Purdue University Purdue e-Pubs Open Access Dissertations Theses and Dissertations Fall 2014 Investigation of condensed and early stage gas phase hypergolic reactions Jacob Daniel Dennis Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_dissertations Part of the Propulsion and Power Commons Recommended Citation Dennis, Jacob Daniel, "Investigation of condensed and early stage gas phase hypergolic reactions" (2014). Open Access Dissertations. 256. https://docs.lib.purdue.edu/open_access_dissertations/256 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. i INVESTIGATION OF CONDENSED AND EARLY STAGE GAS PHASE HYPERGOLIC REACTIONS A Dissertation Submitted to the Faculty of Purdue University by Jacob Daniel Dennis In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy December 2014 Purdue University West Lafayette, Indiana ii To my parents, Jay and Susan Dennis, who have always pushed me to be the person they know I am capable of being. Also to my wife, Claresta Dennis, who not only tolerated me but suffered along with me throughout graduate school. I love you and am so proud of you! iii ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my advisor, Dr. Timothée Pourpoint, for guiding me over the past four years and helping me become the researcher that I am today. In addition I would like to thank the rest of my PhD Committee for the insight and guidance. I would also like to acknowledge the help provided by my fellow graduate students who spent time with me in the lab: Travis Kubal, Yair Solomon, Robb Janesheski, Jordan Forness, Jonathan Chrzanowski, Jared Willits, and Jason Gabl. Thank you to Rob McGuire for all of the machining and manufacturing advice as well as being available to help fix any parts that I managed to damage or destroy over the past four years. Also thank you to Scott Meyer for all of his hard work keeping Zucrow labs and the hypergolic propellant lab safe and operational as well as his guidance during numerous CDR and TRR presentations. iv TABLE OF CONTENTS Page LIST OF TABLES ...................................................................................................... vii LIST OF FIGURES ..................................................................................................... ix NOMENCLATURE .................................................................................................. xvi ABSTRACT ........................................................................................................ xx CHAPTER 1. INTRODUCTION ............................................................................ 1 1.1 Motivation ............................................................................................1 1.2 Research Objective ...............................................................................4 CHAPTER 2. BACKGROUND .............................................................................. 6 2.1 Hypergolic Propellant History .............................................................6 2.2 Hypergolic Ignition Process .................................................................7 2.3 Traditional Experimental Methods.....................................................11 2.3.1 Drop Test Experiments ...............................................................11 2.3.2 Impinging Jet Experiments .........................................................16 2.3.3 Forced Mixing Experiments .......................................................19 2.3.4 Reaction Calorimetry ..................................................................24 2.4 Propellant Properties ..........................................................................30 2.5 Chemical Reaction Fundamentals ......................................................31 2.5.1 Acid-Base Chemistry ..................................................................31 2.5.2 Reaction Rate Equations .............................................................32 2.6 Early Stage Hypergolic Reaction Mechanisms ..................................33 2.7 Gas Phase Hypergolic Reaction Mechanisms ....................................41 2.2 Spectroscopic Measurement Techniques ...........................................48 2.2.1 Fourier Transform Infrared (FTIR) Spectroscopy ......................48 v Page 2.2.2 Ultraviolet and Visible Spectroscopy .........................................51 2.3 Species of Interest ..............................................................................51 2.3.1 Monomethylhydrazine ................................................................51 2.3.1.1 Infrared spectra of Monomethylhydrazine ..................................51 2.3.1.2 Aqueous Solutions of Monomethylhydrazine .............................53 2.3.2 Nitric Acid ..................................................................................54 2.3.2.1 Infrared Spectrum of Nitric Acid ................................................54 2.3.3 Potential Product Species ...........................................................59 CHAPTER 3. EXPERIMENTAL SYSTEMS ...................................................... 65 3.1 Hypertester .........................................................................................65 3.2 Impinging Jet System .........................................................................66 3.3 Hypergolic Bomb Reactor ..................................................................68 3.4 Instrumentation...................................................................................71 3.5 Diagnostic Tools ................................................................................71 3.5.1 UV-Visible Streak Camera Spectrometer ...................................71 3.5.2 Fourier Transform IR Spectrometer ...........................................75 CHAPTER 4. RESULTS ....................................................................................... 83 4.1 Impinging Jet Experiments ................................................................83 4.1.1 Ignition Results ...........................................................................83 4.1.1.1 Injection Conditions ....................................................................85 4.1.1.2 Data Analysis ..............................................................................88 4.1.1.3 Results .........................................................................................89 4.1.1.4 Ignition Results ...........................................................................90 4.1.1.5 Application of Thermal Ignition Theory .....................................95 4.1.1.6 Reactive Stream Separation ......................................................101 4.2 Forced Mixing Experiments .............................................................103 4.3 FTIR Spectral Measurement ............................................................109 4.3.1 FT-IR Spectra of Propellant Mixtures ......................................109 4.3.1.1 Deionized Water .......................................................................109 vi Page 4.3.1.2 Monomethylhydrazine ..............................................................110 4.3.1.3 Nitric Acid .................................................................................114 4.3.2 FTIR Spectra Condensed Phase Reactions ...............................118 4.3.2.1 Stirred Reactor Final Products ..................................................118 4.3.2.2 Rapid Scan Drop on Drop Experiments ....................................124 4.3.2.3 Reaction Order Measurements ..................................................129 4.3.2.4 Activation Energy and Frequency Factor Measurements .........137 4.3.3 Flow Through Experiments ......................................................140 4.4 Ultraviolet and Visible Spectroscopy of Gas Phase Reactions ........153 4.4.1 Hypertester Measurements .......................................................153 CHAPTER 5. CONCLUSIONS .......................................................................... 156 5.1 Impinging Jet Experiment Conclusions ...........................................156 5.2 Forced Mixing Experiments .............................................................157 5.3 FTIR Spectroscopy ...........................................................................158 5.3.1 Condensed Phase MMH and Nitric Acid .................................158 5.3.2 Condensed Phase MMH/Nitric Acid Reactions .......................158 5.3.3 Early Stage Gas Phase Reactions .............................................160 5.4 Contributions to Knowledge Base ...................................................160 5.5 Future Work .....................................................................................160 5.5.1 Forced Mixing Experiments .....................................................160 5.5.2 FTIR Spectroscopy ...................................................................161 WORKS CITED ...................................................................................................... 163 APPENDICES Appendix A Hypergolic Bomb Reactor Drawings/P&ID ............................173 Appendix B Hypergolic Bomb Reactor Procedures ....................................194 VITA ...................................................................................................... 198 PUBLICATIONS .....................................................................................................