Purdue University Graduate School
Thesis - Nitrogen Tetroxide to Mixed Oxides of Nitrogen - Andrew Head (11-17-2021).pdf (4.01 MB)

Nitrogen Tetroxide to Mixed Oxides of Nitrogen: History, Usage, Synthesis, and Composition Determination

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posted on 2021-11-22, 13:37 authored by Andrew W HeadAndrew W Head
Since as early as the 1920s, dinitrogen tetroxide (N2O4) has been regarded as a promising oxidizer in rocket propulsion systems. In more recent times, its predecessor, mixed oxides of nitrogen (MON), remains a top contender among oxidizers, due to its unique characteristics such as low freezing temperature and compatibility with common spacecraft materials. Today, these N2O4-based oxidizers are the preferred choice in many upper stages, launch escape systems, reaction control systems, liquid apogee engines, and in-space primary propulsion systems. N2O4-based oxidizers are a key factor in rocket propulsion, and thoroughly understanding their history, development, characteristics, synthesis, and composition analysis are crucial for space exploration today and into the future.

To fully understand and predict the physical properties of a MON sample, it is important to measure and quantify its chemical composition. The recommended method for MON composition analysis, as prescribed by the Department of Defense’s Defense Specification (MIL-SPEC) document on N2O4, involves the oxidation of NO and dinitrogen trioxide (N2O3) in the MON sample to determine their amounts. An equation unofficially called the “MIL-SPEC equation” is then used to determine the amount of NO needed to mix with N2O4 to synthesize that particular MON sample. However, no explanation is given as to how the equation was derived, or its significance.

This thesis aims to collect and organize key information on the synthesis, handling, and composition analysis of MON propellant. First, the history of development of N2O4-based oxidizers was researched, and current and future uses of N2O4 and MON propellants were identified. Then a method for synthesis and composition analysis was devised and tested. Water contamination was expected of skewing the results, so the process of water contamination was examined analytically. Then a detailed derivation of the MIL-SPEC equation was conducted, to fully understand its mechanics. An attempt was then made to reverse-engineer an unexplained numerical value in the equation, labeled by the author as the “solubility factor”. Several derivations were provided with varying degrees of complexity, producing alternative solubility factors of varying accuracies. Finally, experimental data was applied to these derived, hypothetical solubility factors and the MIL-SPEC solubility factor, with the intent of determining whether improvements could be made to the MON composition determination process.

The results suggest that the MIL-SPEC equation is sufficient for providing a relatively accurate measurement of the composition of a MON sample, while also being easy to implement, both in taking the necessary measurements and in conducting the numerical calculation. However, some minor adjustments to the equation could produce consistently more accurate composition measurements without adding any more difficulty or complication.


Degree Type

  • Master of Science


  • Aeronautics and Astronautics

Campus location

  • West Lafayette

Advisor/Supervisor/Committee Chair

Timothee Pourpoint

Advisor/Supervisor/Committee co-chair

Carson D. Slabaugh

Additional Committee Member 2

Alexey Shashurin