decay rate of the radiation. Therefore, to add to the relatively small amount of experimental data for these highly non-equilibrium radiating flow conditions, experiments were performed on the X2 shock tube at The University of Queensland with the aim of producing a comprehensive set of benchmark data for Titan entry. The data obtained from these experiments have been used to validate the results from the NASA Ames testing, and due to the large parametric variation, as a source for code validation. In addition to the experimental component of this thesis, an investigation into the simulation of CN non-equilibrium radiation was conducted. It has been previously concluded that there was a significant discrepancy between the experimentally measured radiation decay rate and the predicted value from CR models. Therefore, the primary aim of the simulation work presented in this thesis is to explain the reason behind this discrepancy. Through a parametric study of important reactions combined with an analysis of the reaction set, it was concluded that the coupling between the dissociation of N2 and the formation of CN (through the reaction N2 + C ↔ CN + N) controlled the radiation decay rate. The reason for the super equilibrium concentrations was identified to be a result of the N2 + C ↔ CN + N reaction continuing to over-produce CN after nominal equilibrium values are reached. This is due to the slow build up of N to drive the reverse reaction. Thus it has been shown in this thesis that the behaviour of the CN concentration is controlled by the rate of N2 dissociation. This led to the implementation of a more thorough method for simulating the dissociation process of molecular nitrogen. Therefore, a mono-quantum vibration state specific model that includes excitation and de-excitation reactions for all the vibrational states of nitrogen was incorporated into the CR model developed by Magin et al. The nitrogen vibration state specific model that was implemented was developed by Pierott and is based on SSH theory. The model developed in this thesis is known as the ViSpeN CR model (Vibrationally Specific Nitrogen). The ViSpeN results show significantly better agreement with experimental data in terms of the decay rate, initial rise of the radiation and the overall trends in the data. However, the work in this thesis has shown there are still discrepancies in predicting the absolute level of radiation measured in shock tunnel experiments. This led to the development of a modification to the ViSpeN model (known as ViSpeN-L) which includes a proposed new value for the radiative lifetime of the CN violet transition. The agreement between the experimental data and the ViSpeN-L model is excellent for conditions relevant to Titan entry.

Kinetic data is presented for a variety of ion-neutral reactions which are relevant to the atmosphere of Titan and to the chemistry occurring in interstellar clouds. The data were recorded with a Selected Ion Flow Tube (SIFT) operating at room temperature (294 ± 4 K) and at a pressure of 0.46 Torr. Results of the recent Cassini-Huygens mission to Saturn and Titan have identified several species in the atmosphere of Titan not predicted by pre-Cassini models of the atmosphere. In order to determine the fate of three of these species (methylenimine, propionitrile and cyanodiacetylene) in Titan's ionosphere, their reactivity with the principal ions in Titan's upper ionosphere has been examined. As expected, collision rate proton transfer reactions dominate the chemistry with association channels also observed with many of the hydrocarbon ions. The results of the Cassini mission also identified several individual reactions as being of potential importance to models of Titan's atmosphere and this chemistry has also been examined. The above studies are also relevant to the interstellar medium where each of the neutral reactants have also been detected. The results of some proton transfer equilibrium studies are also presented. The gas phase basicities of propyne and acetylene have been determined to be 681 kJ mol⁻¹ and 617.4 kJ mol⁻¹ respectively. Their relative proton affinities can be estimated from these values. A combined experimental/theoretical study of the proton affinity of cyanodiacetylene (HC₅N) has enabled this value to be estimated at 770 ± 20 kJ mol⁻¹. Details of an attempt to complete the first laboratory measurement of the crucial reaction between H₃⁺ and atomic carbon are presented. The generation of atomic carbon in sufficient quantities for reaction in the SIFT was not possible with the microwave discharge source used. Other generation methods have also been explored with the laser photolysis of carbon suboxide expected to provide a possible solution to the problems encountered. The results of an investigation into the applicability of lithium ions (Li⁺) to SIFT-MS are presented. The lithium ions associated with each of the twenty-one neutral analytes examined to form pseudo-molecular ions. The association reactions were rapid (k ~ 10⁻⁹ cm³ s⁻¹) for large hydrocarbons but were much slower for smaller analytes (k < 10⁻¹¹ cm³ s⁻¹). In order to clarify some unusual experimental observations, the effect of water molecules on the observed chemistry has been examined in detail. The measured chemistry has important consequences for the applicability of Li⁺ to SIFT-MS where the presence and detection of an identifiable ion of the analyte is essential. Details of new SIFT operating software which can be run on a modern computer are given. Mass spectra and kinetic data recorded with the new software are also presented.

Zugl.: Berlin, Techn. Univ., Diss., 2009

Zugl.: Aachen, Techn. Hochsch., Diss., 2008

Thesis (M.A.)--Indiana University, 2009. / Title from screen (viewed on August 26, 2009). Department of English, Indiana University-Purdue University Indianapolis (IUPUI). Advisor(s): Jonathan Eller, John Rudy, Thomas Marvin. Includes vita. Includes bibliographical references (leaves 67-68).

Chemnitz, Techn. Univ., Diplomarb., 1999.

Zürich, Techn. Hochsch., Diss., 2002. / Zürich, ETH, Diss., 2002.

Universiẗat, Diss., 2000--Dortmund. / Dateiformat: PDF.

Techn. Hochsch., Diss., 2001--Aachen.

University, Diss., 2002--Bonn.